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Performance Fabrics Obtained by In Situ Growth of Metal–Organic Frameworks in Electrospun Fibers
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Applications of Polymer, Composite, and Coating Materials

Performance Fabrics Obtained by In Situ Growth of Metal–Organic Frameworks in Electrospun Fibers
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  • Maya Molco
    Maya Molco
    School of Chemistry and the Tel-Aviv University Center for NanoScience and Nanotechnology, Tel Aviv University, Tel Aviv 6997801, Israel,
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  • Fabrice Laye
    Fabrice Laye
    Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen 76344, Germany
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  • Enrique Samperio
    Enrique Samperio
    Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen 76344, Germany
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  • Shiran Ziv Sharabani
    Shiran Ziv Sharabani
    School of Chemistry and the Tel-Aviv University Center for NanoScience and Nanotechnology, Tel Aviv University, Tel Aviv 6997801, Israel,
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  • Victor Fourman
    Victor Fourman
    School of Mechanical Engineering, Tel-Aviv University, Tel-Aviv 6997801, Israel
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  • Dov Sherman
    Dov Sherman
    School of Mechanical Engineering, Tel-Aviv University, Tel-Aviv 6997801, Israel
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  • Manuel Tsotsalas
    Manuel Tsotsalas
    Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen 76344, Germany
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    Orcidhttp://orcid.org/0000-0002-9557-2903
  • Christof Wöll
    Christof Wöll
    Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen 76344, Germany
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    Orcidhttp://orcid.org/0000-0003-1078-3304
  • Joerg Lahann
    Joerg Lahann
    Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen 76344, Germany
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    Orcidhttp://orcid.org/0000-0002-3334-2053
  • Amit Sitt*
    Amit Sitt
    School of Chemistry and the Tel-Aviv University Center for NanoScience and Nanotechnology, Tel Aviv University, Tel Aviv 6997801, Israel,
    *Email: [email protected]
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    Orcidhttp://orcid.org/0000-0002-8129-7007
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ACS Applied Materials & Interfaces

Cite this: ACS Appl. Mater. Interfaces 2021, 13, 10, 12491–12500
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https://doi.org/10.1021/acsami.0c22729
Published March 4, 2021

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Abstract

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Metal–organic frameworks (MOFs) exhibit an exceptional surface area-to-volume ratio, variable pore sizes, and selective binding, and hence, there is an ongoing effort to advance their processability for broadening their utilization in different applications. In this work, we demonstrate a general scheme for fabricating freestanding MOF-embedded polymeric fibers, in which the fibers themselves act as microreactors for the in situ growth of the MOF crystals. The MOF-embedded fibers are obtained via a two-step process, in which, initially, polymer solutions containing the MOF precursors are electrospun to obtain microfibers, and then, the growth of MOF crystals is initiated and performed via antisolvent-induced crystallization. Using this approach, we demonstrate the fabrication of composite microfibers containing two types of MOFs: copper (II) benzene-1,3,5-tricarboxylic acid (HKUST-1) and zinc (II) 2-methylimidazole (ZIF-8). The MOF crystals grow from the fiber’s core toward its outer rims, leading to exposed MOF crystals that are well rooted within the polymer matrix. The MOF fibers obtained using this method can reach lengths of hundreds of meters and exhibit mechanical strength that allows arranging them into dense, flexible, and highly durable nonwoven meshes. We also examined the use of the MOF fiber meshes for the immobilization of the enzymes catalase and horse radish peroxidase (HRP), and the enzyme-MOF fabrics exhibit improved performance. The MOF-embedded fibers, demonstrated in this work, hold promise for different applications including separation of specific chemical species, selective catalysis, and sensing and pave the way to new MOF-containing performance fabrics and active membranes.

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Introduction

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Porous solid materials with nanoscale porosity that exhibit an extremely high surface area-to-volume ratio have long been used for a variety of applications including adsorption, separation, ion exchange, and heterogeneous catalysis. (1,2) Of this family, metal–organic frameworks (MOFs), which are made of metallic ions interconnected with organic ligands via coordination bonds, have raised a major interest because of their large surface area, the variability of the pore sizes, and the control over the chemistry of the organic ligands that enables specific and selective binding. (1−8) In parallel to the development of new MOFs and characterization of their properties, there has been an ongoing effort for creating mesoscopic superstructures of MOFs that can enhance the MOFs’ performance and increase their processability for different applications. (9−11) A leading approach for introducing new functional capabilities is to conjugate MOF nano- or microcrystals to other materials. (12−15) In particular, incorporating MOFs into and onto polymeric fibers allows taking advantage of the highly developed technological capabilities of fiber processing and paves the way toward fabrication of performance fabrics and value-added textiles with a highly porous surface. (16−20) Such fabrics hold high promise for a variety of applications, including filtering for specific chemical species, catalytic membranes, enzyme immobilization, and sensors. (21)
To date, several different methods for embedding or decorating polymeric fibers with MOFs have been reported. (22,23) The most direct method is mixing presynthesized MOF crystals with a polymer in a melt or solution and spinning fibers of the polymer-MOF mixture. (24−30) Another established method is the direct growth of MOFs on the surface of prespun fibers via solvothermal synthesis, sometimes utilizing a “reactive seed” approach. (23,31−35) Such decorated fibers were utilized to a variety of applications including drug release, (36) fabrication of antimicrobial surfaces, (37) gas entrapment, (25,27,38) and catalysis. (39,40) While these approaches provide functional MOF-conjugated electrospun fibers, they may exhibit some limitations. In the case of adding presynthesized MOFs to the polymeric solution and spinning them together, most MOF crystals located inside of the fibers are not exposed to the environment. In the case of MOF growth on prespun fibers, the MOFs may be susceptible to detachment when significant mechanical loads are applied.
In this work, we demonstrate a new approach for embedding MOFs into electrospun microfibers. In this approach, the fibers contain the MOF precursors and act as microreactors that promote the in situ formation of MOF crystals inside of the fiber and facilitate their growth toward the outer surface of the fiber upon exposure to antisolvent vapor. Therefore, the fibers themselves template the geometry of the MOF layer. Using this in situ synthetic approach, we demonstrate the formation of polymeric fibers that exhibit well-exposed yet strongly embedded MOF microcrystals on their surface. The approach was established for two MOF systems: copper (II) benzene-1,3,5-tricarboxylic acid (HKUST-1) (41) and zinc (II) 2-methylimidazole (ZIF-8). (42,43) The resulting fibers contain more than 20% HKUST-1 and 15% ZIF-8 crystals by weight. Using this method, we obtained MOF fibers of microscale diameters that can reach lengths of several meters and utilized them for forming unwoven meshes that exhibit good mechanical properties and high durability without apparent loss of material over time. In addition, we demonstrate the immobilization of enzymes on the MOF fibers and demonstrate that the performance of the MOF-enzyme system surpasses that of fibers of similar composition without MOFs grown on their surface.
In a typical MOF synthesis, the ionic metal centers react with the organic multidentate ligands to form a network via coordination bonds. The obtained products and the reaction rate are strongly affected by the selected precursors and by the parameters of the synthesis including the solvent, temperature, pressure, compositions, and additives. Thus, the approaches for MOF synthesis are highly diverse and can vary significantly for different MOFs. (44,45) Synthesizing MOFs within a polymeric matrix has several key hindrances that must be overcome. First, to achieve a homogeneous distribution of the precursors, the selected solvent must dissolve a sufficient amount of both the precursors and the polymer. Second, the precursors’ concentration must be high enough to enable the growth of the MOF crystals, which results in a solution with a relatively high ionic strength. Many polymers tend to salt out of solution at such high ionic concentrations, and thus, a polymer that stabilizes the salt and does not salt out is required as a scaffold polymer. Third, as the MOF growth process occurs post-fabrication, there should exist an antisolvent that can penetrate the polymer matrix and induce the formation of the MOF crystals inside it. Last, the MOF precursors must be able to transport through the polymer matrix to maintain the growth of the crystals as they form.
As a proof of concept for the feasibility of the method, two MOFs were chosen: HKUST-1, which is composed of copper (II) ions and benzene-1,3,5-tricarboxylic acid (BTC), and ZIF-8, which is a member of the zeolitic imidazolate framework (ZIF) family and is composed of zinc (II) ions and 2-methylimidazole. The growth of the HKUST-1 and ZIF-8 fibers was done in a two-step process, depicted schematically in Figure 1a. In the first step, a core–shell fiber, which contains the MOF precursors, was obtained using electrospinning. (46) In a typical procedure, the MOF precursors that consist of a metal salt and an organic linker were dissolved together with polyvinylpyrrolidone (PVP) in dimethyl sulfoxide (DMSO). PVP was chosen as the carrier polymer because it chelates the metal ions, anchoring them into the backbone of the fiber, and hence assures a homogeneous distribution of the precursors throughout the fiber. (47−49) In addition, the PVP acts as a thickening agent that increases the viscosity of the core solution and stabilizes the electrospinning. Despite the stabilization induced by the PVP, obtaining a stable spinning of PVP loaded with the precursors is hard to maintain due to the high content of free ions in the solution. Electrospinning of the system in a core–shell architecture with a solution of polylactic-co-glycolic acid (PLGA) as a shell resulted in a significant stabilization of the jetting process and in the formation of uniform and continuous fibers. This architecture is obtained by dispensing the core and shell solutions simultaneously through a metallic needle composed of two coaxial needles, one inside the other. Due to the laminar flow of the polymer solutions, the core–shell morphology dictated by the needles’ architecture is kept within the fiber. In the second step, the obtained fibers are exposed to ethanol vapor. The ethanol vapor penetrates the polymer fibers and acts as an antisolvent for the MOF precursors, leading to the in situ crystallization and growth of the MOFs toward the surface of the fiber. A similar approach was demonstrated before by Ameloot et al. (50) and Cravillon et al. (51) for the growth of MOFs in the liquid phase and the gas phase; (50−52) however, to the best of our knowledge, it is the first time the method is deployed for the growth of MOFs in a polymer matrix.

