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Cross-Linking of Sugar-Derived Polyethers and Boronic Acids for Renewable, Self-Healing, and Single-Ion Conducting Organogel Polymer Electrolytes
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  • Emma L. Daniels
    Emma L. Daniels
    University of Bath Institute for Sustainability, Claverton Down, Bath BA2 7AY, U.K.
    Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
    Materials for Health Lab, Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
    More by Emma L. Daniels
    Orcidhttps://orcid.org/0000-0002-3227-049X
  • James R. Runge
    James R. Runge
    University of Bath Institute for Sustainability, Claverton Down, Bath BA2 7AY, U.K.
    Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
    More by James R. Runge
  • Matthew Oshinowo
    Matthew Oshinowo
    University of Bath Institute for Sustainability, Claverton Down, Bath BA2 7AY, U.K.
    Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
    More by Matthew Oshinowo
  • Hannah S. Leese*
    Hannah S. Leese
    University of Bath Institute for Sustainability, Claverton Down, Bath BA2 7AY, U.K.
    Materials for Health Lab, Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
    *Hannah Leese. Email: [email protected]
    More by Hannah S. Leese
    Orcidhttps://orcid.org/0000-0003-4523-3804
  • Antoine Buchard*
    Antoine Buchard
    University of Bath Institute for Sustainability, Claverton Down, Bath BA2 7AY, U.K.
    Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
    *Antoine Buchard. Email: [email protected]
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    Orcidhttps://orcid.org/0000-0003-3417-5194
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ACS Applied Energy Materials

Cite this: ACS Appl. Energy Mater. 2023, 6, 5, 2924–2935
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https://doi.org/10.1021/acsaem.2c03937
Published February 21, 2023

Copyright © 2023 The Authors. Published by American Chemical Society. This publication is licensed under

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Abstract

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This report describes the synthesis and characterization of organogels by reaction of a diol-containing polyether, derived from the sugar d-xylose, with 1,4-phenylenediboronic acid (PDBA). The cross-linked materials were analyzed by infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA), scanning electron microscopy (FE-SEM), and rheology. The rheological material properties could be tuned: gel or viscoelastic behavior depended on the concentration of polymer, and mechanical stiffness increased with the amount of PDBA cross-linker. Organogels demonstrated self-healing capabilities and recovered their storage and loss moduli instantaneously after application and subsequent strain release. Lithiated organogels were synthesized through incorporation of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) into the cross-linked matrix. These lithium–borate polymer gels showed a high ionic conductivity value of up to 3.71 × 10–3 S cm–1 at 25 °C, high lithium transference numbers (t+ = 0.88–0.92), and electrochemical stability (4.51 V). The gels were compatible with lithium-metal electrodes, showing stable polarization profiles in plating/stripping tests. This system provides a promising platform for the production of self-healing gel polymer electrolytes (GPEs) derived from renewable feedstocks for battery applications.

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1. Introduction

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The reversible reaction of boronic acids with cis-1,2 or cis-1,3 diols to form boronate esters has been leveraged in applications such as glucose and chemosensors, (1−6) drug delivery systems, (7−9) and chromatography. (10−12) When combined with polymeric materials, this reversible chemistry can generate functional, cross-linked hydro- or organogel networks. The formation of boronate ester cross-links is reversible, depending on pH, temperature, and the presence of other hydroxylated compounds. (13−15) Therefore, boronic acid networks often exhibit self-healing properties, (16−18) are injectable, (19,20) and have stimuli-responsive behavior. (21) The alginate-boronic acid hydrogel developed by Hong et al. demonstrates for example many of the desirable properties of boronic acid-diol cross-linking: it shows self-healing and high strain to failure and is responsive to pH and glucose concentration. (22)
Many of these self-healing networks are made from reaction of a boronic-acid-containing polymer (often a polymer containing phenylboronic acid (PBA) side chains) with a second, diol-containing polymer, such as poly(vinyl alcohol) (PVA), or catechol derivatives of polymers. (14,16−18,23) Alternatively, both components can exist within the same polymer, leading to intramolecular cross-linking and gel formation. (20−22)
Cross-linking can also be achieved by reaction of a diol-containing polymer with a small molecule, a diboronic acid cross-linker. Cross-linking of PVA with borax or boric acid, for example, is well-known to easily form a gel. (24−26) 1,4-Phenylenediboronic acid (PDBA) is soluble in many organic solvents and so can be used to synthesize various organogels. Duncan et al. demonstrated the formation of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and methanol gels from PDBA and hydrolyzed poly(vinyl acetate) (PVAc). (27,28) Gelation between PDBA and PVA or guar is also possible, with the latter able to form hollow microspheres by the extrusion of PVA into PDBA solutions. (29,30) Hydrogels of PDBA can also be formed indirectly, by immersion of organogels in water. Nishiyabu et al. for example combined PDBA, PVA, and a dansyl-modified boronic acid in DMSO to afford a fluorescent gel capable of the detection of aqueous copper ions. (3) A hydrogel has also been made from the meta derivative, 1,3-phenylenediboronic acid, and catechol-derivatized poly(ethyleneglycol) (PEG). (13)
The Lewis acidity of boron allows further functionality to be installed into the networks to create ion-conductive organogels for application as gel polymer electrolytes (GPEs). GPEs are attractive materials for use in lithium-ion technologies as they show improved safety compared to liquid electrolytes while maintaining high ionic conductivity relative to inorganic and solid polymer electrolytes (SPEs). (31,32) Indeed, boron atoms possess vacant p-orbitals which can coordinate to Lewis bases, such as hydroxide anions. (12,33) This forms a new sp3, anionic, tetrahedral boron center, immobilized within the polymer structure creating a single-ion conducting effect. Therefore, only the cations can dissociate through the polymer matrix, resulting in increased ionic conductivity and transference numbers close to unity. The electron-deficient sp2 boron center can also coordinate anions of lithium salts, acting as an “anion-trap”, enhancing dissociation of cation–anion pairs to further improve the conductivity and transference number. (33,34)
Several groups have exploited the single-ion conducting (35−40) and anion-trapping (41−44) capabilities of boron in polymer electrolyte systems. Among these, Mecerreyes and co-workers have recently reported single-ion conducting GPEs with high ambient ionic conductivity (0.71 × 10–3 S cm–1 at 25 °C) and transference numbers of up to 0.85 based upon lithium borate methacrylate polymers. (45,46) Meanwhile, Chen et al. have developed a hydrogel electrolyte through the copolymerization of methacrylate and acrylamide monomers in the presence of borate. The resulting GPE showed excellent ambient ionic conductivity of 4.5 × 10–3 S cm–1 while being able to self-heal during to the dynamic nature of its borate-diol cross-links. (47) The GPE developed by Shim et al. shows a similarly high ionic conductivity of 4.2 × 10–3 S cm–1 at 30 °C. This GPE, which is based upon a semi-interpenetrating network containing poly(vinylidene fluoride) (PVDF) and cross-linkers containing ethylene oxide chains and anion-trapping boron groups, also shows a high transference number of 0.82 due to the introduction of the boron moieties. (31) However, these examples, and most examples of boronic acid hydro- or organogels, rely on polymers derived from petrochemicals.
Our group, (48−52) among many others, (53−56) has identified monosaccharides as a promising sustainable feedstock for polymer synthesis, owing to their low cost, low toxicity, and high abundance as well as their potential for pre- or postpolymerization functionalization, due to the presence of multiple hydroxy groups. (57−59) Herein, we report a novel organogel system from the cross-linking of a sugar-derived polyether with PDBA. The polyether, previously studied in our group, is derived from d-xylose and can be modified by postpolymerization to reveal cis-1,2-diols along the polymer backbone. (50) These hydroxy groups have been utilized to generate DMSO organogels with tunable rheological properties and self-healing capabilities. Cross-linking in the presence of a lithium salt exploited the Lewis acidity of the boron-based cross-links and produced conductive organogels, which have been further investigated as a single-ion conducting gel polymer electrolyte.

2. Results and Discussion

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2.1. Organogel Synthesis

A sugar-derived, diol-containing polymer was synthesized through postpolymerization modification of a polyether derived from d-xylose (Scheme 1). As previously reported, (50) an oxetane-type monomer, d-1, was synthezised in three steps from d-xylose. Anionic ring-opening polymerization (ROP) of d-1 with potassium tert-butoxide and 18-crown-6, in a monomer:KOtBu:18-crown-6 ratio of 100:1:1, yielded a regioregular polyether, poly(d-1), with Mn,SEC of 12,500 g mol–1 (ĐM = 1.23; vs poly(lactide) standards in THF). By acid hydrolysis, near quantitative deprotection of acetal groups was achieved (>95% deprotection), yielding DMSO and water-soluble polyethers, dp-poly(d-1), with Mn,SEC of 20,000 g mol–1 (ĐM = 1.21; vs poly(methyl methacrylate) standards in DMAc/LiBr).

Scheme 1

Scheme 1. Synthesis of Monomer d-1, Subsequent Anionic Ring-Opening Polymerization, and Post-Polymerization Acetal Deprotection to Yield Hydroxy-Polymer, dp-poly(d-1)
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The newly revealed hydroxy groups in dp-poly(d-1) could then be reacted with difunctional boronic acids to form cross-linked organogels. 0.5 equiv of PDBA (with respect to the deprotected monomer unit, assuming quantitative acetal deprotection) was added to a 0.287 mol L–1 solution of dp-poly(d-1) in DMSO (Scheme 2). When stirred at room temperature (rt), the formation of a gel occurred within 5 min, as proved qualitatively via a vial inversion test (Figures 1 a–c). Reaction mixtures in the absence of either dp-poly(d-1) or PDBA remained liquid. By altering either the equivalents of PDBA or the concentration of polymer in solution, the conditions required for gelation were found (Figure 1d). The formation of a gel, as determined by the vial inversion test, is more likely in samples with high polymer concentrations and PDBA equivalents (SI, Figures S11–S14). In some cases, gel-like material was observed, but vial inversion was not successful. Hence, a partial gel event was defined.

Scheme 2

Scheme 2. Cross-Linking of dp-poly(d-1) and 1,4-Phenylenediboronic Acid (PDBA)
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Figure 1

Figure 1. Vial inversion tests of (a) a 24 mg mL–1 solution of PDBA in DMSO, (b) a 0.287 mol L–1 solution of dp-poly(d-1), and (c) a reaction between dp-poly(d-1) and PDBA observed over several hours. (d) Phase diagram of the dp-poly(d-1)/PDBA system in DMSO at room temperature.

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The equilibrium between boronate esters and diols/boronic acids is known to be pH dependent, with dissociation into free boronic acid and diols favored at pH values below the pKa of the boronic acid. (7,13,16,21,30,41) As expected, the pH reduction of the gel solutions below 2 by addition of hydrochloric acid disrupted cross-linking and caused dissolution of the polymer network, as qualitatively indicated by failure of the vial inversion test. Similarly, gels were not stable under basic conditions, with dissolution occurring above pH 13. Small amounts of gel could be reformed by addition of acid to the basic solution (Figure S15).
FT-IR analysis revealed several new chemical environments in the gels, when compared to dp-poly(d-1) and PDBA. Particularly, cross-linking was evidenced by a new signal at 696 cm–1 corresponding to new boronate ester bonds, and at new C–O stretching frequencies at 1205 cm–1 (Figure 2), the intensity of the latter increases with the degree of cross-linking (Figures S16–S18). However, the extent of cross-linking cannot be determined, as after gelation the materials were insoluble in all common solvents, hindering NMR analysis. Monosubstituted moieties, in which PDBA reacts with just one diol unit as shown in Scheme S1, may also be present within the organogels.

Figure 2

Figure 2. FT-IR spectra of dp-poly(d-1) (black), PDBA (red), and organogel (blue) made from dp-poly(d-1) (0.287 mol L–1) and 0.5 equiv of PDBA (with respect to monomer unit).

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2.2. Rheology and Self-Healing Properties

Rheology was employed to gain further insight into the organogel materials. Frequency sweep experiments from 0 to 100 Hz showed most materials to be viscoelastic (Figure 3a). At lower frequencies, typically less than 13 Hz, the storage modulus (G′) is less than the loss modulus (G″). Beyond a cross-over frequency (ωc, 13.5–49.6 Hz), a gel-like region exists in which G′ is greater than G″. Looking at the 0.287 mol L–1/PDBA (0.25 equiv.) system in detail, G′ (793 Pa at 1 Hz) < G″ (2737 Pa at 1 Hz) was observed at rotating frequencies below 13.5 Hz, while G′ (9963 Pa at 20 Hz) > G″ (6648 Pa at 20 Hz) at frequencies greater than 13.5 Hz (Figure 3a, black trace). Such frequency-dependent moduli, with G′ > G″ only at higher frequencies, indicate the presence of dynamic cross-links. (16) At long time scales (low frequencies) the network can reorganize with viscous behavior, while at short time scales (high frequencies) the cross-linked network is more rigid, with elastic behavior. (42) The organogel stiffness depends on its composition, with increased PDBA content yielding increased storage and loss moduli across all frequencies due to higher degrees of cross-linking. Similar trends have been observed in other PDBA organogel systems. (27) The crossover frequency also increased as samples became more cross-linked, occurring at 13.5, 22.3, and 24.6 Hz for materials made with 0.25, 0.50, and 1.00 equiv of PDBA, respectively. The polymer concentration also affected the rheological behavior of the cross-linked materials. Those made with 0.144 mol L–1 polymer solutions exhibit true gel behavior, with G′ > G″ across all frequencies (Figure 3b). (22) This polymer concentration produced materials with consistent gel-like behavior, irrespective of the amount of PDBA (Figures S22–S24).

Figure 3

Figure 3. (a) Dynamic frequency sweep of organogels made from dp-poly(d-1) (0.287 mol L–1) and increasing PDBA equiv. (b) Dynamic frequency sweep of organogels made from dp-poly(d-1) (increasing concentrations) and PDBA (1 equiv).

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The self-healing ability of the system was also investigated. An organogel made from a 0.144 mol L–1 solution of dp-poly(d-1) with 0.50 equiv of PDBA was chosen for this analysis, as it showed gel-like behavior across all frequencies and demonstrated relatively high G′ and G″ values. First, the critical strain required to break the cross-linking network was identified by increasing the applied strain on 1 Hz oscillatory measurements. After 5% strain, the material showed liquid behavior, with G″ > G′, indicating disruption of the gel network (Figure S26). Upon strain release (back to 0.007%), the cross-links were able to reform, and the original moduli values were immediately restored (Figure 4). The organogel showed a G′ of 8457 Pa and G″ of 352 Pa before the application of strain. After release, the material recovered its gel-like behavior (G′ > G″), exhibiting average moduli of 8452 and 622 Pa for G′ and G″, respectively.

Figure 4

Figure 4. Change in moduli during a strain ramp of an organogel (0.144 mol L–1 dp-poly(d-1), 0.50 equiv of PDBA) measured at a frequency of 1 Hz. The percentage strain was increased from 0.007% to 100%; then strain was released; and the moduli were measured at 0.007% strain.

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The ability of the organogel to self-heal was further demonstrated in step-strain measurements performed at 1 Hz (Figure 5). The percentage strain was varied in sequential strain steps: 0% to 10% to 0% to 20% to 0% to 40% to 0% to 60% to 0% to 80% to 0% to 100% to 0%. Each time the strain was relaxed (up to 80% strain), the material fully recovered its original storage modulus. Even after release of the highest strains (80 and 100% strain), 84 and 74% of the original storage, modulus was recovered, with average values of 8640 and 7810 Pa, respectively. These results show that the material quickly recovers its structural properties after experiencing mechanical strain.

Figure 5

Figure 5. Gel fracture and self-healing in sequential strain steps. Top shows the measured storage moduli at each strain step, as described in the bottom plot (0% → 10% → 0% → 20% → 0% → 40% → 0% → 60% → 0% → 80% → 0% → 100% → 0%, measured at 1 Hz).

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2.3. Lyophilized Gel Microstructure and Thermal Properties

To investigate the microstructure of the gel materials, samples made from a 0.144 mol L–1 solution of dp-poly(d-1) with 0.25–1.00 equiv of PDBA were analyzed by field emission scanning electron microscopy (FE-SEM). To remove DMSO from the system, the gels were first flash frozen in liquid nitrogen and then dried under vacuum in a process akin to freeze-drying. Materials exhibited large, irregular pores throughout. The microstructure showed a dependency on the cross-linking density (Figure 6). Cross-sectional imaging of the 0.25 material showed many globular pores, of up to 0.124 mm in length (in an observed area of 0.474 mm2). Increasing the proportion of PDBA to 0.50 equiv formed a less dense structure with directional, elongated pores (up to 0.415 mm in length, observed from 4.226 mm2). Further increase of cross-linking density produced a denser structure, with fewer observable pores (up to 0.118 mm observed in 0.473 mm2, also see Figures S35–S38). This structure could be due to more prominent monosubstitution of polymer chains (see Scheme S1).

Figure 6

Figure 6. FE-SEM imaging of lyophilized organogels made from 0.144 M solutions of dp-poly(d-1) in DMSO with 0.25–1.00 equiv of PDBA.

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The thermal characteristics of the lyophilized gels were analyzed. Compared to the non-cross-linked dp-poly(d-1), thermal gravimetric analysis (TGA) of dried gel samples showed that cross-linking increased thermal stability. The sample with 0.25 equiv of PDBA showed a Td,max of 368 °C, compared to 272 °C for dp-poly(d-1). This increased thermal stability is expected from the introduction of cross-linking and the presence of rigid phenyl rings. Increasing the amount of PDBA to 0.50 equiv provides more cross-linking opportunities, which is reflected by a further increase in the onset of thermal degradation to Td,max = 376 °C. As the amount of PDBA was increased further to 1.00 equiv, the onset of degradation decreased slightly, to 356 °C (Figure 7a). This change could again be explained by an excess of PDBA favoring monosubstitution of dp-poly(d-1), leaving more diol moieties along the polymer chains. The presence of diol moieties is known to reduce the thermal stability of this polyether (Td,max,poly(d-1) = 372 °C vs Td,max,dp-poly(d-1) = 272 °C, Figures S39–S40); (50) hence, monosubstitution would decrease the observed Td,max. (54) Most cross-linked materials showed an absence of glass transition, crystallization, and melting events by differential scanning calorimetry (DSC, Figures S49–S51), although a small glass transition can be observed in the material made with 0.50 equiv of PDBA (Tg = 112 °C, Figure S47).

Figure 7

Figure 7. TGA of (a) lyophilized and (b) nonlyophilized organogel samples made from dp-poly(d-1) and PDBA with a polymer concentration of 0.144 mol L–1 and PDBA equiv of 0.25–1.00. Annotations of the Td,max values of each sample.

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Nonlyophilized materials were also analyzed by TGA. A similar trend to the lyophilized materials was observed: the thermal stability increased as the amount of cross-linking increased until monosubstitution became favored at high PDBA equiv (Figure 7b). TGA analysis of nonlyophilized materials also allowed the gel solvent content to be quantified. Samples were held at 100 °C for two hours to remove all the DMSO solvent (Figures S44–S46), resulting in 75, 68, and 71% mass loss for materials (and therefore mass solvent percentage) made with 0.50, 0.50, and 1.00 equiv of PDBA, respectively.

2.4. Gel Polymer Electrolytes and Electrochemical Properties

As well as facilitating gelation and self-healing, cross-linking with boronic acids allows additional functionality to be installed via the empty p-orbital of boron. After reacting with the diols of dp-poly(d-1), the boron center is sp2 hybridized and can coordinate with an additional nucleophilic group to become anionic and sp3 hybridized. (31) Balancing the charge with lithium counter cations introduces conductivity. Thus, cross-linking dp-poly(d-1) with PDBA (0.5 equiv) in the presence of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, 1.0 equiv) produced single-ion conductive organogels (Scheme 3).

Scheme 3

Scheme 3. Cross-Linking of dp-poly(d-1) and PDBA in the Presence of a Lithium Salt (LiTFSI)
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The presence of LiTFSI in the cross-linked network changed the material’s rheological behavior. The material made from 0.144 mol L–1 solution of dp-poly(d-1) and 0.50 equiv of PDBA still showed gel behavior (G′ > G″) and self-healing capabilities (Figures S27–S29), akin to its nonlithiated analogue, but was softer with reduced storage and loss moduli (at 1 Hz, G′Li = 2227 Pa vs G′non,Li = 10233 Pa, G″Li = 1099 Pa vs G″non,Li = 2923 Pa). Materials made with a 0.287 mol L–1 solution of dp-poly(d-1) and 0.50 equiv of PDBA were viscoelastic in the absence of LiTFSI but showed gel-like behavior and self-healing when lithiated (Figures S30–S32). The effect LiTFSI had on the rheological properties of these materials confirms that it is fully incorporated within the cross-linked polymeric network.
The temperature within electrochemical devices is variable during battery operation. Therefore, temperature-dependent rheological measurements were conducted on the lithiated gels, to gain further insight into their mechanical integrity. Both materials retained gel-like behavior across the temperature range studied (25–70 °C). Although the 0.144 mol L–1 material softened with increasing temperature (decrease of storage and loss moduli, Figure S33), the 0.287 mol L–1 material showed good thermal stability, with only small differences between the storage and loss moduli measured at 25 and 70 °C (G′25 °C = 1237 Pa, G′75 °C = 1037 Pa, 84% decrease, Figure S34). Retention of properties at elevated temperatures indicated that this latter material was suitable for electrochemical analysis and had potential to be a self-healing, renewable gel polymer electrolyte.
The conductivity of this organogel (referred to as Li-gel in the following) was assessed using electrochemical impedance spectroscopy (EIS). Typical Nyquist plots were obtained, with partial semicircles representing bulk resistance (Rb) followed by diagonal lines showing Warburg diffusion (Figure S52). The gel showed a room temperature (25 °C) ionic conductivity of 3.71 × 10–3 S cm–1. As shown by the Arrhenius plots in Figure 8, conductivity was further enhanced at elevated temperatures as Rb decreased, reaching 4.99 × 10–3 S cm–1 at 60 °C (Figure S54, Table S1). As a control, a nonlithiated gel analogue was also analyzed by EIS and showed reduced ionic conductivity across all temperatures compared to the sample containing LiTFSI (Figures S53–S54, Table S2). These initial EIS experiments demonstrate the potential for this system to be used as a gel polymer electrolyte, or GPE. GPEs are attractive electrolyte materials as they alleviate the safety concerns of liquid electrolytes while achieving higher ionic conductivities than solid polymer electrolyte (SPE) alternatives. (31,32) The ambient ionic conductivity of our system (3.71 × 10–3 S cm–1 at 25 °C) matches or exceeds recently reported, boron-containing GPEs (see Table S3). (60−63)

Figure 8

Figure 8. Temperature dependence of ionic conductivity (σ) for lithiated (1 equiv of LiTFSI, 0.144 mol L–1; Li-gel) and nonlithiated (control) organogels made from dp-poly(d-1) (0.287 mol L–1 with respect to the repeating unit) with 0.50 equiv of PDBA.

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In terms of single-ion conducting GPEs featuring anion-trapping boron moieties, the ionic conductivity values reported for Li-gel in this study are comparable to those achieved by Ma and co-workers (2.33 × 10–3 S cm–1 at room temperature) (60) and Dai et al. (8.4 × 10–4 S cm–1 at 30 °C). (61) Similarly, Shi and co-workers have recently reported a novel single-ion conducting boron-centered GPE, which showed ionic conductivity (1.03 × 10–3 S cm–1 at 32 °C) in the same order of magnitude as the system reported in this study. (62) Moreover, Xu et al. have reported a self-healing hydrogel polymer electrolyte, based upon copolymers of glycerol monomethacrylate and acrylamide with dynamic borate cross-links, which showed comparable ionic conductivity of 4.5 × 10–3 S cm–1 at room temperature. (63)
Further electrochemical characterization was carried out. Electrochemical stability was determined by linear sweep voltammetry (Figure S56). Li-gel displayed anodic stability up to 4.51 V (vs Li/Li+), therefore beyond the 4.2 V stability to oxidation required for practical application. The lithium transference number was also determined using the Bruce–Vincent method, combining DC polarization chronoamperometry and EIS measurements in a symmetrical Li|GPE|Li cell. Although equilibrium was not obtained, Li-gel presented high tLi+ values between 0.88 and 0.92 during combined EIS and chronoamperometry measurements (average of 3 repeats, Table S4 and Figure S57). This data provides an estimate of the tLi+ of Li-gel and is consistent with single-ion conducting behavior, demonstrating the potential of the GPE.
Finally, the performance of Li-gel for the stripping/plating behavior of Li+ was investigated by recording polarization profiles in a symmetrical Li|GPE|Li cell at 25 °C (Figure 9). Li-gel exhibited good cycling behavior for at least 10 full cycles (20 h) at consecutive current densities of 0.1, 0.5, and 1.0 mA cm–2, with small overpotentials ≤0.05 V (vs Li/Li+) for the latter current density. When a large current density of 2.5 mA cm–2 was applied, a severe voltage noise was observed which was attributed to short circuits due to lithium dendrites emerging from the electrode surfaces. (64) Nevertheless, the ability of the material to withstand a critical current density of up to 1.0 mA cm–2 is highly promising and compares well with recent single-ion gel polymer electrolytes based on borate pendant groups, even if more studies are needed, including over a longer time frame and in Li|Li-gel|cathode cells. However, preliminary results using Li|Li-gel|LiFePO4 showed poor charging/discharging behavior, suggesting that lithium iron phosphate may not be an appropriate cathode material for this GPE. The dynamic nature of boronic acid cross-linking and the generation of water upon cross-linking may also explain this and the fluctuation in current during the measurement of tLi+. More investigations are currently underway and will be reported in due course.

Figure 9

Figure 9. Li+ stripping/plating voltage profile of Li-gel in a symmetrical Li|Li-gel|Li cell at 25 °C. The half-cycle duration was 1 h with a cutoff voltage of ±1.0 V.

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Like the majority of polymer electrolytes, the leading boron-containing GPEs rely on fossil fuel derived polymers. Several GPEs have recently been developed from renewable, biobased materials, such as derivatives of cellulose, natural rubber, and chitosan. (65−69) The electrochemical performance of the sugar-derived system reported here rivals many of these examples and combines the benefits of anion trapping with the sustainability benefits of renewable polymers. Further investigation is therefore warranted to study and optimize the anion-trapping capabilities of PDBA in these systems and its effect on the electrochemical performance of the renewable and self-healing GPE.

3. Conclusions

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A new self-healing organogel system has been developed from the room-temperature cross-linking of a sugar-derived polyether and 1,4-phenylenediboronic acid (PDBA) in DMSO. The effect of cross-linking density and polymer concentration on the material properties has been demonstrated, with viscoelastic and gel materials favored at polymer concentrations above and below 0.144 mol L–1, respectively. As expected, the stiffness of the materials can be tuned according to the equivalents of PDBA: stiffer materials are produced from higher cross-linking densities. Due to the dynamic nature of the boronate ester bonds, the materials show excellent self-healing abilities. After application of up to 100% strain, materials immediately recover at least 74% of their original storage modulus. The boronate ester moieties also allowed lithium ions to be incorporated throughout the cross-linked polymer matrix network, producing single-ion conductive organogels. Gels retain their self-healing nature after lithiation, enabling the production of self-healing, gel polymer electrolytes (GPEs). Initial electrochemical impedance spectroscopy (EIS) measurements show that this system is a promising candidate for Li battery applications. The organogel demonstrates high ambient ionic conductivities of 3.71 × 10–3 S cm–1, matching or outperforming recently reported GPEs. It also showed high anodic stability (4.51 V vs Li/Li+), high transference numbers (0.88–92), and high critical current density (1 mA cm–2). This promising electrical performance, coupled with the self-healing properties and renewable nature of the xylose-derived polymer, means there is scope to optimize electrochemical performance (including in whole cell setups) while investigating gelation in common electrolyte solutions, such as ethylene (EC), propylene (PC), or dimethyl carbonate (DMC).

4. Experimental Section

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4.1. Materials and Methods

All reagents were used all purchased, without further purification. d-Xylose and 1,2-O-isopropylidene-α,d-xylofuranose were purchased from Carbosynth. Sulfuric acid (H2SO4) was purchased from VWR. Potassium carbonate (K2CO3), trifluoroacetic acid (TFA), triethylamine (NEt3), and potassium methoxide (KOMe) were purchased from Fischer scientific. Tosylchloride (TsCl), potassium tert-butoxide (KOtBu), and 1,4-phenylenediboronic acid (PDBA) were purchased from Merck. 18-Crown-6 was purchased from Acros Organics.

4.2. Characterization Methods

4.2.1. NMR Spectroscopy

NMR spectra were recorded in either CDCl3, DMSO, or D2O on a Bruker-400 or -500 MHz instrument referenced to the corresponding residual solvent as an internal standard: 1H NMR spectra (400 or 500 MHz) δH = 7.26, δH = 2.50, and δH 4.79 ppm for residual protiated CDCl3, DMSO, and D2O, respectively: 13C NMR spectra (101 or 126 MHz) δC = 77.16, δC = 39.52 ppm for CDCl3, DMSO-d6, and D2O, respectively.

4.2.2. Size-Exclusion Chromatography (SEC)

The number-average molar mass, Mn, and dispersity, ĐM, of polymer samples were determined by size exclusion chromatography (SEC) in a THF or dimethylacetamide (DMAc) eluent (DMAc contains 0.1% w/v LiBr). Polymer samples were dissolved to a concentration of ∼2 mg/mL. Multianalysis software was used to process the data. THF samples were recorded on an Agilent 1260 Infinity series instrument at 1 mL min–1 at 35 °C using two PLgel 5 μm MIXED-D 300 × 7.5 mm columns in series. Samples were detected with a differential refractive index (RI) detector. Number-average molar mass (Mn,SEC) and dispersities (ĐM (Mw/Mn)) were calculated against a polystyrene calibration (11 polystyrene standards of narrow molar mass, ranging from Mw 615 to 568000 Da). DMAc samples were measured on an Agilent 1260 SEC MDS instrument at 0.5 mL min–1 at 50 °C using a Polargel-M 300 × 7.5 mm column. Samples were detected using an RI detector. Mn,SEC and ĐM were calculated against a polymethylmethacrylate calibration (11 polymethylmethacrylate standards of narrow molar mass ranging from Mw 885 to 260900).

4.2.3. Thermogravimetric Analysis (TGA)

TGA was performed on a Setsys Evolution TGA 16/18 from Setaram. The Calisto program was used to collect and process data. Samples were loaded into a 170 μL alumina crucible and heated from 30 to 500 °C at a rate of 10 °C min–1.

4.2.4. Differential Scanning Calorimetry (DSC)

Glass transition temperatures, Tg, of polymer samples were found using DSC on a Q20 machine from TA Instruments, controlled by the Q Series program. Samples were loaded into a 10 μL Tzero aluminum pan. Samples were heated and cooled at a rate of 10 °C min–1 and immediately submitted to a second heating and cooling cycle at the same rate. The heat flow was recorded against an empty reference 10 μL Tzero aluminum reference pan.

4.2.5. IR Spectroscopy

IR spectra were recorded using a Spectrum 100 FT-IR spectrometer from Perkin-Elmer and were baseline corrected in MatLab.

4.2.6. pH

Measurements were conducted using an MD 8000 L pHenomenal pH meter from VWR.

4.2.7. Rheology

Measurements were conducted using a Discovery HR-2 hybrid rheometer from TA Instruments with a 25 mm parallel plate geometry. Unless otherwise specified, a temperature of 25 °C was maintained throughout the experiments. Oscillatory frequency sweep measurements were conducted at 0.007% strain. Oscillatory strain amplitude measurements were conducted at a frequency of 1 Hz.

4.2.8. Microscopy

Images were taken using a JEOL JSM-7900F field emission scanning electron microscope (FE-SEM) from JEOL U.K., Ltd. Before imaging, samples were coated with 20 nm of gold using a Quorum Q150T S sputter coater from Quorum Tech. Analysis of images was conducted using the Image J software (Java 1.8.0_112 64 bit).

4.2.9. Electrochemistry

Measurements were performed using a modified version of a TCS battery cell (RHD instruments) with blocking stainless steel current collectors (exposed area diameter = 0.8 cm) connected to a Metrohm Autolab PGSTAT204 potentiostat with a FRA32M module. The cell components were dried in a vacuum oven at 70 °C prior to assembly. Temperature control of the cell was achieved using an Autolab Microcell HC temperature-controlled cell stand and temperature controller designed by RHD instruments. The cell was equilibrated for 1 h at each temperature before measurements were taken. Ionic conductivity (σ) was determined by a two-electrode electrochemical impedance spectroscopy (EIS) measurement in the typical frequency range of 0.1 Hz to 0.5 MHz with an applied amplitude of 50 mV in a symmetrical SS|GPE|SS cell. Results shown are averages of five repeat measurements taken at each temperature value. NOVA 2.1 (Metrohm) software was used to analyze the results. The bulk resistance (Rb) was taken as the high-frequency intercept of the Z′ axis on the Nyquist plot. (70) The ionic conductivity values were then calculated using
σ=lRbA
where l is the thickness of the gel (determined by triplicate measurements with digital callipers), and A is the area of the electrode surface.
Linear sweep voltammetry was used to determine the electrochemical stability in a Li|GPE|SS cell using a lithium counter/reference electrode at 25 °C. The open-cell voltage (OCV) was first determined, and then the voltage swept from the OCV to +6 V with a scan rate of 1 mV s–1.
Lithium transference number (t+) was determined using a combined EIS and chronoamperometry method using a Li|GPE|Li symmetrical cell using lithium foil of 0.75 mm thickness and an applied voltage of 10 mV. The measurement was recorded at 25 °C, and t+ was calculated using the Bruce–Vincent equation
t+=Iss(ΔV−I0Rb,0)I0(ΔV−IssRb,SS)
where ΔV is the applied voltage and I0 and ISS represent the initial and steady state current before and after DC polarization. Rb,0 and Rb,SS represent the bulk resistance obtained from EIS measurements before and after DC polarization.
The Li+ stripping/plating behavior was measured in symmetrical Li/Li cells (Li thickness = 750 μm) with half-cycle durations of 1 h at 25 °C. Ten full cycles with ±1.0 V cutoff voltages were performed for each current density until the experiment was stopped due to cell failure.