Figure 1

Figure 1. (a) Schematic illustration of the core–shell architecture for the fabrication of the MOF fiber mesh. The core solution (in green) contains PVP + MOF precursors (Cu(NO3)2·3H2O and BTC for HKUST-1; Zn(O2CCH3)2·2H2O and Hmim for ZIF-8), and the shell solution (in blue) contains PLGA. The two solutions are injected simultaneously to achieve a core–shell structure (left). After the fabrication of the fibers, they are flushed with ethanol vapor, inducing the growth of the MOF crystals (right). (b) Molecular structures of the precursors of the two MOFs: HKUST-1 precursors (left) and ZIF-8 precursors (right).

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Figure 2a shows a mesh made of the HKUST-1 fibers before (left) and after (right) exposure to ethanol vapor. Upon exposure to the vapor, a significant change in the fibers’ color from pale to dark cyan is observed. Scanning electron microscopy (SEM) micrographs of single fibers indicate that before exposure to ethanol vapor, the fiber is relatively smooth (Figure 2b, left). After exposure to ethanol vapor (Figure 2b, right), a dense layer of microcrystalline material emerges on the surface of the fiber. The obtained crystals are well embedded in the polymer fibers, indicating that the crystal growth started within the polymer matrix and advanced toward the surface. Size distribution measurements based on SEM micrographs indicate an average fiber diameter of 19 ± 4 μm (Figure S1a). The MOF crystal average diameter is 0.94 ± 0.31 μm (Figure S1b) and they exhibit octahedral morphology, typical of HKUST-1.

Figure 2

Figure 2. (a) Electrospun mesh of fibers containing HKUST-1 precursors before (left) and after (right) exposure to ethanol. (b) The growth of the HKUST-1 crystals is clearly seen when comparing a single fiber before (left) and after (right) exposure to ethanol. (c) Obtained XRD pattern (top) in comparison to the theoretical pattern for HKUST-1 (bottom). The inset shows a zoom-in of the obtained HKUST-1 crystals.

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Further identification of the crystal structure was obtained using X-ray diffraction (XRD). Figure 2c shows the XRD pattern of a sample of fibers after exposure to ethanol vapor (blue, solid line). The positions of these peaks correspond well with the positions of the theoretical peaks obtained from the theoretical model of HKUST-1 (black peaks, lower panel). However, a few small additional peaks that could not be identified are apparent and might indicate the existence of small contamination in the sample.
To analyze the yield of the MOF growth process, we utilized several different approaches to quantify the mass percentage of the MOFs in the fibers. Thermogravimetric analysis (TGA) of the HKUST-1 fibers indicated that the fibers contain ∼9% copper by weight (Figure S3a). The total amount of copper added to the solution is 9%, indicating that the amount of copper in the fibers is preserved at the jetting stage. However, this TGA cannot distinguish between unreacted copper and copper in the MOF crystals.
Quantitative analysis of the ratio of crystalline to amorphous phases from the XRD measurement for the HKUST-1 fibers indicated 23% crystalline material by weight. Assuming that the polymer phase is almost completely amorphous, the crystalline phase can be predominantly attributed to HKUST-1. Direct gravimetric analysis of the HKUST-1 content was performed by weighing a mesh of HKUST-1 fibers and then dipping it in a mixture of methanol and chloroform (1:1 in volume). The solution completely dissolved only the precursors and polymers (PVP and PLGA), leaving behind the undissolved HKUST-1 crystals. The crystals were washed and centrifuged several times to remove any residues of polymers and unreacted precursors. The remaining pellet containing only the HKUST-1 crystals was dried and weighed. The process was performed on four different samples, yielding an HKUST-1 weight percentage of 22 ± 8%, in consistency with the XRD analysis.
According to the initial amounts of copper and BTC that were loaded in the system, in the case that all the precursors reacted to form HKUST-1 MOF, the content of the MOF in the sample should be 45% by weight. According to the above-mentioned analysis obtained using two different techniques, we obtained that the fibers consist of ∼22% HKUST-1 by weight; thus, the yield of the synthesis is approximately 50%.
A similar fabrication scheme was used to jet fibers and meshes embedded with ZIF-8 precursors, as depicted in Figure 3a. TGA measurement indicated a weight percentage of 10% zinc in the sample, in accordance with the initial amounts of zinc in the solution (Figure S3b). SEM micrographs indicate the formation of microcrystals that cover the surface of the fiber upon exposure to ethanol vapor (Figure 3b). Size distribution measurements indicate a fiber average diameter of 17 ± 3 μm (Figure S1c) and an MOF crystal average diameter of 0.84 ± 0.32 μm (Figure S1d). Figure 3c depicts the XRD pattern of the sample after exposure to ethanol vapor. The diffraction pattern obtained from the fibers (blue, solid line) fits well the theoretically calculated pattern of ZIF-8 (black, lower panel), indicating the existence of ZIF-8 MOFs in the fibers. Again, a few small additional peaks that could not be identified appeared in the spectrum, which can point toward the existence of a small amount of contamination in the sample.

Figure 3

Figure 3. (a) Electrospun mesh of fibers containing ZIF-8 precursors before (left) and after (right) exposure to ethanol. (b) The growth of the ZIF-8 crystals is clearly seen when comparing a single fiber before (left) and after (right) exposure to ethanol. (c) Obtained XRD pattern (top) in comparison to the theoretical pattern for ZIF-8 (bottom). The inset shows a zoom-in of the obtained ZIF-8 crystals.

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Quantitative analysis of the ratio of crystalline to amorphous phases from the XRD measurement for the ZIF-8 fibers gave a value of 15% crystalline material by weight. This value is consistent with the gravimetric analysis of the ZIF-8 content, which yielded a weight percentage of 18%. The precursors added to this system were 49% by weight; therefore, ∼15% of ZIF-8 crystals on the fibers give a yield of ∼31%. We attribute the incomplete consumption of the precursors to the anchoring of the copper or zinc ions to the PVP backbone, which reduces their availability for reacting and composing the MOFs. (56) The summary of the crystal percentages in both systems is presented in section S3 in the Supporting Information.
In both HKUST-1 and ZIF-8 MOF fibers described above, the fibers are smooth after the jetting, and only after exposure of the fibers to ethanol vapor, MOF crystals emerge and appear on the surface of the fibers (Figures 2b and 3b). For both systems, the formed crystals are well embedded in the fibers, indicating that the crystals grew from the inside toward the outer surface of the fibers. This is further emphasized when inspecting fibers that were mechanically pulled in the scanning electron microscope. Figure 4 shows a micrograph of an HKUST-1 composite fiber that was pulled after exposure to ethanol and the growth of the crystals. Before pulling, the outer MOF layer is intact and covers the entire fiber (Figure 4a). After pulling, some fibers exhibit fractures in the MOF layer, exposing the polymer fiber smooth backbone (Figure 4b). Further pulling of the fibers led to stretching of the polymer backbone until it tore down (Figure 4c). Inspecting the torn fibers in the scanning electron microscope clearly shows that the MOF crystals form a dense shell around the fiber backbone, which is kept intact even upon the rupturing of the fiber. Furthermore, there is no evidence for the formation of crystals inside the fiber itself. Similar indication was obtained also in sectioned fibers of HKUST-1 (Figure S4) and for ZIF-8 fibers that were mechanically pulled (Figure S5).

Figure 4

Figure 4. Upon stretching of an HKUST-1 embedded fiber, initially, the polymeric fiber extends (a), leading to the formation of fractures in the external crystal layer (b). Eventually, the polymer fiber backbone is torn, revealing an embedded crystal shell wrapping the polymeric fiber backbone (c).

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To further elucidate the growth process, the elemental content of the surface of HKUST-1 composite fibers was examined by X-ray photoelectron spectroscopy (XPS) before and after exposure to ethanol vapor. The XPS measurement indicates the average elemental and chemical composition of the fibers’ surface up to a thickness of ∼10 nm and can give direct information regarding the changes in the metal content throughout the process.
Figure 5a shows the XPS spectra of the fibers before (black) and after exposure to ethanol vapor (red). The assignment of the peaks is reported in the graph. In both spectra, strong peaks for oxygen and carbon are detected and can be attributed to the polymers. However, upon exposure to ethanol, additional peaks, which correspond to copper and nitrogen, emerge. The only sources of nitrogen in the fibers are the PVP and the copper salt, and hence, these results indicate that, initially, there are almost no copper atoms and no PVP on the surface of the fibers. This is indeed expected because both materials reside in the core of the fiber. However, upon exposure to the vapor, migration of both copper and PVP from the core toward the surface of the fibers is initiated. This is further emphasized when examining the amounts of atoms extracted from the XPS measurements summarized in Table 1. The concentration of copper on the surface rises from ∼0 to 6% mass, which is close to the average weight percentage of copper in the entire fiber, as calculated according to the jetting parameters.

Figure 5

Figure 5. (a) XPS spectra of the fibers before (black) and after (red) exposure to ethanol vapor. The peak assignment is reported above the peaks, indicating the emergence of copper and nitrogen on the surface after the exposure. (b) Schematic illustration of the proposed growth scheme. At the first stage, the precursors are positioned only at the core. As the ethanol vapor penetrates the fiber, the precursors diffuse toward the surface (stage 2), and once the ethanol concentration increases enough in the fibers, the growth process begins, and MOF crystals are formed on the surface of the fibers (stage 3).

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Table 1. Elemental Surface Weight Percent of the Fiber before and after Exposure to Ethanol Compared to the Weight Percent of the Atoms (Excluding Hydrogen) in the Fiber Based on the Jetting Parameters
 surface weight % before exposuresurface weight % after exposureweight % in the entire fiber
copper0.936.0410.21
nitrogen0.192.306.41
carbon51.8348.4638.98
oxygen47.0543.2044.41
Based on these results, we propose a possible growth scheme that consists of two processes that occur simultaneously upon exposure to ethanol. On the one hand, the ethanol vapor penetrates the polymer matrix and leads to its plasticization. This promotes the diffusion of the PVP and the MOF precursors toward the fiber edges along the concentration gradient. (53−55) On the other hand, ethanol is an antisolvent for the MOF precursors, and thus, once the concentrations of ethanol and the precursors increase the formation and growth of the MOF crystals occurs. The exact position of the crystal growth depends on both the concentration gradients and diffusion rates of the ethanol and the precursors across the fiber, but based on the obtained results, it occurs close to the surface of the fiber, and the precursors migrate rapidly so that the significant growth of the crystals occurs from the surface outward.
A key aspect of utilizing such systems for different applications is the mechanical strength of the obtained fibers and of the nonwoven fabrics formed from them. Figure 6a shows a representative example of a 12 cm × 7 cm mesh made of HKUST-1 composite fibers that were spun back and forth over a rotating drum, followed by exposure to ethanol vapor. As shown in Movie S1 and Figure 6b–d, the obtained mesh can be skewed, stretched, rolled, and folded without tearing the mesh or the fibers and without the release of any of the embedded MOF crystals. The mechanical strength of the MOF layer is also observed in the single fiber level, and mechanical deformation of the single fiber did not yield detachment of the crystals (Figure S6 and section S6).

Figure 6

Figure 6. (a) A 12 cm × 7 cm nonwoven mesh fabric of HKUST-1 fibers after exposure to ethanol vapor can go through (b) rolling and (c, d) folding without tearing of the fibers or apparent release of the embedded MOF crystals.

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To examine the effect of the MOF growth on the mechanical properties of the fibers, tensile strength measurements were performed on nonwoven HKUST-1 fabrics before and after exposure to ethanol vapor. Figure 7 shows the tensile strength distribution graph of 28 HKUST-1 fabric samples of similar dimensions and fiber densities: 14 before exposure to ethanol vapor (untreated fabrics) and 14 HKUST-1 fabric samples after exposure to ethanol vapor (treated fabrics). While all the untreated fabrics exhibit a tensile strength below 10 N, all the fabric samples after the growth of the MOF crystals exhibit a clear increase in the tensile strength to above 10 N. Weibull statistical analysis performed on the results indicates a significant statistical difference between the two sample types (Figure S9), with average tensile loads of 8.17 ± 1.10 and 11.63 ± 0.91 N for the untreated and treated samples, respectively, and a Weibull modulus of 6.07 compares to 13.92, respectively, indicating the durability of the latter. These significant differences indicate that the crystals enhance the mechanical strength of the fibers and decrease the amount of defects in the fibers, possibly by forming a strong interaction with the polymer matrix. Full description of the tensile measurements, including the Weibull statistical formulations, the Young modulus, and the distributions, is provided in section S7 in the Supporting Information.