4.3. Synthetic Procedures

4.3.1. 1,2-O-Isopropylidene-xylofuranose (IPXF)

Following an adapted literature procedure: (1)d-xylose (20.00 g, 133.34 mmol, 1.00 equiv), nonanhydrous acetone (500 mL), and 95–98% concentrated H2SO4 (20 mL, 373.16 mmol, 2.80 equiv) were combined to form a pale-yellow suspension. The suspension was left to stir until the solid had fully dissolved to form a yellow solution (ca. 1 h). Upon full dissolution, an aqueous solution of K2CO3 (224 mL, 1.10 mol L–1, 246.01 mmol, 1.84 equiv) was slowly added. The resultant white suspension was allowed to stir at room temperature with aliquots taken at regular intervals to monitor the deprotection by TLC (1:1 HCCl3:acetone eluent) and NMR (d6-DMSO). After approximately 90 min, near-quantitative formation of the monoprotected sugar was observed. Solid K2CO3 (17.80 g, 128.79 mmol, 1.04 equiv) was added slowly at room temperature and the pH adjusted until 7–8 by litmus paper. The suspension was then filtered and the acetone removed in vacuo at 40 °C. The aqueous phase was washed with DCM (100 mL, ×3), and the organic phases were collected and back extracted with water (50 mL, ×3). The aqueous phases were collected, and the water was removed in vacuo at 50 °C. The resultant oil was dissolved in EtOAc and stirred over MgSO4 overnight. The suspension was filtered and the solvent removed in vacuo at 40 °C to yield 1,2-O-isopropylidene-α-xylofuranose (IPXF) as a clear oil (19.76 g, 78%).

4.3.2. 1,2-O-Isopropylidene-5-O-tosyl-xylofuranose (Ts-IPXF)

IPXF (20.00 g, 105.16 mmol, 1.00 equiv) and tosyl chloride (22.06 g, 115.68 mmol, 1.10 equiv) were dissolved in dichloromethane (200 mL). The reaction vessel was cooled over ice, and triethylamine (100 mL, 574.17 mmol, 5.46 equiv) was added. The vessel was left to warm to 20 °C overnight. Ethyl acetate (200 mL) was added, and the mixture was transferred to a separating funnel. The organic phase was then washed with brine (150 mL, ×1), 1 mol L–1 sodium hydrogen carbonate (150 mL, ×1), and water (150 mL, ×1). The organic phase was collected and dried over magnesium sulfate, filtered, and concentrated in vacuo at 40 °C to give a white solid. The solid was then stirred over cold Et2O (−18 °C, 150 mL) for 10 min, filtered over a glass frit, and rinsed again with cold Et2O (50 mL). The precipitate was left to dry in a vacuum oven overnight at 50 °C to give the product as an off-white solid (28.32 g, 82.59 mmol, 79%). Synthesized or commercial IPXF can be used. Quoted yield uses commercial IPXF.

4.3.3. Monomer d-1

To a round-bottom flask was charged Ts-IPXF (15.90 g, 46.04 mmol, 1.00 equiv) and acetonitrile (160 mL). The suspension was agitated at 400 rpm until a clear colorless homogeneous solution was obtained. Potassium methoxide (6.84 g, 96.68 mmol, 2.10 equiv) was added to the solution which was then heated to reflux (80 °C) for 1 h. The resulting dark brown reaction was quenched by addition of water (80 mL). The acetonitrile was removed in vacuo at 40 °C. The aqueous phase was extracted with Et2O (100 mL, ×3). The organic phases were collected and washed with brine (100 mL, ×1), 1 mol L–1 sodium hydrogen carbonate (100 mL, ×1), and water (100 mL, ×1). The organic phases were collected, dried over MgSO4, filtered, and concentrated in vacuo at 40 °C to give d-1 as a clear oil. For further purification, the oil was stirred over CaH2 at 80 °C overnight and vacuum distilled (1 × 10–2 mbar, 40 °C) to yield the oxetane as a clear oil (5.52 g, 32.11 mmol, 70%).

4.3.4. General Procedure for the Polymerization of d-1

Under an argon atmosphere, a centrifuge tube was charged with the oxetane monomer (2.00 g, 11.63 mmol, 100.00 equiv), KOtBu (232 μL, 0.5 mol L–1 in THF, 1.00 equiv), and 18-crown-6 (232 μL, 0.5 mol L–1 in THF, 1.00 equiv). The tube was sealed and heated to 120 °C with stirring. After 22 h, the vial was cooled, and the solid was dissolved in the minimum amount of CHCl3 and then precipitated from cold Et2O. The suspension was centrifuged (3500 rpm, 5 min), and the solid phase was collected. The polymer was then redissolved in CHCl3 and precipitated twice more from cold Et2O with centrifugation (3500 rpm, 5 min). The solid was collected and dried in a vacuum oven for 24 h at 100 °C to yield the polyether (1.59 g, 9.26 mmol, 80%).

4.3.5. General Procedure for the Deprotection of Polyethers

Following an adapted literature procedure: to a dram vial was added poly(d-1) (1.86 g, 10.83 mmol, Mn,SEC 7250–12,600 g mol–1, ĐM = 1.2) and DCM (7.40 mL). Upon dissolution, the reaction mixture was cooled to 0 °C, and a 4:1 TFA:H2O solution (18.00 mL) was added. After 8 h, the produce was precipitated from cold Et2O, and the resulting suspension was centrifuged (3500 rpm, 5 min). The solid phase was collected and rinsed twice more in cold Et2O or until the supernatant was neutral by a litmus test. The solid phase was collected, but not dried, to yield the polyether deprotected at 91% (calculated by relative integration of protected and deprotected anomeric environments in 1H NMR spectroscopy, see Section 4.2.5). The product was immediately dissolved into an appropriate solvent for analysis or further reaction (1.40 g, 10.60 mmol, 98%, Mn,SEC 20,300–24,300 g mol–1, ĐM = 1.21–1.71).

4.3.6. General Procedure for the Cross-Linking of dp-poly(d-1) and PDBA

In a dram vial, PDBA (0.05–1.00 equiv with respect to the deprotected polymer repeat unit; an example calculation of the amount of PDBA used in the synthesis can be found in the Supporting Information) was added to a solution of dp-poly(d-1) in DMSO (0.072–0.409 mol L–1). The mixture was stirred at room temperature until gelation occurred (as confirmed by a vial inversion test). For rheological and self-healing measurements, the mixture was transferred into a glass Petri dish (diameter = 3.5 cm, depth = approximately 0.8 cm) before the point of gelation. The mixture was covered and allowed to mature overnight at room temperature.

4.3.7. General Procedure for the Formation of Conductive Organogels

In a dram vial, PDBA (0.50 equiv with respect to the deprotected polymer repeat unit) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, 1.00 equiv) were added to a solution of dp-poly(d-1) in DMSO (0.144 or 0.287 mol L–1). The mixture was stirred at room temperature and then was transferred into a glass Petri dish (diameter = 3.5 cm, depth = approximately 0.8 cm) before the point of gelation. The mixture was covered and allowed to mature at room temperature. To perform EIS, a disc of diameter 1.1 cm was cut from the gel after 3–4 h of curing. The gel was then transferred into the electrochemical cell for analysis: the disc of gel was placed onto a stainless-steel current collector (diameter of exposed area = 0.8 cm) electrode inside a TSC battery cell (RHD Instruments). The second electrode was placed on top of the gel, and the cell was closed and tightened to ensure sufficient electrode contact. For LSV and DC polarization measurements where lithium electrodes (d = 1.0 cm) were used, the electrodes were first polished with a nylon brush before contact with the gel was made.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsaem.2c03937.

  • Cross-linking procedures, NMR spectra, photographs of vial inversion tests, FT-IR spectra, detailed rheological characterizations, FE-SEM microscopy, TGA and DSC traces, and additional electrochemistry results (PDF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

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  • Corresponding Authors
  • Authors
    • Emma L. Daniels - University of Bath Institute for Sustainability, Claverton Down, Bath BA2 7AY, U.K.;  Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.;  Materials for Health Lab, Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, U.K.;  Orcidhttps://orcid.org/0000-0002-3227-049X
    • James R. Runge - University of Bath Institute for Sustainability, Claverton Down, Bath BA2 7AY, U.K.;  Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
    • Matthew Oshinowo - University of Bath Institute for Sustainability, Claverton Down, Bath BA2 7AY, U.K.;  Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
  • Author Contributions

    The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. ELD: polymer and material synthesis and characterization, investigation, and manuscript writing. JRR and MO: electrochemical analysis, methodology, and manuscript writing. Electrochemical analysis was performed by JRR. HSL and AB: conceptualization, manuscript writing – review and editing, supervision, and funding acquisition.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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We thank Konstantinos Myronidis for help and useful discussions regarding rheological measurements and Prof Frank Marken for advice on EIS. Analytical facilities were provided through the Material and Chemical Characterization Facility (MC2) at the University of Bath. We thank Dr. Philip Fletcher for assistance with FE-SEM imaging. Research funding from the Engineering and Physical Sciences Research Council (DTP studentship to JRR, EP/L016354/1 CDT in Sustainable Chemical Technologies Studentship to ELD), the University of Bath (studentship to MO), and the Royal Society (UF/160021 and URF\R\221027, fellowship to AB) is also acknowledged.

ABBREVIATIONS

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PDBA

1,4-phenylenediboronic acid

FT-IR

Fourier-transform infrared

TGA

thermal gravimetric analysis

DSC

differential scanning calorimetry

LiTFSI

lithium bis(trifluoromethanesulfonyl)imide

GPE

polymer gel electrolyte

PVA

poly(vinyl alcohol)

DMSO

dimethyl sulfoxide

DMF

dimethylformamide

PVAc

poly(vinyl acetate)

PEG

poly(ethyleneglycol)

SPE

solid polymer electrolyte

ROP

ring-opening polymerization

DMAc

dimethylacetamide

LiBr

lithium bromide

EIS

electrochemical impedance spectroscopy

DC

direct current

SEC

size exclusion chromatography

THF

tetrahydrofuran

References

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This article references 70 other publications.