Figure 7

Figure 7. Tensile strength for HKUST-1 fabrics before (purple) and after (green) exposure to ethanol vapor. Average value for each set of samples is depicted as a black triangle marker in the center of mass of each set. Ellipsoids are guidance to the eye.

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In recent years, MOFs have been proven to be highly potent solid scaffolds for the immobilization and stabilization of enzymes, (56−59) and the immobilization of a variety of enzymes on different MOFs was demonstrated. (59−63) The MOF composite fibers offer a unique combination of both strong and protective support for the enzymes and the flexibility and ease of handling of the fabrics and open the path for the fabrication of active catalytic membranes for industrial and environmental applications.
To illustrate the potential of the MOF fibers as scaffolds for enzyme immobilization, we chose to examine the immobilization of the enzyme horseradish peroxidase (HRP) on the MOF fibers. (59,63,64) HRP is a metalloenzyme that utilizes hydrogen peroxide to catalyze the oxidation of different organic substrates. In particular, HRP catalyzes the oxidation of fluorogenic substrates that form a fluorescent product, which allows following the reaction kinetics through the fluorescence intensity of the product.
In a typical procedure, meshes of similar fiber densities containing the MOF precursors before and after exposure to ethanol were soaked in a solution containing an enzyme for a couple of hours. The meshes were then thoroughly washed in distilled water to remove the residual unbound enzyme. Next, the meshes were immersed in a solution containing the enzyme’s substrates—hydrogen peroxide and Amplex Red (AR). Throughout the catalysis process, AR is oxidized to the fluorophore resorufin (Figure 8a), and the fluorescence intensity of AR (Ex, 571 nm; Em, 585 nm) in the solution was monitored as a function of time to follow the reaction kinetics (Figures S9 and S10 in the Supporting Information).

Figure 8

Figure 8. (a) Catalysis of Amplex Red to resorufin by HRP. (b) Resorufin emission intensity as a function of time for a ZIF-8 mesh that was exposed to ethanol and was not soaked in HRP solution (black, squares), a mesh that was not exposed to ethanol but was soaked with HRP (red circles), and a mesh that was exposed to ethanol and was soaked in HRP solution (blue triangles). All measurements were performed with meshes of similar fiber densities and with similar concentrations of reagents. (c) Similar experiment repeated with HKUST-1 meshes.

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Figure 8b depicts a comparison of the resorufin fluorescence intensity as a function of time for three different meshes containing ZIF-8 precursors: (a) a mesh that was exposed to ethanol and developed ZIF-8 crystals but was not immersed in the HRP solution, (b) a mesh that was not exposed to ethanol but was immersed in the HRP solution, and (c) a mesh that was exposed to ethanol (grew ZIF-8 crystals) and immersed in the HRP solution. All the meshes were exposed to similar concentrations of the substrates AR and hydrogen peroxide.
In the first system (Figure 8b, black squares), almost no catalytic activity was observed, indicating that the MOFs themselves do not act as catalysts for the reaction. The second system exhibited a moderate catalytic activity (Figure 8b, red circles), which can be attributed to enzymes that physisorbed to the surface of the polymeric fibers. However, in the third system, in which ZIF-8 crystals were grown, a significantly higher activity is reached, and the substrates were fully consumed after ∼5 min (Figure 8b, blue triangles). The catalysis rate was quadrupled with respect to the mesh that was not exposed to ethanol. We attribute the significantly higher activity to the improved immobilization of HRP to the ZIF-8 crystals.
Figure 8c shows a comparison of the fluorescence intensity of resorufin in the solution as a function of time for three different HKUST-1 meshes exposed to similar concentrations of the substrates AR and hydrogen peroxide. A similar trend to the ZIF-8 system is also seen here; however, the overall performance is lower. This reduced activity is attributed to the lower stability of HKUST-1 in the aqueous environment, which leads to its decomposition over time and, hence, to reduced enzyme immobilization.
In addition to HRP, we also examined the immobilization of the enzyme catalase to ZIF-8 meshes. (65−67) Catalase decomposed hydrogen peroxide to water and oxygen, and hence, the performance can be qualitatively examined by the formation of oxygen bubbles on the mesh. Figure S10 shows photographs of ZIF-8 meshes exposed to the substrate hydrogen peroxide. In the case of meshes that were not immersed in a catalase solution, no oxygen bubbles were formed. A mesh that was not exposed to ethanol exhibited only a small amount of oxygen formation. The mesh with ZIF-8 crystals exhibited significantly higher formation of bubbles, indicating an improved immobilization of catalase. Furthermore, even a week after preparation, the MOF-containing meshes still exhibited high activity, suggesting that the MOFs also stabilized the immobilized enzymes. These results demonstrate the potential of the MOF meshes as durable and flexible solid scaffolds for enzyme immobilization and stabilization.

Conclusions

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In this article, we demonstrated a new synthetic route for the in situ growth of two types of MOFs on electrospun microfibers. The obtained fibers exhibit loading of more than 20% by weight of HKUST-1 crystals and 15% by weight of ZIF-8 crystals, which are strongly embedded inside the polymer matrix, and stay intact upon application of a mechanical load. In addition, the growth of the MOF crystals enhances the fiber mechanical strength, and the MOF fibers exhibit improved immobilization of enzymes, leading to the formation of meshes with high catalytic activity. The obtained results demonstrate the use of electrospun polymeric fibers as microreactors for performing chemical reactions that modify the properties of the fibers, lead to new functionalities, and pattern active material on top and inside the fiber. The scheme demonstrated here can be extended to hierarchical structures of various MOFs that could lead to performance fabrics with high potential for various applications, including filtering membranes and catalysis, in the near future.

Experimental Section

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Materials

Polylactic-co-glycolic acid (PLGA) (lactide-to-glycolide ratio = 85:15; MW = 50–75 kDa), polyvinylpyrrolidone (PVP) (MW, ∼1,300,000), copper (II) nitrate trihydrate (Cu(NO3)2·3H2O; 99.9%), benzene-1,3,5-tricarboxylic acid (BTC) (≥98%), zinc acetate dihydrate (Zn(O2CCH3)2·2H2O; 99.0%), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), and dimethylformamide (DMF) were purchased from Sigma-Aldrich. Ethanol and methanol were purchased from BioLab. 2-Methylimidazole (Hmim) was purchased from Alfa Aesar. All the materials were used as bought without further purification.

Jetting Solutions

For all the solutions described below, the concentrations are given in gram polymer to milliliter solvent. For the spinning of PLGA, a PLGA solution of 0.400 g/mL was prepared by dissolving 0.400 g of PLGA in a mixture of 0.5 mL of THF and 0.5 mL of DMF (1:1, v/v). The PVP/HKUST-1 precursor solution was prepared by dissolving 0.100 g of PVP, 0.280 g of copper nitrate trihydrate (1.16 M), and 0.129 g of BTC (0.614 M) in 1 mL of DMSO. (50) The PVP/ZIF-8 precursor solution was prepared by dissolving 0.100 g of PVP, 0.280 g of zinc acetate dihydrate (1.27 M), and 0.210 g of Hmim (2.55 M) in 1 mL of DMSO. (51)

Fiber Electrospinning

The experimental setup contained two syringe pumps (New Era), a power supply (DC voltage source, Gamma High Voltage Research, USA), and a rotating drum collector. The relative humidity in the room was between 50 and 65%. Above 70% humidity, the growth of the MOF crystals was significantly hindered, and no growth was observed.
The PLGA and PVP/precursor solutions were dispensed via a metallic coaxial core–shell needle made in-house using a 23-gauge needle and a 14-gauge needle. The PVP solution was dispensed at a constant flow rate of 0.200 mL·h–1, and the PLGA solution was also dispensed at a constant flow rate of 0.200 mL·h–1. A driving voltage of 1.5–2 kV resulted in a stable jet and the core–shell fibers were collected on a collecting drum at a tip-to-ground distance of 14 cm and a drum velocity of 80 rpm. Nonwoven meshes were formed by repeatedly moving the dispensing tip back and forth hundreds of times at a velocity of 0.1 cm per second.