  1. 1
    Asher, S. A.; Alexeev, V. L.; Goponenko, A. V.; Sharma, A. C.; Lednev, I. K.; Wilcox, C. S.; Finegold, D. N. Photonic Crystal Carbohydrate Sensors: Low Ionic Strength Sugar Sensing. J. Am. Chem. Soc. 2003, 125 (11), 3322– 3329,  DOI: 10.1021/ja021037h
    Google Scholar
    1
    Photonic crystal carbohydrate sensors: Low ionic strength sugar sensing
    Asher, Sanford A.; Alexeev, Vladimir L.; Goponenko, Alexander V.; Sharma, Anjal C.; Lednev, Igor K.; Wilcox, Craig S.; Finegold, David N.
    Journal of the American Chemical Society (2003), 125 (11), 3322-3329CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    We developed a carbohydrate sensing material, which consists of a cryst. colloidal array (CCA) incorporated into a polyacrylamide hydrogel (PCCA) with pendent boronic acid groups. The embedded CCA diffracts visible light, and the PCCA diffraction wavelength reports on the hydrogel vol. This boronic acid PCCA responds to species contg. vicinal cis diols such as carbohydrates. This PCCA photonic crystal sensing material responds to glucose in low ionic strength aq. solns. by swelling and red shifting its diffraction as the glucose concn. increases. The hydrogel swelling results from a Donnan potential due to formation of boronate anion; the boronic acid pKa decreases upon glucose binding. This sensing material responds to glucose and other sugars at <50 μM concns. in low ionic strength solns.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXhtlCjurw%253D&md5=c9bb215f15a2ba470cfee40614f07513
  2. 2
    Lerner, M. B.; Kybert, N.; Mendoza, R.; Villechenon, R.; Bonilla Lopez, M. A.; Charlie Johnson, A. T. Scalable, non-invasive glucose sensor based on boronic acid functionalized carbon nanotube transistors. Appl. Phys. Lett. 2013, 102 (18), 183113,  DOI: 10.1063/1.4804438
    Google Scholar
    2
    Scalable, non-invasive glucose sensor based on boronic acid functionalized carbon nanotube transistors
    Lerner, Mitchell B.; Kybert, Nicholas; Mendoza, Ryan; Villechenon, Romain; Bonilla Lopez, Manuel A.; Charlie Johnson, A. T.
    Applied Physics Letters (2013), 102 (18), 183113/1-183113/4CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)
    The authors developed a scalable, label-free all-electronic sensor for D-glucose based on a carbon nanotube transistor functionalized with pyrene-1-boronic acid. This sensor responds to glucose in the range 1 μM-100 mM, which includes typical glucose concns. in human blood and saliva. Control expts. establish that functionalization with the boronic acid provides high sensitivity and selectivity for glucose. The devices show better sensitivity than com. blood glucose meters and could represent a general strategy to bloodless glucose monitoring by detecting low concns. of glucose in saliva. (c) 2013 American Institute of Physics.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXnsVyqsr8%253D&md5=61fd44d3e2790d91b7aa1fabad2a105b
  3. 3
    Nishiyabu, R.; Kobayashi, H.; Kubo, Y. Dansyl-containing boronate hydrogel film as fluorescent chemosensor of copper ions in water. RSC Adv. 2012, 2 (16), 6555– 6561,  DOI: 10.1039/c2ra20516e
    Google Scholar
    3
    Dansyl-containing boronate hydrogel film as fluorescent chemosensor of copper ions in water
    Nishiyabu, Ryuhei; Kobayashi, Hiroyasu; Kubo, Yuji
    RSC Advances (2012), 2 (16), 6555-6561CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
    A new type of boronate hydrogel with covalently bound dansyldiethylenetriamine as an indicator has been developed; the gel networks are based on boronate esterification of poly(vinylalc.) with benzene-1,4-diboronic acid. In this approach, phenylboronic acid-appended N-dansyldiethylenetriamine 1 was newly synthesized to be incorporated into the gel matrix. The resulting gel film showed an absorption band at 336 nm and fluorescence at 511 nm when excited at 340 nm in water. The fluorescence measurements indicated that at neutral conditions using a HEPES buffer, the gel film was selectively quenched after immersion in an aq. soln. of Cu2+ for 30 min. The response had minimal interference from other metal ions such as Na+, K+, Mg2+, Ca2+, Fe3+, Co2+, Ni2+, Zn2+, Cd2+, Hg2+, Al3+, and Pb2+, which was noteworthy because dansyldiethylenetriamine alone responds to Hg2+ and Ni2+ in addn. to Cu2+ in water. The reversible sensing capability was also evaluated by rinsing the film with an aq. soln. of EDTA (EDTA). The gel was found to be a reusable and free-standing film capable of visually detecting Cu2+, providing a simple and expedient tool for on-site monitoring of Cu2+ in environmental applications such as water anal.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtVeis7fK&md5=4fa6d3591257f445e46b6bc4149a3255
  4. 4
    Awino, J. K.; Gunasekara, R. W.; Zhao, Y. Selective Recognition of d-Aldohexoses in Water by Boronic Acid-Functionalized, Molecularly Imprinted Cross-Linked Micelles. J. Am. Chem. Soc. 2016, 138 (31), 9759– 9762,  DOI: 10.1021/jacs.6b04613
    Google Scholar
    4
    Selective Recognition of D-Aldohexoses in Water by Boronic Acid-Functionalized, Molecularly Imprinted Cross-Linked Micelles
    Awino, Joseph K.; Gunasekara, Roshan W.; Zhao, Yan
    Journal of the American Chemical Society (2016), 138 (31), 9759-9762CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Mol. imprinting within crosslinked micelles using 4-vinylphenylboronate derivs. of carbohydrates provided water-sol. nanoparticle receptors selective for the carbohydrate templates. Complete differentiation of D-aldohexoses could be achieved by these receptors if a single inversion of hydroxyl occurred at C2 or C4 of the sugar or if two or more inversions took place. Glycosides with a hydrophobic aglycan displayed stronger binding due to increased hydrophobic interactions.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xht1SktLrF&md5=d23af4dcc769acd82c9f739a88b93aa5
  5. 5
    Chen, W.; Guo, Z.; Yu, H.; Liu, Q.; Fu, M. Molecularly imprinted colloidal array with multi-boronic acid sites for glycoprotein detection under neutral pH. J. Colloid Interface Sci. 2022, 607, 1163– 1172,  DOI: 10.1016/j.jcis.2021.09.048
    Google Scholar
    5
    Molecularly imprinted colloidal array with multi-boronic acid sites for glycoprotein detection under neutral pH
    Chen, Wei; Guo, Zhiyang; Yu, Hao; Liu, Qingyun; Fu, Min
    Journal of Colloid and Interface Science (2022), 607 (Part_2), 1163-1172CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)
    Glycoproteins play vital roles in living organisms and often serve as biomarkers for some disease. However, due to the low content of glycoprotein in biol. fluids, selective detection of glycoproteins is still a challenging issue that needs to be addressed. In this study, molecularly imprinted colloidal array with multi-boronic acid sites for glycoprotein detection under physiol. pH was proposed. Monodispersed glycoprotein imprinted particles (SiO2@PEI/MIPs) was first prepd. based on surface imprinting strategy using horseradish peroxidase (HRP) as template, and polyethyleneimine (PEI) was used to increase the no. of boronic acid groups. The binding expt. indicated that the SiO2@PEI/MIPs hold satisfactory adsorption capacity (1.41μmol/g), rapid adsorption rate (40 min) and preferable selectivity toward HRP. Then the SiO2@PEI/MIPs was assembled into close-packed colloidal array to construct a label free optical sensor (denoted as GICA). Benefiting from the high ordered photonic crystal structure, binding of HRP onto the GICA could be directly readout from the changes in structure color and diffracted wavelength. The structure color of the GICA changed from bright blue to yellow with the diffraction wavelength red shifted 59 nm when the HRP concn. increased from 2.5 to 15μmol/L. Importantly, the GICA was capable of detecting HRP from human serum samples. All those results indicated the potential of the GICA for naked-eye detection of glycoprotein.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitV2ls7nO&md5=644276fcbf46502c91615ddb38b354d0
  6. 6
    He, P.; Zhu, H.; Ma, Y.; Liu, N.; Niu, X.; Wei, M.; Pan, J. Rational design and fabrication of surface molecularly imprinted polymers based on multi-boronic acid sites for selective capture glycoproteins. Chem. Eng. J. 2019, 367, 55– 63,  DOI: 10.1016/j.cej.2019.02.140
    Google Scholar
    6
    Rational design and fabrication of surface molecularly imprinted polymers based on multi-boronic acid sites for selective capture glycoproteins
    He, Peiyan; Zhu, Hengjia; Ma, Yue; Liu, Na; Niu, Xiangheng; Wei, Maobin; Pan, Jianming
    Chemical Engineering Journal (Amsterdam, Netherlands) (2019), 367 (), 55-63CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
    Increasing the no. of recognition sites is an available way to improve the efficiency of the identification of surface mol. imprinting polymers. Glycoprotein imprinted nanoparticles (SiO2-MIPs) based on multi-boronic acid sites were prepd. via surface imprinting processes. Polyethylene polyamine (PPI), contg. enough active amino groups, is firstly grafted to the surface of silica nanoparticles. Boronic acid mols. are post-modified onto silica nanoparticles via amine aldehyde condensation reaction, and then dopamine (DA) as the monomer is adopted to form a surface imprinted polymer layer onto the functionalized silica nanoparticles under a gentle condition after binding the template ovalbumin (OVA) mols. As-prepd. SiO2-MIPs have quick adsorption kinetics (rebinding equil. at 60 min), high max. adsorption capacity (243.4 mg g-1), excellent adsorption selectivity (imprinting factor towards OVA is 4.82), and good reusability after seven regeneration cycles (a slight decrease of ∼5%). Furthermore, the high d. of boronic acids and imprinting effect both play a key role in the enhanced recognition and rebinding OVA. Moreover, this work overcomes the influence of steric hindrance and then the OVA mols. can access the recognition sites of SiO2-MIPs easily.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXjs1Oqsrg%253D&md5=1ad0f6d7758a8e6f78a1e418473aa6e4
  7. 7
    Zhao, Z. W.; Yao, X. M.; Zhang, Z.; Chen, L.; He, C. L.; Chen, X. S. Boronic Acid Shell-Crosslinked Dextran-b-PLA Micelles for Acid-Responsive Drug Delivery. Macromol. Biosci. 2014, 14 (11), 1609– 1618,  DOI: 10.1002/mabi.201400251
    Google Scholar
    7
    Boronic Acid Shell-Crosslinked Dextran-b-PLA Micelles for Acid-Responsive Drug Delivery
    Zhao, Ziwei; Yao, Xuemei; Zhang, Zhe; Chen, Li; He, Chaoliang; Chen, Xuesi
    Macromolecular Bioscience (2014), 14 (11), 1609-1618CODEN: MBAIBU; ISSN:1616-5187. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Herein, 3-carboxy-5-nitrophenylboronic acid (CNPBA) shell-crosslinked micelles based on amphiphilic dextran-block-polylactide (Dex-b-PLA) are prepd. and used for efficient intracellular drug deliveries. Due to the reversible pH-dependent binding with diols to form boronate esters, CNPBA modified Dex-b-PLA shows excellent pH-sensitivity. In neutral aq. conditions, CNPBA-Dex-b-PLA forms shell-crosslinked micelles to enable DOX loading, while in acid conditions, the boronate esters hydrolyze and the micelles de-crosslink to release loaded DOX. In vitro release studies indicate that the release of the DOX cargo is minimized at physiol. conditions, while there is a burst release in response to low pHs. The cell viability of CNPBA-Dex-b-PLA investigated by MTT assay was more than 90%, indicating that, as a drug delivery system, CNPBA-Dex-b-PLA has good cytocompatibility. These features suggest that the pH-responsive biodegradable CNPBA-Dex-b-PLA can efficiently load and deliver DOX into tumor cells and enhance the inhibition of cellular proliferation in vitro, providing a favorable platform as a drug delivery system for cancer therapy.
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  8. 8
    Li, Y. P.; Xiao, W. W.; Xiao, K.; Berti, L.; Luo, J. T.; Tseng, H. P.; Fung, G.; Lam, K. S. Well-Defined, Reversible Boronate Crosslinked Nanocarriers for Targeted Drug Delivery in Response to Acidic pH Values and cis-Diols. Angew. Chem., Int. Ed. 2012, 51 (12), 2864– 2869,  DOI: 10.1002/anie.201107144
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    8
    Well-Defined, Reversible Boronate Crosslinked Nanocarriers for Targeted Drug Delivery in Response to Acidic pH Values and cis-Diols
    Li, Yuanpei; Xiao, Wenwu; Xiao, Kai; Berti, Lorenzo; Luo, Juntao; Tseng, Harry P.; Fung, Gabriel; Lam, Kit S.
    Angewandte Chemie, International Edition (2012), 51 (12), 2864-2869, S2864/1-S2864/25CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Stimuli-responsive nanoparticles are gaining considerable attention in the field of drug delivery because of their useful physicochem. changes in response to specific triggers, such as pH value, temp., enzymes, or redox conditions, present in certain physiol. or disease microenvironments of interest. Among these nanoparticles, stimuli-responsive crosslinked micelles (SCMs) represent a versatile nanocarrier system for tumor-targeting drug delivery. Remarkable progress in this field has led to the development of SCMs responsive to a single stimulus. Various cleavable linkages have been introduced in SCMs, such as reducible disulfide bonds, pH cleavable, or hydrolysable ester bonds. Currently, second-generation SCMs able to respond to multiple stimuli are being actively pursued as tools for accomplishing the multistage delivery of drugs to the complex in vivo microenvironment. Boronic acids are able to bind diols reversibly forming boronate esters that exhibit Fast dual responsiveness to external pH value and competing diols. Based on this interaction, there has been increasing interest in using boronic acids as building blocks to design carbohydrate sensors, nano-reactors, drug delivery systems, and self-healing materials. Among diols, catechols are an excellent reactant for the formation of complexes with boronic acids, thanks to the favorable syn-peri-planar arrangement of the arom. hydroxy groups combined with their electron-donating character. Herein, we present the first report on the synthesis of a novel class of dual-responsive boronate crosslinked micelles (BCM) for drug delivery based on the self-assembly and in situ complexation of boronic acid contg. polymers and catechol contg. polymers. We hypothesize that these BCMs will retain the encapsulated drug under physiol. conditions, while releasing the payload quickly when triggered by the lower pH value of the tumor environment or when exposed to exogenous competing diols. Addnl., we are presenting a Forster resonance energy transfer (FRET) reporter system to evaluate the in vivo stability of these micelles. This characterization is usually difficult to accomplish in vivo due to the lack of suitable anal. techniques.
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  9. 9
    Su, J.; Chen, F.; Cryns, V. L.; Messersmith, P. B. Catechol Polymers for pH-Responsive, Targeted Drug Delivery to Cancer Cells. J. Am. Chem. Soc. 2011, 133 (31), 11850– 11853,  DOI: 10.1021/ja203077x
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    9
    Catechol Polymers for pH-Responsive, Targeted Drug Delivery to Cancer Cells
    Su, Jing; Chen, Feng; Cryns, Vincent L.; Messersmith, Phillip B.
    Journal of the American Chemical Society (2011), 133 (31), 11850-11853CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    A novel cell-targeting, pH-sensitive polymeric carrier was employed in this study for delivery of the anticancer drug bortezomib (BTZ) to cancer cells. Our strategy is based on facile conjugation of BTZ to catechol-contg. polymeric carriers that are designed to be taken up selectively by cancer cells through cell surface receptor-mediated mechanisms. The polymer used as a building block in this study was poly(ethylene glycol), which was chosen for its ability to reduce nonspecific interactions with proteins and cells. The catechol moiety was exploited for its ability to bind and release borate-contg. therapeutics such as BTZ in a pH-dependent manner. In acidic environments, such as in cancer tissue or the subcellular endosome, BTZ dissocs. from the polymer-bound catechol groups to liberate the free drug, which inhibits proteasome function. A cancer-cell-targeting ligand, biotin, was presented on the polymer carriers to facilitate targeted entry of drug-loaded polymer carriers into cancer cells. Our study demonstrated that the cancer-targeting drug-polymer conjugates dramatically enhanced cellular uptake, proteasome inhibition, and cytotoxicity toward breast carcinoma cells in comparison with nontargeting drug-polymer conjugates. The pH-sensitive catechol-boronate binding mechanism provides a chemoselective approach for controlling the release of BTZ in targeted cancer cells, establishing a concept that may be applied in the future toward other boronic acid-contg. therapeutics to treat a broad range of diseases.
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  10. 10
    Jiang, H.-P.; Qi, C.-B.; Chu, J.-M.; Yuan, B.-F.; Feng, Y.-Q. Profiling of cis-Diol-containing Nucleosides and Ribosylated Metabolites by Boronate-affinity Organic-silica Hybrid Monolithic Capillary Liquid Chromatography/Mass Spectrometry. Sci. Rep. 2015, 5 (1), 7785,  DOI: 10.1038/srep07785
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    10
    Profiling of cis-Diol-containing Nucleosides and Ribosylated Metabolites by Boronate-affinity Organic-silica Hybrid Monolithic Capillary Liquid Chromatography/Mass Spectrometry
    Jiang, Han-Peng; Qi, Chu-Bo; Chu, Jie-Mei; Yuan, Bi-Feng; Feng, Yu-Qi
    Scientific Reports (2015), 5 (), 7785CODEN: SRCEC3; ISSN:2045-2322. (Nature Publishing Group)
    RNA contains a large no. of modified nucleosides. In the metabolic re-exchange of RNA, modified nucleosides cannot be recycled and are thus excreted from cells into biol. fluids. Detn. of endogenous modified nucleosides in biol. fluids may serve as non-invasive cancers diagnostic methods. Here we prepd. boronate-affinity org.-silica hybrid capillary monolithic column (BOHCMC) that exhibited excellent selectivity toward the cis-diol-contg. compds. We then used the prepd. BOHCMC as the online solid-phase microextn. (SPME) column and developed an online SPME-LC-MS/MS method to comprehensively profile cis-diol-contg. nucleosides and ribosylated metabolites in human urine. Forty-five cis-diol-contg. nucleosides and ribosylated metabolites were successfully identified in human urine. And five ribose conjugates, for the first time, were identified existence in human urine in the current study. Furthermore, the relative quantification suggested 4 cis-diol-contg. compds. (5'-deoxy-5'-methylthioadenosine, N4-acetylcytidine, 1-ribosyl-N-propionylhistamine and N2,N2,7-trimethylguanosine) increased more than 1.5 folds in all the 3 types of examd. cancers (lung cancer, colorectal cancer, and nasopharyngeal cancer) compared to healthy controls. The online SPME-LC-MS/MS method demonstrates a promising method for the comprehensive profiling of cis-diol-contg. ribose conjugates in human urines, which provides an efficient strategy for the identification and discovery of biomarkers and may be used for the screening of cancers.
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  11. 11
    Koyama, T.; Terauchi, K.-i. Synthesis and application of boronic acid-immobilized porous polymer particles: a novel packing for high-performance liquid affinity chromatography. J. Chromatogr. B: Biomed. Sci. Appl. 1996, 679 (1), 31– 40,  DOI: 10.1016/0378-4347(96)00006-0
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    11
    Synthesis and application of boronic acid-immobilized porous polymer particles: a novel packing for high-performance liquid affinity chromatography
    Koyama, Toshitaka; Terauchi, Ken-ichi
    Journal of Chromatography B: Biomedical Sciences and Applications (1996), 679 (1 + 2), 31-40CODEN: JCBBEP; ISSN:0378-4347. (Elsevier)
    A prepn. method of a novel type of packing materials for high-performance liq. affinity chromatog. to det. glycated proteins was studied, and a fundamental study on its application to diabetic serum was conducted. To quantify glycated proteins such as glycated serum albumin, a new hydrophilic and durable porous polymer particle recently developed in the lab. was used as the basic matrix. The matrix was activated with 1,1'-carbonyldiimidazole (CDI), and optimization of the coupling reaction between these CDI-activated matrix and m-aminophenylboronic acid hemisulfate (APBA) as affinity ligand was investigated. The optimum value for the APBA coupling yield was obtained under acidic conditions very different from the data reported by previous workers. Using this APBA-immobilized matrix an affinity column was prepd., and its usefulness in HPLC sepn. of glycated serum proteins was investigated. Also, the fundamental and preliminary results for diagnosis of diabetes mellitus are discussed in this paper.
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  12. 12
    Brooks, W. L. A.; Sumerlin, B. S. Synthesis and Applications of Boronic Acid-Containing Polymers: From Materials to Medicine. Chem. Rev. 2016, 116 (3), 1375– 1397,  DOI: 10.1021/acs.chemrev.5b00300
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    12
    Synthesis and Applications of Boronic Acid-Containing Polymers: From Materials to Medicine
    Brooks, William L. A.; Sumerlin, Brent S.
    Chemical Reviews (Washington, DC, United States) (2016), 116 (3), 1375-1397CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. Boronic acid-contg. macromols. have been utilized in a no. of biomedical applications, including use in dynamic covalent materials, dual thermo and saccharide responsive hydrogels, sensors, and nanomaterials, often with the goal of detection and treatment of type-1 diabetes, which requires const. monitoring of blood glucose levels and proactive insulin management. The ability of boronic acids to bind with saccharides and potentially undergo an ionization transition makes the materials ideal for diabetes-related applications. Other biomedical applications of boronic acid contg. macromols. include use as potential HIV barriers, sepns. and chromatog., cell capture and culture, enzymic inhibition, and in site-specific radiation therapy. The review addresses each of these potential and current areas of application, with particular attention to the fundamental chem. involved.
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  13. 13
    He, L. H.; Fullenkamp, D. E.; Rivera, J. G.; Messersmith, P. B. pH responsive self-healing hydrogels formed by boronate-catechol complexation. Chem. Commun. 2011, 47 (26), 7497– 7499,  DOI: 10.1039/c1cc11928a
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    13
    pH responsive self-healing hydrogels formed by boronate-catechol complexation
    He, Lihong; Fullenkamp, Dominic E.; Rivera, Jose G.; Messersmith, Phillip B.
    Chemical Communications (Cambridge, United Kingdom) (2011), 47 (26), 7497-7499CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    Here we report the synthesis and characterization of pH-responsive, self-healing hydrogels based on boronate-catechol complexation.
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  14. 14
    Figueiredo, T.; Cosenza, V.; Ogawa, Y.; Jeacomine, I.; Vallet, A.; Ortega, S.; Michel, R.; Olsson, J. D. M.; Gerfaud, T.; Boiteau, J. G.; Jing, J.; Harris, C.; Auzely-Velty, R. Boronic acid and diol-containing polymers: how to choose the correct couple to form ″strong″ hydrogels at physiological pH. Soft Matter 2020, 16 (15), 3628– 3641,  DOI: 10.1039/D0SM00178C
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    14
    Boronic acid and diol-containing polymers: how to choose the correct couple to form "strong" hydrogels at physiological pH
    Figueiredo, Tamiris; Cosenza, Vanina; Ogawa, Yu; Jeacomine, Isabelle; Vallet, Alicia; Ortega, Sonia; Michel, Raphael; Olsson, Johan D. M.; Gerfaud, Thibaud; Boiteau, Jean-Guy; Jing, Jing; Harris, Craig; Auzely-Velty, Rachel
    Soft Matter (2020), 16 (15), 3628-3641CODEN: SMOABF; ISSN:1744-6848. (Royal Society of Chemistry)
    Dynamic covalent hydrogels crosslinked by boronate ester bonds are promising materials for biomedical applications. However, little is known about the impact of the crosslink structure on the mech. behavior of the resulting network. Herein, we provide a mechanistic study on boronate ester crosslinking upon mixing hyaluronic acid (HA) backbones modified, on the one hand, with two different arylboronic acids, and on the other hand, with three different saccharide units. Combining rheol., NMR and computational anal., we demonstrate that carefully selecting the arylboronic-polyol couple allows for tuning the thermodn. and mol. exchange kinetics of the boronate ester bond, thereby controlling the rheol. properties of the gel. In particular, we report the formation of "strong" gels (i.e. featuring slow relaxation dynamics) through the formation of original complex structures (tridentate or bidentate complexes). These findings offer new prospects for the rational design of hydrogel scaffolds with tailored mech. response.
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  15. 15
    Brooks, W. L. A.; Deng, C. C.; Sumerlin, B. S. Structure-Reactivity Relationships in Boronic Acid-Diol Complexation. ACS Omega 2018, 3 (12), 17863– 17870,  DOI: 10.1021/acsomega.8b02999
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    15
    Structure-Reactivity Relationships in Boronic Acid-Diol Complexation
    Brooks, William L. A.; Deng, Christopher C.; Sumerlin, Brent S.
    ACS Omega (2018), 3 (12), 17863-17870CODEN: ACSODF; ISSN:2470-1343. (American Chemical Society)
    Boronic acids have found widespread use in the field of biomaterials, primarily through their ability to bind with biol. relevant 1,2- and 1,3-diols, including saccharides and peptidoglycans, or with polyols to prep. hydrogels with dynamic covalent or responsive behavior. Despite a wide range of boronic acid architectures that have been previously considered, there is a need for greater understanding of the structure-reactivity relationships that govern binding affinity to diols. In this study, various boronic acids and other organoboron compds. were investigated to det. their pKa and their binding consts. with the biol. relevant diols including sorbitol, fructose, and glucose. Boronic acid pKa values were detd. through spectroscopic titrn., whereas binding consts. were detd. by fluorescence spectroscopy during competitive binding studies. Key structure-reactivity relationships clearly indicated that both boronic acid structure and soln. pH must be carefully considered. By considering a variety of boronic acids with systematically varied electronics and sterics, these results provide guidance during selection of organoboron compds. in sensing, delivery, and materials chem.
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  16. 16
    Deng, C. C.; Brooks, W. L. A.; Abboud, K. A.; Sumerlin, B. S. Boronic Acid-Based Hydrogels Undergo Self-Healing at Neutral and Acidic pH. ACS Macro Lett. 2015, 4 (2), 220– 224,  DOI: 10.1021/acsmacrolett.5b00018
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    16
    Boronic Acid-Based Hydrogels Undergo Self-Healing at Neutral and Acidic pH
    Deng, Christopher C.; Brooks, William L. A.; Abboud, Khalil A.; Sumerlin, Brent S.
    ACS Macro Letters (2015), 4 (2), 220-224CODEN: AMLCCD; ISSN:2161-1653. (American Chemical Society)
    This report describes the synthesis and characterization of boronate ester-crosslinked hydrogels capable of self-healing behavior at neutral and acidic pH. This atypically wide pH range over which healing behavior is obsd. was achieved through the use of an intramol. coordinating boronic acid monomer, 2-acrylamidophenylboronic acid (2APBA), where the internal coordination helped to stabilize crosslinks formed at acidic and neutral pH. Two different hydrogels were formed from a 2APBA copolymer crosslinked with either poly(vinyl alc.) or a catechol-functionalized copolymer. The self-healing ability of these hydrogels was characterized through phys. testing and rheol. studies. Furthermore, the catechol crosslinked hydrogel was shown to be oxygen sensitive, demonstrating reduced self-healing and stress relaxation after partial oxidn. The synthesis of these hydrogels demonstrates a new strategy to produce boronic acid materials capable of self-healing at physiol. pH.
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  17. 17
    Smithmyer, M. E.; Deng, C. C.; Cassel, S. E.; LeValley, P. J.; Sumerlin, B. S.; Kloxin, A. M. Self-Healing Boronic Acid-Based Hydrogels for 3D Co-cultures. ACS Macro Lett. 2018, 7 (9), 1105– 1110,  DOI: 10.1021/acsmacrolett.8b00462
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    17
    Self-Healing Boronic Acid-Based Hydrogels for 3D Co-cultures
    Smithmyer, Megan E.; Deng, Christopher C.; Cassel, Samantha E.; LeValley, Paige J.; Sumerlin, Brent S.; Kloxin, April M.
    ACS Macro Letters (2018), 7 (9), 1105-1110CODEN: AMLCCD; ISSN:2161-1653. (American Chemical Society)
    Synthetic hydrogels have been widely adopted as well-defined matrixes for three-dimensional (3D) cell culture, with increasing interest in systems that enable the coculture of multiple cell types for probing both cell-matrix and cell-cell interactions in studies of tissue regeneration and disease. We hypothesized that the unique dynamic covalent chem. of self-healing hydrogels could be harnessed for not only the encapsulation and culture of human cells but also the subsequent construction of layered hydrogels for 3D co-cultures. To test this, we formed hydrogels using boronic acid-functionalized polymers and demonstrated their self-healing in the presence of physiol. relevant cell culture media. Two model human cell lines, MDA-MB-231 breast cancer cells and CCL151 pulmonary fibroblasts, were encapsulated within these dynamic materials, and good viability was obsd. over time. Finally, self-healing of cut hydrogel "blocks" laden with these different cell types was used to create layered hydrogels for the generation of a dynamic coculture system. This work demonstrates the utility of self-healing materials for multidimensional cultures and establishes approaches broadly useful for a variety of biol. applications.
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  18. 18
    Wang, X.-T.; Deng, X.; Zhang, T.-D.; Zhang, X.; Shi, W.-P.; Lai, J.; Zhou, H.; Ye, Y.-J.; Zhang, C.-Y.; Yin, D.-C. Biocompatible self-healing hydrogels based on boronic acid-functionalized polymer and laponite nanocomposite for water pollutant removal. Environ. Chem. Lett. 2022, 20 (1), 81– 90,  DOI: 10.1007/s10311-021-01350-4
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    18
    Biocompatible self-healing hydrogels based on boronic acid-functionalized polymer and laponite nanocomposite for water pollutant removal
    Wang, Xue-Ting; Deng, Xudong; Zhang, Tuo-Di; Zhang, Xi; Shi, Wen-Pu; Lai, Jialiang; Zhou, Hongwei; Ye, Ya-Jing; Zhang, Chen-Yan; Yin, Da-Chuan
    Environmental Chemistry Letters (2022), 20 (1), 81-90CODEN: ECLNBJ; ISSN:1610-3653. (Springer)
    Global water pollution by org. dyes and metals may be solved by adsorption. In particular, hydrogel adsorbents display unique advantages due to their three-dimensional porous structure. Here, a new type of self-healing hydrogels based on boronate and amide bonds were prepd. The precursor polymer, 2-aminophenylboronic acid-modified polyacrylic acid (PAA-2APBA), was firstly synthesized by amidation, then, the poly(vinyl alc.) and laponite were mixed with PAA-2APBA to form a nanocomposite hydrogel. This hydrogel has good self-healing and injectable properties, as well as good biocompatibility. The introduction of laponite nanoparticles into the hydrogel improved the stability, mech. strength, and the adsorption efficiency of metal ions and org. dyes. The max. adsorption of copper ion, cadmium ion, lead ion, and iron ion was 259.1 mg/g, 243.4 mg/g, 217.4 mg/g, and 166.2 mg/g, resp. For org. dyes, 71% of methylene blue and 81% of malachite green were removed in 28 h.
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  19. 19
    Huang, Z. J.; Delparastan, P.; Burch, P.; Cheng, J.; Cao, Y.; Messersmith, P. B. Injectable dynamic covalent hydrogels of boronic acid polymers cross-linked by bioactive plant-derived polyphenols. Biomater. Sci. 2018, 6 (9), 2487– 2495,  DOI: 10.1039/C8BM00453F
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    19
    Injectable dynamic covalent hydrogels of boronic acid polymers cross-linked by bioactive plant-derived polyphenols
    Huang, Zhuojun; Delparastan, Peyman; Burch, Patrick; Cheng, Jing; Cao, Yi; Messersmith, Phillip B.
    Biomaterials Science (2018), 6 (9), 2487-2495CODEN: BSICCH; ISSN:2047-4849. (Royal Society of Chemistry)
    We report here the development of hydrogels formed at physiol. conditions using PEG (polyethylene glycol) based polymers modified with boronic acids (BAs) as backbones and the plant derived polyphenols ellagic acid (EA), epigallocatechin gallate (EGCG), tannic acid (TA), nordihydroguaiaretic acid (NDGA), rutin trihydrate (RT), rosmarinic acid (RA) and carminic acid (CA) as linkers. Rheol. frequency sweep and single mol. force spectroscopy (SMFS) expts. show that hydrogels linked with EGCG and TA are mech. stiff, arising from the dynamic covalent bond formed by the polyphenol linker and boronic acid functionalized polymer. Stability tests of the hydrogels in physiol. conditions revealed that gels linked with EA, EGCG, and TA are stable. We furthermore showed that EA- and EGCG-linked hydrogels can be formed via in situ gelation in pH 7.4 buffer, and provide long-term steady state release of bioactive EA. In vitro expts. showed that EA-linked hydrogel significantly reduced the viability of CAL-27 human oral cancer cells via gradual release of EA.
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  20. 20
    Dong, Y. Z.; Wang, W. H.; Veiseh, O.; Appel, E. A.; Xue, K.; Webber, M. J.; Tang, B. C.; Yang, X. W.; Weir, G. C.; Langer, R.; Anderson, D. G. Injectable and Glucose-Responsive Hydrogels Based on Boronic Acid-Glucose Complexation. Langmuir 2016, 32 (34), 8743– 8747,  DOI: 10.1021/acs.langmuir.5b04755
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    20
    Injectable and Glucose-Responsive Hydrogels Based on Boronic Acid-Glucose Complexation
    Dong, Yizhou; Wang, Weiheng; Veiseh, Omid; Appel, Eric A.; Xue, Kun; Webber, Matthew J.; Tang, Benjamin C.; Yang, Xi-Wen; Weir, Gordon C.; Langer, Robert; Anderson, Daniel G.
    Langmuir (2016), 32 (34), 8743-8747CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
    Injectable hydrogels have been widely used for a no. of biomedical applications. Here, we report a new strategy to form an injectable and glucose-responsive hydrogel using the boronic acid-glucose complexation. The ratio of boronic acid and glucose functional groups is crit. for hydrogel formation. In our system, polymers with 10-60% boronic acid, with the balance being glucose-modified, are favorable to form hydrogels. These hydrogels are shear-thinning and self-healing, recovering from shear-induced flow to a gel state within seconds. More importantly, these polymers displayed glucose-responsive release of an encapsulated model drug. The hydrogel reported here is an injectable and glucose-responsive hydrogel constructed from the complexation of boronic acid and glucose within a single component polymeric material.
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  21. 21
    Pettignano, A.; Grijalvo, S.; Haring, M.; Eritja, R.; Tanchoux, N.; Quignard, F.; Diaz, D. D. Boronic acid-modified alginate enables direct formation of injectable, self-healing and multistimuli-responsive hydrogels. Chem. Commun. 2017, 53 (23), 3350– 3353,  DOI: 10.1039/C7CC00765E
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    21
    Boronic acid-modified alginate enables direct formation of injectable, self-healing and multistimuli-responsive hydrogels
    Pettignano, Asja; Grijalvo, Santiago; Haering, Marleen; Eritja, Ramon; Tanchoux, Nathalie; Quignard, Francoise; Diaz Diaz, David
    Chemical Communications (Cambridge, United Kingdom) (2017), 53 (23), 3350-3353CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    One-step functionalization of alginate with boronic acid groups allowed spontaneous formation of biocompatible hydrogels under basic conditions without addnl. complementary mols. or crosslinking agents. The dynamic nature of boronate ester bonds formed with vicinal diols present on alginate pyranose rings provided remarkable self-healing, injectable and multi-stimuli responsive properties to the material.
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  22. 22
    Hong, S. H.; Kim, S.; Park, J. P.; Shin, M.; Kim, K.; Ryu, J. H.; Lee, H. Dynamic Bonds between Boronic Acid and Alginate: Hydrogels with Stretchable, Self-Healing, Stimuli-Responsive, Remoldable, and Adhesive Properties. Biomacromolecules 2018, 19 (6), 2053– 2061,  DOI: 10.1021/acs.biomac.8b00144
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    22
    Dynamic bonds between boronic acid and alginate: Hydrogels with stretchable, self-healing, stimuli-responsive, remoldable, and adhesive properties
    Hong, Sang Hyeon; Kim, Sunjin; Park, Joseph P.; Shin, Mikyung; Kim, Keumyeon; Ryu, Ji Hyun; Lee, Haeshin
    Biomacromolecules (2018), 19 (6), 2053-2061CODEN: BOMAF6; ISSN:1525-7797. (American Chemical Society)
    For the increasing demand of soft materials with wide ranges of applications, hydrogels have been developed exhibiting variety of functions (e.g., stretchable, self-healing, stimuli-responsive, and etc.). So far, add-in components such as inorg. nanoparticles, carbon materials, clays, and many others to main polymers have been used to achieve various unique functions of hydrogels. The multicomponent hydrogel systems often exhibit batch-dependent inconsistent results and problems in multicomponent mixings, require labors during prepns., and accompany unpredictable cross-talk between the added components. Here, we developed 'single polymeric component', alginate-boronic acid (alginate-BA) hydrogel to overcome the aforementioned problems. It exhibits unprecedented multifunctionalities simultaneously, such as high stretchability, self-healing, shear-thinning, pH- and glucose-sensitivities, adhesive properties, and reshaping properties. Multifunctionalities of alginate-BA hydrogel is resulted from the reversible inter- and intramol. interactions by dynamic equil. of boronic acid-diol complexation and dissocn., which was proved by single mol. level Atomic Force Microscopy (AFM) pulling expts. We also found that the alginate-BA gel showed enhanced in vivo retentions along gastrointestinal (GI) tract. Our findings suggest that rational polymer designs can result in minimizing the no. of a participating component for multifunctional hydrogels, instead of increasing complexity by adding various addnl. components.
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  23. 23
    Li, W. W.; Gao, F. X.; Wang, X. Q.; Zhang, N.; Ma, M. M. Strong and Robust Polyaniline-Based Supramolecular Hydrogels for Flexible Supercapacitors. Angew. Chem., Int. Ed. 2016, 55 (32), 9196– 9201,  DOI: 10.1002/anie.201603417
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    23
    Strong and Robust Polyaniline-Based Supramolecular Hydrogels for Flexible Supercapacitors
    Li, Wanwan; Gao, Fengxian; Wang, Xiaoqian; Zhang, Ning; Ma, Mingming
    Angewandte Chemie, International Edition (2016), 55 (32), 9196-9201CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    We report a supramol. strategy to prep. conductive hydrogels with outstanding mech. and electrochem. properties, which are utilized for flexible solid-state supercapacitors (SCs) with high performance. The supramol. assembly of polyaniline and polyvinyl alc. through dynamic boronate bond yields the polyaniline-polyvinyl alc. hydrogel (PPH), which shows remarkable tensile strength (5.3 MPa) and electrochem. capacitance (928 F g-1). The flexible solid-state supercapacitor based on PPH provides a large capacitance (306 mF cm-2 and 153 F g-1) and a high energy d. of 13.6 Wh kg-1, superior to other flexible supercapacitors. The robustness of the PPH-based supercapacitor is demonstrated by the 100 % capacitance retention after 1000 mech. folding cycles, and the 90 % capacitance retention after 1000 galvanostatic charge-discharge cycles. The high activity and robustness enable the PPH-based supercapacitor as a promising power device for flexible electronics.
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  24. 24
    Casassa, E. Z.; Sarquis, A. M.; Vandyke, C. H. The Gelation of Polyvinyl-Alcohol with Borax - a Novel Class Participation Experiment Involving the Preparation and Properties of a Slime. J. Chem. Educ. 1986, 63 (1), 57– 60,  DOI: 10.1021/ed063p57
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    24
    The gelation of polyvinyl alcohol with borax. A novel class participation experiment involving the preparation and properties of a "slime"
    Casassa, E. Z.; Sarquis, A. M.; Van Dyke, C. H.
    Journal of Chemical Education (1986), 63 (1), 57-60CODEN: JCEDA8; ISSN:0021-9584.
    A classroom student expt. is presented involving the prepn. of a borate crosslinked poly(vinyl alc.) gel which has several interesting properties to interest the student. Topics are listed pertinent to the demonstration as well as the chem. of the system.
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  25. 25
    Sinton, S. W. Complexation Chemistry of Sodium-Borate with Polyvinyl-Alcohol) and Small Diols - a B-11 NMR-Study. Macromolecules 1987, 20 (10), 2430– 2441,  DOI: 10.1021/ma00176a018
    Google Scholar
    25
    Complexation chemistry of sodium borate with poly(vinyl alcohol) and small diols: a boron-11 NMR study
    Sinton, Steve W.
    Macromolecules (1987), 20 (10), 2430-41CODEN: MAMOBX; ISSN:0024-9297.
    The crosslinked structure in poly(vinyl alc.) (I)-borax (II) system was deduced by comparison of 11B NMR spectra of 2,4-pentanediol-I model system with that of the polymer system. The complexation and crosslinking of I with II was exothermic with a reaction enthalpy of -8.3 kcal/mol. There were 2 11B signal components from I-II system which had different spin relaxation rates. The relationships between NMR parameters and viscosity in the I-II system were discussed.
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  26. 26
    Wang, H. H.; Shyr, T. W.; Hu, M. S. The elastic property of polyvinyl alcohol gel with boric acid as a crosslinking agent. J. Am. Chem. Soc. 1999, 74 (13), 3046– 3052,  DOI: 10.1002/(SICI)1097-4628(19991220)74:13<3046::AID-APP6>3.0.CO;2-1
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    There is no corresponding record for this reference.
  27. 27
    Duncan, T. T.; Berrie, B. H.; Weiss, R. G. Soft, Peelable Organogels from Partially Hydrolyzed Poly(vinyl acetate) and Benzene-1,4-diboronic Acid: Applications to Clean Works of Art. ACS Appl. Mater. Interfaces 2017, 9 (33), 28069– 28078,  DOI: 10.1021/acsami.7b09473
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    27
    Soft, Peelable Organogels from Partially Hydrolyzed Poly(vinyl acetate) and Benzene-1,4-diboronic Acid: Applications to Clean Works of Art
    Duncan, Teresa T.; Berrie, Barbara H.; Weiss, Richard G.
    ACS Applied Materials & Interfaces (2017), 9 (33), 28069-28078CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    We have developed soft, peelable organogels from 40% hydrolyzed poly(vinyl acetate) (40PVAc) and benzene-1,4-diboronic acid (BDBA). The org. liqs. gelated include DMSO, DMF, THF, 2-ethoxyethanol, and methanol. The rheol. of these soft materials can be tuned by altering the concn. of the polymer and/or crosslinker. Insights into the mechanisms leading to gelation were obtained from 1H NMR expts., fluorescence measurements, and studies comparing properties of materials made from BDBA and phenylboronic acid, a mol. incapable of forming covalent crosslinks between the polymer chains. These organogels can be easily peeled off a surface, leaving no residue detectable by UV-vis spectroscopy. They are demonstrated to be effective at softening and removing deteriorated coatings from water-sensitive works of art and delicate surfaces. They have the needed characteristics to clean topog. complex surfaces: good contact with the surface, easy removal, and little to no residue after removal. A 2-ethoxyethanol organogel was used to remove oxidized varnish from a 16th century reliquary decorated with painted gold leaf, and an ethanol gel was used to remove solvent-resistant coatings from 16th and 18th century oil paintings.
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  28. 28
    Duncan, T. T.; Weiss, R. G. Influence of length and structure of aryl boronic acid crosslinkers on organogels with partially hydrolyzed poly(vinyl acetate). Colloid Polym. Sci. 2018, 296 (6), 1047– 1056,  DOI: 10.1007/s00396-018-4326-7
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    28
    Influence of length and structure of aryl boronic acid crosslinkers on organogels with partially hydrolyzed poly(vinyl acetate)
    Duncan, Teresa T.; Weiss, Richard G.
    Colloid and Polymer Science (2018), 296 (6), 1047-1056CODEN: CPMSB6; ISSN:0303-402X. (Springer)
    Organogels composed of 40% hydrolyzed poly(vinyl acetate) (40PVAc) and three arylboronic acids were formed and characterized in several liqs. to gain insights into the role of crosslinker length and structure on the properties of the gels. Data from 1H NMR, steady-state and time-resolved fluorescence, and rheol. were employed to correlate the degrees of crosslinking and the bulk phys. properties of the gels. Benzene-1,4-diboronic acid (1,4-BDBA) and 4,4'-biphenyldiboronic acid (bPDBA) formed gels with 40PVAc that were stable for longer periods than those with benzene-1,3-diboronic acid. Surprisingly, the steady-state and time-resolved fluorescence properties of 1,4-BDBA or bPDBA were affected little in soln. upon addn. of two model diols (1,3-propanediol and 1,2-ethanediol) or even 40PVAc. Furthermore, 40PVAc appeared to form crosslinks more efficiently, resulting in stiffer gels, with bPDBA than with 1,4-BDBA. We attribute these trends to the greater length, flexibility, and linearity of bPBPA. Overall, the results reported here demonstrate that minor structural changes in the crosslinker can alter significantly many of the bulk properties of two-component organogel networks. They also provide a clear 'blueprint' for making gels with specific desired properties for a range of applications that require virtually water-free systems.
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  29. 29
    Nunes, M. A. P.; Gois, P. M. P.; Rosa, M. E.; Martins, S.; Fernandes, P. C. B.; Ribeiro, M. H. L. Boronic acids as efficient cross linkers for PVA: synthesis and application of tunable hollow microspheres in biocatalysis. Tetrahedron 2016, 72 (46), 7293– 7305,  DOI: 10.1016/j.tet.2016.02.017
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    29
    Boronic acids as efficient cross linkers for PVA: synthesis and application of tunable hollow microspheres in biocatalysis
    Nunes, Mario A. P.; Gois, Pedro M. P.; Rosa, M. Emilia; Martins, Samuel; Fernandes, Pedro C. B.; Ribeiro, Maria H. L.
    Tetrahedron (2016), 72 (46), 7293-7305CODEN: TETRAB; ISSN:0040-4020. (Elsevier Ltd.)
    Herein is reported an innovative and reproducible systemic approach for the fabrication of customized 3D hollow microspheres of polyvinyl alc. (PVA) based on the use of arom. boronic acids (ABAs) as crosslinkers. A dedicated exptl. set-up was developed to enable microsphere formulation. Most of the boronic acids tested were able to produce hollow microspheres. Depending on the ABA used and the prodn. conditions, hollow PVA/ABA microspheres with different morphologies, mass transfer characteristics and unprecedented thermal (up to 121 °C) stability were obtained. The crosslinking temp. proved to be an operational parameter to control membrane thickness. The hollow microspheres were evaluated in biocatalysis, with naringin hydrolysis as model system, using encapsulated naringinase. The results highlighted a naringinase high operational stability, namely in PVA microspheres crosslinked with 1,4-phenylenediboronic acid and with phenylboronic acid, with no evident loss of activity throughout seven consecutive runs, theor. resulting in an infinite half-life.
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  30. 30
    Parris, M. D.; MacKay, B. A.; Rathke, J. W.; Klingler, R. J.; Gerald, R. E. Influence of Pressure on Boron Cross-Linked Polymer Gels. Macromolecules 2008, 41 (21), 8181– 8186,  DOI: 10.1021/ma801187q
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    30
    Influence of Pressure on Boron Cross-Linked Polymer Gels
    Parris, Michael D.; MacKay, Bruce A.; Rathke, Jerome W.; Klingler, Robert J.; Gerald, Rex E.
    Macromolecules (Washington, DC, United States) (2008), 41 (21), 8181-8186CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
    Using steady-shear rheometry in combination with high-pressure 11B NMR spectroscopy (11B NMR), it was detd. that gels formed from water-sol. polymers contg. vicinal hydroxyl groups cross-linked with various boron-contg. compds. undergo significant structural changes that result in a pronounced loss of viscosity when placed under pressure. Importantly, gels from other crosslinking agents tested, including Ti(IV) and Zr(IV), did not show this loss in viscosity. The exptl. study probed pressure-induced changes to both galactomannan and poly(vinyl alc.) (PVA) gels cross-linked with either aryl boronic acids or alkali metal boron-contg. salts under pressure from atm. to 680 bar and temps. 20-65°. Significantly, the pressure-induced losses in viscosity and, to a somewhat lesser extent, the concomitant pressure-induced 11B NMR spectral changes were reversed upon lowering the pressure. The gels are of interest for use for hydraulic fracturing of petroleum bearing rocks.
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  31. 31
    Shim, J.; Lee, J. S.; Lee, J. H.; Kim, H. J.; Lee, J.-C. Gel Polymer Electrolytes Containing Anion-Trapping Boron Moieties for Lithium-Ion Battery Applications. ACS Appl. Mater. Interfaces 2016, 8 (41), 27740– 27752,  DOI: 10.1021/acsami.6b09601
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    31
    Gel Polymer Electrolytes Containing Anion-Trapping Boron Moieties for Lithium-Ion Battery Applications
    Shim, Jimin; Lee, Ji Su; Lee, Jin Hong; Kim, Hee Joong; Lee, Jong-Chan
    ACS Applied Materials & Interfaces (2016), 8 (41), 27740-27752CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Gel polymer electrolytes (GPEs) based on semi-interpenetrating polymer network (IPN) structure for lithium-ion batteries were prepd. by mixing boron-contg. cross-linker (BC) composed of ethylene oxide (EO) chains, cross-linkable methacrylate group, and anion-trapping boron moiety with poly(vinylidene fluoride) (PVDF) followed by UV light-induced curing process. Various phys. and electrochem. properties of the GPEs were systematically investigated by varying the EO chain length and boron content. Dimensional stability at high temp. without thermal shrinkage, if any, was obsd. due to the presence of thermally stable PVDF in the GPEs. GPE having 80 wt % of BC and 20 wt % of PVDF exhibited an ionic cond. of 4.2 mS cm-1 at 30 °C which is 1 order of magnitude larger than that of the liq. electrolyte system contg. the com. Celgard separator (0.4 mS cm-1) owing to the facile electrolyte uptake ability of EO chain and anion-trapping ability of the boron moiety. As a result, the lithium-ion battery cell prepd. using the GPE with BC showed an excellent cycle performance at 1.0 C maintaining 87% of capacity during 100 cycles.
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  32. 32
    Wang, X.; Liu, Z.; Kong, Q.; Jiang, W.; Yao, J.; Zhang, C.; Cui, G. A single-ion gel polymer electrolyte based on polymeric lithium tartaric acid borate and its superior battery performance. Solid State Ionics 2014, 262, 747– 753,  DOI: 10.1016/j.ssi.2013.09.007
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    32
    A single-ion gel polymer electrolyte based on polymeric lithium tartaric acid borate and its superior battery performance
    Wang, Xuejiang; Liu, Zhihong; Kong, Qingshan; Jiang, Wen; Yao, Jianhua; Zhang, Chuanjian; Cui, Guanglei
    Solid State Ionics (2014), 262 (), 747-753CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
    A single-ion gel polymer electrolyte of PLTB@PVDF-HFP (polymeric lithium tartaric acid borate@poly(vinylidene fluoride-co-hexafluoropropene)) was prepd. and its ionic cond. was optimized via solvent compn. tailoring. It was manifested that the ethylene carbonate/dimethyl carbonate (EC/DMC) swollen PLTB@PVDF-HFP exhibited a superior lithium ionic cond. at room temp. to that of the traditional liq. electrolyte system (1 M LiPF6/EC/DMC). The Li4Ti5O12/LiFePO4 cells using the EC/DMC swollen PLTB@PVDF-HFP as polymer electrolyte showed stable charge/discharge voltage profiles with small voltage hysteresis, preferable rate capability and excellent cycle performance at room temp. These superior performances of EC/DMC swollen PLTB@PVDF-HFP could endow this class of gel polymer electrolyte a very promising alternative to state of the art liq. electrolyte system.
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  33. 33
    Dai, K.; Zheng, Y.; Wei, W. F. Organoboron-Containing Polymer Electrolytes for High-Performance Lithium Batteries. Adv. Funct. Mater. 2021, 31 (13), 2008632,  DOI: 10.1002/adfm.202008632
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    33
    Organoboron-Containing Polymer Electrolytes for High-Performance Lithium Batteries
    Dai, Kuan; Zheng, Yuan; Wei, Weifeng
    Advanced Functional Materials (2021), 31 (13), 2008632CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. Polymer electrolytes (PEs) have been deemed as a sought-after candidate for next-generation lithium batteries. Substantial effort has been dedicated to exploiting PEs with improved comprehensive performance. Organoboron compds. have aroused great interest in PEs due to their distinct characteristics such as high design diversity, excellent thermal stability, promoting lithium-ion transportation, and raising Li+ transference no. Organoboron compds. also have unique functions that facilitate the development of a stable solid electrolyte interface on the electrode surface. Their diversified structures and multiple functions are fundamentally assocd. with boron's hybridization form that dets. the electronic structure of boron as a central atom. Here, recent advancement in organoboron-contg. PEs is ed in the aspect of polymer matrixes with boron moieties and organoboron additives for PEs. This aims to highlight the diverse roles and high application potentials of organoboron compds. utilized in PEs. It is anticipated to provide a clear perspective of organoboron-contg. PEs and to spur more research interests for the exploration of safe and efficient lithium batteries.
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  34. 34
    Kato, Y.; Ishihara, T.; Ikuta, H.; Uchimoto, Y.; Wakihara, M. A high electrode-reaction rate for high-power-density lithium-ion secondary batteries by the addition of a lewis acid. Angew. Chem., Int. Ed. 2004, 43 (15), 1966– 1969,  DOI: 10.1002/anie.200353220
    Google Scholar
    34
    A high electrode-reaction rate for high-power-density lithium-ion secondary batteries achieved by the addition of a Lewis acid
    Kato, Yuki; Ishihara, Takenobu; Ikuta, Hiromasa; Uchimoto, Yoshiharu; Wakihara, Masataka
    Angewandte Chemie, International Edition (2004), 43 (15), 1966-1969CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The charge-transfer reaction at the electrode/electrolyte interfaces is important in the fabrication of high-power-d. lithium-ion secondary batteries. This reaction rate is increased by adding a poly(ethylene glycol)-borate ester Lewis acid to the electrolyte. Because the Lewis acid interacts preferentially with anions (X-), an increase in the activity of lithium ions is induced by enhancing the dissocn. of lithium salts (Li+X-).
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  35. 35
    Zhu, Y. S.; Wang, X. J.; Hou, Y. Y.; Gao, X. W.; Liu, L. L.; Wu, Y. P.; Shimizu, M. A new single-ion polymer electrolyte based on polyvinyl alcohol for lithium ion batteries. Electrochim. Acta 2013, 87, 113– 118,  DOI: 10.1016/j.electacta.2012.08.114
    Google Scholar
    35
    A new single-ion polymer electrolyte based on polyvinyl alcohol for lithium ion batteries
    Zhu, Y. S.; Wang, X. J.; Hou, Y. Y.; Gao, X. W.; Liu, L. L.; Wu, Y. P.; Shimizu, M.
    Electrochimica Acta (2013), 87 (), 113-118CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)
    A novel single-ion conducting polymer electrolyte, lithium polyvinyl alc. oxalate borate (LiPVAOB), was prepd. by reaction of polyvinyl alc. with different molar ratio of boric acid, oxalic acid and lithium carbonate. The prepd. materials were characterized by FTIR spectroscopy, x-ray diffraction, SEM, thermogravimetry, DTA, electrochem. impedance spectroscopy and linear sweep voltammetry. Ionic cond. of these polymer electrolytes contg. an additive (∼20 wt.% propylene carbonate) is dependent on molar ratio of the reactants and can be as high as 6.11 × 10-6 S/cm at ambient temp. Their electrochem. window can be stable up to 7 V (vs. Li+/Li), which is suitable for high-voltage lithium-ion batteries with high energy d.
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  36. 36
    Zhang, Y.; Cai, W.; Rohan, R.; Pan, M.; Liu, Y.; Liu, X.; Li, C.; Sun, Y.; Cheng, H. Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte. J. Power Sources 2016, 306, 152– 161,  DOI: 10.1016/j.jpowsour.2015.12.010
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    36
    Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte
    Zhang, Yunfeng; Cai, Weiwei; Rupesh, Rohan; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong
    Journal of Power Sources (2016), 306 (), 152-161CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    The ionic cond. decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concn. is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic cond. studies, the fabricated S-BSMs showed decreased m.ps. and increased ionic cond. as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temp. performance of the all-solid-state lithium batteries. The fabricated Li|S-BSMs| LiFePO4 cells exhibit highly electrochem. stability and excellent cycling at temp. below m.p. of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.
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  37. 37
    Sun, X.-G.; Liu, G.; Xie, J.; Han, Y.; Kerr, J. B. New gel polyelectrolytes for rechargeable lithium batteries. Solid State Ionics 2004, 175 (1), 713– 716,  DOI: 10.1016/j.ssi.2003.11.043
    Google Scholar
    37
    New gel polyelectrolytes for rechargeable lithium batteries
    Sun, Xiao-Guang; Liu, Gao; Xie, Jiangbing; Han, Yongbong; Kerr, John B.
    Solid State Ionics (2004), 175 (1-4), 713-716CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
    New polyelectrolytes were synthesized by grafting the allyl group contg. lithium salt, lithium bis(allylmalonato)borate (LiBAMB), onto poly[pentaethylene glycol Me ether acrylate-co-allyoxyethyl acrylate] through hydrosilylation chem. Gel polyelectrolytes were obtained by adding 50% of different 1/1 (wt./wt.) mixts. of propylene carbonate (PC), ethylene carbonate (EC), di-Me carbonate (DMC) and tetraethyleneglycol di-Me ether (TEGDME). The highest ambient cond. was 2.7 × 10-8 S cm-1 for the dry single ion conductors and 7.9 × 10-6 S cm-1 for the gel single ion conductor contg. 50% of EC/DMC (1/1, wt./wt.), and both are obtained for the sample with an EO/Li ratio of 40/1. The cond. order of gel electrolytes contg. the same amt. of different mixed solvents suggests that the cond. of the gel is more detd. by the dielec. const. rather than by the viscosity of the solvent. The preliminary Li/Li cycling profile of a dry single ion conductor is encouraging, as almost no concn. polarization and relaxation was obsd. However, some fluctuation of potential occurred, which might be due to the reactions of the electrolyte on the surface of lithium metal.
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  38. 38
    Deng, K.; Wang, S.; Ren, S.; Han, D.; Xiao, M.; Meng, Y. Network type sp3 boron-based single-ion conducting polymer electrolytes for lithium ion batteries. J. Power Sources 2017, 360, 98– 105,  DOI: 10.1016/j.jpowsour.2017.06.006
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    38
    Network type sp3 boron-based single-ion conducting polymer electrolytes for lithium ion batteries
    Deng, Kuirong; Wang, Shuanjin; Ren, Shan; Han, Dongmei; Xiao, Min; Meng, Yuezhong
    Journal of Power Sources (2017), 360 (), 98-105CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    Electrolytes play a vital role in modulating lithium ion battery performance. An outstanding electrolyte should possess both high ionic cond. and unity lithium ion transference no. Here, we present a facile method to fabricate a network type sp3 boron-based single-ion conducting polymer electrolyte (SIPE) with high ionic cond. and lithium ion transference no. approaching unity. The SIPE was synthesized by coupling of lithium bis(allylmalonato)borate (LiBAMB) and pentaerythritol tetrakis(2-mercaptoacetate) (PETMP) via one-step photoinitiated in situ thiol-ene click reaction in plasticizers. Influence of kinds and content of plasticizers was investigated and the optimized electrolytes show both outstanding ionic cond. (1.47 × 10-3 S cm-1 at 25 °C) and high lithium transference no. of 0.89. This ionic cond. is among the highest ionic cond. exhibited by SIPEs reported to date. Its electrochem. stability window is up to 5.2 V. More importantly, Li/LiFePO4 cells with the prepd. single-ion conducting electrolytes as the electrolyte as well as the separator display highly reversible capacity and excellent rate capacity under room temp. It also demonstrates excellent long-term stability and reliability as it maintains capacity of 124 mA h g-1 at 1 C rate even after 500 cycles without obvious decay.
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  39. 39
    Guzmán-González, G.; Ávila-Paredes, H. J.; Rivera, E.; González, I. Electrochemical Characterization of Single Lithium-Ion Conducting Polymer Electrolytes Based on sp3 Boron and Poly(ethylene glycol) Bridges. ACS Appl. Mater. Interfaces 2018, 10 (36), 30247– 30256,  DOI: 10.1021/acsami.8b02519
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    39
    Electrochemical Characterization of Single Lithium-Ion Conducting Polymer Electrolytes Based on sp3 Boron and Poly(ethylene glycol) Bridges
    Guzman-Gonzalez, Gregorio; Avila-Paredes, Hugo J.; Rivera, Ernesto; Gonzalez, Ignacio
    ACS Applied Materials & Interfaces (2018), 10 (36), 30247-30256CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    A novel series of single lithium-ion conducting polymer electrolytes (SLICPE) based on sp3 boron and poly(ethylene glycol) (PEG) bridges is presented, in the context of the development of a new generation of batteries, with the aim to overcome the problems related to concn. overpotential and low ion transport nos. in conventional solid polymer electrolytes (SPE). The phase sepn. generated by the phys. mixt. of SPE with plasticizers such as poly(ethylene oxide) is still a serious problem. In this work, the use of PEG with different chain lengths, for the polycondensation reaction with LiB(OCH3)4, to synthesize SLICPE allows preventing phase sepn. while tuning the predominant conduction mechanism, and thus the elec. properties, esp. the lithium-ion transference no. The ionic transport is promoted by chain mobility as the chain length is increased. SLICPE with the best ionic cond. values (4.95 ± 0.05) × 10-6 S cm-1 was the one synthesized from poly(ethylene glycol) with an av. MN of 400 (BEG8), having an O/Li+ ratio of 20. The lithium transference no. (tLi+) and electrochem. stability window of SLICPE membranes at 25° decreased as the PEG bridge length between sp3 boron atoms increased from 0.97 to 0.88 and 5.4 to 4.2 V vs. Li0/Li+, resp., for SLICPE synthesized from PEG with an av. MN of 50-400 (BEG1 to BEG8).
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  40. 40
    Van Humbeck, J. F.; Aubrey, M. L.; Alsbaiee, A.; Ameloot, R.; Coates, G. W.; Dichtel, W. R.; Long, J. R. Tetraarylborate polymer networks as single-ion conducting solid electrolytes. Chem. Sci. 2015, 6 (10), 5499– 5505,  DOI: 10.1039/C5SC02052B
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    40
    Tetraarylborate polymer networks as single-ion conducting solid electrolytes
    Van Humbeck, Jeffrey F.; Aubrey, Michael L.; Alsbaiee, Alaaeddin; Ameloot, Rob; Coates, Geoffrey W.; Dichtel, William R.; Long, Jeffrey R.
    Chemical Science (2015), 6 (10), 5499-5505CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
    A new family of solid polymer electrolytes based upon anionic tetrakis(phenyl)borate tetrahedral nodes and linear bis-alkyne linkers is reported. Sonogashira polymns. using tetrakis(4-iodophenyl)borate, tetrakis(4-iodo-2,3,5,6-tetrafluorophenyl)borate and tetrakis(4-bromo-2,3,5,6-tetrafluorophenyl)borate delivered highly cross-linked polymer networks with both 1,4-diethynylbeznene and a tri(ethylene glycol) substituted deriv. Promising initial cond. metrics have been obsd., including high room temp. conductivities (up to 2.7 × 10-4 S cm-1), moderate activation energies (0.25-0.28 eV), and high lithium ion transport nos. (up to tLi+ = 0.93). Initial investigations into the effects of important materials parameters such as bulk morphol., porosity, fluorination, and other chem. modification, provide starting design parameters for further development of this new class of solid electrolytes.
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  41. 41
    Shim, J.; Kim, D.-G.; Kim, H. J.; Lee, J. H.; Lee, J.-C. Polymer Composite Electrolytes Having Core-Shell Silica Fillers with Anion-Trapping Boron Moiety in the Shell Layer for All-Solid-State Lithium-Ion Batteries. ACS Appl. Mater. Interfaces 2015, 7 (14), 7690– 7701,  DOI: 10.1021/acsami.5b00618
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    41
    Polymer Composite Electrolytes Having Core-Shell Silica Fillers with Anion-Trapping Boron Moiety in the Shell Layer for All-Solid-State Lithium-Ion Batteries
    Shim, Jimin; Kim, Dong-Gyun; Kim, Hee Joong; Lee, Jin Hong; Lee, Jong-Chan
    ACS Applied Materials & Interfaces (2015), 7 (14), 7690-7701CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Core-shell SiO2 particles with ion-conducting poly(ethylene glycol) and anion-trapping B moiety in the shell layer were prepd. to be used as fillers for polymer composite electrolytes based on org./inorg. hybrid branched copolymer as polymer matrix for all-solid-state Li-ion battery applications. The core-shell SiO2 particles improve mech. strength and thermal stability of the polymer matrix and poly(ethylene glycol) and B moiety in the shell layer increase compatibility between filler and polymer matrix. Also, B moiety in the shell layer increases both ionic cond. and Li transference no. of the polymer matrix because Li salt can be more easily dissocd. by the anion-trapping B. Interfacial compatibility with Li metal anode is also improved because well-dispersed SiO2 particles serve as protective layer against interfacial side reactions. As a result, all-solid-state battery performance is enhanced when the copolymer having core-shell SiO2 particles with the B moiety was used as solid polymer electrolyte.
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  42. 42
    Li, S. B.; Zuo, C.; Zhang, Y.; Wang, J. R.; Gan, H. H.; Li, S. Q.; Yu, L. P.; Zhou, B. H.; Xue, Z. G. Covalently cross-linked polymer stabilized electrolytes with self-healing performance via boronic ester bonds. Polym. Chem. 2020, 11 (36), 5893– 5902,  DOI: 10.1039/D0PY00728E
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    42
    Covalently cross-linked polymer stabilized electrolytes with self-healing performance via boronic ester bonds
    Li, Sibo; Zuo, Cai; Zhang, Yong; Wang, Jirong; Gan, Huihui; Li, Shaoqiao; Yu, Liping; Zhou, Binghua; Xue, Zhigang
    Polymer Chemistry (2020), 11 (36), 5893-5902CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)
    Herein, solid polymer electrolytes (SPEs) were designed and fabricated via the photopolymn. of a macromol. crosslinker with boronic ester bonds and poly(ethylene glycol) diacrylate (PEGDA) with different mol. wts. under UV irradn. in the presence of a photoinitiator. The boronic ester-based crosslinker was synthesized via the dehydration reaction of ortho-aminomethyl-phenylboronic acid-terminated poly(propylene glycol)-b-poly(ethylene glycol)-b-poly(propylene glycol) and 2,3-dihydroxypropyl methacrylate. The covalently crosslinked polymer stabilized electrolytes (PSEs) contg. boronic ester bonds possessed improved ionic cond., self-healing properties, and a wide electrochem. window (5.3 V vs. Li+/Li).
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  43. 43
    Wang, L.; Yan, J.; Zhong, M.; Zhang, J.; Shen, W.; Guo, S. Regulating Lithium-Ion Transference Number of a Poly(vinyl alcohol)-Based Gel Electrolyte by the Incorporation of H3BO3 as an Anion Trapper. ACS Appl. Energy Mater. 2022, 5 (3), 2873– 2880,  DOI: 10.1021/acsaem.1c03549
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    43
    Regulating Lithium-Ion Transference Number of a Poly(vinyl alcohol)-Based Gel Electrolyte by the Incorporation of H3BO3 as an Anion Trapper
    Wang, Lei; Yan, Jiawei; Zhong, Min; Zhang, Jiali; Shen, Wenzhuo; Guo, Shouwu
    ACS Applied Energy Materials (2022), 5 (3), 2873-2880CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    Gel electrolytes hold great promise for improving the safety of lithium-ion batteries (LIBs); however, their low lithium-ion transference no. (tLi+ < 0.4) remains to be improved. Herein, boron-contg. poly(vinyl alc.) (B-PVA) solns. are prepd. based on the simple reaction between PVA and H3BO3 and then electrospun to obtain the B-PVA nanofiber matrixes. The gel electrolytes are formed by loading the liq. electrolytes into the as-obtained porous B-PVA matrixes. We demonstrate that the tLi+ of B-PVA8 (with 8 wt % H3BO3 added) gel electrolyte can reach 0.81, much higher than that of the conventional PVA gel electrolyte (0.32). The B-PVA8 gel electrolyte also shows the highest Li+ cond. of 1.81 x 10-3 S cm-1 compared to PVA. The B-PVA8 gel electrolyte enables a small Li nucleation overpotential of 129.8 mV when Li is plated and reduces the concn. polarization of Li||Li batteries. The mesocarbon microbead (MCMB) half-coin cells with the B-PVA8 gel electrolyte exhibit excellent rate capability and exceptional charge/discharge cycling stability.
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  44. 44
    Hong, D. G.; Baik, J.-H.; Kim, S.; Lee, J.-C. Solid polymer electrolytes based on polysiloxane with anion-trapping boron moieties for all-solid-state lithium metal batteries. Polymer 2022, 240, 124517,  DOI: 10.1016/j.polymer.2022.124517
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    44
    Solid polymer electrolytes based on polysiloxane with anion-trapping boron moieties for all-solid-state lithium metal batteries
    Hong, Dong Gi; Baik, Ji-Hoon; Kim, Sangwan; Lee, Jong-Chan
    Polymer (2022), 240 (), 124517CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)
    Cross-linked solid polymer electrolytes (SPEs) based on ion-conducting poly(ethylene glycol) (PEG), flexible polysiloxane, and anion-trapping boron cross-linker (BPC) were prepd. via thiol-ene click reaction for lithium metal batteries. Various thermal and electrochem. properties of SPEs were systematically investigated by varying the content of BPC. Thermally stable free-standing SPE systems could be obtained due to the cross-linked structure, while relatively high ionic cond. of about 1.3 x 10-4 S cm-1 at 60 °C was obtained at the same time by the flexible polysiloxane moiety. The boron moiety in BPC could increase the lithium ion transference no. compared to the corresponding boron-free SPE due to the anion-trapping capability of boron atom. The formation and growth of lithium dendrites were effectively suppressed by the anion-trapping capability and mech. stable cross-linked structure of the SPE.
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  45. 45
    Guzman-Gonzalez, G.; Vauthier, S.; Alvarez-Tirado, M.; Cotte, S.; Castro, L.; Gueguen, A.; Casado, N.; Mecerreyes, D. Single-Ion Lithium Conducting Polymers with High Ionic Conductivity Based on Borate Pendant Groups. Angew. Chem., Int. Ed. 2022, 61 (8), e202114024,  DOI: 10.1002/anie.202114024
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    45
    Single-Ion Lithium Conducting Polymers with High Ionic Conductivity Based on Borate Pendant Groups
    Guzman-Gonzalez, Gregorio; Vauthier, Soline; Alvarez-Tirado, Marta; Cotte, Stephane; Castro, Laurent; Gueguen, Aurelie; Casado, Nerea; Mecerreyes, David
    Angewandte Chemie, International Edition (2022), 61 (7), e202114024CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A family of single-ion lithium conducting polymer electrolytes based on highly delocalized borate groups is reported. The effect of the nature of the substituents on the boron atom on the ionic cond. of the resultant methacrylic polymers was analyzed. To the best of our knowledge the lithium borate polymers endowed with flexible and electron-withdrawing substituents present the highest ionic cond. reported for a lithium single-ion conducting homopolymer (1.65x10-4 S cm-1 at 60°C). This together with its high lithium transference no. tLi+ =0.93 and electrochem. stability window of 4.2 V vs Li0/Li+ show promise for application in lithium batteries. To illustrate this, a lithium borate monomer was integrated into a single-ion gel polymer electrolyte which showed good performance on lithium sym. cells (<0.85 V at ±0.2 mA cm-2 for 175 h).
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  46. 46
    Alvarez-Tirado, M.; Guzman-Gonzalez, G.; Vauthier, S.; Cotte, S.; Gueguen, A.; Castro, L.; Mecerreyes, D. Designing Boron-Based Single-Ion Gel Polymer Electrolytes for Lithium Batteries by Photopolymerization. Macromol. Chem. Phys. 2022, 223 (8), 2100407,  DOI: 10.1002/macp.202100407
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    46
    Designing Boron-Based Single-Ion Gel Polymer Electrolytes for Lithium Batteries by Photopolymerization
    Alvarez-Tirado, Marta; Guzman-Gonzalez, Gregorio; Vauthier, Soline; Cotte, Stephane; Gueguen, Aurelie; Castro, Laurent; Mecerreyes, David
    Macromolecular Chemistry and Physics (2022), 223 (8), 2100407CODEN: MCHPES; ISSN:1022-1352. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Single-ion lithium conducting polymer electrolytes based on delocalized borate groups are designed and synthesized by rapid UV-photopolymn. For this purpose, three different functional lithium boron sp3 anionic monomers, contg. fluorinated, ethoxy, or a blend of both functionalities are synthesized. These monomers are photopolymd. in the presence of a poly(ethylene glycol) dimethacrylate crosslinker and tetraglyme as plasticizer. By this method, gel polymer electrolytes endowed with lithium single-ion conduction are prepd. (SIGPEs). The impact generated by the different functionalities of the borate groups and the addn. of plasticizer on the electrochem. and ion conducting properties of the synthesized polymer electrolytes are analyzed in detail. These polymer electrolytes show high ionic cond. (1.71 x 10-4 S cm-1 at 25 °C) and high lithium transference no. values (up to 0.85). Finally, they are investigated as solid electrolytes in lithium metal sym. cells showing good performance (<0.85 V at ±0.2 mA cm-2 for 175 h).
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  47. 47
    Chen, Q.; Shi, Y.; Sheng, K.; Zheng, J.; Xu, C. Dynamically Cross-Linked Hydrogel Electrolyte with Remarkable Stretchability and Self-Healing Capability for Flexible Electrochromic Devices. ACS Appl. Mater. Interfaces 2021, 13 (47), 56544– 56553,  DOI: 10.1021/acsami.1c15432
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    47
    Dynamically Cross-Linked Hydrogel Electrolyte with Remarkable Stretchability and Self-Healing Capability for Flexible Electrochromic Devices
    Chen, Qijun; Shi, Yuchen; Sheng, Kai; Zheng, Jianming; Xu, Chunye
    ACS Applied Materials & Interfaces (2021), 13 (47), 56544-56553CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    It is desired to develop self-healing gel electrolytes for flexible electrochromic devices (ECDs) due to the demand of healing damages caused during operations. We here report a hydrogel electrolyte with remarkable self-healing capability, excellent stretchability, and ionic cond. The hydrogel electrolyte was synthesized via one-step copolymn. of glycerol monomethacrylate (GMA) and acrylamide (AAm) in the presence of borate. Within the hydrogel electrolyte, dynamic crosslinking is expected to be formed due to the borate-didiol complexation and hydrogen-bonding interactions. As a result, the hydrogel electrolyte demonstrates an excellent self-healing efficiency of up to 97%, a fracture strain of 1155%, a fracture toughness of 136.6 kJ m-3, and a fracture stress of 13.0 kPa. Addnl., a flexible ECD based on the hydrogel electrolyte and an electrochromic layer of poly(3,4-(2,2-dimethyl-propylenedioxy)thiophene) (PProDOT-Me2) was assembled and evaluated. The device is found to be stable in both mech. and optical properties over 1000 operation cycles. This study may provide a promising way for self-healing electrolyte gels to be utilized in a variety of flexible electrochem. devices, including ECDs, supercapacitors, and batteries.
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  48. 48
    Gregory, G. L.; Jenisch, L. M.; Charles, B.; Kociok-Köhn, G.; Buchard, A. Polymers from Sugars and CO2: Synthesis and Polymerization of a d-Mannose-Based Cyclic Carbonate. Macromolecules 2016, 49 (19), 7165– 7169,  DOI: 10.1021/acs.macromol.6b01492
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    48
    Polymers from Sugars and CO2: Synthesis and Polymerization of a D-Mannose-Based Cyclic Carbonate
    Gregory, Georgina L.; Jenisch, Liliana M.; Charles, Bethan; Kociok-Kohn, Gabriele; Buchard, Antoine
    Macromolecules (Washington, DC, United States) (2016), 49 (19), 7165-7169CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