Instrumentation

Scanning electron microscopy (SEM) was performed using a Quanta 200FEG environmental scanning electron microscope in a high vacuum (WD, ∼10 mm; 3–20 kV).
Powder X-ray diffraction (PXRD) was performed using a Bruker D8 Advance diffractometer in parallel beam configuration, with a linear detector LYNXEYE_XE. The pattern was collected by 2θ scan between 4° and 60° with an omega angle fixed at 4° with CuKα monochromatic radiation (λ = 1.5418 Å), operated at 40 kV and 40 mA. The scan speed was 1 s/step and the step size was 0.025°. Structural modeling was performed on the Cerius2 software suite.
Thermogravimetric analysis (TGA) was performed on a TGA Q5000 V3.17 Build 265 instrument in a nitrogen environment in a temperature range of 40–1000 °C (20 °C/min). TGA was carried out in a nitrogen atmosphere with a purge rate of 25 mL/min.
X-ray photoelectron spectroscopy (XPS) measurements were performed in UHV (2.5 × 10–10 Torr base pressure) using a 5600 Multi-Technique System (PHI, USA). The sample was irradiated with an AlKα monochromated source (1486.6 eV) and the outcome electrons were analyzed by a spherical capacitor analyzer using the slit aperture of 0.8 mm. The samples were charged during measurements and a charge neutralizer was used for charge compensation.
Tensile measuements were performed using the Instron system with a load cell of maximum 100 N and the samples were pulled in a constant speed of 1 mm/min. LaVision’s Davis software was used to record and process the data.
Fluorescence measurement of resorufin for deducing the enzyme activity was performed using an Agilent Technologies Cary Eclipse fluorescence spectrometer. The excitation was performed at a wavelength of 550 nm, and emission was collected in the range of 560–650 nm (scan rate, 600 nm/min; averaging time, 0.1 s; excitation and emission slit openings, 2.5 nm; PMT detector voltage, 600 V).

Enzyme Immobilization

Horse radish peroxidase (HRP) or catalase were adsorbed to the surface of meshes of ZIF-8 or HKUST-1 fibers before and after exposure to ethanol vapor. All of the ZIF-8 and the HKUST-1 meshes were of similar density.
Enzyme surface inmmobilization was performed for both the ZIF-8 and the HKUST-1 systems (for each system, before and after exposure to ethanol vapor) similarly. One milliliter of the enzyme in solutiom (1 mg/mL in phosphate buffer, pH 6) was added into a Petri dish. Meshes of ZIF-8 fibers or HKUST-1 (for each system, both before and after exposure to ethanol vapors) were added to the Petri dish and were left to gently stir at room temperature for a couple of hours. The meshes were then thoroughly washed with distilled water to remove unbound enzyme.

HRP Activity Test

After the HRP immobilization, the ZIF-8 and HKUST-1 meshes were put into a solution containing the enzyme’s substrates—5 μL of Ampliflu Red (10 mM in DMSO), 5 μL of hydrogen peroxide solution (20 mM in water), and 5000 μL of phosphate buffer (pH 7). Upon catalysis, AR is oxidized by HRP in the presence of hydrogen peroxide to produce resorufin, a fluorescent compound whose concentration can be monitored through the fluorescence intensity (λex = 571 nm and λem = 585 nm).
The activity of the catalase immobilized to the ZIF-8 and HKUST-1 systems was tested by adding the meshes into the substrate solution—1 mL of hydrogen peroxide solution (20 mM in water). Catalase decomposes hydrogen peroxide and oxygen bubbles are formed on the fibers.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.0c22729.

  • Average diameters of the fibers and the crystals for HKUST-1 and ZIF-8 composite fibers, thermogravimetric analysis (TGA), MOF weight percentage in MOF composite fibers, a cross section of HKUST-1 fiber after exposure to ethanol, mechanically pulled ZIF-8 fiber SEM micrograph, SEM micrographs of a folded HKUST-1 fiber, tensile measurements of HKUST-1 fabrics, and catalase enzyme immobilization on MOF nonwoven meshes (PDF)

  • Mechanical deformation of nonwoven HKUST-1 fabric (Movie S1) (MP4)

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 Author
  • Authors
    • Maya Molco - School of Chemistry and the Tel-Aviv University Center for NanoScience and Nanotechnology, Tel Aviv University, Tel Aviv 6997801, Israel,
    • Fabrice Laye - Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen 76344, Germany
    • Enrique Samperio - Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen 76344, Germany
    • Shiran Ziv Sharabani - School of Chemistry and the Tel-Aviv University Center for NanoScience and Nanotechnology, Tel Aviv University, Tel Aviv 6997801, Israel,
    • Victor Fourman - School of Mechanical Engineering, Tel-Aviv University, Tel-Aviv 6997801, Israel
    • Dov Sherman - School of Mechanical Engineering, Tel-Aviv University, Tel-Aviv 6997801, Israel
    • Manuel Tsotsalas - Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen 76344, Germany;  Orcidhttp://orcid.org/0000-0002-9557-2903
    • Christof Wöll - Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen 76344, Germany;  Orcidhttp://orcid.org/0000-0003-1078-3304
    • Joerg Lahann - Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen 76344, Germany;  Orcidhttp://orcid.org/0000-0002-3334-2053
  • Funding

    The research was sponsored by the RDECOM-Atlantic and U.S. Army Research Office under grant number W911NF-18-1-0321. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing the official policies, either expressed or implied, of the U.S. Government. The U.S. Government is authorized to reproduce and distribute reprints for Government purposes notwithstanding any copyright notation herein.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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A.S. acknowledges the generous support from the Azrieli Foundation. We also thank Dr. Jaewon Yoon, University of Michigan, for preliminary studies leading up to this research project.