    A six-membered cyclic carbonate derived from natural sugar D-mannose was prepd. using CO2 as a C1 building block at room temp. and atm. pressure. The monomer was synthesized in two steps from a com. available mannopyranose deriv. Polycarbonates were rapidly prepd. at ambient temp. by controlled ring-opening polymn. (ROP) of the monomer, initiated by 4-methylbenzyl alc. in the presence of 1,5,7-triazabicyclo[5.4.0]dec-5-ene (TBD) as the organocatalyst. Head-to-tail regiochem. was indicated by NMR spectroscopy and is supported by DFT calcns. These aliph. polycarbonates exhibit high-temp. resistance and demonstrate potential for postpolymn. functionalization, suggesting future application as high-performance commodity and biomedical materials.
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  49. 49
    Piccini, M.; Leak, D. J.; Chuck, C. J.; Buchard, A. Polymers from sugars and unsaturated fatty acids: ADMET polymerisation of monomers derived from d-xylose, d-mannose and castor oil. Polym. Chem. 2020, 11 (15), 2681– 2691,  DOI: 10.1039/C9PY01809C
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    49
    Polymers from sugars and unsaturated fatty acids: ADMET polymerisation of monomers derived from D-xylose, D-mannose and castor oil
    Piccini, Marco; Leak, David J.; Chuck, Christopher J.; Buchard, Antoine
    Polymer Chemistry (2020), 11 (15), 2681-2691CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)
    α, ω-Unsatd. glycolipids derived from natural monosaccharides D-xylose and D-mannose, and from a castor oil deriv., 10-undecenoic acid, were synthesized and polymd. via acyclic diene metathesis (ADMET), using Grubbs second generation catalyst. The synthesis of these polymers, which combine a rigid isopropylidene-functionalised carbohydrate core with flexible unsatd. aliph. chains, was confirmed by NMR spectroscopy and size exclusion chromatog.. The effect of different parameters on the polymns. were investigated, including temp., catalyst loading, absence/presence of solvents, effect of a mol. wt. moderator and mixing technique. Polyesters with high mol. wts. (up to 71 kg mol-1) could be obtained in elevated yields (85%). These amorphous polymers were highly thermally (up to 355°C) and hydrolytically (pH 7, 0, 14) stable, and showed relatively low glass transition temps. (-28 to -8°C), imparted by the flexible fatty acid chain. Deprotection of ketal groups on the polymer backbone was possible up to 72% and changed the material properties, leading to partial crystallinity and insoly. These partially deprotected polymers allowed the prodn. of transparent thin polymer films and were amenable to further functionalisation.
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  50. 50
    McGuire, T. M.; Bowles, J.; Deane, E.; Farrar, E. H. E.; Grayson, M. N.; Buchard, A. Control of Crystallinity and Stereocomplexation of Synthetic Carbohydrate Polymers from d- and l-Xylose. Angew. Chem., Int. Ed. 2021, 60 (9), 4524– 4528,  DOI: 10.1002/anie.202013562
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    50
    Control of Crystallinity and Stereocomplexation of Synthetic Carbohydrate Polymers from D- and L-Xylose
    McGuire, Thomas M.; Bowles, Jessica; Deane, Edward; Farrar, Elliot H. E.; Grayson, Matthew N.; Buchard, Antoine
    Angewandte Chemie, International Edition (2021), 60 (9), 4524-4528CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Manipulating the stereochem. of polymers is a powerful method to alter their phys. properties. Despite the chirality of monosaccharides, reports on the impact of stereochem. in natural polysaccharides and synthetic carbohydrate polymers remain absent. Herein, we report the cocrystn. of regio- and stereoregular polyethers derived from D- and L-xylose, leading to enhanced thermal properties compared to the enantiopure polymers. To the best of our knowledge, this is the first example of a stereocomplex between carbohydrate polymers of opposite chirality. In contrast, atactic polymers obtained from a racemic mixt. of monomers are amorphous. We also show that the polymer hydroxyl groups are amenable to post-polymn. functionalization. These strategies afford a family of carbohydrate polyethers, the phys. and chem. properties of which can both be controlled, and which opens new possibilities for polysaccharide mimics in biomedical applications or as advanced materials.
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  51. 51
    McGuire, T. M.; Clark, E. F.; Buchard, A. Polymers from Sugars and Cyclic Anhydrides: Ring-Opening Copolymerization of a d-Xylose Anhydrosugar Oxetane. Macromolecules 2021, 54 (11), 5094– 5105,  DOI: 10.1021/acs.macromol.1c00365
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    51
    Polymers from Sugars and Cyclic Anhydrides: Ring-Opening Copolymerization of a D-Xylose Anhydrosugar Oxetane
    McGuire, Thomas M.; Clark, Ella F.; Buchard, Antoine
    Macromolecules (Washington, DC, United States) (2021), 54 (11), 5094-5105CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
    A D-xylose 3,5-anhydrosugar deriv. has been used as an oxetane co-monomer in the ring-opening copolymn. (ROCOP) with cyclic anhydrides, to form a family of seven novel sugar-derived polyesters, with up to 100% renewable content. ROCOP proceeds with high alternating selectivity to form AB-type copolymers that are thermally robust (Td,onset > 212°C) and exhibit a broad range of glass-transition temps. (Tg 60-145°C). These polyesters are amenable to further postpolymn. functionalization. The hydroxy group of the sugar moiety can be unveiled, then functionalized further, e.g., phosphorylated. The internal alkene of some of the anhydride moieties can also be subject to thiol-ene reactions. Combining those orthogonal strategies affords AB copolyesters with alternating functional substituents. By exploiting the living character of the ROCOP process, block copolymers have also been synthesized through sequential co-monomer addn. expts.
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  52. 52
    Gregory, G. L.; Kociok-Kohn, G.; Buchard, A. Polymers from sugars and CO2: ring-opening polymerisation and copolymerisation of cyclic carbonates derived from 2-deoxy-d-ribose. Polym. Chem. 2017, 8 (13), 2093– 2104,  DOI: 10.1039/C7PY00236J
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    52
    Polymers from sugars and CO2: ring-opening polymerization and copolymerization of cyclic carbonates derived from 2-deoxy-D-ribose
    Gregory, Georgina L.; Kociok-Kohn, Gabriele; Buchard, Antoine
    Polymer Chemistry (2017), 8 (13), 2093-2104CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)
    Bio-based aliph. polycarbonates (APCs) are attractive synthetic materials for biomedical applications because of their biodegradability and biocompatibility properties. A high yielding 3-step process that utilizes CO2 as a C1 synthon is presented for converting raw sugar, 2-deoxy-D-ribose into a novel 6-membered cyclic carbonate for ring-opening polymn. (ROP) into carbohydrate-based APCs. The α- and β-anomers of the monomer could be isolated and revealed very different polymerizability, as rationalized by DFT calcns. Whereas the β-anomer could not be polymd. under the conditions tested, organocatalytic homopolymn. of the α-anomer, in soln. at room temp. (rt) or under melt conditions, yielded highly insol. polycarbonates, composed of both cyclic and linear topologies, and exhibiting a glass transition temp. (Tg) of ∼58°C. Random copolymers with controllable incorporation of this new sugar monomer were prepd. with trimethylene carbonate (TMC) at rt in the bulk or in soln. with Mn up to 64 000 g mol-1. With increasing sugar content, the Tg values of the copolymers increased and their thermal degradability was enhanced, giving access to a new class of APCs with tailored properties.
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  53. 53
    Kumar, R.; Gao, W.; Gross, R. A. Functionalized Polylactides: Preparation and Characterization of [l]-Lactide-co-Pentofuranose. Macromolecules 2002, 35 (18), 6835– 6844,  DOI: 10.1021/ma020041a
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    53
    Functionalized Polylactides: Preparation and Characterization of [L]-Lactide-co-Pentofuranose
    Kumar, Rajesh; Gao, Wei; Gross, Richard A.
    Macromolecules (2002), 35 (18), 6835-6844CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
    The new monomer 1,2-O-isopropylidene-3-benzyloxy-pentofuranose-4,4'-cyclic carbonate (IPPTC) was prepd. IPPTC has both a ketal-protected diol and a benzyl ether-protected hydroxyl. Thus, these two sets of hydroxyl groups can be independently deprotected to give IPPTC repeat units with one, two, or three free hydroxyl groups. Stannous octanoate at 130° was used for the copolymn. of [L]-LA (L-lactide) with IPPTC. When monomer feed ratio fLA/fIPPTC was 91/9, the percent yield, Mn, and percent incorporation of IPPTC units were 78%, 77,800 g/mol, and 4 mol%, resp. By the method of Fineman and Ross, the [L]-LA and IPPTC comonomer reactivity ratios were 8.6 and 0.51, resp. Relative to poly([L]-LA), incorporation of IPPTC units into [L]-LA/IPPTC copolymers gave products that are lower melting (112°, 14 mol% IPPTC) and have higher thermal stabilities and higher glass transition temps. (69°, 100 mol% IPPTC). The liberation of hydroxyl pendant groups by the selective removal of the benzyl ether, the ketal groups, or both was possible without substantial loss in the product mol. wt. The removal of the protecting groups of poly([L]-LA-co-4.0 mol% IPPTC) did not change the Tm value (160°) but did alter the copolymer crystn. kinetics and thermal stability.
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  54. 54
    Felder, S. E.; Redding, M. J.; Noel, A.; Grayson, S. M.; Wooley, K. L. Organocatalyzed ROP of a Glucopyranoside Derived Five-Membered Cyclic Carbonate. Macromolecules 2018, 51 (5), 1787– 1797,  DOI: 10.1021/acs.macromol.7b01785
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    54
    Organocatalyzed ROP of a Glucopyranoside Derived Five-Membered Cyclic Carbonate
    Felder, Simcha E.; Redding, McKenna J.; Noel, Amandine; Grayson, Scott M.; Wooley, Karen L.
    Macromolecules (Washington, DC, United States) (2018), 51 (5), 1787-1797CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
    Saccharides, based on their wide bioavailability, high chem. functionality and stereochem. diversity, are attractive starting materials for the development of new synthetic polymers. Established carbonylation methodologies were used to synthesize a 5-membered cyclic carbonate monomer, 4,6-O-benzylidene-2,3-O-carbonyl-α-D-glucopyranoside (MBGC), in high yield (>95%) from a com. available D-glucopyranoside deriv. The ability of this monomer to undergo ring-opening polymn. (ROP) with a range of organocatalysts, rather than the previously reported anionic initiators, was investigated. These new conditions were developed to widen the functional group tolerance in the polymn., and achieve better control over the final properties of the polymers. The most promising of the catalysts examd., 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), was used in a kinetic study to confirm the well-controlled nature of the ROP. Optimized conditions were then successfully applied to the synthesis of polymers of different mol. wts. Two post-polymn. modifications were completed via the removal of the benzylidene acetal protecting group to release a water-sol. poly(glucose carbonate), and then addn. of acetyl groups to facilitate characterization studies. MALDI-TOF MS anal. was performed to further probe the chem. of the polymn. and deprotection. A wide range of thermal decompn. temps. (233-347 °C), glass transition temps. (87-233 °C), and water contact angles (38-128°) was achieved by this series of polymers. The hydrolytic degradability of these polymers was also examd., demonstrating differing degrdn. mechanisms based on the acidic vs. basic conditions used. Consequently, this single monomer was successfully employed in the straightforward synthesis of a polymeric system with tunable properties based on the mol. wt. and repeat unit compn.
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  55. 55
    Fenouillot, F.; Rousseau, A.; Colomines, G.; Saint-Loup, R.; Pascault, J. P. Polymers from renewable 1,4:3,6-dianhydrohexitols (isosorbide, isomannide and isoidide): A review. Prog. Polym. sci. 2010, 35 (5), 578– 622,  DOI: 10.1016/j.progpolymsci.2009.10.001
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    55
    Polymers from renewable 1,4:3,6-dianhydrohexitols (isosorbide, isomannide and isoidide): A review
    Fenouillot, F.; Rousseau, A.; Colomines, G.; Saint-Loup, R.; Pascault, J.-P.
    Progress in Polymer Science (2010), 35 (5), 578-622CODEN: PRPSB8; ISSN:0079-6700. (Elsevier Ltd.)
    A review. The use of the 1,4:3,6-dianhydrohexitols isosorbide, isomannide, and isoidide in polymers is reviewed. 1,4:3,6-Dianhydrohexitols are derived from renewable resources from cereal-based polysaccharides. 1,4:3,6-Dianhydrohexitols are derived from renewable resources from cereal-based polysaccharides. In the field of polymeric materials, these diols are essentially employed to synthesize or modify polycondensates. Their attractive features as monomers are linked to their rigidity, chirality, non-toxicity, and the fact that they are not derived from petroleum. First, the synthesis of high glass transition temp. polymers with good thermomech. resistance is possible. Second, the chiral nature of 1,4:3,6-dianhydrohexitols may lead to specific optical properties. Finally, biodegradable polymers can be obtained. The prodn. of isosorbide on an industrial scale with a purity satisfying the requirements for polymer synthesis suggests that isosorbide will soon emerge in industrial polymer applications. However, a deciding factor will be the redn. of polymn. time of these low-reactivity monomers to values compatible with economically viable prodn. processes to give polyesters, polyamides, poly(amide esters), poly(ester imides), polycarbonates, polyurethanes, and polyethers.
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  56. 56
    Xiao, R.; Grinstaff, M. W. Chemical synthesis of polysaccharides and polysaccharide mimetics. Prog. Polym. sci. 2017, 74, 78– 116,  DOI: 10.1016/j.progpolymsci.2017.07.009
    Google Scholar
    56
    Chemical synthesis of polysaccharides and polysaccharide mimetics
    Xiao, Ruiqing; Grinstaff, Mark W.
    Progress in Polymer Science (2017), 74 (), 78-116CODEN: PRPSB8; ISSN:0079-6700. (Elsevier Ltd.)
    A review. Polysaccharides are ubiquitous in nature, and play many crit. roles in biol. As such, the synthesis of polysaccharides and of polymers mimicking the structure or function of polysaccharides is of keen interest in order to reveal structure-function relationships and to prep. biocompatible and biodegradable materials for research and com. applications. Recent developments in polymn. methodologies are enabling the synthesis of polysaccharides and polysaccharide mimetics with a variety of structures and architectures. While there have been significant advances in overcoming the difficulties in controlling the regioselectivity and stereospecificity of glycosidic bond formation during polymn., the development of efficient synthetic routes with general applicability to stereoregular and structurally complex polysaccharides remains a challenge. This review comprehensively describes the chem. polymn. methods to synthesize polysaccharides with different compns. and architectures (linear, branched, and hyperbranched) and the synthetic procedures to polysaccharide mimetics possessing, for example, amine linkages, amide linkages, and carbonate linkages. It begins with a discussion of the challenges and strategies for the synthesis of polysaccharides. We highlight the complexity obsd. in theses macromols. due to the no. and variety of stereo- and regio-types of glycosidic linkages present between monosaccharide residues. With regards to polysaccharide mimetics, we focus on polymers displaying important structural features present in natural polysaccharides, such as a rigid polymer backbone contg. heterocyclic ring structures, short linkages with less than three atoms, as well as multiple hydroxyl groups. Both condensation polymn. and ring-opening polymn. are used to prep. linear polysaccharides, branched polysaccharides, hyperbranched polysaccharides, non-O-glycosidic linked polysaccharide mimetics, and pseudopolysaccharides. The review concludes with reflections and suggestions for future directions of investigation.
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  57. 57
    Zhu, Y.; Romain, C.; Williams, C. K. Sustainable polymers from renewable resources. Nature 2016, 540 (7633), 354– 362,  DOI: 10.1038/nature21001
    Google Scholar
    57
    Sustainable polymers from renewable resources
    Zhu, Yunqing; Romain, Charles; Williams, Charlotte K.
    Nature (London, United Kingdom) (2016), 540 (7633), 354-362CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
    Renewable resources are used increasingly in the prodn. of polymers. In particular, monomers such as carbon dioxide, terpenes, vegetable oils and carbohydrates can be used as feedstocks for the manuf. of a variety of sustainable materials and products, including elastomers, plastics, hydrogels, flexible electronics, resins, engineering polymers and composites. Efficient catalysis is required to produce monomers, to facilitate selective polymns. and to enable recycling or upcycling of waste materials. There are opportunities to use such sustainable polymers in both high-value areas and in basic applications such as packaging. Life-cycle assessment can be used to quantify the environmental benefits of sustainable polymers.
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  58. 58
    Galbis, J. A.; García-Martín, M. d. G.; de Paz, M. V.; Galbis, E. Synthetic Polymers from Sugar-Based Monomers. Chem. Rev. 2016, 116 (3), 1600– 1636,  DOI: 10.1021/acs.chemrev.5b00242
    Google Scholar
    58
    Synthetic Polymers from Sugar-Based Monomers
    Galbis, Juan A.; Garcia-Martin, M. de Gracia; de Paz, M. Violante; Galbis, Elsa
    Chemical Reviews (Washington, DC, United States) (2016), 116 (3), 1600-1636CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. This article reports the sugar-based polymers.
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  59. 59
    Gregory, G. L.; Lopez-Vidal, E. M.; Buchard, A. Polymers from sugars: cyclic monomer synthesis, ring-opening polymerisation, material properties and applications. Chem. Commun. 2017, 53 (14), 2198– 2217,  DOI: 10.1039/C6CC09578J
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    59
    Polymers from sugars: cyclic monomer synthesis, ring-opening polymerisation, material properties and applications
    Gregory, Georgina L.; Lopez-Vidal, Eva M.; Buchard, Antoine
    Chemical Communications (Cambridge, United Kingdom) (2017), 53 (14), 2198-2217CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    A review. Plastics are ubiquitous in modern society. However, the reliance on fossil fuels and the environmental persistence of most polymers make them unsustainable. Scientists are facing the challenge of developing cost-effective and performance-competitive polymers from renewable resources. Carbohydrates are a renewable feedstock with tremendous potential: sugars are widely available, environmentally benign and are likely to impart biocompatibility and degradability properties to polymers due to their high oxygen content. Sugars are also a feedstock with great structurally diversity and functionalisation potential that can enable fine tuning of the resulting polymer properties. In recent years, ring-opening polymn. (ROP) has emerged as the method of choice for the controlled polymn. of renewable cyclic monomers, in particular lactones and cyclic carbonates, to allow the precise synthesis of complex polymer architectures and address commodity and specialist applications. This feature article gives an overview of sugar-based polymers that can be made by ROP. In particular, recent advances in the synthetic routes towards monomers that preserve the original carbohydrate core structure are presented. The performances of various homogeneous catalysts and the properties of the resultant polymers are given, and future opportunities highlighted for the development of both the materials and catalysts.
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  60. 60
    Ma, L.; Jin, M.; Yan, C.; Guo, H.; Ma, X. Gel Polymer Electrolyte with Anion-Trapping Boron Moieties via One-Step Synthesis for Symmetrical Supercapacitors. Macromol. Mater. Eng. 2020, 305 (7), 1900807,  DOI: 10.1002/mame.201900807
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    60
    Gel Polymer Electrolyte with Anion-Trapping Boron Moieties via One-Step Synthesis for Symmetrical Supercapacitors
    Ma, Longli; Jin, Mengyuan; Yan, Chaojing; Guo, Hao; Ma, Xiaohua
    Macromolecular Materials and Engineering (2020), 305 (7), 1900807CODEN: MMENFA; ISSN:1438-7492. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A novel gel polymer electrolyte (GPE) which is based on new synthesized boron-contg. monomer, benzyl methacrylate, 1 M LiClO4/N,N-dimethylformamidel liq. electrolyte soln. is prepd. through a one-step synthesis method. The boron-contg. GPE (B-GPE) not only displays excellent mech. behavior, favorable thermal stability, but also exhibits an outstanding ionic cond. of 2.33 mS cm-1 at room temp. owing to the presence of anion-trapping boron sites. The lithium ion transference in this gel polymer film at ambient temp. is 0.60. Furthermore, the sym. supercapacitor which is fabricated with B-GPE as electrolyte and reduced graphene oxide as electrode demonstrates a broad potential window of 2.3 V. The specific capacitance of sym. B-GPE supercapacitors retains 90% after 3000 charge-discharge cycles at c.d. of 1 A g-1.
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  61. 61
    Dai, K.; Ma, C.; Feng, Y.; Zhou, L.; Kuang, G.; Zhang, Y.; Lai, Y.; Cui, X.; Wei, W. A borate-rich, cross-linked gel polymer electrolyte with near-single ion conduction for lithium metal batteries. J. Mater. Chem. A 2019, 7 (31), 18547– 18557,  DOI: 10.1039/C9TA05938E
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    61
    A borate-rich, cross-linked gel polymer electrolyte with near-single ion conduction for lithium metal batteries
    Dai, Kuan; Ma, Cheng; Feng, Yiming; Zhou, Liangjun; Kuang, Guichao; Zhang, Yun; Lai, Yanqing; Cui, Xinwei; Wei, Weifeng
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (31), 18547-18557CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    Lithium metal batteries (LMBs) show tremendous potential in energy storage due to ultrahigh energy densities. Nevertheless, maintaining a stable solid electrolyte interphase (SEI) and suppressing the growth of dendrites are hard to achieve with conventional liq. electrolytes. Gel/solid polymer electrolytes are sought-after candidates to block dendrite growth, while they still suffer from poor ionic cond. and an incompatible interphase. Herein, a borate-rich gel polymer electrolyte with a 3D cross-linked structure (3D-BGPE) is designed to settle these problems. By incorporating anion-trapping boron moieties into a 3D configuration via an in situ strategy, the 3D-BGPE presents high ionic cond. (8.4 × 10-4 S cm-1), near single ion conduction (Li+ transference no. of 0.76) and constructs a stable and conductive SEI layer on the lithium anode. Accordingly, the LMBs employing the 3D-BGPE can effectively inhibit the dendrite growth and maintain 89.73% capacity retention after 400 cycles. A promising approach to design highly effective electrolytes for safe and long-life LMBs is provided in this work.
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  62. 62
    Zeng, X.; Dong, L.; Fu, J.; Chen, L.; Zhou, J.; Zong, P.; Liu, G.; Shi, L. Enhanced interfacial stability with a novel boron-centered crosslinked hybrid polymer gel electrolytes for lithium metal batteries. Chem. Eng. J. 2022, 428, 131100,  DOI: 10.1016/j.cej.2021.131100
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    62
    Enhanced interfacial stability with a novel boron-centered crosslinked hybrid polymer gel electrolytes for lithium metal batteries
    Zeng, Xingfa; Dong, Linna; Fu, Jifang; Chen, Liya; Zhou, Jia; Zong, Peisong; Liu, Guozhen; Shi, Liyi
    Chemical Engineering Journal (Amsterdam, Netherlands) (2022), 428 (), 131100CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
    Low coulombic efficiency and serious safety issues due to uncontrollable lithium dendrite growth has severely impeded the practical application of lithium-ion batteries (LIBs) with lithium metal as the anode. In this work, we design and fabricate a novel single ion conducting crosslinked polymer gel electrolytes contg. neg. charged delocalized state borate structures and rich EO units via one-step photoinitiated in-situ radical polymn. in presence of PVDF-HFP as reinforcing materials. Herein, we synthesize a novel lithium bis(macid acid) borate to give anion covalently bonded to the polymer main chain and vinyl monomers contg. rich EO units are chosen to build polymer framework to ensure fast ion transport. As expected, the tailored boron-centered single-ion-conducting polymer gel electrolytes exhibit high ionic cond. up to 1.03x10-3 S cm-1 at 32°C, excellent oxidn. potential up to 5.05 V vs Li+/Li at 1 mV/s, and a near-single ion conducting behavior (lithium ion transference no. of 0.65). The Lithium (Li) metal sym. cells assembled with the novel boron-centered single-ion-conducting polymer gel electrolytes show long-term stable cycling over >700 h at room temp. without short circuit, which implies the excellent stability of blend membranes during lithium metal deposition and stripping processes. Moreover, the Li/LiFePO4 cells assembled with the boron-centered single-ion-conducting polymer gel electrolytes exhibit excellent rate performance and cycling performance. The initial discharge capacity is 161.3 mAh g-1 at 0.1 C and a capacity of 127.7 mAh g-1 maintains with nearly 100% coulombic efficiency after 100 cycles. Moreover, the Li/LiFePO4 cells deliver stable coulombic efficiency close to 100% at 0.5 C after 300 cycles.
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  63. 63
    Chen, Q.; Shi, Y.; Sheng, K.; Zheng, J.; Xu, C. Dynamically Cross-Linked Hydrogel Electrolyte with Remarkable Stretchability and Self-Healing Capability for Flexible Electrochromic Devices. ACS Appl. Mater. Interfaces 2021, 13 (47), 56544– 56553,  DOI: 10.1021/acsami.1c15432
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    63
    Dynamically Cross-Linked Hydrogel Electrolyte with Remarkable Stretchability and Self-Healing Capability for Flexible Electrochromic Devices
    Chen, Qijun; Shi, Yuchen; Sheng, Kai; Zheng, Jianming; Xu, Chunye
    ACS Applied Materials & Interfaces (2021), 13 (47), 56544-56553CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    It is desired to develop self-healing gel electrolytes for flexible electrochromic devices (ECDs) due to the demand of healing damages caused during operations. We here report a hydrogel electrolyte with remarkable self-healing capability, excellent stretchability, and ionic cond. The hydrogel electrolyte was synthesized via one-step copolymn. of glycerol monomethacrylate (GMA) and acrylamide (AAm) in the presence of borate. Within the hydrogel electrolyte, dynamic crosslinking is expected to be formed due to the borate-didiol complexation and hydrogen-bonding interactions. As a result, the hydrogel electrolyte demonstrates an excellent self-healing efficiency of up to 97%, a fracture strain of 1155%, a fracture toughness of 136.6 kJ m-3, and a fracture stress of 13.0 kPa. Addnl., a flexible ECD based on the hydrogel electrolyte and an electrochromic layer of poly(3,4-(2,2-dimethyl-propylenedioxy)thiophene) (PProDOT-Me2) was assembled and evaluated. The device is found to be stable in both mech. and optical properties over 1000 operation cycles. This study may provide a promising way for self-healing electrolyte gels to be utilized in a variety of flexible electrochem. devices, including ECDs, supercapacitors, and batteries.
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  64. 64
    Homann, G.; Stolz, L.; Winter, M.; Kasnatscheew, J. Elimination of ″Voltage Noise″ of Poly (Ethylene Oxide)-Based Solid Electrolytes in High-Voltage Lithium Batteries: Linear versus Network Polymers. Iscience 2020, 23 (6), 101225,  DOI: 10.1016/j.isci.2020.101225
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    64
    Elimination of "Voltage Noise" of Poly (Ethylene Oxide)-Based Solid Electrolytes in High-Voltage Lithium Batteries: Linear versus Network Polymers
    Homann, Gerrit; Stolz, Lukas; Winter, Martin; Kasnatscheew, Johannes
    iScience (2020), 23 (6), 101225CODEN: ISCICE; ISSN:2589-0042. (Elsevier B.V.)
    Frequently, poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) reveal a failure with high-voltage electrodes, e.g. LiNi0.6Mn0.2Co0.2O2 in lithium metal batteries, which can be monitored as an arbitrary appearance of a "voltage noise" during charge and can be attributed to Li dendrite-induced cell micro short circuits. This failure behavior disappears when incorporating linear PEO-based SPE in a semi-interpenetrating network (s-IPN) and even enables an adequate charge/discharge cycling performance at 40°C. An impact of any electrolyte oxidn. reactions on the performance difference can be excluded, as both SPEs reveal similar (high) bulk oxidn. onset potentials of ≈4.6 V vs. Li|Li+. Instead, improved mech. properties of the SPE, as revealed by compression tests, are assumed to be detg., as they mech. better withstand Li dendrite penetration and better maintain the distance of the two electrodes, both rendering cell shorts less likely.
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  65. 65
    Gou, J. R.; Liu, W. Y.; Tang, A. M. A renewable gel polymer electrolyte based on the different sized carboxylated cellulose with satisfactory comprehensive performance for rechargeable lithium ion battery. Polymer 2020, 208, 122943,  DOI: 10.1016/j.polymer.2020.122943
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    65
    A renewable gel polymer electrolyte based on the different sized carboxylated cellulose with satisfactory comprehensive performance for rechargeable lithium ion battery
    Gou, Jingren; Liu, Wangyu; Tang, Aimin
    Polymer (2020), 208 (), 122943CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)
    Gel polymer electrolyte (GPE) comprising the merits of liq. electrolyte (LE) and solid state electrolyte (SSE) has attracted soaring attention. Herein, we develop a GPE with good comprehensive performance by means of mixing the micro carboxylated cellulose fibril (MCCF) and nano carboxylated cellulose fibril (NCCF) in different proportions. In this composite structure, MCCF forms the skeleton of the host membrane of GPE and provides aplenty pores. While NCCF reinforces the connections of the micron cellulose filaments, enhancing the mech. properties of the membrane. Obtained from the exptl. results, the GPE contg. 1%wt nano cellulose exhibits a high tensile strength of 40.1 MPa, a good ionic cond. of 1.84 mS cm-1 at 25°C and a stable thermal performance up to 220°C. Simultaneously, the NCM523//Li half cell assembled with this GPE shows a moderate cyclic performance at the ambient temp. of 25°C. Moreover, such cellulose based GPE is renewable and biodegradable, which can contribute to the environmental protection-oriented development of lithium ion battery industry.
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  66. 66
    Gou, J. R.; Liu, W. Y.; Tang, A. M.; Xie, H. A phosphorylated nanocellulose/hydroxypropyl methylcellulose composite matrix: A biodegradable, flame-retardant and self-standing gel polymer electrolyte towards eco-friendly and high safety lithium ion batteries. Eur. Polym. J. 2021, 158, 110703,  DOI: 10.1016/j.eurpolymj.2021.110703
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    66
    A phosphorylated nanocellulose/hydroxypropyl methylcellulose composite matrix: A biodegradable, flame-retardant and self-standing gel polymer electrolyte towards eco-friendly and high safety lithium ion batteries
    Gou, Jingren; Liu, Wangyu; Tang, Aimin; Xie, Hong
    European Polymer Journal (2021), 158 (), 110703CODEN: EUPJAG; ISSN:0014-3057. (Elsevier Ltd.)
    Gel polymer electrolyte (GPE) is considered as a midway soln. of liq. electrolyte and solid polymer electrolyte. Nowadays, the biodegradable and renewable cellulose based GPEs are adopted as promising substitutes for GPEs based on other polymers like PVDF and PMMA. However, the safety concerns derived from the flammability of cellulose still hinders the practical application of the cellulose based GPEs. Simultaneously, the conventional methods to improve the flame-resistance of the host membranes are either unreliable or often invalidate the biodegradability of the GPEs based on cellulose. To achieve the unique combination of biodegradability and high safety, we report the prepn. of composite GPEs with flame-retardancy resulted from hydrolysis between phosphorylated nanocellulose (PNC) and hydroxypropyl methylcellulose (HPMC). Besides, the present GPEs are demonstrated to be self-standing and mech. robust with the advent of PNC. In comparison of the GPEs with various content of PNC, MPC50%/GPC50% are considered as the suitable options thanks to the high tensile strength, satisfactory electrochem. performances and good flame-retardancy. Finally, the LiFePO4/GPC50%/Li coin battery performs a remarkable cycling performance with a high capacity retention of 88.9% at 0.2C and a good rate capability in the battery test. It is anticipated that the as-constructed GPE can contribute to the design on the eco-friendly and high safety batteries in the future.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvVSks73F&md5=577d190eaa3c3c402ccfe4f82f913f5e
  67. 67
    Li, M. X.; Wang, X. W.; Yang, Y. Q.; Chang, Z.; Wu, Y. P.; Holze, R. A dense cellulose-based membrane as a renewable host for gel polymer electrolyte of lithium ion batteries. J. Membr. sci. 2015, 476, 112– 118,  DOI: 10.1016/j.memsci.2014.10.056
    Google Scholar
    67
    A dense cellulose-based membrane as a renewable host for gel polymer electrolyte of lithium ion batteries
    Li, M. X.; Wang, X. W.; Yang, Y. Q.; Chang, Z.; Wu, Y. P.; Holze, R.
    Journal of Membrane Science (2015), 476 (), 112-118CODEN: JMESDO; ISSN:0376-7388. (Elsevier B.V.)
    A dense instead of porous gel polymer electrolyte for lithium ion batteries is reported for the first time. Its host is a renewable and environment friendly polymer, hydroxyethyl cellulose (HEC). The prepn. of HEC membrane is very simple. The membrane is stable up to 280 °C, much higher than the m.ps. of those com. separators based on polyolefin. The evapn. temp. of the org. electrolyte in the prepd. gel polymer electrolytes is up to 75 °C. In addn., the gel polymer electrolyte shows good electrochem. performance including high ionic cond. at room temp., and a high lithium ion transference no. When tested as separator and electrolyte, a LiFePO4 pos. electrode displays satisfactory electrochem. properties including high discharge capacity and stable cycling. These results indicate a very promising direction for a low cost and renewable gel polymer electrolyte for lithium ion batteries.
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  68. 68
    Yang, H. Z.; Liu, Y.; Kong, L. B.; Kang, L.; Ran, F. Biopolymer-based carboxylated chitosan hydrogel film crosslinked by HCl as gel polymer electrolyte for all-solid-sate supercapacitors. J. Power Sources 2019, 426, 47– 54,  DOI: 10.1016/j.jpowsour.2019.04.023
    Google Scholar
    68
    Biopolymer-based carboxylated chitosan hydrogel film crosslinked by HCl as gel polymer electrolyte for all-solid-sate supercapacitors
    Yang, Hezhen; Liu, Ying; Kong, Lingbin; Kang, Long; Ran, Fen
    Journal of Power Sources (2019), 426 (), 47-54CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    Gel polymer electrolyte for flexible energy storage devices such as supercapacitors and rechargeable batteries attracts widespread attentions. Herein, we fabricate a flexible, transparent, and eco-friendly gel polymer electrolyte film based on biodegradable polymer of the carboxylated chitosan via phase sepn. of carboxylated chitosan hydrogel in hydrochloric acid. HCl is the key chem. for crosslinking of film forming, and the process is simple, rapid and non-polluting. The obtained carboxylated chitosan hydrogel film with excellent flexibility exhibits a highest electrolyte uptake rate of 742.0 wt%, and a highest ionic cond. of 8.69 × 10-2 S cm-1. A sym. all-solid-state supercapacitors using carbon cloth as current collectors, activated carbon film as electrodes, and carboxylated chitosan hydrogel film as a gel polymer electrolyte shows a high specific capacitance of 45.9 F g-1 at 0.5 A g-1, and the max. energy d. of 5.2 Wh kg-1 at a power d. of 226.6 W kg-1. To our knowledge, this is the first time that carboxylated chitosan hydrogel film being used as gel polymer electrolyte for supercapacitors electrolyte. The good results indicate that the carboxylated chitosan as a new gel polymer electrolyte material has great potential in practical applications of all-solid-state, flexible, and portable energy storage devices.
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  69. 69
    Kamisan, A. S.; Kudin, T. I. T.; Ali, A. M. M.; Yahya, M. Z. A. Electrical and physical studies on 49% methyl-grafted natural rubber-based composite polymer gel electrolytes. Electrochim. Acta 2011, 57, 207– 211,  DOI: 10.1016/j.electacta.2011.06.096
    Google Scholar
    69
    Electrical and physical studies on 49% methyl-grafted natural rubber-based composite polymer gel electrolytes
    Kamisan, A. S.; Kudin, T. I. T.; Ali, A. M. M.; Yahya, M. Z. A.
    Electrochimica Acta (2011), 57 (), 207-211CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)
    The elec. properties of composite polymer electrolyte systems composed of 49% poly(Me methacrylate) (PMMA) grafted natural rubber (MG49) host polymer, ammonium triflate (NH4CF3SO3) salt, and SiO2 as a filler were studied by impedance spectroscopy technique. Attenuated total reflectance-Fourier transformed IR (ATR-FTIR) spectra were also measured and indicated the occurrence of polymer-salt-filler interaction. The cond. for the composite ammonium triflate-doped MG49 polymer was studied as a function of temp. between 303 K and 373 K The cond. was found to exhibit Arrhenius behavior indicating that it is thermally activated. Viscosity measurements were also carried out and showed that the mech. properties of the composite polymer gel electrolytes (CPGEs) are improved. The highest elec. cond. of the composite electrolyte system (∼7.55 × 10-3 S cm-1) was obsd. for the sample contg. 8.0% SiO2. The viscosity for that material was high (∼69 cP) compared with the electrolyte contg. no SiO2 (∼10 cP).
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhsFWru77M&md5=d4be2237a3f6ff00137e41bda0f0ff9e
  70. 70
    Careem, M. A.; Noor, I. S. M.; Arof, A. K., Impedance Spectroscopy in Polymer Electrolyte Characterisation. In Polymer Electrolytes: Characterization Techniques and Energy Applications, 1st ed.; Winie, T., Arof, A. K., Thomas, S., Eds.; Wiley-VCH verlag GmbH & Co.: Weinheim Germany, 2020; pp 23– 64.
    Google Scholar
    There is no corresponding record for this reference.

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  • Abstract

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    Scheme 1

    Scheme 1. Synthesis of Monomer d-1, Subsequent Anionic Ring-Opening Polymerization, and Post-Polymerization Acetal Deprotection to Yield Hydroxy-Polymer, dp-poly(d-1)
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    Scheme 2

    Scheme 2. Cross-Linking of dp-poly(d-1) and 1,4-Phenylenediboronic Acid (PDBA)
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    Figure 1

    Figure 1. Vial inversion tests of (a) a 24 mg mL–1 solution of PDBA in DMSO, (b) a 0.287 mol L–1 solution of dp-poly(d-1), and (c) a reaction between dp-poly(d-1) and PDBA observed over several hours. (d) Phase diagram of the dp-poly(d-1)/PDBA system in DMSO at room temperature.

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    Figure 2

    Figure 2. FT-IR spectra of dp-poly(d-1) (black), PDBA (red), and organogel (blue) made from dp-poly(d-1) (0.287 mol L–1) and 0.5 equiv of PDBA (with respect to monomer unit).

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    Figure 3

    Figure 3. (a) Dynamic frequency sweep of organogels made from dp-poly(d-1) (0.287 mol L–1) and increasing PDBA equiv. (b) Dynamic frequency sweep of organogels made from dp-poly(d-1) (increasing concentrations) and PDBA (1 equiv).

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    Figure 4

    Figure 4. Change in moduli during a strain ramp of an organogel (0.144 mol L–1 dp-poly(d-1), 0.50 equiv of PDBA) measured at a frequency of 1 Hz. The percentage strain was increased from 0.007% to 100%; then strain was released; and the moduli were measured at 0.007% strain.

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    Figure 5

    Figure 5. Gel fracture and self-healing in sequential strain steps. Top shows the measured storage moduli at each strain step, as described in the bottom plot (0% → 10% → 0% → 20% → 0% → 40% → 0% → 60% → 0% → 80% → 0% → 100% → 0%, measured at 1 Hz).

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    Figure 6

    Figure 6. FE-SEM imaging of lyophilized organogels made from 0.144 M solutions of dp-poly(d-1) in DMSO with 0.25–1.00 equiv of PDBA.

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    Figure 7

    Figure 7. TGA of (a) lyophilized and (b) nonlyophilized organogel samples made from dp-poly(d-1) and PDBA with a polymer concentration of 0.144 mol L–1 and PDBA equiv of 0.25–1.00. Annotations of the Td,max values of each sample.

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    Scheme 3

    Scheme 3. Cross-Linking of dp-poly(d-1) and PDBA in the Presence of a Lithium Salt (LiTFSI)
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    Figure 8

    Figure 8. Temperature dependence of ionic conductivity (σ) for lithiated (1 equiv of LiTFSI, 0.144 mol L–1; Li-gel) and nonlithiated (control) organogels made from dp-poly(d-1) (0.287 mol L–1 with respect to the repeating unit) with 0.50 equiv of PDBA.

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    Figure 9

    Figure 9. Li+ stripping/plating voltage profile of Li-gel in a symmetrical Li|Li-gel|Li cell at 25 °C. The half-cycle duration was 1 h with a cutoff voltage of ±1.0 V.

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  • References

    This article references 70 other publications.