References

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    The conjugation of metal-org. frameworks (MOFs) with other materials is an excellent strategy for the prodn. of advanced materials having desired properties and so appropriate applicability. In particular, the integration of MOFs with a flexible paper is expected to form valuable materials in sepn. technol. Here authors report a simple method for the generation of MOF papers through the compact and uniform growth of MOF nanoparticles on the cellulose surface of a carboxymethylated filter paper. The resulting MOF papers show a selective capture ability for neg. charged org. dyes and they can be used for dye sepn. through simple filtration of a dye soln. on the MOF papers. In addn., MOF papers can be reused after a simple washing process without losing their effective dye capture ability.
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  15. 15
    Zanchetta, E.; Malfatti, L.; Ricco, R.; Styles, M. J.; Lisi, F.; Coghlan, C. J.; Doonan, C. J.; Hill, A. J.; Brusatin, G.; Falcaro, P. ZnO as an Efficient Nucleating Agent for Rapid, Room Temperature Synthesis and Patterning of Zn-Based Metal–Organic Frameworks. Chem. Mater. 2015, 27, 690– 699,  DOI: 10.1021/cm502882a
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    15
    ZnO as an Efficient Nucleating Agent for Rapid, Room Temperature Synthesis and Patterning of Zn-Based Metal-Organic Frameworks
    Zanchetta, Erika; Malfatti, Luca; Ricco, Raffaele; Styles, Mark J.; Lisi, Fabio; Coghlan, Campbell J.; Doonan, Christian J.; Hill, Anita J.; Brusatin, Giovanna; Falcaro, Paolo
    Chemistry of Materials (2015), 27 (3), 690-699CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    The use of ZnO particles as efficient agents for seeding, growing, and precisely positioning metal-org. frameworks (MOFs) is described. Ceramic seeds were successfully used for the prepn. of Zn-based MOFs with a no. of different carboxylic acids: terephthalic acid, 2-aminoterephthalic acid, 1,3,5-benzenetricarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 4,4'-biphenyldicarboxylic acid. In situ synchrotron small-angle x-ray scattering and electron microscopy expts. were employed to det. the effect of the concn. of ZnO nanoparticles, temp., and time on MOF growth. Under optimized conditions, MOF crystals form in several minutes. This unprecedented capacity to seed MOF formation was used to control the growth of crystals in precise locations. Accordingly, the authors employed this seeding technique to position porous MOF crystals on paper strips (lateral flow), or within glass and PDMS microchannels (120 μm width and 100 μm height). ZnO nanoparticles are versatile seeding agents for the growth of porous crystals in a no. of different microfluidic platforms.
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  16. 16
    Neufeld, M. J.; Harding, J. L.; Reynolds, M. M. Immobilization of Metal-Organic Framework Copper(II) Benzene-1,3,5-Tricarboxylate (CuBTC) onto Cotton Fabric as a Nitric Oxide Release Catalyst. ACS Appl. Mater. Interfaces 2015, 7, 26742– 26750,  DOI: 10.1021/acsami.5b08773
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    16
    Immobilization of Metal-Organic Framework Copper(II) Benzene-1,3,5-tricarboxylate (CuBTC) onto Cotton Fabric as a Nitric Oxide Release Catalyst
    Neufeld, Megan J.; Harding, Jacqueline L.; Reynolds, Melissa M.
    ACS Applied Materials & Interfaces (2015), 7 (48), 26742-26750CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Immobilization of metal-org. frameworks (MOFs) onto flexible polymeric substrates as secondary supports expands the versatility of MOFs for surface coatings for the development of functional materials. In this work, we demonstrate the deposition of copper(II) benzene-1,3,5-tricarboxylate (CuBTC) crystals directly onto the surface of carboxyl-functionalized cotton capable of generating the therapeutic bioagent nitric oxide (NO) from endogenous sources. Characterization of the CuBTC-cotton material by XRD, ATR-IR, and UV-vis indicate that CuBTC is successfully immobilized on the cotton fabric. In addn., SEM imaging reveals excellent surface coverage with well-defined CuBTC crystals. Subsequently, the CuBTC-cotton material was evaluated as a supported heterogeneous catalyst for the generation of NO using S-nitrosocysteamine as the substrate. The resulting reactivity is consistent with the activity obsd. for unsupported CuBTC particles. Overall, this work demonstrates deposition of MOFs onto a flexible polymeric material with excellent coverage as well as catalytic NO release from S-nitrosocysteamine at therapeutic levels.
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  17. 17
    Ma, K.; Islamoglu, T.; Chen, Z.; Li, P.; Wasson, M. C.; Chen, Y.; Wang, Y.; Peterson, G. W.; Xin, J. H.; Farha, O. K. Scalable and Template-Free Aqueous Synthesis of Zirconium-Based Metal-Organic Framework Coating on Textile Fiber. J. Am. Chem. Soc. 2019, 141, 15626– 15633,  DOI: 10.1021/jacs.9b07301
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    17
    Scalable and Template-Free Aqueous Synthesis of Zirconium-Based Metal-Organic Framework Coating on Textile Fiber
    Ma, Kaikai; Islamoglu, Timur; Chen, Zhijie; Li, Peng; Wasson, Megan C.; Chen, Yongwei; Wang, Yuanfeng; Peterson, Gregory W.; Xin, John H.; Farha, Omar K.
    Journal of the American Chemical Society (2019), 141 (39), 15626-15633CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Organophosphonate-based nerve agents, such as VX, Sarin (GB), and Soman (GD), are among the most toxic chems. to humankind. Recently, we have shown that Zr-based metal-org. frameworks (Zr-MOFs) can effectively catalyze the hydrolysis of these toxic chems. for diminishing their toxicity. On the other hand, utilizing these materials in powder form is not practical, and developing scalable and economical processes for integrating these materials onto fibers is crucial for protective gear. Herein, we report a scalable, template-free, and aq. soln.-based synthesis strategy for the prodn. of Zr-MOF-coated textiles. Among all MOF/fiber composites reported to date, the MOF-808/polyester fibers exhibit the highest rates of nerve agent hydrolysis. Moreover, such highly porous fiber composites display significantly higher protection time compared to that of its parent fabric for a mustard gas simulant, 2-chloroethyl Et sulfide (CEES). A decreased diffusion rate of toxic chems. through the MOF layer can provide time needed for the destruction of the harmful species.
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  18. 18
    Cao, R.; Chen, Z.; Chen, Y.; Idrees, K. B.; Hanna, S. L.; Wang, X.; Goetjen, T. A.; Sun, Q.; Islamoglu, T.; Farha, O. K. Benign Integration of a Zn-Azolate Metal–Organic Framework onto Textile Fiber for Ammonia Capture. ACS Appl. Mater. Interfaces 2020, 12, 47747– 47753,  DOI: 10.1021/acsami.0c14316
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    18
    Benign Integration of a Zn-Azolate Metal-Organic Framework onto Textile Fiber for Ammonia Capture
    Cao, Ran; Chen, Zhijie; Chen, Yongwei; Idrees, Karam B.; Hanna, Sylvia L.; Wang, Xingjie; Goetjen, Timothy A.; Sun, Qijun; Islamoglu, Timur; Farha, Omar K.
    ACS Applied Materials & Interfaces (2020), 12 (42), 47747-47753CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Ammonia (NH3) exposure has a serious impact on human health because of its toxic and corrosive nature. Therefore, efficient personal protective equipment (PPE) such as masks is necessary to eliminate and mitigate NH3 exposure risks. Because economically and environmentally viable conditions are of interest for large-scale manuf. of PPE, we herein report a benign procedure to synthesize a Zn-azolate metal-org. framework (MOF), MFU-4, for NH3 capture. The surface area and morphol. of MFU-4 obtained in alc. solvents at room temp. is consistent with that of traditionally synthesized MFU-4 in N,N-dimethylformamide at 140 °C. In addn. to its large NH3 uptake capacity at 1 bar (17.7 mmol/g), MFU-4 shows outstanding performance in capturing NH3 at low concn. (10.8 mmol/g at 0.05 bar). Furthermore, the mild synthetic conditions implemented make it facile to immobilize MFU-4 onto cotton textile fiber. Enhanced NH3 capture ability of the MFU-4/fiber composite was also attributed to the well-exposed MOF particles. The benign synthetic MFU-4 procedure, high NH3 uptake, and easy integration onto fiber pave the way toward implementation of similar materials in PPE.