    1. 1
      Asher, S. A.; Alexeev, V. L.; Goponenko, A. V.; Sharma, A. C.; Lednev, I. K.; Wilcox, C. S.; Finegold, D. N. Photonic Crystal Carbohydrate Sensors: Low Ionic Strength Sugar Sensing. J. Am. Chem. Soc. 2003, 125 (11), 3322– 3329,  DOI: 10.1021/ja021037h
      1
      Photonic crystal carbohydrate sensors: Low ionic strength sugar sensing
      Asher, Sanford A.; Alexeev, Vladimir L.; Goponenko, Alexander V.; Sharma, Anjal C.; Lednev, Igor K.; Wilcox, Craig S.; Finegold, David N.
      Journal of the American Chemical Society (2003), 125 (11), 3322-3329CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      We developed a carbohydrate sensing material, which consists of a cryst. colloidal array (CCA) incorporated into a polyacrylamide hydrogel (PCCA) with pendent boronic acid groups. The embedded CCA diffracts visible light, and the PCCA diffraction wavelength reports on the hydrogel vol. This boronic acid PCCA responds to species contg. vicinal cis diols such as carbohydrates. This PCCA photonic crystal sensing material responds to glucose in low ionic strength aq. solns. by swelling and red shifting its diffraction as the glucose concn. increases. The hydrogel swelling results from a Donnan potential due to formation of boronate anion; the boronic acid pKa decreases upon glucose binding. This sensing material responds to glucose and other sugars at <50 μM concns. in low ionic strength solns.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXhtlCjurw%253D&md5=c9bb215f15a2ba470cfee40614f07513
    2. 2
      Lerner, M. B.; Kybert, N.; Mendoza, R.; Villechenon, R.; Bonilla Lopez, M. A.; Charlie Johnson, A. T. Scalable, non-invasive glucose sensor based on boronic acid functionalized carbon nanotube transistors. Appl. Phys. Lett. 2013, 102 (18), 183113,  DOI: 10.1063/1.4804438
      2
      Scalable, non-invasive glucose sensor based on boronic acid functionalized carbon nanotube transistors
      Lerner, Mitchell B.; Kybert, Nicholas; Mendoza, Ryan; Villechenon, Romain; Bonilla Lopez, Manuel A.; Charlie Johnson, A. T.
      Applied Physics Letters (2013), 102 (18), 183113/1-183113/4CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)
      The authors developed a scalable, label-free all-electronic sensor for D-glucose based on a carbon nanotube transistor functionalized with pyrene-1-boronic acid. This sensor responds to glucose in the range 1 μM-100 mM, which includes typical glucose concns. in human blood and saliva. Control expts. establish that functionalization with the boronic acid provides high sensitivity and selectivity for glucose. The devices show better sensitivity than com. blood glucose meters and could represent a general strategy to bloodless glucose monitoring by detecting low concns. of glucose in saliva. (c) 2013 American Institute of Physics.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXnsVyqsr8%253D&md5=61fd44d3e2790d91b7aa1fabad2a105b
    3. 3
      Nishiyabu, R.; Kobayashi, H.; Kubo, Y. Dansyl-containing boronate hydrogel film as fluorescent chemosensor of copper ions in water. RSC Adv. 2012, 2 (16), 6555– 6561,  DOI: 10.1039/c2ra20516e
      3
      Dansyl-containing boronate hydrogel film as fluorescent chemosensor of copper ions in water
      Nishiyabu, Ryuhei; Kobayashi, Hiroyasu; Kubo, Yuji
      RSC Advances (2012), 2 (16), 6555-6561CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
      A new type of boronate hydrogel with covalently bound dansyldiethylenetriamine as an indicator has been developed; the gel networks are based on boronate esterification of poly(vinylalc.) with benzene-1,4-diboronic acid. In this approach, phenylboronic acid-appended N-dansyldiethylenetriamine 1 was newly synthesized to be incorporated into the gel matrix. The resulting gel film showed an absorption band at 336 nm and fluorescence at 511 nm when excited at 340 nm in water. The fluorescence measurements indicated that at neutral conditions using a HEPES buffer, the gel film was selectively quenched after immersion in an aq. soln. of Cu2+ for 30 min. The response had minimal interference from other metal ions such as Na+, K+, Mg2+, Ca2+, Fe3+, Co2+, Ni2+, Zn2+, Cd2+, Hg2+, Al3+, and Pb2+, which was noteworthy because dansyldiethylenetriamine alone responds to Hg2+ and Ni2+ in addn. to Cu2+ in water. The reversible sensing capability was also evaluated by rinsing the film with an aq. soln. of EDTA (EDTA). The gel was found to be a reusable and free-standing film capable of visually detecting Cu2+, providing a simple and expedient tool for on-site monitoring of Cu2+ in environmental applications such as water anal.
      >> More from SciFinder ®
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    4. 4
      Awino, J. K.; Gunasekara, R. W.; Zhao, Y. Selective Recognition of d-Aldohexoses in Water by Boronic Acid-Functionalized, Molecularly Imprinted Cross-Linked Micelles. J. Am. Chem. Soc. 2016, 138 (31), 9759– 9762,  DOI: 10.1021/jacs.6b04613
      4
      Selective Recognition of D-Aldohexoses in Water by Boronic Acid-Functionalized, Molecularly Imprinted Cross-Linked Micelles
      Awino, Joseph K.; Gunasekara, Roshan W.; Zhao, Yan
      Journal of the American Chemical Society (2016), 138 (31), 9759-9762CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Mol. imprinting within crosslinked micelles using 4-vinylphenylboronate derivs. of carbohydrates provided water-sol. nanoparticle receptors selective for the carbohydrate templates. Complete differentiation of D-aldohexoses could be achieved by these receptors if a single inversion of hydroxyl occurred at C2 or C4 of the sugar or if two or more inversions took place. Glycosides with a hydrophobic aglycan displayed stronger binding due to increased hydrophobic interactions.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xht1SktLrF&md5=d23af4dcc769acd82c9f739a88b93aa5
    5. 5
      Chen, W.; Guo, Z.; Yu, H.; Liu, Q.; Fu, M. Molecularly imprinted colloidal array with multi-boronic acid sites for glycoprotein detection under neutral pH. J. Colloid Interface Sci. 2022, 607, 1163– 1172,  DOI: 10.1016/j.jcis.2021.09.048
      5
      Molecularly imprinted colloidal array with multi-boronic acid sites for glycoprotein detection under neutral pH
      Chen, Wei; Guo, Zhiyang; Yu, Hao; Liu, Qingyun; Fu, Min
      Journal of Colloid and Interface Science (2022), 607 (Part_2), 1163-1172CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)
      Glycoproteins play vital roles in living organisms and often serve as biomarkers for some disease. However, due to the low content of glycoprotein in biol. fluids, selective detection of glycoproteins is still a challenging issue that needs to be addressed. In this study, molecularly imprinted colloidal array with multi-boronic acid sites for glycoprotein detection under physiol. pH was proposed. Monodispersed glycoprotein imprinted particles (SiO2@PEI/MIPs) was first prepd. based on surface imprinting strategy using horseradish peroxidase (HRP) as template, and polyethyleneimine (PEI) was used to increase the no. of boronic acid groups. The binding expt. indicated that the SiO2@PEI/MIPs hold satisfactory adsorption capacity (1.41μmol/g), rapid adsorption rate (40 min) and preferable selectivity toward HRP. Then the SiO2@PEI/MIPs was assembled into close-packed colloidal array to construct a label free optical sensor (denoted as GICA). Benefiting from the high ordered photonic crystal structure, binding of HRP onto the GICA could be directly readout from the changes in structure color and diffracted wavelength. The structure color of the GICA changed from bright blue to yellow with the diffraction wavelength red shifted 59 nm when the HRP concn. increased from 2.5 to 15μmol/L. Importantly, the GICA was capable of detecting HRP from human serum samples. All those results indicated the potential of the GICA for naked-eye detection of glycoprotein.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitV2ls7nO&md5=644276fcbf46502c91615ddb38b354d0
    6. 6
      He, P.; Zhu, H.; Ma, Y.; Liu, N.; Niu, X.; Wei, M.; Pan, J. Rational design and fabrication of surface molecularly imprinted polymers based on multi-boronic acid sites for selective capture glycoproteins. Chem. Eng. J. 2019, 367, 55– 63,  DOI: 10.1016/j.cej.2019.02.140
      6
      Rational design and fabrication of surface molecularly imprinted polymers based on multi-boronic acid sites for selective capture glycoproteins
      He, Peiyan; Zhu, Hengjia; Ma, Yue; Liu, Na; Niu, Xiangheng; Wei, Maobin; Pan, Jianming
      Chemical Engineering Journal (Amsterdam, Netherlands) (2019), 367 (), 55-63CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
      Increasing the no. of recognition sites is an available way to improve the efficiency of the identification of surface mol. imprinting polymers. Glycoprotein imprinted nanoparticles (SiO2-MIPs) based on multi-boronic acid sites were prepd. via surface imprinting processes. Polyethylene polyamine (PPI), contg. enough active amino groups, is firstly grafted to the surface of silica nanoparticles. Boronic acid mols. are post-modified onto silica nanoparticles via amine aldehyde condensation reaction, and then dopamine (DA) as the monomer is adopted to form a surface imprinted polymer layer onto the functionalized silica nanoparticles under a gentle condition after binding the template ovalbumin (OVA) mols. As-prepd. SiO2-MIPs have quick adsorption kinetics (rebinding equil. at 60 min), high max. adsorption capacity (243.4 mg g-1), excellent adsorption selectivity (imprinting factor towards OVA is 4.82), and good reusability after seven regeneration cycles (a slight decrease of ∼5%). Furthermore, the high d. of boronic acids and imprinting effect both play a key role in the enhanced recognition and rebinding OVA. Moreover, this work overcomes the influence of steric hindrance and then the OVA mols. can access the recognition sites of SiO2-MIPs easily.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXjs1Oqsrg%253D&md5=1ad0f6d7758a8e6f78a1e418473aa6e4
    7. 7
      Zhao, Z. W.; Yao, X. M.; Zhang, Z.; Chen, L.; He, C. L.; Chen, X. S. Boronic Acid Shell-Crosslinked Dextran-b-PLA Micelles for Acid-Responsive Drug Delivery. Macromol. Biosci. 2014, 14 (11), 1609– 1618,  DOI: 10.1002/mabi.201400251
      7
      Boronic Acid Shell-Crosslinked Dextran-b-PLA Micelles for Acid-Responsive Drug Delivery
      Zhao, Ziwei; Yao, Xuemei; Zhang, Zhe; Chen, Li; He, Chaoliang; Chen, Xuesi
      Macromolecular Bioscience (2014), 14 (11), 1609-1618CODEN: MBAIBU; ISSN:1616-5187. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Herein, 3-carboxy-5-nitrophenylboronic acid (CNPBA) shell-crosslinked micelles based on amphiphilic dextran-block-polylactide (Dex-b-PLA) are prepd. and used for efficient intracellular drug deliveries. Due to the reversible pH-dependent binding with diols to form boronate esters, CNPBA modified Dex-b-PLA shows excellent pH-sensitivity. In neutral aq. conditions, CNPBA-Dex-b-PLA forms shell-crosslinked micelles to enable DOX loading, while in acid conditions, the boronate esters hydrolyze and the micelles de-crosslink to release loaded DOX. In vitro release studies indicate that the release of the DOX cargo is minimized at physiol. conditions, while there is a burst release in response to low pHs. The cell viability of CNPBA-Dex-b-PLA investigated by MTT assay was more than 90%, indicating that, as a drug delivery system, CNPBA-Dex-b-PLA has good cytocompatibility. These features suggest that the pH-responsive biodegradable CNPBA-Dex-b-PLA can efficiently load and deliver DOX into tumor cells and enhance the inhibition of cellular proliferation in vitro, providing a favorable platform as a drug delivery system for cancer therapy.
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    8. 8
      Li, Y. P.; Xiao, W. W.; Xiao, K.; Berti, L.; Luo, J. T.; Tseng, H. P.; Fung, G.; Lam, K. S. Well-Defined, Reversible Boronate Crosslinked Nanocarriers for Targeted Drug Delivery in Response to Acidic pH Values and cis-Diols. Angew. Chem., Int. Ed. 2012, 51 (12), 2864– 2869,  DOI: 10.1002/anie.201107144
      8
      Well-Defined, Reversible Boronate Crosslinked Nanocarriers for Targeted Drug Delivery in Response to Acidic pH Values and cis-Diols
      Li, Yuanpei; Xiao, Wenwu; Xiao, Kai; Berti, Lorenzo; Luo, Juntao; Tseng, Harry P.; Fung, Gabriel; Lam, Kit S.
      Angewandte Chemie, International Edition (2012), 51 (12), 2864-2869, S2864/1-S2864/25CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Stimuli-responsive nanoparticles are gaining considerable attention in the field of drug delivery because of their useful physicochem. changes in response to specific triggers, such as pH value, temp., enzymes, or redox conditions, present in certain physiol. or disease microenvironments of interest. Among these nanoparticles, stimuli-responsive crosslinked micelles (SCMs) represent a versatile nanocarrier system for tumor-targeting drug delivery. Remarkable progress in this field has led to the development of SCMs responsive to a single stimulus. Various cleavable linkages have been introduced in SCMs, such as reducible disulfide bonds, pH cleavable, or hydrolysable ester bonds. Currently, second-generation SCMs able to respond to multiple stimuli are being actively pursued as tools for accomplishing the multistage delivery of drugs to the complex in vivo microenvironment. Boronic acids are able to bind diols reversibly forming boronate esters that exhibit Fast dual responsiveness to external pH value and competing diols. Based on this interaction, there has been increasing interest in using boronic acids as building blocks to design carbohydrate sensors, nano-reactors, drug delivery systems, and self-healing materials. Among diols, catechols are an excellent reactant for the formation of complexes with boronic acids, thanks to the favorable syn-peri-planar arrangement of the arom. hydroxy groups combined with their electron-donating character. Herein, we present the first report on the synthesis of a novel class of dual-responsive boronate crosslinked micelles (BCM) for drug delivery based on the self-assembly and in situ complexation of boronic acid contg. polymers and catechol contg. polymers. We hypothesize that these BCMs will retain the encapsulated drug under physiol. conditions, while releasing the payload quickly when triggered by the lower pH value of the tumor environment or when exposed to exogenous competing diols. Addnl., we are presenting a Forster resonance energy transfer (FRET) reporter system to evaluate the in vivo stability of these micelles. This characterization is usually difficult to accomplish in vivo due to the lack of suitable anal. techniques.
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    9. 9
      Su, J.; Chen, F.; Cryns, V. L.; Messersmith, P. B. Catechol Polymers for pH-Responsive, Targeted Drug Delivery to Cancer Cells. J. Am. Chem. Soc. 2011, 133 (31), 11850– 11853,  DOI: 10.1021/ja203077x
      9
      Catechol Polymers for pH-Responsive, Targeted Drug Delivery to Cancer Cells
      Su, Jing; Chen, Feng; Cryns, Vincent L.; Messersmith, Phillip B.
      Journal of the American Chemical Society (2011), 133 (31), 11850-11853CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A novel cell-targeting, pH-sensitive polymeric carrier was employed in this study for delivery of the anticancer drug bortezomib (BTZ) to cancer cells. Our strategy is based on facile conjugation of BTZ to catechol-contg. polymeric carriers that are designed to be taken up selectively by cancer cells through cell surface receptor-mediated mechanisms. The polymer used as a building block in this study was poly(ethylene glycol), which was chosen for its ability to reduce nonspecific interactions with proteins and cells. The catechol moiety was exploited for its ability to bind and release borate-contg. therapeutics such as BTZ in a pH-dependent manner. In acidic environments, such as in cancer tissue or the subcellular endosome, BTZ dissocs. from the polymer-bound catechol groups to liberate the free drug, which inhibits proteasome function. A cancer-cell-targeting ligand, biotin, was presented on the polymer carriers to facilitate targeted entry of drug-loaded polymer carriers into cancer cells. Our study demonstrated that the cancer-targeting drug-polymer conjugates dramatically enhanced cellular uptake, proteasome inhibition, and cytotoxicity toward breast carcinoma cells in comparison with nontargeting drug-polymer conjugates. The pH-sensitive catechol-boronate binding mechanism provides a chemoselective approach for controlling the release of BTZ in targeted cancer cells, establishing a concept that may be applied in the future toward other boronic acid-contg. therapeutics to treat a broad range of diseases.
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    10. 10
      Jiang, H.-P.; Qi, C.-B.; Chu, J.-M.; Yuan, B.-F.; Feng, Y.-Q. Profiling of cis-Diol-containing Nucleosides and Ribosylated Metabolites by Boronate-affinity Organic-silica Hybrid Monolithic Capillary Liquid Chromatography/Mass Spectrometry. Sci. Rep. 2015, 5 (1), 7785,  DOI: 10.1038/srep07785
      10
      Profiling of cis-Diol-containing Nucleosides and Ribosylated Metabolites by Boronate-affinity Organic-silica Hybrid Monolithic Capillary Liquid Chromatography/Mass Spectrometry
      Jiang, Han-Peng; Qi, Chu-Bo; Chu, Jie-Mei; Yuan, Bi-Feng; Feng, Yu-Qi
      Scientific Reports (2015), 5 (), 7785CODEN: SRCEC3; ISSN:2045-2322. (Nature Publishing Group)
      RNA contains a large no. of modified nucleosides. In the metabolic re-exchange of RNA, modified nucleosides cannot be recycled and are thus excreted from cells into biol. fluids. Detn. of endogenous modified nucleosides in biol. fluids may serve as non-invasive cancers diagnostic methods. Here we prepd. boronate-affinity org.-silica hybrid capillary monolithic column (BOHCMC) that exhibited excellent selectivity toward the cis-diol-contg. compds. We then used the prepd. BOHCMC as the online solid-phase microextn. (SPME) column and developed an online SPME-LC-MS/MS method to comprehensively profile cis-diol-contg. nucleosides and ribosylated metabolites in human urine. Forty-five cis-diol-contg. nucleosides and ribosylated metabolites were successfully identified in human urine. And five ribose conjugates, for the first time, were identified existence in human urine in the current study. Furthermore, the relative quantification suggested 4 cis-diol-contg. compds. (5'-deoxy-5'-methylthioadenosine, N4-acetylcytidine, 1-ribosyl-N-propionylhistamine and N2,N2,7-trimethylguanosine) increased more than 1.5 folds in all the 3 types of examd. cancers (lung cancer, colorectal cancer, and nasopharyngeal cancer) compared to healthy controls. The online SPME-LC-MS/MS method demonstrates a promising method for the comprehensive profiling of cis-diol-contg. ribose conjugates in human urines, which provides an efficient strategy for the identification and discovery of biomarkers and may be used for the screening of cancers.
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    11. 11
      Koyama, T.; Terauchi, K.-i. Synthesis and application of boronic acid-immobilized porous polymer particles: a novel packing for high-performance liquid affinity chromatography. J. Chromatogr. B: Biomed. Sci. Appl. 1996, 679 (1), 31– 40,  DOI: 10.1016/0378-4347(96)00006-0
      11
      Synthesis and application of boronic acid-immobilized porous polymer particles: a novel packing for high-performance liquid affinity chromatography
      Koyama, Toshitaka; Terauchi, Ken-ichi
      Journal of Chromatography B: Biomedical Sciences and Applications (1996), 679 (1 + 2), 31-40CODEN: JCBBEP; ISSN:0378-4347. (Elsevier)
      A prepn. method of a novel type of packing materials for high-performance liq. affinity chromatog. to det. glycated proteins was studied, and a fundamental study on its application to diabetic serum was conducted. To quantify glycated proteins such as glycated serum albumin, a new hydrophilic and durable porous polymer particle recently developed in the lab. was used as the basic matrix. The matrix was activated with 1,1'-carbonyldiimidazole (CDI), and optimization of the coupling reaction between these CDI-activated matrix and m-aminophenylboronic acid hemisulfate (APBA) as affinity ligand was investigated. The optimum value for the APBA coupling yield was obtained under acidic conditions very different from the data reported by previous workers. Using this APBA-immobilized matrix an affinity column was prepd., and its usefulness in HPLC sepn. of glycated serum proteins was investigated. Also, the fundamental and preliminary results for diagnosis of diabetes mellitus are discussed in this paper.
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    12. 12
      Brooks, W. L. A.; Sumerlin, B. S. Synthesis and Applications of Boronic Acid-Containing Polymers: From Materials to Medicine. Chem. Rev. 2016, 116 (3), 1375– 1397,  DOI: 10.1021/acs.chemrev.5b00300
      12
      Synthesis and Applications of Boronic Acid-Containing Polymers: From Materials to Medicine
      Brooks, William L. A.; Sumerlin, Brent S.
      Chemical Reviews (Washington, DC, United States) (2016), 116 (3), 1375-1397CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. Boronic acid-contg. macromols. have been utilized in a no. of biomedical applications, including use in dynamic covalent materials, dual thermo and saccharide responsive hydrogels, sensors, and nanomaterials, often with the goal of detection and treatment of type-1 diabetes, which requires const. monitoring of blood glucose levels and proactive insulin management. The ability of boronic acids to bind with saccharides and potentially undergo an ionization transition makes the materials ideal for diabetes-related applications. Other biomedical applications of boronic acid contg. macromols. include use as potential HIV barriers, sepns. and chromatog., cell capture and culture, enzymic inhibition, and in site-specific radiation therapy. The review addresses each of these potential and current areas of application, with particular attention to the fundamental chem. involved.
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    13. 13
      He, L. H.; Fullenkamp, D. E.; Rivera, J. G.; Messersmith, P. B. pH responsive self-healing hydrogels formed by boronate-catechol complexation. Chem. Commun. 2011, 47 (26), 7497– 7499,  DOI: 10.1039/c1cc11928a
      13
      pH responsive self-healing hydrogels formed by boronate-catechol complexation
      He, Lihong; Fullenkamp, Dominic E.; Rivera, Jose G.; Messersmith, Phillip B.
      Chemical Communications (Cambridge, United Kingdom) (2011), 47 (26), 7497-7499CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      Here we report the synthesis and characterization of pH-responsive, self-healing hydrogels based on boronate-catechol complexation.
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    14. 14
      Figueiredo, T.; Cosenza, V.; Ogawa, Y.; Jeacomine, I.; Vallet, A.; Ortega, S.; Michel, R.; Olsson, J. D. M.; Gerfaud, T.; Boiteau, J. G.; Jing, J.; Harris, C.; Auzely-Velty, R. Boronic acid and diol-containing polymers: how to choose the correct couple to form ″strong″ hydrogels at physiological pH. Soft Matter 2020, 16 (15), 3628– 3641,  DOI: 10.1039/D0SM00178C
      14
      Boronic acid and diol-containing polymers: how to choose the correct couple to form "strong" hydrogels at physiological pH
      Figueiredo, Tamiris; Cosenza, Vanina; Ogawa, Yu; Jeacomine, Isabelle; Vallet, Alicia; Ortega, Sonia; Michel, Raphael; Olsson, Johan D. M.; Gerfaud, Thibaud; Boiteau, Jean-Guy; Jing, Jing; Harris, Craig; Auzely-Velty, Rachel
      Soft Matter (2020), 16 (15), 3628-3641CODEN: SMOABF; ISSN:1744-6848. (Royal Society of Chemistry)
      Dynamic covalent hydrogels crosslinked by boronate ester bonds are promising materials for biomedical applications. However, little is known about the impact of the crosslink structure on the mech. behavior of the resulting network. Herein, we provide a mechanistic study on boronate ester crosslinking upon mixing hyaluronic acid (HA) backbones modified, on the one hand, with two different arylboronic acids, and on the other hand, with three different saccharide units. Combining rheol., NMR and computational anal., we demonstrate that carefully selecting the arylboronic-polyol couple allows for tuning the thermodn. and mol. exchange kinetics of the boronate ester bond, thereby controlling the rheol. properties of the gel. In particular, we report the formation of "strong" gels (i.e. featuring slow relaxation dynamics) through the formation of original complex structures (tridentate or bidentate complexes). These findings offer new prospects for the rational design of hydrogel scaffolds with tailored mech. response.
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    15. 15
      Brooks, W. L. A.; Deng, C. C.; Sumerlin, B. S. Structure-Reactivity Relationships in Boronic Acid-Diol Complexation. ACS Omega 2018, 3 (12), 17863– 17870,  DOI: 10.1021/acsomega.8b02999
      15
      Structure-Reactivity Relationships in Boronic Acid-Diol Complexation
      Brooks, William L. A.; Deng, Christopher C.; Sumerlin, Brent S.
      ACS Omega (2018), 3 (12), 17863-17870CODEN: ACSODF; ISSN:2470-1343. (American Chemical Society)
      Boronic acids have found widespread use in the field of biomaterials, primarily through their ability to bind with biol. relevant 1,2- and 1,3-diols, including saccharides and peptidoglycans, or with polyols to prep. hydrogels with dynamic covalent or responsive behavior. Despite a wide range of boronic acid architectures that have been previously considered, there is a need for greater understanding of the structure-reactivity relationships that govern binding affinity to diols. In this study, various boronic acids and other organoboron compds. were investigated to det. their pKa and their binding consts. with the biol. relevant diols including sorbitol, fructose, and glucose. Boronic acid pKa values were detd. through spectroscopic titrn., whereas binding consts. were detd. by fluorescence spectroscopy during competitive binding studies. Key structure-reactivity relationships clearly indicated that both boronic acid structure and soln. pH must be carefully considered. By considering a variety of boronic acids with systematically varied electronics and sterics, these results provide guidance during selection of organoboron compds. in sensing, delivery, and materials chem.
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    16. 16
      Deng, C. C.; Brooks, W. L. A.; Abboud, K. A.; Sumerlin, B. S. Boronic Acid-Based Hydrogels Undergo Self-Healing at Neutral and Acidic pH. ACS Macro Lett. 2015, 4 (2), 220– 224,  DOI: 10.1021/acsmacrolett.5b00018
      16
      Boronic Acid-Based Hydrogels Undergo Self-Healing at Neutral and Acidic pH
      Deng, Christopher C.; Brooks, William L. A.; Abboud, Khalil A.; Sumerlin, Brent S.
      ACS Macro Letters (2015), 4 (2), 220-224CODEN: AMLCCD; ISSN:2161-1653. (American Chemical Society)
      This report describes the synthesis and characterization of boronate ester-crosslinked hydrogels capable of self-healing behavior at neutral and acidic pH. This atypically wide pH range over which healing behavior is obsd. was achieved through the use of an intramol. coordinating boronic acid monomer, 2-acrylamidophenylboronic acid (2APBA), where the internal coordination helped to stabilize crosslinks formed at acidic and neutral pH. Two different hydrogels were formed from a 2APBA copolymer crosslinked with either poly(vinyl alc.) or a catechol-functionalized copolymer. The self-healing ability of these hydrogels was characterized through phys. testing and rheol. studies. Furthermore, the catechol crosslinked hydrogel was shown to be oxygen sensitive, demonstrating reduced self-healing and stress relaxation after partial oxidn. The synthesis of these hydrogels demonstrates a new strategy to produce boronic acid materials capable of self-healing at physiol. pH.
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    17. 17
      Smithmyer, M. E.; Deng, C. C.; Cassel, S. E.; LeValley, P. J.; Sumerlin, B. S.; Kloxin, A. M. Self-Healing Boronic Acid-Based Hydrogels for 3D Co-cultures. ACS Macro Lett. 2018, 7 (9), 1105– 1110,  DOI: 10.1021/acsmacrolett.8b00462
      17
      Self-Healing Boronic Acid-Based Hydrogels for 3D Co-cultures
      Smithmyer, Megan E.; Deng, Christopher C.; Cassel, Samantha E.; LeValley, Paige J.; Sumerlin, Brent S.; Kloxin, April M.
      ACS Macro Letters (2018), 7 (9), 1105-1110CODEN: AMLCCD; ISSN:2161-1653. (American Chemical Society)
      Synthetic hydrogels have been widely adopted as well-defined matrixes for three-dimensional (3D) cell culture, with increasing interest in systems that enable the coculture of multiple cell types for probing both cell-matrix and cell-cell interactions in studies of tissue regeneration and disease. We hypothesized that the unique dynamic covalent chem. of self-healing hydrogels could be harnessed for not only the encapsulation and culture of human cells but also the subsequent construction of layered hydrogels for 3D co-cultures. To test this, we formed hydrogels using boronic acid-functionalized polymers and demonstrated their self-healing in the presence of physiol. relevant cell culture media. Two model human cell lines, MDA-MB-231 breast cancer cells and CCL151 pulmonary fibroblasts, were encapsulated within these dynamic materials, and good viability was obsd. over time. Finally, self-healing of cut hydrogel "blocks" laden with these different cell types was used to create layered hydrogels for the generation of a dynamic coculture system. This work demonstrates the utility of self-healing materials for multidimensional cultures and establishes approaches broadly useful for a variety of biol. applications.
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    18. 18
      Wang, X.-T.; Deng, X.; Zhang, T.-D.; Zhang, X.; Shi, W.-P.; Lai, J.; Zhou, H.; Ye, Y.-J.; Zhang, C.-Y.; Yin, D.-C. Biocompatible self-healing hydrogels based on boronic acid-functionalized polymer and laponite nanocomposite for water pollutant removal. Environ. Chem. Lett. 2022, 20 (1), 81– 90,  DOI: 10.1007/s10311-021-01350-4
      18
      Biocompatible self-healing hydrogels based on boronic acid-functionalized polymer and laponite nanocomposite for water pollutant removal
      Wang, Xue-Ting; Deng, Xudong; Zhang, Tuo-Di; Zhang, Xi; Shi, Wen-Pu; Lai, Jialiang; Zhou, Hongwei; Ye, Ya-Jing; Zhang, Chen-Yan; Yin, Da-Chuan
      Environmental Chemistry Letters (2022), 20 (1), 81-90CODEN: ECLNBJ; ISSN:1610-3653. (Springer)
      Global water pollution by org. dyes and metals may be solved by adsorption. In particular, hydrogel adsorbents display unique advantages due to their three-dimensional porous structure. Here, a new type of self-healing hydrogels based on boronate and amide bonds were prepd. The precursor polymer, 2-aminophenylboronic acid-modified polyacrylic acid (PAA-2APBA), was firstly synthesized by amidation, then, the poly(vinyl alc.) and laponite were mixed with PAA-2APBA to form a nanocomposite hydrogel. This hydrogel has good self-healing and injectable properties, as well as good biocompatibility. The introduction of laponite nanoparticles into the hydrogel improved the stability, mech. strength, and the adsorption efficiency of metal ions and org. dyes. The max. adsorption of copper ion, cadmium ion, lead ion, and iron ion was 259.1 mg/g, 243.4 mg/g, 217.4 mg/g, and 166.2 mg/g, resp. For org. dyes, 71% of methylene blue and 81% of malachite green were removed in 28 h.
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    19. 19
      Huang, Z. J.; Delparastan, P.; Burch, P.; Cheng, J.; Cao, Y.; Messersmith, P. B. Injectable dynamic covalent hydrogels of boronic acid polymers cross-linked by bioactive plant-derived polyphenols. Biomater. Sci. 2018, 6 (9), 2487– 2495,  DOI: 10.1039/C8BM00453F
      19
      Injectable dynamic covalent hydrogels of boronic acid polymers cross-linked by bioactive plant-derived polyphenols
      Huang, Zhuojun; Delparastan, Peyman; Burch, Patrick; Cheng, Jing; Cao, Yi; Messersmith, Phillip B.
      Biomaterials Science (2018), 6 (9), 2487-2495CODEN: BSICCH; ISSN:2047-4849. (Royal Society of Chemistry)
      We report here the development of hydrogels formed at physiol. conditions using PEG (polyethylene glycol) based polymers modified with boronic acids (BAs) as backbones and the plant derived polyphenols ellagic acid (EA), epigallocatechin gallate (EGCG), tannic acid (TA), nordihydroguaiaretic acid (NDGA), rutin trihydrate (RT), rosmarinic acid (RA) and carminic acid (CA) as linkers. Rheol. frequency sweep and single mol. force spectroscopy (SMFS) expts. show that hydrogels linked with EGCG and TA are mech. stiff, arising from the dynamic covalent bond formed by the polyphenol linker and boronic acid functionalized polymer. Stability tests of the hydrogels in physiol. conditions revealed that gels linked with EA, EGCG, and TA are stable. We furthermore showed that EA- and EGCG-linked hydrogels can be formed via in situ gelation in pH 7.4 buffer, and provide long-term steady state release of bioactive EA. In vitro expts. showed that EA-linked hydrogel significantly reduced the viability of CAL-27 human oral cancer cells via gradual release of EA.
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    20. 20
      Dong, Y. Z.; Wang, W. H.; Veiseh, O.; Appel, E. A.; Xue, K.; Webber, M. J.; Tang, B. C.; Yang, X. W.; Weir, G. C.; Langer, R.; Anderson, D. G. Injectable and Glucose-Responsive Hydrogels Based on Boronic Acid-Glucose Complexation. Langmuir 2016, 32 (34), 8743– 8747,  DOI: 10.1021/acs.langmuir.5b04755
      20
      Injectable and Glucose-Responsive Hydrogels Based on Boronic Acid-Glucose Complexation
      Dong, Yizhou; Wang, Weiheng; Veiseh, Omid; Appel, Eric A.; Xue, Kun; Webber, Matthew J.; Tang, Benjamin C.; Yang, Xi-Wen; Weir, Gordon C.; Langer, Robert; Anderson, Daniel G.
      Langmuir (2016), 32 (34), 8743-8747CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
      Injectable hydrogels have been widely used for a no. of biomedical applications. Here, we report a new strategy to form an injectable and glucose-responsive hydrogel using the boronic acid-glucose complexation. The ratio of boronic acid and glucose functional groups is crit. for hydrogel formation. In our system, polymers with 10-60% boronic acid, with the balance being glucose-modified, are favorable to form hydrogels. These hydrogels are shear-thinning and self-healing, recovering from shear-induced flow to a gel state within seconds. More importantly, these polymers displayed glucose-responsive release of an encapsulated model drug. The hydrogel reported here is an injectable and glucose-responsive hydrogel constructed from the complexation of boronic acid and glucose within a single component polymeric material.
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    21. 21
      Pettignano, A.; Grijalvo, S.; Haring, M.; Eritja, R.; Tanchoux, N.; Quignard, F.; Diaz, D. D. Boronic acid-modified alginate enables direct formation of injectable, self-healing and multistimuli-responsive hydrogels. Chem. Commun. 2017, 53 (23), 3350– 3353,  DOI: 10.1039/C7CC00765E
      21
      Boronic acid-modified alginate enables direct formation of injectable, self-healing and multistimuli-responsive hydrogels
      Pettignano, Asja; Grijalvo, Santiago; Haering, Marleen; Eritja, Ramon; Tanchoux, Nathalie; Quignard, Francoise; Diaz Diaz, David
      Chemical Communications (Cambridge, United Kingdom) (2017), 53 (23), 3350-3353CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      One-step functionalization of alginate with boronic acid groups allowed spontaneous formation of biocompatible hydrogels under basic conditions without addnl. complementary mols. or crosslinking agents. The dynamic nature of boronate ester bonds formed with vicinal diols present on alginate pyranose rings provided remarkable self-healing, injectable and multi-stimuli responsive properties to the material.
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    22. 22
      Hong, S. H.; Kim, S.; Park, J. P.; Shin, M.; Kim, K.; Ryu, J. H.; Lee, H. Dynamic Bonds between Boronic Acid and Alginate: Hydrogels with Stretchable, Self-Healing, Stimuli-Responsive, Remoldable, and Adhesive Properties. Biomacromolecules 2018, 19 (6), 2053– 2061,  DOI: 10.1021/acs.biomac.8b00144
      22
      Dynamic bonds between boronic acid and alginate: Hydrogels with stretchable, self-healing, stimuli-responsive, remoldable, and adhesive properties
      Hong, Sang Hyeon; Kim, Sunjin; Park, Joseph P.; Shin, Mikyung; Kim, Keumyeon; Ryu, Ji Hyun; Lee, Haeshin
      Biomacromolecules (2018), 19 (6), 2053-2061CODEN: BOMAF6; ISSN:1525-7797. (American Chemical Society)
      For the increasing demand of soft materials with wide ranges of applications, hydrogels have been developed exhibiting variety of functions (e.g., stretchable, self-healing, stimuli-responsive, and etc.). So far, add-in components such as inorg. nanoparticles, carbon materials, clays, and many others to main polymers have been used to achieve various unique functions of hydrogels. The multicomponent hydrogel systems often exhibit batch-dependent inconsistent results and problems in multicomponent mixings, require labors during prepns., and accompany unpredictable cross-talk between the added components. Here, we developed 'single polymeric component', alginate-boronic acid (alginate-BA) hydrogel to overcome the aforementioned problems. It exhibits unprecedented multifunctionalities simultaneously, such as high stretchability, self-healing, shear-thinning, pH- and glucose-sensitivities, adhesive properties, and reshaping properties. Multifunctionalities of alginate-BA hydrogel is resulted from the reversible inter- and intramol. interactions by dynamic equil. of boronic acid-diol complexation and dissocn., which was proved by single mol. level Atomic Force Microscopy (AFM) pulling expts. We also found that the alginate-BA gel showed enhanced in vivo retentions along gastrointestinal (GI) tract. Our findings suggest that rational polymer designs can result in minimizing the no. of a participating component for multifunctional hydrogels, instead of increasing complexity by adding various addnl. components.
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    23. 23
      Li, W. W.; Gao, F. X.; Wang, X. Q.; Zhang, N.; Ma, M. M. Strong and Robust Polyaniline-Based Supramolecular Hydrogels for Flexible Supercapacitors. Angew. Chem., Int. Ed. 2016, 55 (32), 9196– 9201,  DOI: 10.1002/anie.201603417
      23
      Strong and Robust Polyaniline-Based Supramolecular Hydrogels for Flexible Supercapacitors
      Li, Wanwan; Gao, Fengxian; Wang, Xiaoqian; Zhang, Ning; Ma, Mingming
      Angewandte Chemie, International Edition (2016), 55 (32), 9196-9201CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      We report a supramol. strategy to prep. conductive hydrogels with outstanding mech. and electrochem. properties, which are utilized for flexible solid-state supercapacitors (SCs) with high performance. The supramol. assembly of polyaniline and polyvinyl alc. through dynamic boronate bond yields the polyaniline-polyvinyl alc. hydrogel (PPH), which shows remarkable tensile strength (5.3 MPa) and electrochem. capacitance (928 F g-1). The flexible solid-state supercapacitor based on PPH provides a large capacitance (306 mF cm-2 and 153 F g-1) and a high energy d. of 13.6 Wh kg-1, superior to other flexible supercapacitors. The robustness of the PPH-based supercapacitor is demonstrated by the 100 % capacitance retention after 1000 mech. folding cycles, and the 90 % capacitance retention after 1000 galvanostatic charge-discharge cycles. The high activity and robustness enable the PPH-based supercapacitor as a promising power device for flexible electronics.
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    24. 24
      Casassa, E. Z.; Sarquis, A. M.; Vandyke, C. H. The Gelation of Polyvinyl-Alcohol with Borax - a Novel Class Participation Experiment Involving the Preparation and Properties of a Slime. J. Chem. Educ. 1986, 63 (1), 57– 60,  DOI: 10.1021/ed063p57
      24
      The gelation of polyvinyl alcohol with borax. A novel class participation experiment involving the preparation and properties of a "slime"
      Casassa, E. Z.; Sarquis, A. M.; Van Dyke, C. H.
      Journal of Chemical Education (1986), 63 (1), 57-60CODEN: JCEDA8; ISSN:0021-9584.
      A classroom student expt. is presented involving the prepn. of a borate crosslinked poly(vinyl alc.) gel which has several interesting properties to interest the student. Topics are listed pertinent to the demonstration as well as the chem. of the system.
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    25. 25
      Sinton, S. W. Complexation Chemistry of Sodium-Borate with Polyvinyl-Alcohol) and Small Diols - a B-11 NMR-Study. Macromolecules 1987, 20 (10), 2430– 2441,  DOI: 10.1021/ma00176a018
      25
      Complexation chemistry of sodium borate with poly(vinyl alcohol) and small diols: a boron-11 NMR study
      Sinton, Steve W.
      Macromolecules (1987), 20 (10), 2430-41CODEN: MAMOBX; ISSN:0024-9297.
      The crosslinked structure in poly(vinyl alc.) (I)-borax (II) system was deduced by comparison of 11B NMR spectra of 2,4-pentanediol-I model system with that of the polymer system. The complexation and crosslinking of I with II was exothermic with a reaction enthalpy of -8.3 kcal/mol. There were 2 11B signal components from I-II system which had different spin relaxation rates. The relationships between NMR parameters and viscosity in the I-II system were discussed.
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    26. 26
      Wang, H. H.; Shyr, T. W.; Hu, M. S. The elastic property of polyvinyl alcohol gel with boric acid as a crosslinking agent. J. Am. Chem. Soc. 1999, 74 (13), 3046– 3052,  DOI: 10.1002/(SICI)1097-4628(19991220)74:13<3046::AID-APP6>3.0.CO;2-1
      There is no corresponding record for this reference.
    27. 27
      Duncan, T. T.; Berrie, B. H.; Weiss, R. G. Soft, Peelable Organogels from Partially Hydrolyzed Poly(vinyl acetate) and Benzene-1,4-diboronic Acid: Applications to Clean Works of Art. ACS Appl. Mater. Interfaces 2017, 9 (33), 28069– 28078,  DOI: 10.1021/acsami.7b09473
      27
      Soft, Peelable Organogels from Partially Hydrolyzed Poly(vinyl acetate) and Benzene-1,4-diboronic Acid: Applications to Clean Works of Art
      Duncan, Teresa T.; Berrie, Barbara H.; Weiss, Richard G.
      ACS Applied Materials & Interfaces (2017), 9 (33), 28069-28078CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      We have developed soft, peelable organogels from 40% hydrolyzed poly(vinyl acetate) (40PVAc) and benzene-1,4-diboronic acid (BDBA). The org. liqs. gelated include DMSO, DMF, THF, 2-ethoxyethanol, and methanol. The rheol. of these soft materials can be tuned by altering the concn. of the polymer and/or crosslinker. Insights into the mechanisms leading to gelation were obtained from 1H NMR expts., fluorescence measurements, and studies comparing properties of materials made from BDBA and phenylboronic acid, a mol. incapable of forming covalent crosslinks between the polymer chains. These organogels can be easily peeled off a surface, leaving no residue detectable by UV-vis spectroscopy. They are demonstrated to be effective at softening and removing deteriorated coatings from water-sensitive works of art and delicate surfaces. They have the needed characteristics to clean topog. complex surfaces: good contact with the surface, easy removal, and little to no residue after removal. A 2-ethoxyethanol organogel was used to remove oxidized varnish from a 16th century reliquary decorated with painted gold leaf, and an ethanol gel was used to remove solvent-resistant coatings from 16th and 18th century oil paintings.
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    28. 28
      Duncan, T. T.; Weiss, R. G. Influence of length and structure of aryl boronic acid crosslinkers on organogels with partially hydrolyzed poly(vinyl acetate). Colloid Polym. Sci. 2018, 296 (6), 1047– 1056,  DOI: 10.1007/s00396-018-4326-7
      28
      Influence of length and structure of aryl boronic acid crosslinkers on organogels with partially hydrolyzed poly(vinyl acetate)
      Duncan, Teresa T.; Weiss, Richard G.
      Colloid and Polymer Science (2018), 296 (6), 1047-1056CODEN: CPMSB6; ISSN:0303-402X. (Springer)
      Organogels composed of 40% hydrolyzed poly(vinyl acetate) (40PVAc) and three arylboronic acids were formed and characterized in several liqs. to gain insights into the role of crosslinker length and structure on the properties of the gels. Data from 1H NMR, steady-state and time-resolved fluorescence, and rheol. were employed to correlate the degrees of crosslinking and the bulk phys. properties of the gels. Benzene-1,4-diboronic acid (1,4-BDBA) and 4,4'-biphenyldiboronic acid (bPDBA) formed gels with 40PVAc that were stable for longer periods than those with benzene-1,3-diboronic acid. Surprisingly, the steady-state and time-resolved fluorescence properties of 1,4-BDBA or bPDBA were affected little in soln. upon addn. of two model diols (1,3-propanediol and 1,2-ethanediol) or even 40PVAc. Furthermore, 40PVAc appeared to form crosslinks more efficiently, resulting in stiffer gels, with bPDBA than with 1,4-BDBA. We attribute these trends to the greater length, flexibility, and linearity of bPBPA. Overall, the results reported here demonstrate that minor structural changes in the crosslinker can alter significantly many of the bulk properties of two-component organogel networks. They also provide a clear 'blueprint' for making gels with specific desired properties for a range of applications that require virtually water-free systems.
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    29. 29
      Nunes, M. A. P.; Gois, P. M. P.; Rosa, M. E.; Martins, S.; Fernandes, P. C. B.; Ribeiro, M. H. L. Boronic acids as efficient cross linkers for PVA: synthesis and application of tunable hollow microspheres in biocatalysis. Tetrahedron 2016, 72 (46), 7293– 7305,  DOI: 10.1016/j.tet.2016.02.017
      29
      Boronic acids as efficient cross linkers for PVA: synthesis and application of tunable hollow microspheres in biocatalysis
      Nunes, Mario A. P.; Gois, Pedro M. P.; Rosa, M. Emilia; Martins, Samuel; Fernandes, Pedro C. B.; Ribeiro, Maria H. L.
      Tetrahedron (2016), 72 (46), 7293-7305CODEN: TETRAB; ISSN:0040-4020. (Elsevier Ltd.)
      Herein is reported an innovative and reproducible systemic approach for the fabrication of customized 3D hollow microspheres of polyvinyl alc. (PVA) based on the use of arom. boronic acids (ABAs) as crosslinkers. A dedicated exptl. set-up was developed to enable microsphere formulation. Most of the boronic acids tested were able to produce hollow microspheres. Depending on the ABA used and the prodn. conditions, hollow PVA/ABA microspheres with different morphologies, mass transfer characteristics and unprecedented thermal (up to 121 °C) stability were obtained. The crosslinking temp. proved to be an operational parameter to control membrane thickness. The hollow microspheres were evaluated in biocatalysis, with naringin hydrolysis as model system, using encapsulated naringinase. The results highlighted a naringinase high operational stability, namely in PVA microspheres crosslinked with 1,4-phenylenediboronic acid and with phenylboronic acid, with no evident loss of activity throughout seven consecutive runs, theor. resulting in an infinite half-life.
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    30. 30
      Parris, M. D.; MacKay, B. A.; Rathke, J. W.; Klingler, R. J.; Gerald, R. E. Influence of Pressure on Boron Cross-Linked Polymer Gels. Macromolecules 2008, 41 (21), 8181– 8186,  DOI: 10.1021/ma801187q
      30
      Influence of Pressure on Boron Cross-Linked Polymer Gels
      Parris, Michael D.; MacKay, Bruce A.; Rathke, Jerome W.; Klingler, Robert J.; Gerald, Rex E.
      Macromolecules (Washington, DC, United States) (2008), 41 (21), 8181-8186CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
      Using steady-shear rheometry in combination with high-pressure 11B NMR spectroscopy (11B NMR), it was detd. that gels formed from water-sol. polymers contg. vicinal hydroxyl groups cross-linked with various boron-contg. compds. undergo significant structural changes that result in a pronounced loss of viscosity when placed under pressure. Importantly, gels from other crosslinking agents tested, including Ti(IV) and Zr(IV), did not show this loss in viscosity. The exptl. study probed pressure-induced changes to both galactomannan and poly(vinyl alc.) (PVA) gels cross-linked with either aryl boronic acids or alkali metal boron-contg. salts under pressure from atm. to 680 bar and temps. 20-65°. Significantly, the pressure-induced losses in viscosity and, to a somewhat lesser extent, the concomitant pressure-induced 11B NMR spectral changes were reversed upon lowering the pressure. The gels are of interest for use for hydraulic fracturing of petroleum bearing rocks.
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    31. 31
      Shim, J.; Lee, J. S.; Lee, J. H.; Kim, H. J.; Lee, J.-C. Gel Polymer Electrolytes Containing Anion-Trapping Boron Moieties for Lithium-Ion Battery Applications. ACS Appl. Mater. Interfaces 2016, 8 (41), 27740– 27752,  DOI: 10.1021/acsami.6b09601
      31
      Gel Polymer Electrolytes Containing Anion-Trapping Boron Moieties for Lithium-Ion Battery Applications
      Shim, Jimin; Lee, Ji Su; Lee, Jin Hong; Kim, Hee Joong; Lee, Jong-Chan
      ACS Applied Materials & Interfaces (2016), 8 (41), 27740-27752CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Gel polymer electrolytes (GPEs) based on semi-interpenetrating polymer network (IPN) structure for lithium-ion batteries were prepd. by mixing boron-contg. cross-linker (BC) composed of ethylene oxide (EO) chains, cross-linkable methacrylate group, and anion-trapping boron moiety with poly(vinylidene fluoride) (PVDF) followed by UV light-induced curing process. Various phys. and electrochem. properties of the GPEs were systematically investigated by varying the EO chain length and boron content. Dimensional stability at high temp. without thermal shrinkage, if any, was obsd. due to the presence of thermally stable PVDF in the GPEs. GPE having 80 wt % of BC and 20 wt % of PVDF exhibited an ionic cond. of 4.2 mS cm-1 at 30 °C which is 1 order of magnitude larger than that of the liq. electrolyte system contg. the com. Celgard separator (0.4 mS cm-1) owing to the facile electrolyte uptake ability of EO chain and anion-trapping ability of the boron moiety. As a result, the lithium-ion battery cell prepd. using the GPE with BC showed an excellent cycle performance at 1.0 C maintaining 87% of capacity during 100 cycles.
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    32. 32
      Wang, X.; Liu, Z.; Kong, Q.; Jiang, W.; Yao, J.; Zhang, C.; Cui, G. A single-ion gel polymer electrolyte based on polymeric lithium tartaric acid borate and its superior battery performance. Solid State Ionics 2014, 262, 747– 753,  DOI: 10.1016/j.ssi.2013.09.007
      32
      A single-ion gel polymer electrolyte based on polymeric lithium tartaric acid borate and its superior battery performance
      Wang, Xuejiang; Liu, Zhihong; Kong, Qingshan; Jiang, Wen; Yao, Jianhua; Zhang, Chuanjian; Cui, Guanglei
      Solid State Ionics (2014), 262 (), 747-753CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
      A single-ion gel polymer electrolyte of PLTB@PVDF-HFP (polymeric lithium tartaric acid borate@poly(vinylidene fluoride-co-hexafluoropropene)) was prepd. and its ionic cond. was optimized via solvent compn. tailoring. It was manifested that the ethylene carbonate/dimethyl carbonate (EC/DMC) swollen PLTB@PVDF-HFP exhibited a superior lithium ionic cond. at room temp. to that of the traditional liq. electrolyte system (1 M LiPF6/EC/DMC). The Li4Ti5O12/LiFePO4 cells using the EC/DMC swollen PLTB@PVDF-HFP as polymer electrolyte showed stable charge/discharge voltage profiles with small voltage hysteresis, preferable rate capability and excellent cycle performance at room temp. These superior performances of EC/DMC swollen PLTB@PVDF-HFP could endow this class of gel polymer electrolyte a very promising alternative to state of the art liq. electrolyte system.
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    33. 33
      Dai, K.; Zheng, Y.; Wei, W. F. Organoboron-Containing Polymer Electrolytes for High-Performance Lithium Batteries. Adv. Funct. Mater. 2021, 31 (13), 2008632,  DOI: 10.1002/adfm.202008632
      33
      Organoboron-Containing Polymer Electrolytes for High-Performance Lithium Batteries
      Dai, Kuan; Zheng, Yuan; Wei, Weifeng
      Advanced Functional Materials (2021), 31 (13), 2008632CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Polymer electrolytes (PEs) have been deemed as a sought-after candidate for next-generation lithium batteries. Substantial effort has been dedicated to exploiting PEs with improved comprehensive performance. Organoboron compds. have aroused great interest in PEs due to their distinct characteristics such as high design diversity, excellent thermal stability, promoting lithium-ion transportation, and raising Li+ transference no. Organoboron compds. also have unique functions that facilitate the development of a stable solid electrolyte interface on the electrode surface. Their diversified structures and multiple functions are fundamentally assocd. with boron's hybridization form that dets. the electronic structure of boron as a central atom. Here, recent advancement in organoboron-contg. PEs is ed in the aspect of polymer matrixes with boron moieties and organoboron additives for PEs. This aims to highlight the diverse roles and high application potentials of organoboron compds. utilized in PEs. It is anticipated to provide a clear perspective of organoboron-contg. PEs and to spur more research interests for the exploration of safe and efficient lithium batteries.
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    34. 34
      Kato, Y.; Ishihara, T.; Ikuta, H.; Uchimoto, Y.; Wakihara, M. A high electrode-reaction rate for high-power-density lithium-ion secondary batteries by the addition of a lewis acid. Angew. Chem., Int. Ed. 2004, 43 (15), 1966– 1969,  DOI: 10.1002/anie.200353220
      34
      A high electrode-reaction rate for high-power-density lithium-ion secondary batteries achieved by the addition of a Lewis acid
      Kato, Yuki; Ishihara, Takenobu; Ikuta, Hiromasa; Uchimoto, Yoshiharu; Wakihara, Masataka
      Angewandte Chemie, International Edition (2004), 43 (15), 1966-1969CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The charge-transfer reaction at the electrode/electrolyte interfaces is important in the fabrication of high-power-d. lithium-ion secondary batteries. This reaction rate is increased by adding a poly(ethylene glycol)-borate ester Lewis acid to the electrolyte. Because the Lewis acid interacts preferentially with anions (X-), an increase in the activity of lithium ions is induced by enhancing the dissocn. of lithium salts (Li+X-).
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    35. 35
      Zhu, Y. S.; Wang, X. J.; Hou, Y. Y.; Gao, X. W.; Liu, L. L.; Wu, Y. P.; Shimizu, M. A new single-ion polymer electrolyte based on polyvinyl alcohol for lithium ion batteries. Electrochim. Acta 2013, 87, 113– 118,  DOI: 10.1016/j.electacta.2012.08.114
      35
      A new single-ion polymer electrolyte based on polyvinyl alcohol for lithium ion batteries
      Zhu, Y. S.; Wang, X. J.; Hou, Y. Y.; Gao, X. W.; Liu, L. L.; Wu, Y. P.; Shimizu, M.
      Electrochimica Acta (2013), 87 (), 113-118CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)
      A novel single-ion conducting polymer electrolyte, lithium polyvinyl alc. oxalate borate (LiPVAOB), was prepd. by reaction of polyvinyl alc. with different molar ratio of boric acid, oxalic acid and lithium carbonate. The prepd. materials were characterized by FTIR spectroscopy, x-ray diffraction, SEM, thermogravimetry, DTA, electrochem. impedance spectroscopy and linear sweep voltammetry. Ionic cond. of these polymer electrolytes contg. an additive (∼20 wt.% propylene carbonate) is dependent on molar ratio of the reactants and can be as high as 6.11 × 10-6 S/cm at ambient temp. Their electrochem. window can be stable up to 7 V (vs. Li+/Li), which is suitable for high-voltage lithium-ion batteries with high energy d.
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    36. 36
      Zhang, Y.; Cai, W.; Rohan, R.; Pan, M.; Liu, Y.; Liu, X.; Li, C.; Sun, Y.; Cheng, H. Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte. J. Power Sources 2016, 306, 152– 161,  DOI: 10.1016/j.jpowsour.2015.12.010
      36
      Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte
      Zhang, Yunfeng; Cai, Weiwei; Rupesh, Rohan; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong
      Journal of Power Sources (2016), 306 (), 152-161CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      The ionic cond. decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concn. is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic cond. studies, the fabricated S-BSMs showed decreased m.ps. and increased ionic cond. as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temp. performance of the all-solid-state lithium batteries. The fabricated Li|S-BSMs| LiFePO4 cells exhibit highly electrochem. stability and excellent cycling at temp. below m.p. of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.
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    37. 37
      Sun, X.-G.; Liu, G.; Xie, J.; Han, Y.; Kerr, J. B. New gel polyelectrolytes for rechargeable lithium batteries. Solid State Ionics 2004, 175 (1), 713– 716,  DOI: 10.1016/j.ssi.2003.11.043
      37
      New gel polyelectrolytes for rechargeable lithium batteries
      Sun, Xiao-Guang; Liu, Gao; Xie, Jiangbing; Han, Yongbong; Kerr, John B.
      Solid State Ionics (2004), 175 (1-4), 713-716CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