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  19. 19
    Ma, K.; Wang, Y.; Chen, Z.; Islamoglu, T.; Lai, C.; Wang, X.; Fei, B.; Farha, O. K.; Xin, J. H. Facile and Scalable Coating of Metal–Organic Frameworks on Fibrous Substrates by a Coordination Replication Method at Room Temperature. ACS Appl. Mater. Interfaces 2019, 11, 22714– 22721,  DOI: 10.1021/acsami.9b04780
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    19
    Facile and Scalable Coating of Metal-Organic Frameworks on Fibrous Substrates by a Coordination Replication Method at Room Temperature
    Ma, Kaikai; Wang, Yuanfeng; Chen, Zhijie; Islamoglu, Timur; Lai, Chuilin; Wang, Xiaowen; Fei, Bin; Farha, Omar K.; Xin, John H.
    ACS Applied Materials & Interfaces (2019), 11 (25), 22714-22721CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Coating of metal-org. frameworks (MOFs) on flexible substrates is a crucial technol. for applications such as purifn./sepn., sensing, and catalysis. In this work, a facile coordination replication strategy was developed to coat various MOFs onto flexible fibrous materials where a dense layer of an insol. precursor template, such as a layered hydroxide salt, was first deposited onto a fiber substrate via a mild interfacial reaction and then rapidly transformed into a MOF coating in a ligand soln. at room temp. Spatiotemporal harmonization of solid precursor dissoln. and MOF crystn. enabled precise replication of the precursor layer morphol. to form a continuous MOF coating composed of intergrown crystals. The resulting flexible, highly robust, and processable fibrous MOF/textile composites demonstrated tremendous potential for industrially relevant applications such as continuous removal of the organosulfur compd. dibenzothiophene from simulated gasoline and ammonia capture. This rapid, versatile, eco-friendly, and scalable MOF coating process at room temp. gives rise to new possibilities for prepg. MOF-coated functional materials.
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  20. 20
    Rubin, H. N.; Neufeld, B. H.; Reynolds, M. M. Surface-Anchored Metal-Organic Framework-Cotton Material for Tunable Antibacterial Copper Delivery. ACS Appl. Mater. Interfaces 2018, 10, 15189– 15199,  DOI: 10.1021/acsami.7b19455
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    20
    Surface-anchored metal-organic framework-cotton material for tunable antibacterial copper delivery
    Rubin, Heather N.; Neufeld, Bella H.; Reynolds, Melissa M.
    ACS Applied Materials & Interfaces (2018), 10 (17), 15189-15199CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    In the present study, a new copper metal-org. framework (MOF)-cotton material was strategically fabricated to exploit its antibacterial properties for postsynthetic modification (PSM) to introduce a free amine to tune the physicochem. properties of the material. A modified methodol. for carboxymethylation of natural cotton was utilized to enhance the no. of nucleation sites for the MOF growth. Subsequently, MOF Cu3(NH2BTC)2 was synthesized into a homogenous surface-supported film via a layer-by-layer dip-coating process. The resultant materials contained uniformly distributed 1 μm × 1 μm octahedral MOF crystals around each carboxymethylated fiber. Importantly, the accessible free amine of the MOF ligand allowed for the PSM of the MOF-cotton surface with valeric anhydride, yielding 23.5 ± 2.2% modified. The Cu2+ ion-releasing performance of the materials was probed under biol. conditions per submersion in complex media at 37 °C. Indeed, PSM induces a change in the copper flux of the material over the first 6 h. The materials continue to slowly release Cu2+ ions beyond 24 h tested at a flux of 0.22 ± 0.003 μmol·cm-2·h-1 with the unmodified MOF-cotton and at 0.25 ± 0.004 μmol·cm-2·h-1 with the modified MOF-cotton. The antibacterial activity of the material was explored using Escherichia coli by testing the planktonic and attached bacteria under a variety of conditions. MOF-cotton materials elicit antibacterial effects, yielding a 4-log redn. or greater, after 24 h of exposure. Addnl., the MOF-cotton materials inhibit the attachment of bacteria, under both dry and wet conditions. A material of this type would be ideal for clothing, bandages, and other textile applications. As such, this work serves as a precedence toward developing uniform, tunable MOF-composite textile materials that can kill bacteria and prevent the attachment of bacteria to the surface.
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  21. 21
    Ma, K.; Idrees, K. B.; Son, F. A.; Maldonado, R.; Wasson, M. C.; Zhang, X.; Wang, X.; Shehayeb, E.; Merhi, A.; Kaafarani, B. R.; Islamoglu, T.; Xin, J. H.; Farha, O. K. Fiber Composites of Metal-Organic Frameworks. Chem. Mater. 2020, 32, 7120– 7140,  DOI: 10.1021/acs.chemmater.0c02379
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    21
    Fiber Composites of Metal-Organic Frameworks
    Ma, Kaikai; Idrees, Karam B.; Son, Florencia A.; Maldonado, Rodrigo; Wasson, Megan C.; Zhang, Xuan; Wang, Xingjie; Shehayeb, Elissa; Merhi, Areej; Kaafarani, Bilal R.; Islamoglu, Timur; Xin, John H.; Farha, Omar K.
    Chemistry of Materials (2020), 32 (17), 7120-7140CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    A review. The high chem. and structural diversity of metal-org. frameworks (MOFs), which are porous cryst. materials, has attracted significant academic and industrial interest. However, the poor processability of MOF powders limits their full potential in practical applications. Toward this end, MOF-based composite materials increase the framework robustness and subsequent utility. Among these hybrid materials, MOF composites prepd. on com. available textile fibers offer the high flexibility needed for important applications-such as heterogeneous catalysis, chem. sensing, pollutant removal, and drug release-while maintaining the functional properties of MOFs. The ability to further tailor these composites' shapes for incorporation into industrial equipment increases their potential in applications such as adsorption devices and protective gears. In this Review, we summarize recently reported MOF/fiber fabrication methods and applications. Our discussion on the advancements and remaining issues of these prodn. methods segues into several highlighted applications of MOF/fiber composites, esp. within adsorption devices and protective gears.
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    Liu, M.; Cai, N.; Chan, V.; Yu, F. Development and Applications of MOFs Derivative One-Dimensional Nanofibers via Electrospinning:A Mini-Review. Nanomaterials 2019, 9, 1306,  DOI: 10.3390/nano9091306
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    22
    Development and applications of MOFs derivative one-dimensional nanofibers via electrospinning: a mini-review
    Liu, Mingming; Cai, Ning; Chan, Vincent; Yu, Faquan
    Nanomaterials (2019), 9 (9), 1306CODEN: NANOKO; ISSN:2079-4991. (MDPI AG)
    Metal org. frameworks (MOFs) have been exploited for various applications in science and engineering due to the possibility of forming di erent mesoscopic frameworks and pore structures. To date, further development of MOFs for practical applications in areas such as energy storage and conversion have encountered tremendous challenge owing to the unitary porous structure (almost filled entirely with micropores) and conventional morphol. (e.g., sphere, polyhedron, and rod shape). More recently, one-dimensional (1D) MOFs/nanofibers composites emerged as a new mol. system with highly engineered novel structures for tailored applications. In this mini-review, the recent progress in the development of MOFs-based 1D nanofibers via electrospinning will be elaborated. In particular, the promising applications and underlying mol. mechanism of electrospun MOF-derived carbon nanofibers are primarily focused and analyzed here. This review is instrumental in providing certain guiding principles for the prepn. and structural anal. of MOFs/electrospun nanofibers (M-NFs) composites and electrospun MOF-derived nanomaterials.