      New polyelectrolytes were synthesized by grafting the allyl group contg. lithium salt, lithium bis(allylmalonato)borate (LiBAMB), onto poly[pentaethylene glycol Me ether acrylate-co-allyoxyethyl acrylate] through hydrosilylation chem. Gel polyelectrolytes were obtained by adding 50% of different 1/1 (wt./wt.) mixts. of propylene carbonate (PC), ethylene carbonate (EC), di-Me carbonate (DMC) and tetraethyleneglycol di-Me ether (TEGDME). The highest ambient cond. was 2.7 × 10-8 S cm-1 for the dry single ion conductors and 7.9 × 10-6 S cm-1 for the gel single ion conductor contg. 50% of EC/DMC (1/1, wt./wt.), and both are obtained for the sample with an EO/Li ratio of 40/1. The cond. order of gel electrolytes contg. the same amt. of different mixed solvents suggests that the cond. of the gel is more detd. by the dielec. const. rather than by the viscosity of the solvent. The preliminary Li/Li cycling profile of a dry single ion conductor is encouraging, as almost no concn. polarization and relaxation was obsd. However, some fluctuation of potential occurred, which might be due to the reactions of the electrolyte on the surface of lithium metal.
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    38. 38
      Deng, K.; Wang, S.; Ren, S.; Han, D.; Xiao, M.; Meng, Y. Network type sp3 boron-based single-ion conducting polymer electrolytes for lithium ion batteries. J. Power Sources 2017, 360, 98– 105,  DOI: 10.1016/j.jpowsour.2017.06.006
      38
      Network type sp3 boron-based single-ion conducting polymer electrolytes for lithium ion batteries
      Deng, Kuirong; Wang, Shuanjin; Ren, Shan; Han, Dongmei; Xiao, Min; Meng, Yuezhong
      Journal of Power Sources (2017), 360 (), 98-105CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      Electrolytes play a vital role in modulating lithium ion battery performance. An outstanding electrolyte should possess both high ionic cond. and unity lithium ion transference no. Here, we present a facile method to fabricate a network type sp3 boron-based single-ion conducting polymer electrolyte (SIPE) with high ionic cond. and lithium ion transference no. approaching unity. The SIPE was synthesized by coupling of lithium bis(allylmalonato)borate (LiBAMB) and pentaerythritol tetrakis(2-mercaptoacetate) (PETMP) via one-step photoinitiated in situ thiol-ene click reaction in plasticizers. Influence of kinds and content of plasticizers was investigated and the optimized electrolytes show both outstanding ionic cond. (1.47 × 10-3 S cm-1 at 25 °C) and high lithium transference no. of 0.89. This ionic cond. is among the highest ionic cond. exhibited by SIPEs reported to date. Its electrochem. stability window is up to 5.2 V. More importantly, Li/LiFePO4 cells with the prepd. single-ion conducting electrolytes as the electrolyte as well as the separator display highly reversible capacity and excellent rate capacity under room temp. It also demonstrates excellent long-term stability and reliability as it maintains capacity of 124 mA h g-1 at 1 C rate even after 500 cycles without obvious decay.
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    39. 39
      Guzmán-González, G.; Ávila-Paredes, H. J.; Rivera, E.; González, I. Electrochemical Characterization of Single Lithium-Ion Conducting Polymer Electrolytes Based on sp3 Boron and Poly(ethylene glycol) Bridges. ACS Appl. Mater. Interfaces 2018, 10 (36), 30247– 30256,  DOI: 10.1021/acsami.8b02519
      39
      Electrochemical Characterization of Single Lithium-Ion Conducting Polymer Electrolytes Based on sp3 Boron and Poly(ethylene glycol) Bridges
      Guzman-Gonzalez, Gregorio; Avila-Paredes, Hugo J.; Rivera, Ernesto; Gonzalez, Ignacio
      ACS Applied Materials & Interfaces (2018), 10 (36), 30247-30256CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      A novel series of single lithium-ion conducting polymer electrolytes (SLICPE) based on sp3 boron and poly(ethylene glycol) (PEG) bridges is presented, in the context of the development of a new generation of batteries, with the aim to overcome the problems related to concn. overpotential and low ion transport nos. in conventional solid polymer electrolytes (SPE). The phase sepn. generated by the phys. mixt. of SPE with plasticizers such as poly(ethylene oxide) is still a serious problem. In this work, the use of PEG with different chain lengths, for the polycondensation reaction with LiB(OCH3)4, to synthesize SLICPE allows preventing phase sepn. while tuning the predominant conduction mechanism, and thus the elec. properties, esp. the lithium-ion transference no. The ionic transport is promoted by chain mobility as the chain length is increased. SLICPE with the best ionic cond. values (4.95 ± 0.05) × 10-6 S cm-1 was the one synthesized from poly(ethylene glycol) with an av. MN of 400 (BEG8), having an O/Li+ ratio of 20. The lithium transference no. (tLi+) and electrochem. stability window of SLICPE membranes at 25° decreased as the PEG bridge length between sp3 boron atoms increased from 0.97 to 0.88 and 5.4 to 4.2 V vs. Li0/Li+, resp., for SLICPE synthesized from PEG with an av. MN of 50-400 (BEG1 to BEG8).
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    40. 40
      Van Humbeck, J. F.; Aubrey, M. L.; Alsbaiee, A.; Ameloot, R.; Coates, G. W.; Dichtel, W. R.; Long, J. R. Tetraarylborate polymer networks as single-ion conducting solid electrolytes. Chem. Sci. 2015, 6 (10), 5499– 5505,  DOI: 10.1039/C5SC02052B
      40
      Tetraarylborate polymer networks as single-ion conducting solid electrolytes
      Van Humbeck, Jeffrey F.; Aubrey, Michael L.; Alsbaiee, Alaaeddin; Ameloot, Rob; Coates, Geoffrey W.; Dichtel, William R.; Long, Jeffrey R.
      Chemical Science (2015), 6 (10), 5499-5505CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
      A new family of solid polymer electrolytes based upon anionic tetrakis(phenyl)borate tetrahedral nodes and linear bis-alkyne linkers is reported. Sonogashira polymns. using tetrakis(4-iodophenyl)borate, tetrakis(4-iodo-2,3,5,6-tetrafluorophenyl)borate and tetrakis(4-bromo-2,3,5,6-tetrafluorophenyl)borate delivered highly cross-linked polymer networks with both 1,4-diethynylbeznene and a tri(ethylene glycol) substituted deriv. Promising initial cond. metrics have been obsd., including high room temp. conductivities (up to 2.7 × 10-4 S cm-1), moderate activation energies (0.25-0.28 eV), and high lithium ion transport nos. (up to tLi+ = 0.93). Initial investigations into the effects of important materials parameters such as bulk morphol., porosity, fluorination, and other chem. modification, provide starting design parameters for further development of this new class of solid electrolytes.
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    41. 41
      Shim, J.; Kim, D.-G.; Kim, H. J.; Lee, J. H.; Lee, J.-C. Polymer Composite Electrolytes Having Core-Shell Silica Fillers with Anion-Trapping Boron Moiety in the Shell Layer for All-Solid-State Lithium-Ion Batteries. ACS Appl. Mater. Interfaces 2015, 7 (14), 7690– 7701,  DOI: 10.1021/acsami.5b00618
      41
      Polymer Composite Electrolytes Having Core-Shell Silica Fillers with Anion-Trapping Boron Moiety in the Shell Layer for All-Solid-State Lithium-Ion Batteries
      Shim, Jimin; Kim, Dong-Gyun; Kim, Hee Joong; Lee, Jin Hong; Lee, Jong-Chan
      ACS Applied Materials & Interfaces (2015), 7 (14), 7690-7701CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Core-shell SiO2 particles with ion-conducting poly(ethylene glycol) and anion-trapping B moiety in the shell layer were prepd. to be used as fillers for polymer composite electrolytes based on org./inorg. hybrid branched copolymer as polymer matrix for all-solid-state Li-ion battery applications. The core-shell SiO2 particles improve mech. strength and thermal stability of the polymer matrix and poly(ethylene glycol) and B moiety in the shell layer increase compatibility between filler and polymer matrix. Also, B moiety in the shell layer increases both ionic cond. and Li transference no. of the polymer matrix because Li salt can be more easily dissocd. by the anion-trapping B. Interfacial compatibility with Li metal anode is also improved because well-dispersed SiO2 particles serve as protective layer against interfacial side reactions. As a result, all-solid-state battery performance is enhanced when the copolymer having core-shell SiO2 particles with the B moiety was used as solid polymer electrolyte.
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    42. 42
      Li, S. B.; Zuo, C.; Zhang, Y.; Wang, J. R.; Gan, H. H.; Li, S. Q.; Yu, L. P.; Zhou, B. H.; Xue, Z. G. Covalently cross-linked polymer stabilized electrolytes with self-healing performance via boronic ester bonds. Polym. Chem. 2020, 11 (36), 5893– 5902,  DOI: 10.1039/D0PY00728E
      42
      Covalently cross-linked polymer stabilized electrolytes with self-healing performance via boronic ester bonds
      Li, Sibo; Zuo, Cai; Zhang, Yong; Wang, Jirong; Gan, Huihui; Li, Shaoqiao; Yu, Liping; Zhou, Binghua; Xue, Zhigang
      Polymer Chemistry (2020), 11 (36), 5893-5902CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)
      Herein, solid polymer electrolytes (SPEs) were designed and fabricated via the photopolymn. of a macromol. crosslinker with boronic ester bonds and poly(ethylene glycol) diacrylate (PEGDA) with different mol. wts. under UV irradn. in the presence of a photoinitiator. The boronic ester-based crosslinker was synthesized via the dehydration reaction of ortho-aminomethyl-phenylboronic acid-terminated poly(propylene glycol)-b-poly(ethylene glycol)-b-poly(propylene glycol) and 2,3-dihydroxypropyl methacrylate. The covalently crosslinked polymer stabilized electrolytes (PSEs) contg. boronic ester bonds possessed improved ionic cond., self-healing properties, and a wide electrochem. window (5.3 V vs. Li+/Li).
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    43. 43
      Wang, L.; Yan, J.; Zhong, M.; Zhang, J.; Shen, W.; Guo, S. Regulating Lithium-Ion Transference Number of a Poly(vinyl alcohol)-Based Gel Electrolyte by the Incorporation of H3BO3 as an Anion Trapper. ACS Appl. Energy Mater. 2022, 5 (3), 2873– 2880,  DOI: 10.1021/acsaem.1c03549
      43
      Regulating Lithium-Ion Transference Number of a Poly(vinyl alcohol)-Based Gel Electrolyte by the Incorporation of H3BO3 as an Anion Trapper
      Wang, Lei; Yan, Jiawei; Zhong, Min; Zhang, Jiali; Shen, Wenzhuo; Guo, Shouwu
      ACS Applied Energy Materials (2022), 5 (3), 2873-2880CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      Gel electrolytes hold great promise for improving the safety of lithium-ion batteries (LIBs); however, their low lithium-ion transference no. (tLi+ < 0.4) remains to be improved. Herein, boron-contg. poly(vinyl alc.) (B-PVA) solns. are prepd. based on the simple reaction between PVA and H3BO3 and then electrospun to obtain the B-PVA nanofiber matrixes. The gel electrolytes are formed by loading the liq. electrolytes into the as-obtained porous B-PVA matrixes. We demonstrate that the tLi+ of B-PVA8 (with 8 wt % H3BO3 added) gel electrolyte can reach 0.81, much higher than that of the conventional PVA gel electrolyte (0.32). The B-PVA8 gel electrolyte also shows the highest Li+ cond. of 1.81 x 10-3 S cm-1 compared to PVA. The B-PVA8 gel electrolyte enables a small Li nucleation overpotential of 129.8 mV when Li is plated and reduces the concn. polarization of Li||Li batteries. The mesocarbon microbead (MCMB) half-coin cells with the B-PVA8 gel electrolyte exhibit excellent rate capability and exceptional charge/discharge cycling stability.
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    44. 44
      Hong, D. G.; Baik, J.-H.; Kim, S.; Lee, J.-C. Solid polymer electrolytes based on polysiloxane with anion-trapping boron moieties for all-solid-state lithium metal batteries. Polymer 2022, 240, 124517,  DOI: 10.1016/j.polymer.2022.124517
      44
      Solid polymer electrolytes based on polysiloxane with anion-trapping boron moieties for all-solid-state lithium metal batteries
      Hong, Dong Gi; Baik, Ji-Hoon; Kim, Sangwan; Lee, Jong-Chan
      Polymer (2022), 240 (), 124517CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)
      Cross-linked solid polymer electrolytes (SPEs) based on ion-conducting poly(ethylene glycol) (PEG), flexible polysiloxane, and anion-trapping boron cross-linker (BPC) were prepd. via thiol-ene click reaction for lithium metal batteries. Various thermal and electrochem. properties of SPEs were systematically investigated by varying the content of BPC. Thermally stable free-standing SPE systems could be obtained due to the cross-linked structure, while relatively high ionic cond. of about 1.3 x 10-4 S cm-1 at 60 °C was obtained at the same time by the flexible polysiloxane moiety. The boron moiety in BPC could increase the lithium ion transference no. compared to the corresponding boron-free SPE due to the anion-trapping capability of boron atom. The formation and growth of lithium dendrites were effectively suppressed by the anion-trapping capability and mech. stable cross-linked structure of the SPE.
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    45. 45
      Guzman-Gonzalez, G.; Vauthier, S.; Alvarez-Tirado, M.; Cotte, S.; Castro, L.; Gueguen, A.; Casado, N.; Mecerreyes, D. Single-Ion Lithium Conducting Polymers with High Ionic Conductivity Based on Borate Pendant Groups. Angew. Chem., Int. Ed. 2022, 61 (8), e202114024,  DOI: 10.1002/anie.202114024
      45
      Single-Ion Lithium Conducting Polymers with High Ionic Conductivity Based on Borate Pendant Groups
      Guzman-Gonzalez, Gregorio; Vauthier, Soline; Alvarez-Tirado, Marta; Cotte, Stephane; Castro, Laurent; Gueguen, Aurelie; Casado, Nerea; Mecerreyes, David
      Angewandte Chemie, International Edition (2022), 61 (7), e202114024CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A family of single-ion lithium conducting polymer electrolytes based on highly delocalized borate groups is reported. The effect of the nature of the substituents on the boron atom on the ionic cond. of the resultant methacrylic polymers was analyzed. To the best of our knowledge the lithium borate polymers endowed with flexible and electron-withdrawing substituents present the highest ionic cond. reported for a lithium single-ion conducting homopolymer (1.65x10-4 S cm-1 at 60°C). This together with its high lithium transference no. tLi+ =0.93 and electrochem. stability window of 4.2 V vs Li0/Li+ show promise for application in lithium batteries. To illustrate this, a lithium borate monomer was integrated into a single-ion gel polymer electrolyte which showed good performance on lithium sym. cells (<0.85 V at ±0.2 mA cm-2 for 175 h).
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    46. 46
      Alvarez-Tirado, M.; Guzman-Gonzalez, G.; Vauthier, S.; Cotte, S.; Gueguen, A.; Castro, L.; Mecerreyes, D. Designing Boron-Based Single-Ion Gel Polymer Electrolytes for Lithium Batteries by Photopolymerization. Macromol. Chem. Phys. 2022, 223 (8), 2100407,  DOI: 10.1002/macp.202100407
      46
      Designing Boron-Based Single-Ion Gel Polymer Electrolytes for Lithium Batteries by Photopolymerization
      Alvarez-Tirado, Marta; Guzman-Gonzalez, Gregorio; Vauthier, Soline; Cotte, Stephane; Gueguen, Aurelie; Castro, Laurent; Mecerreyes, David
      Macromolecular Chemistry and Physics (2022), 223 (8), 2100407CODEN: MCHPES; ISSN:1022-1352. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Single-ion lithium conducting polymer electrolytes based on delocalized borate groups are designed and synthesized by rapid UV-photopolymn. For this purpose, three different functional lithium boron sp3 anionic monomers, contg. fluorinated, ethoxy, or a blend of both functionalities are synthesized. These monomers are photopolymd. in the presence of a poly(ethylene glycol) dimethacrylate crosslinker and tetraglyme as plasticizer. By this method, gel polymer electrolytes endowed with lithium single-ion conduction are prepd. (SIGPEs). The impact generated by the different functionalities of the borate groups and the addn. of plasticizer on the electrochem. and ion conducting properties of the synthesized polymer electrolytes are analyzed in detail. These polymer electrolytes show high ionic cond. (1.71 x 10-4 S cm-1 at 25 °C) and high lithium transference no. values (up to 0.85). Finally, they are investigated as solid electrolytes in lithium metal sym. cells showing good performance (<0.85 V at ±0.2 mA cm-2 for 175 h).
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    47. 47
      Chen, Q.; Shi, Y.; Sheng, K.; Zheng, J.; Xu, C. Dynamically Cross-Linked Hydrogel Electrolyte with Remarkable Stretchability and Self-Healing Capability for Flexible Electrochromic Devices. ACS Appl. Mater. Interfaces 2021, 13 (47), 56544– 56553,  DOI: 10.1021/acsami.1c15432
      47
      Dynamically Cross-Linked Hydrogel Electrolyte with Remarkable Stretchability and Self-Healing Capability for Flexible Electrochromic Devices
      Chen, Qijun; Shi, Yuchen; Sheng, Kai; Zheng, Jianming; Xu, Chunye
      ACS Applied Materials & Interfaces (2021), 13 (47), 56544-56553CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      It is desired to develop self-healing gel electrolytes for flexible electrochromic devices (ECDs) due to the demand of healing damages caused during operations. We here report a hydrogel electrolyte with remarkable self-healing capability, excellent stretchability, and ionic cond. The hydrogel electrolyte was synthesized via one-step copolymn. of glycerol monomethacrylate (GMA) and acrylamide (AAm) in the presence of borate. Within the hydrogel electrolyte, dynamic crosslinking is expected to be formed due to the borate-didiol complexation and hydrogen-bonding interactions. As a result, the hydrogel electrolyte demonstrates an excellent self-healing efficiency of up to 97%, a fracture strain of 1155%, a fracture toughness of 136.6 kJ m-3, and a fracture stress of 13.0 kPa. Addnl., a flexible ECD based on the hydrogel electrolyte and an electrochromic layer of poly(3,4-(2,2-dimethyl-propylenedioxy)thiophene) (PProDOT-Me2) was assembled and evaluated. The device is found to be stable in both mech. and optical properties over 1000 operation cycles. This study may provide a promising way for self-healing electrolyte gels to be utilized in a variety of flexible electrochem. devices, including ECDs, supercapacitors, and batteries.
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    48. 48
      Gregory, G. L.; Jenisch, L. M.; Charles, B.; Kociok-Köhn, G.; Buchard, A. Polymers from Sugars and CO2: Synthesis and Polymerization of a d-Mannose-Based Cyclic Carbonate. Macromolecules 2016, 49 (19), 7165– 7169,  DOI: 10.1021/acs.macromol.6b01492
      48
      Polymers from Sugars and CO2: Synthesis and Polymerization of a D-Mannose-Based Cyclic Carbonate
      Gregory, Georgina L.; Jenisch, Liliana M.; Charles, Bethan; Kociok-Kohn, Gabriele; Buchard, Antoine
      Macromolecules (Washington, DC, United States) (2016), 49 (19), 7165-7169CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
      A six-membered cyclic carbonate derived from natural sugar D-mannose was prepd. using CO2 as a C1 building block at room temp. and atm. pressure. The monomer was synthesized in two steps from a com. available mannopyranose deriv. Polycarbonates were rapidly prepd. at ambient temp. by controlled ring-opening polymn. (ROP) of the monomer, initiated by 4-methylbenzyl alc. in the presence of 1,5,7-triazabicyclo[5.4.0]dec-5-ene (TBD) as the organocatalyst. Head-to-tail regiochem. was indicated by NMR spectroscopy and is supported by DFT calcns. These aliph. polycarbonates exhibit high-temp. resistance and demonstrate potential for postpolymn. functionalization, suggesting future application as high-performance commodity and biomedical materials.
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    49. 49
      Piccini, M.; Leak, D. J.; Chuck, C. J.; Buchard, A. Polymers from sugars and unsaturated fatty acids: ADMET polymerisation of monomers derived from d-xylose, d-mannose and castor oil. Polym. Chem. 2020, 11 (15), 2681– 2691,  DOI: 10.1039/C9PY01809C
      49
      Polymers from sugars and unsaturated fatty acids: ADMET polymerisation of monomers derived from D-xylose, D-mannose and castor oil
      Piccini, Marco; Leak, David J.; Chuck, Christopher J.; Buchard, Antoine
      Polymer Chemistry (2020), 11 (15), 2681-2691CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)
      α, ω-Unsatd. glycolipids derived from natural monosaccharides D-xylose and D-mannose, and from a castor oil deriv., 10-undecenoic acid, were synthesized and polymd. via acyclic diene metathesis (ADMET), using Grubbs second generation catalyst. The synthesis of these polymers, which combine a rigid isopropylidene-functionalised carbohydrate core with flexible unsatd. aliph. chains, was confirmed by NMR spectroscopy and size exclusion chromatog.. The effect of different parameters on the polymns. were investigated, including temp., catalyst loading, absence/presence of solvents, effect of a mol. wt. moderator and mixing technique. Polyesters with high mol. wts. (up to 71 kg mol-1) could be obtained in elevated yields (85%). These amorphous polymers were highly thermally (up to 355°C) and hydrolytically (pH 7, 0, 14) stable, and showed relatively low glass transition temps. (-28 to -8°C), imparted by the flexible fatty acid chain. Deprotection of ketal groups on the polymer backbone was possible up to 72% and changed the material properties, leading to partial crystallinity and insoly. These partially deprotected polymers allowed the prodn. of transparent thin polymer films and were amenable to further functionalisation.
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    50. 50
      McGuire, T. M.; Bowles, J.; Deane, E.; Farrar, E. H. E.; Grayson, M. N.; Buchard, A. Control of Crystallinity and Stereocomplexation of Synthetic Carbohydrate Polymers from d- and l-Xylose. Angew. Chem., Int. Ed. 2021, 60 (9), 4524– 4528,  DOI: 10.1002/anie.202013562
      50
      Control of Crystallinity and Stereocomplexation of Synthetic Carbohydrate Polymers from D- and L-Xylose
      McGuire, Thomas M.; Bowles, Jessica; Deane, Edward; Farrar, Elliot H. E.; Grayson, Matthew N.; Buchard, Antoine
      Angewandte Chemie, International Edition (2021), 60 (9), 4524-4528CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Manipulating the stereochem. of polymers is a powerful method to alter their phys. properties. Despite the chirality of monosaccharides, reports on the impact of stereochem. in natural polysaccharides and synthetic carbohydrate polymers remain absent. Herein, we report the cocrystn. of regio- and stereoregular polyethers derived from D- and L-xylose, leading to enhanced thermal properties compared to the enantiopure polymers. To the best of our knowledge, this is the first example of a stereocomplex between carbohydrate polymers of opposite chirality. In contrast, atactic polymers obtained from a racemic mixt. of monomers are amorphous. We also show that the polymer hydroxyl groups are amenable to post-polymn. functionalization. These strategies afford a family of carbohydrate polyethers, the phys. and chem. properties of which can both be controlled, and which opens new possibilities for polysaccharide mimics in biomedical applications or as advanced materials.
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    51. 51
      McGuire, T. M.; Clark, E. F.; Buchard, A. Polymers from Sugars and Cyclic Anhydrides: Ring-Opening Copolymerization of a d-Xylose Anhydrosugar Oxetane. Macromolecules 2021, 54 (11), 5094– 5105,  DOI: 10.1021/acs.macromol.1c00365
      51
      Polymers from Sugars and Cyclic Anhydrides: Ring-Opening Copolymerization of a D-Xylose Anhydrosugar Oxetane
      McGuire, Thomas M.; Clark, Ella F.; Buchard, Antoine
      Macromolecules (Washington, DC, United States) (2021), 54 (11), 5094-5105CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
      A D-xylose 3,5-anhydrosugar deriv. has been used as an oxetane co-monomer in the ring-opening copolymn. (ROCOP) with cyclic anhydrides, to form a family of seven novel sugar-derived polyesters, with up to 100% renewable content. ROCOP proceeds with high alternating selectivity to form AB-type copolymers that are thermally robust (Td,onset > 212°C) and exhibit a broad range of glass-transition temps. (Tg 60-145°C). These polyesters are amenable to further postpolymn. functionalization. The hydroxy group of the sugar moiety can be unveiled, then functionalized further, e.g., phosphorylated. The internal alkene of some of the anhydride moieties can also be subject to thiol-ene reactions. Combining those orthogonal strategies affords AB copolyesters with alternating functional substituents. By exploiting the living character of the ROCOP process, block copolymers have also been synthesized through sequential co-monomer addn. expts.
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    52. 52
      Gregory, G. L.; Kociok-Kohn, G.; Buchard, A. Polymers from sugars and CO2: ring-opening polymerisation and copolymerisation of cyclic carbonates derived from 2-deoxy-d-ribose. Polym. Chem. 2017, 8 (13), 2093– 2104,  DOI: 10.1039/C7PY00236J
      52
      Polymers from sugars and CO2: ring-opening polymerization and copolymerization of cyclic carbonates derived from 2-deoxy-D-ribose
      Gregory, Georgina L.; Kociok-Kohn, Gabriele; Buchard, Antoine
      Polymer Chemistry (2017), 8 (13), 2093-2104CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)
      Bio-based aliph. polycarbonates (APCs) are attractive synthetic materials for biomedical applications because of their biodegradability and biocompatibility properties. A high yielding 3-step process that utilizes CO2 as a C1 synthon is presented for converting raw sugar, 2-deoxy-D-ribose into a novel 6-membered cyclic carbonate for ring-opening polymn. (ROP) into carbohydrate-based APCs. The α- and β-anomers of the monomer could be isolated and revealed very different polymerizability, as rationalized by DFT calcns. Whereas the β-anomer could not be polymd. under the conditions tested, organocatalytic homopolymn. of the α-anomer, in soln. at room temp. (rt) or under melt conditions, yielded highly insol. polycarbonates, composed of both cyclic and linear topologies, and exhibiting a glass transition temp. (Tg) of ∼58°C. Random copolymers with controllable incorporation of this new sugar monomer were prepd. with trimethylene carbonate (TMC) at rt in the bulk or in soln. with Mn up to 64 000 g mol-1. With increasing sugar content, the Tg values of the copolymers increased and their thermal degradability was enhanced, giving access to a new class of APCs with tailored properties.
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    53. 53
      Kumar, R.; Gao, W.; Gross, R. A. Functionalized Polylactides: Preparation and Characterization of [l]-Lactide-co-Pentofuranose. Macromolecules 2002, 35 (18), 6835– 6844,  DOI: 10.1021/ma020041a
      53
      Functionalized Polylactides: Preparation and Characterization of [L]-Lactide-co-Pentofuranose
      Kumar, Rajesh; Gao, Wei; Gross, Richard A.
      Macromolecules (2002), 35 (18), 6835-6844CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
      The new monomer 1,2-O-isopropylidene-3-benzyloxy-pentofuranose-4,4'-cyclic carbonate (IPPTC) was prepd. IPPTC has both a ketal-protected diol and a benzyl ether-protected hydroxyl. Thus, these two sets of hydroxyl groups can be independently deprotected to give IPPTC repeat units with one, two, or three free hydroxyl groups. Stannous octanoate at 130° was used for the copolymn. of [L]-LA (L-lactide) with IPPTC. When monomer feed ratio fLA/fIPPTC was 91/9, the percent yield, Mn, and percent incorporation of IPPTC units were 78%, 77,800 g/mol, and 4 mol%, resp. By the method of Fineman and Ross, the [L]-LA and IPPTC comonomer reactivity ratios were 8.6 and 0.51, resp. Relative to poly([L]-LA), incorporation of IPPTC units into [L]-LA/IPPTC copolymers gave products that are lower melting (112°, 14 mol% IPPTC) and have higher thermal stabilities and higher glass transition temps. (69°, 100 mol% IPPTC). The liberation of hydroxyl pendant groups by the selective removal of the benzyl ether, the ketal groups, or both was possible without substantial loss in the product mol. wt. The removal of the protecting groups of poly([L]-LA-co-4.0 mol% IPPTC) did not change the Tm value (160°) but did alter the copolymer crystn. kinetics and thermal stability.
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    54. 54
      Felder, S. E.; Redding, M. J.; Noel, A.; Grayson, S. M.; Wooley, K. L. Organocatalyzed ROP of a Glucopyranoside Derived Five-Membered Cyclic Carbonate. Macromolecules 2018, 51 (5), 1787– 1797,  DOI: 10.1021/acs.macromol.7b01785
      54
      Organocatalyzed ROP of a Glucopyranoside Derived Five-Membered Cyclic Carbonate
      Felder, Simcha E.; Redding, McKenna J.; Noel, Amandine; Grayson, Scott M.; Wooley, Karen L.
      Macromolecules (Washington, DC, United States) (2018), 51 (5), 1787-1797CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
      Saccharides, based on their wide bioavailability, high chem. functionality and stereochem. diversity, are attractive starting materials for the development of new synthetic polymers. Established carbonylation methodologies were used to synthesize a 5-membered cyclic carbonate monomer, 4,6-O-benzylidene-2,3-O-carbonyl-α-D-glucopyranoside (MBGC), in high yield (>95%) from a com. available D-glucopyranoside deriv. The ability of this monomer to undergo ring-opening polymn. (ROP) with a range of organocatalysts, rather than the previously reported anionic initiators, was investigated. These new conditions were developed to widen the functional group tolerance in the polymn., and achieve better control over the final properties of the polymers. The most promising of the catalysts examd., 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), was used in a kinetic study to confirm the well-controlled nature of the ROP. Optimized conditions were then successfully applied to the synthesis of polymers of different mol. wts. Two post-polymn. modifications were completed via the removal of the benzylidene acetal protecting group to release a water-sol. poly(glucose carbonate), and then addn. of acetyl groups to facilitate characterization studies. MALDI-TOF MS anal. was performed to further probe the chem. of the polymn. and deprotection. A wide range of thermal decompn. temps. (233-347 °C), glass transition temps. (87-233 °C), and water contact angles (38-128°) was achieved by this series of polymers. The hydrolytic degradability of these polymers was also examd., demonstrating differing degrdn. mechanisms based on the acidic vs. basic conditions used. Consequently, this single monomer was successfully employed in the straightforward synthesis of a polymeric system with tunable properties based on the mol. wt. and repeat unit compn.
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    55. 55
      Fenouillot, F.; Rousseau, A.; Colomines, G.; Saint-Loup, R.; Pascault, J. P. Polymers from renewable 1,4:3,6-dianhydrohexitols (isosorbide, isomannide and isoidide): A review. Prog. Polym. sci. 2010, 35 (5), 578– 622,  DOI: 10.1016/j.progpolymsci.2009.10.001
      55
      Polymers from renewable 1,4:3,6-dianhydrohexitols (isosorbide, isomannide and isoidide): A review
      Fenouillot, F.; Rousseau, A.; Colomines, G.; Saint-Loup, R.; Pascault, J.-P.
      Progress in Polymer Science (2010), 35 (5), 578-622CODEN: PRPSB8; ISSN:0079-6700. (Elsevier Ltd.)
      A review. The use of the 1,4:3,6-dianhydrohexitols isosorbide, isomannide, and isoidide in polymers is reviewed. 1,4:3,6-Dianhydrohexitols are derived from renewable resources from cereal-based polysaccharides. 1,4:3,6-Dianhydrohexitols are derived from renewable resources from cereal-based polysaccharides. In the field of polymeric materials, these diols are essentially employed to synthesize or modify polycondensates. Their attractive features as monomers are linked to their rigidity, chirality, non-toxicity, and the fact that they are not derived from petroleum. First, the synthesis of high glass transition temp. polymers with good thermomech. resistance is possible. Second, the chiral nature of 1,4:3,6-dianhydrohexitols may lead to specific optical properties. Finally, biodegradable polymers can be obtained. The prodn. of isosorbide on an industrial scale with a purity satisfying the requirements for polymer synthesis suggests that isosorbide will soon emerge in industrial polymer applications. However, a deciding factor will be the redn. of polymn. time of these low-reactivity monomers to values compatible with economically viable prodn. processes to give polyesters, polyamides, poly(amide esters), poly(ester imides), polycarbonates, polyurethanes, and polyethers.
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    56. 56
      Xiao, R.; Grinstaff, M. W. Chemical synthesis of polysaccharides and polysaccharide mimetics. Prog. Polym. sci. 2017, 74, 78– 116,  DOI: 10.1016/j.progpolymsci.2017.07.009
      56
      Chemical synthesis of polysaccharides and polysaccharide mimetics
      Xiao, Ruiqing; Grinstaff, Mark W.
      Progress in Polymer Science (2017), 74 (), 78-116CODEN: PRPSB8; ISSN:0079-6700. (Elsevier Ltd.)
      A review. Polysaccharides are ubiquitous in nature, and play many crit. roles in biol. As such, the synthesis of polysaccharides and of polymers mimicking the structure or function of polysaccharides is of keen interest in order to reveal structure-function relationships and to prep. biocompatible and biodegradable materials for research and com. applications. Recent developments in polymn. methodologies are enabling the synthesis of polysaccharides and polysaccharide mimetics with a variety of structures and architectures. While there have been significant advances in overcoming the difficulties in controlling the regioselectivity and stereospecificity of glycosidic bond formation during polymn., the development of efficient synthetic routes with general applicability to stereoregular and structurally complex polysaccharides remains a challenge. This review comprehensively describes the chem. polymn. methods to synthesize polysaccharides with different compns. and architectures (linear, branched, and hyperbranched) and the synthetic procedures to polysaccharide mimetics possessing, for example, amine linkages, amide linkages, and carbonate linkages. It begins with a discussion of the challenges and strategies for the synthesis of polysaccharides. We highlight the complexity obsd. in theses macromols. due to the no. and variety of stereo- and regio-types of glycosidic linkages present between monosaccharide residues. With regards to polysaccharide mimetics, we focus on polymers displaying important structural features present in natural polysaccharides, such as a rigid polymer backbone contg. heterocyclic ring structures, short linkages with less than three atoms, as well as multiple hydroxyl groups. Both condensation polymn. and ring-opening polymn. are used to prep. linear polysaccharides, branched polysaccharides, hyperbranched polysaccharides, non-O-glycosidic linked polysaccharide mimetics, and pseudopolysaccharides. The review concludes with reflections and suggestions for future directions of investigation.
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    57. 57
      Zhu, Y.; Romain, C.; Williams, C. K. Sustainable polymers from renewable resources. Nature 2016, 540 (7633), 354– 362,  DOI: 10.1038/nature21001
      57
      Sustainable polymers from renewable resources
      Zhu, Yunqing; Romain, Charles; Williams, Charlotte K.
      Nature (London, United Kingdom) (2016), 540 (7633), 354-362CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
      Renewable resources are used increasingly in the prodn. of polymers. In particular, monomers such as carbon dioxide, terpenes, vegetable oils and carbohydrates can be used as feedstocks for the manuf. of a variety of sustainable materials and products, including elastomers, plastics, hydrogels, flexible electronics, resins, engineering polymers and composites. Efficient catalysis is required to produce monomers, to facilitate selective polymns. and to enable recycling or upcycling of waste materials. There are opportunities to use such sustainable polymers in both high-value areas and in basic applications such as packaging. Life-cycle assessment can be used to quantify the environmental benefits of sustainable polymers.
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    58. 58
      Galbis, J. A.; García-Martín, M. d. G.; de Paz, M. V.; Galbis, E. Synthetic Polymers from Sugar-Based Monomers. Chem. Rev. 2016, 116 (3), 1600– 1636,  DOI: 10.1021/acs.chemrev.5b00242
      58
      Synthetic Polymers from Sugar-Based Monomers
      Galbis, Juan A.; Garcia-Martin, M. de Gracia; de Paz, M. Violante; Galbis, Elsa
      Chemical Reviews (Washington, DC, United States) (2016), 116 (3), 1600-1636CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. This article reports the sugar-based polymers.
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    59. 59
      Gregory, G. L.; Lopez-Vidal, E. M.; Buchard, A. Polymers from sugars: cyclic monomer synthesis, ring-opening polymerisation, material properties and applications. Chem. Commun. 2017, 53 (14), 2198– 2217,  DOI: 10.1039/C6CC09578J
      59
      Polymers from sugars: cyclic monomer synthesis, ring-opening polymerisation, material properties and applications
      Gregory, Georgina L.; Lopez-Vidal, Eva M.; Buchard, Antoine
      Chemical Communications (Cambridge, United Kingdom) (2017), 53 (14), 2198-2217CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      A review. Plastics are ubiquitous in modern society. However, the reliance on fossil fuels and the environmental persistence of most polymers make them unsustainable. Scientists are facing the challenge of developing cost-effective and performance-competitive polymers from renewable resources. Carbohydrates are a renewable feedstock with tremendous potential: sugars are widely available, environmentally benign and are likely to impart biocompatibility and degradability properties to polymers due to their high oxygen content. Sugars are also a feedstock with great structurally diversity and functionalisation potential that can enable fine tuning of the resulting polymer properties. In recent years, ring-opening polymn. (ROP) has emerged as the method of choice for the controlled polymn. of renewable cyclic monomers, in particular lactones and cyclic carbonates, to allow the precise synthesis of complex polymer architectures and address commodity and specialist applications. This feature article gives an overview of sugar-based polymers that can be made by ROP. In particular, recent advances in the synthetic routes towards monomers that preserve the original carbohydrate core structure are presented. The performances of various homogeneous catalysts and the properties of the resultant polymers are given, and future opportunities highlighted for the development of both the materials and catalysts.
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    60. 60
      Ma, L.; Jin, M.; Yan, C.; Guo, H.; Ma, X. Gel Polymer Electrolyte with Anion-Trapping Boron Moieties via One-Step Synthesis for Symmetrical Supercapacitors. Macromol. Mater. Eng. 2020, 305 (7), 1900807,  DOI: 10.1002/mame.201900807
      60
      Gel Polymer Electrolyte with Anion-Trapping Boron Moieties via One-Step Synthesis for Symmetrical Supercapacitors
      Ma, Longli; Jin, Mengyuan; Yan, Chaojing; Guo, Hao; Ma, Xiaohua
      Macromolecular Materials and Engineering (2020), 305 (7), 1900807CODEN: MMENFA; ISSN:1438-7492. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A novel gel polymer electrolyte (GPE) which is based on new synthesized boron-contg. monomer, benzyl methacrylate, 1 M LiClO4/N,N-dimethylformamidel liq. electrolyte soln. is prepd. through a one-step synthesis method. The boron-contg. GPE (B-GPE) not only displays excellent mech. behavior, favorable thermal stability, but also exhibits an outstanding ionic cond. of 2.33 mS cm-1 at room temp. owing to the presence of anion-trapping boron sites. The lithium ion transference in this gel polymer film at ambient temp. is 0.60. Furthermore, the sym. supercapacitor which is fabricated with B-GPE as electrolyte and reduced graphene oxide as electrode demonstrates a broad potential window of 2.3 V. The specific capacitance of sym. B-GPE supercapacitors retains 90% after 3000 charge-discharge cycles at c.d. of 1 A g-1.
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    61. 61
      Dai, K.; Ma, C.; Feng, Y.; Zhou, L.; Kuang, G.; Zhang, Y.; Lai, Y.; Cui, X.; Wei, W. A borate-rich, cross-linked gel polymer electrolyte with near-single ion conduction for lithium metal batteries. J. Mater. Chem. A 2019, 7 (31), 18547– 18557,  DOI: 10.1039/C9TA05938E
      61
      A borate-rich, cross-linked gel polymer electrolyte with near-single ion conduction for lithium metal batteries
      Dai, Kuan; Ma, Cheng; Feng, Yiming; Zhou, Liangjun; Kuang, Guichao; Zhang, Yun; Lai, Yanqing; Cui, Xinwei; Wei, Weifeng
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (31), 18547-18557CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      Lithium metal batteries (LMBs) show tremendous potential in energy storage due to ultrahigh energy densities. Nevertheless, maintaining a stable solid electrolyte interphase (SEI) and suppressing the growth of dendrites are hard to achieve with conventional liq. electrolytes. Gel/solid polymer electrolytes are sought-after candidates to block dendrite growth, while they still suffer from poor ionic cond. and an incompatible interphase. Herein, a borate-rich gel polymer electrolyte with a 3D cross-linked structure (3D-BGPE) is designed to settle these problems. By incorporating anion-trapping boron moieties into a 3D configuration via an in situ strategy, the 3D-BGPE presents high ionic cond. (8.4 × 10-4 S cm-1), near single ion conduction (Li+ transference no. of 0.76) and constructs a stable and conductive SEI layer on the lithium anode. Accordingly, the LMBs employing the 3D-BGPE can effectively inhibit the dendrite growth and maintain 89.73% capacity retention after 400 cycles. A promising approach to design highly effective electrolytes for safe and long-life LMBs is provided in this work.
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    62. 62
      Zeng, X.; Dong, L.; Fu, J.; Chen, L.; Zhou, J.; Zong, P.; Liu, G.; Shi, L. Enhanced interfacial stability with a novel boron-centered crosslinked hybrid polymer gel electrolytes for lithium metal batteries. Chem. Eng. J. 2022, 428, 131100,  DOI: 10.1016/j.cej.2021.131100
      62
      Enhanced interfacial stability with a novel boron-centered crosslinked hybrid polymer gel electrolytes for lithium metal batteries
      Zeng, Xingfa; Dong, Linna; Fu, Jifang; Chen, Liya; Zhou, Jia; Zong, Peisong; Liu, Guozhen; Shi, Liyi
      Chemical Engineering Journal (Amsterdam, Netherlands) (2022), 428 (), 131100CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
      Low coulombic efficiency and serious safety issues due to uncontrollable lithium dendrite growth has severely impeded the practical application of lithium-ion batteries (LIBs) with lithium metal as the anode. In this work, we design and fabricate a novel single ion conducting crosslinked polymer gel electrolytes contg. neg. charged delocalized state borate structures and rich EO units via one-step photoinitiated in-situ radical polymn. in presence of PVDF-HFP as reinforcing materials. Herein, we synthesize a novel lithium bis(macid acid) borate to give anion covalently bonded to the polymer main chain and vinyl monomers contg. rich EO units are chosen to build polymer framework to ensure fast ion transport. As expected, the tailored boron-centered single-ion-conducting polymer gel electrolytes exhibit high ionic cond. up to 1.03x10-3 S cm-1 at 32°C, excellent oxidn. potential up to 5.05 V vs Li+/Li at 1 mV/s, and a near-single ion conducting behavior (lithium ion transference no. of 0.65). The Lithium (Li) metal sym. cells assembled with the novel boron-centered single-ion-conducting polymer gel electrolytes show long-term stable cycling over >700 h at room temp. without short circuit, which implies the excellent stability of blend membranes during lithium metal deposition and stripping processes. Moreover, the Li/LiFePO4 cells assembled with the boron-centered single-ion-conducting polymer gel electrolytes exhibit excellent rate performance and cycling performance. The initial discharge capacity is 161.3 mAh g-1 at 0.1 C and a capacity of 127.7 mAh g-1 maintains with nearly 100% coulombic efficiency after 100 cycles. Moreover, the Li/LiFePO4 cells deliver stable coulombic efficiency close to 100% at 0.5 C after 300 cycles.
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    63. 63
      Chen, Q.; Shi, Y.; Sheng, K.; Zheng, J.; Xu, C. Dynamically Cross-Linked Hydrogel Electrolyte with Remarkable Stretchability and Self-Healing Capability for Flexible Electrochromic Devices. ACS Appl. Mater. Interfaces 2021, 13 (47), 56544– 56553,  DOI: 10.1021/acsami.1c15432
      63
      Dynamically Cross-Linked Hydrogel Electrolyte with Remarkable Stretchability and Self-Healing Capability for Flexible Electrochromic Devices
      Chen, Qijun; Shi, Yuchen; Sheng, Kai; Zheng, Jianming; Xu, Chunye
      ACS Applied Materials & Interfaces (2021), 13 (47), 56544-56553CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      It is desired to develop self-healing gel electrolytes for flexible electrochromic devices (ECDs) due to the demand of healing damages caused during operations. We here report a hydrogel electrolyte with remarkable self-healing capability, excellent stretchability, and ionic cond. The hydrogel electrolyte was synthesized via one-step copolymn. of glycerol monomethacrylate (GMA) and acrylamide (AAm) in the presence of borate. Within the hydrogel electrolyte, dynamic crosslinking is expected to be formed due to the borate-didiol complexation and hydrogen-bonding interactions. As a result, the hydrogel electrolyte demonstrates an excellent self-healing efficiency of up to 97%, a fracture strain of 1155%, a fracture toughness of 136.6 kJ m-3, and a fracture stress of 13.0 kPa. Addnl., a flexible ECD based on the hydrogel electrolyte and an electrochromic layer of poly(3,4-(2,2-dimethyl-propylenedioxy)thiophene) (PProDOT-Me2) was assembled and evaluated. The device is found to be stable in both mech. and optical properties over 1000 operation cycles. This study may provide a promising way for self-healing electrolyte gels to be utilized in a variety of flexible electrochem. devices, including ECDs, supercapacitors, and batteries.
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    64. 64
      Homann, G.; Stolz, L.; Winter, M.; Kasnatscheew, J. Elimination of ″Voltage Noise″ of Poly (Ethylene Oxide)-Based Solid Electrolytes in High-Voltage Lithium Batteries: Linear versus Network Polymers. Iscience 2020, 23 (6), 101225,  DOI: 10.1016/j.isci.2020.101225
      64
      Elimination of "Voltage Noise" of Poly (Ethylene Oxide)-Based Solid Electrolytes in High-Voltage Lithium Batteries: Linear versus Network Polymers
      Homann, Gerrit; Stolz, Lukas; Winter, Martin; Kasnatscheew, Johannes
      iScience (2020), 23 (6), 101225CODEN: ISCICE; ISSN:2589-0042. (Elsevier B.V.)
      Frequently, poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) reveal a failure with high-voltage electrodes, e.g. LiNi0.6Mn0.2Co0.2O2 in lithium metal batteries, which can be monitored as an arbitrary appearance of a "voltage noise" during charge and can be attributed to Li dendrite-induced cell micro short circuits. This failure behavior disappears when incorporating linear PEO-based SPE in a semi-interpenetrating network (s-IPN) and even enables an adequate charge/discharge cycling performance at 40°C. An impact of any electrolyte oxidn. reactions on the performance difference can be excluded, as both SPEs reveal similar (high) bulk oxidn. onset potentials of ≈4.6 V vs. Li|Li+. Instead, improved mech. properties of the SPE, as revealed by compression tests, are assumed to be detg., as they mech. better withstand Li dendrite penetration and better maintain the distance of the two electrodes, both rendering cell shorts less likely.
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    65. 65
      Gou, J. R.; Liu, W. Y.; Tang, A. M. A renewable gel polymer electrolyte based on the different sized carboxylated cellulose with satisfactory comprehensive performance for rechargeable lithium ion battery. Polymer 2020, 208, 122943,  DOI: 10.1016/j.polymer.2020.122943
      65
      A renewable gel polymer electrolyte based on the different sized carboxylated cellulose with satisfactory comprehensive performance for rechargeable lithium ion battery
      Gou, Jingren; Liu, Wangyu; Tang, Aimin
      Polymer (2020), 208 (), 122943CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)
      Gel polymer electrolyte (GPE) comprising the merits of liq. electrolyte (LE) and solid state electrolyte (SSE) has attracted soaring attention. Herein, we develop a GPE with good comprehensive performance by means of mixing the micro carboxylated cellulose fibril (MCCF) and nano carboxylated cellulose fibril (NCCF) in different proportions. In this composite structure, MCCF forms the skeleton of the host membrane of GPE and provides aplenty pores. While NCCF reinforces the connections of the micron cellulose filaments, enhancing the mech. properties of the membrane. Obtained from the exptl. results, the GPE contg. 1%wt nano cellulose exhibits a high tensile strength of 40.1 MPa, a good ionic cond. of 1.84 mS cm-1 at 25°C and a stable thermal performance up to 220°C. Simultaneously, the NCM523//Li half cell assembled with this GPE shows a moderate cyclic performance at the ambient temp. of 25°C. Moreover, such cellulose based GPE is renewable and biodegradable, which can contribute to the environmental protection-oriented development of lithium ion battery industry.
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    66. 66
      Gou, J. R.; Liu, W. Y.; Tang, A. M.; Xie, H. A phosphorylated nanocellulose/hydroxypropyl methylcellulose composite matrix: A biodegradable, flame-retardant and self-standing gel polymer electrolyte towards eco-friendly and high safety lithium ion batteries. Eur. Polym. J. 2021, 158, 110703,  DOI: 10.1016/j.eurpolymj.2021.110703
      66
      A phosphorylated nanocellulose/hydroxypropyl methylcellulose composite matrix: A biodegradable, flame-retardant and self-standing gel polymer electrolyte towards eco-friendly and high safety lithium ion batteries
      Gou, Jingren; Liu, Wangyu; Tang, Aimin; Xie, Hong
      European Polymer Journal (2021), 158 (), 110703CODEN: EUPJAG; ISSN:0014-3057. (Elsevier Ltd.)
      Gel polymer electrolyte (GPE) is considered as a midway soln. of liq. electrolyte and solid polymer electrolyte. Nowadays, the biodegradable and renewable cellulose based GPEs are adopted as promising substitutes for GPEs based on other polymers like PVDF and PMMA. However, the safety concerns derived from the flammability of cellulose still hinders the practical application of the cellulose based GPEs. Simultaneously, the conventional methods to improve the flame-resistance of the host membranes are either unreliable or often invalidate the biodegradability of the GPEs based on cellulose. To achieve the unique combination of biodegradability and high safety, we report the prepn. of composite GPEs with flame-retardancy resulted from hydrolysis between phosphorylated nanocellulose (PNC) and hydroxypropyl methylcellulose (HPMC). Besides, the present GPEs are demonstrated to be self-standing and mech. robust with the advent of PNC. In comparison of the GPEs with various content of PNC, MPC50%/GPC50% are considered as the suitable options thanks to the high tensile strength, satisfactory electrochem. performances and good flame-retardancy. Finally, the LiFePO4/GPC50%/Li coin battery performs a remarkable cycling performance with a high capacity retention of 88.9% at 0.2C and a good rate capability in the battery test. It is anticipated that the as-constructed GPE can contribute to the design on the eco-friendly and high safety batteries in the future.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvVSks73F&md5=577d190eaa3c3c402ccfe4f82f913f5e
    67. 67
      Li, M. X.; Wang, X. W.; Yang, Y. Q.; Chang, Z.; Wu, Y. P.; Holze, R. A dense cellulose-based membrane as a renewable host for gel polymer electrolyte of lithium ion batteries. J. Membr. sci. 2015, 476, 112– 118,  DOI: 10.1016/j.memsci.2014.10.056
      67
      A dense cellulose-based membrane as a renewable host for gel polymer electrolyte of lithium ion batteries
      Li, M. X.; Wang, X. W.; Yang, Y. Q.; Chang, Z.; Wu, Y. P.; Holze, R.
      Journal of Membrane Science (2015), 476 (), 112-118CODEN: JMESDO; ISSN:0376-7388. (Elsevier B.V.)
      A dense instead of porous gel polymer electrolyte for lithium ion batteries is reported for the first time. Its host is a renewable and environment friendly polymer, hydroxyethyl cellulose (HEC). The prepn. of HEC membrane is very simple. The membrane is stable up to 280 °C, much higher than the m.ps. of those com. separators based on polyolefin. The evapn. temp. of the org. electrolyte in the prepd. gel polymer electrolytes is up to 75 °C. In addn., the gel polymer electrolyte shows good electrochem. performance including high ionic cond. at room temp., and a high lithium ion transference no. When tested as separator and electrolyte, a LiFePO4 pos. electrode displays satisfactory electrochem. properties including high discharge capacity and stable cycling. These results indicate a very promising direction for a low cost and renewable gel polymer electrolyte for lithium ion batteries.
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    68. 68
      Yang, H. Z.; Liu, Y.; Kong, L. B.; Kang, L.; Ran, F. Biopolymer-based carboxylated chitosan hydrogel film crosslinked by HCl as gel polymer electrolyte for all-solid-sate supercapacitors. J. Power Sources 2019, 426, 47– 54,  DOI: 10.1016/j.jpowsour.2019.04.023
      68
      Biopolymer-based carboxylated chitosan hydrogel film crosslinked by HCl as gel polymer electrolyte for all-solid-sate supercapacitors
      Yang, Hezhen; Liu, Ying; Kong, Lingbin; Kang, Long; Ran, Fen
      Journal of Power Sources (2019), 426 (), 47-54CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      Gel polymer electrolyte for flexible energy storage devices such as supercapacitors and rechargeable batteries attracts widespread attentions. Herein, we fabricate a flexible, transparent, and eco-friendly gel polymer electrolyte film based on biodegradable polymer of the carboxylated chitosan via phase sepn. of carboxylated chitosan hydrogel in hydrochloric acid. HCl is the key chem. for crosslinking of film forming, and the process is simple, rapid and non-polluting. The obtained carboxylated chitosan hydrogel film with excellent flexibility exhibits a highest electrolyte uptake rate of 742.0 wt%, and a highest ionic cond. of 8.69 × 10-2 S cm-1. A sym. all-solid-state supercapacitors using carbon cloth as current collectors, activated carbon film as electrodes, and carboxylated chitosan hydrogel film as a gel polymer electrolyte shows a high specific capacitance of 45.9 F g-1 at 0.5 A g-1, and the max. energy d. of 5.2 Wh kg-1 at a power d. of 226.6 W kg-1. To our knowledge, this is the first time that carboxylated chitosan hydrogel film being used as gel polymer electrolyte for supercapacitors electrolyte. The good results indicate that the carboxylated chitosan as a new gel polymer electrolyte material has great potential in practical applications of all-solid-state, flexible, and portable energy storage devices.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXntlCjs7g%253D&md5=28a5de65412eecf046bc090b56bccc12
    69. 69
      Kamisan, A. S.; Kudin, T. I. T.; Ali, A. M. M.; Yahya, M. Z. A. Electrical and physical studies on 49% methyl-grafted natural rubber-based composite polymer gel electrolytes. Electrochim. Acta 2011, 57, 207– 211,  DOI: 10.1016/j.electacta.2011.06.096
      69
      Electrical and physical studies on 49% methyl-grafted natural rubber-based composite polymer gel electrolytes
      Kamisan, A. S.; Kudin, T. I. T.; Ali, A. M. M.; Yahya, M. Z. A.
      Electrochimica Acta (2011), 57 (), 207-211CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)
      The elec. properties of composite polymer electrolyte systems composed of 49% poly(Me methacrylate) (PMMA) grafted natural rubber (MG49) host polymer, ammonium triflate (NH4CF3SO3) salt, and SiO2 as a filler were studied by impedance spectroscopy technique. Attenuated total reflectance-Fourier transformed IR (ATR-FTIR) spectra were also measured and indicated the occurrence of polymer-salt-filler interaction. The cond. for the composite ammonium triflate-doped MG49 polymer was studied as a function of temp. between 303 K and 373 K The cond. was found to exhibit Arrhenius behavior indicating that it is thermally activated. Viscosity measurements were also carried out and showed that the mech. properties of the composite polymer gel electrolytes (CPGEs) are improved. The highest elec. cond. of the composite electrolyte system (∼7.55 × 10-3 S cm-1) was obsd. for the sample contg. 8.0% SiO2. The viscosity for that material was high (∼69 cP) compared with the electrolyte contg. no SiO2 (∼10 cP).
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhsFWru77M&md5=d4be2237a3f6ff00137e41bda0f0ff9e
    70. 70
      Careem, M. A.; Noor, I. S. M.; Arof, A. K., Impedance Spectroscopy in Polymer Electrolyte Characterisation. In Polymer Electrolytes: Characterization Techniques and Energy Applications, 1st ed.; Winie, T., Arof, A. K., Thomas, S., Eds.; Wiley-VCH verlag GmbH & Co.: Weinheim Germany, 2020; pp 23– 64.
      There is no corresponding record for this reference.

  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsaem.2c03937.

    • Cross-linking procedures, NMR spectra, photographs of vial inversion tests, FT-IR spectra, detailed rheological characterizations, FE-SEM microscopy, TGA and DSC traces, and additional electrochemistry results (PDF)


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