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    Chang, Z.; Zeng, J. Immobilization Seeding Layers Using Precursor for Fabricating Core-Shell Polyimide/Cu-BTC Hierarchical Nanofibers with High Gas Separation and Adsorption of Methylene Blue from Aqueous Solution. Macromol. Chem. Phys. 2016, 217, 1007– 1013,  DOI: 10.1002/macp.201500327
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    23
    Immobilization Seeding Layers Using Precursor for Fabricating Core-Shell Polyimide/Cu-BTC Hierarchical Nanofibers with High Gas Separation and Adsorption of Methylene Blue from Aqueous Solution
    Chang, Zhenjun; Zeng, Jing
    Macromolecular Chemistry and Physics (2016), 217 (8), 1007-1013CODEN: MCHPES; ISSN:1022-1352. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Metal-org. frameworks (MOFs), also known as porous coordination polymers, are a class of cryst. porous materials consisting of metal ion nodes held together by multitopic org. ligands. Among MOFs, Cu-BTC is a well-studied benchmark MOF. In practical applications, supported porous and stable MOFs on the surface of nanofibers, which provide a high sp. surface area and prevent aggregation of the microstructure, may be very useful. This paper reports a facile strategy for the synthesis of core-shell polyimide/Cu-BTC hierarchical nanofibers by combining electrospinning, step-by-step seeding, and hydrothermal process. The Cu-BTC nanocrystals can be well immobilized onto the surface of polyimide nanofibers. The hierarchical nanofibers exhibited high gas sepn. and adsorption of methylene blue from aq. soln.
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    Ostermann, R.; Cravillon, J.; Weidmann, C.; Wiebcke, M.; Smarsly, B. M. Metal-organic framework nanofibers viaelectrospinning. Chem. Commun. 2011, 47, 442– 444,  DOI: 10.1039/C0CC02271C
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    Metal-organic framework nanofibers via electrospinning
    Ostermann, Rainer; Cravillon, Janosch; Weidmann, Christoph; Wiebcke, Michael; Smarsly, Bernd M.
    Chemical Communications (Cambridge, United Kingdom) (2011), 47 (1), 442-444CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    A hierarchical system of highly porous nanofibers was prepd. by electrospinning MOF (metal-org. framework) nanoparticles with suitable carrier polymers. Nitrogen adsorption proved the MOF nanoparticles to be fully accessible inside the polymeric fibers.
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    Wu, Y.; Li, F.; Liu, H.; Zhu, W.; Teng, M.; Jiang, Y.; Li, W.; Xu, D.; He, D.; Hannam, P.; Li, G. Electrospun Fibrous Mats as Skeletons to Produce Free-Standing MOF Membranes. J. Mater. Chem. 2012, 22, 16971– 16978,  DOI: 10.1039/c2jm32570e
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    Electrospun fibrous mats as skeletons to produce free-standing MOF membranes
    Wu, Yi-nan; Li, Fengting; Liu, Huimin; Zhu, Wei; Teng, Minmin; Jiang, Yin; Li, Weina; Xu, Dan; He, Dehua; Hannam, Phillip; Li, Guangtao
    Journal of Materials Chemistry (2012), 22 (33), 16971-16978CODEN: JMACEP; ISSN:0959-9428. (Royal Society of Chemistry)
    Nanofibrous mats produced by electrospinning are ideal porous substrates for developing chem. systems due to their high sp. surface area, large porosity, and enormous structural and chem. tunability. The authors report the fabrication of free-standing MOF membranes using electrospun nanofibrous mats as skeletons, and demonstrate the great potential of such nonwoven fiber mats as a new type of porous support in MOF research field. Direct deposition and seeded secondary growth approaches could be used to produce MOF materials within different nanofibrous skeletons, indicating that the developed method of generating MOF membranes has a remarkable flexibility. The characterizations performed show that the resulting products combine the unique properties of both electrospun nanofibers and MOFs, and can be regarded as a new class of hierarchically nanostructured functional materials.
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    Rose, M.; Böhringer, B.; Jolly, M.; Fischer, R.; Kaskel, S. MOF Processing by Electrospinning for Functional Textiles. Adv. Eng. Mater. 2011, 13, 356– 360,  DOI: 10.1002/adem.201000246
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    MOF Processing by Electrospinning for Functional Textiles
    Rose, Marcus; Boehringer, Bertram; Jolly, Marc; Fischer, Roland; Kaskel, Stefan
    Advanced Engineering Materials (2011), 13 (4), 356-360CODEN: AENMFY; ISSN:1438-1656. (Wiley-VCH Verlag GmbH & Co. KGaA)
    We present the use of electrospinning for the immobilization of metal-org. framework particles in fibers and the prodn. of homogeneous textile-like layers. HKUST-1 and MIL-100(Fe) are stable during the electrospinning process from a suspension. Excellent high loadings of up to 80 wt% of MOF in the polymeric fibers are achieved. The total accessibility of the inner surface is guaranteed for adsorption processes due to very small fiber diams. in comparison to the particle size. This method provides the know-how for the immobilization of MOFs on flexible, textile-like substrates. Applications such as gas purifn. or removal of toxic compds. in protective clothing are conceivable.
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    Ren, J.; Musyoka, N. M.; Annamalai, P.; Langmi, H. W.; North, B. C.; Mathe, M. Electrospun MOF Nanofibers as Hydrogen Storage Media. Int. J. Hydrogen Energy 2015, 40, 9382– 9387,  DOI: 10.1016/j.ijhydene.2015.05.088
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    Electrospun MOF nanofibers as hydrogen storage media
    Ren, Jianwei; Musyoka, Nicholas M.; Annamalai, Perushini; Langmi, Henrietta W.; North, Brian C.; Mathe, Mkhulu
    International Journal of Hydrogen Energy (2015), 40 (30), 9382-9387CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)
    In this study, Zr-MOF and Cr-MOF were chosen as representatives of the developed MOFs in our lab. and were incorporated into electrospun nanofibers. The obtained MOF nanofibers composites were evaluated as hydrogen storage media. The results showed that the incorporation of vacuum degassing was able to create visible porosity in and/or on the PAN nanofibers and the MOF nanocrystals inside the polymeric nanofibers were fully accessible by N2 and H2 gases. With 20 wt.% loading of MOF nanocrystals, the composites were able to achieve over 50% of the H2 uptake capacity of individual MOF nanocrystals. In addn., the composites also showed good thermal stabilities.
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    Armstrong, M. R.; Arredondo, K. Y. Y.; Liu, C.-Y.; Stevens, J. E.; Mayhob, A.; Shan, B.; Senthilnathan, S.; Balzer, C. J.; Mu, B. UiO-66 MOF and Poly(Vinyl Cinnamate) Nanofiber Composite Membranes Synthesized by a Facile Three-Stage Process. Ind. Eng. Chem. Res. 2015, 54, 12386– 12392,  DOI: 10.1021/acs.iecr.5b03334
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    28
    UiO-66 MOF and Poly(vinyl cinnamate) Nanofiber Composite Membranes Synthesized by a Facile Three-Stage Process
    Armstrong, Mitchell R.; Arredondo, Korinthia Y. Yuriar; Liu, Chao-Yuan; Stevens, Joshua E.; Mayhob, Alexandre; Shan, Bohan; Senthilnathan, Sethuraman; Balzer, Christopher J.; Mu, Bin
    Industrial & Engineering Chemistry Research (2015), 54 (49), 12386-12392CODEN: IECRED; ISSN:0888-5885. (American Chemical Society)
    Electrospun poly(vinyl cinnamate) (PVCi) nanofibers were cross-linked for varying times to study the impact it has on fiber stability at elevated temps. and in DMF solns. UiO-66 impregnated PVCi was cross-linked, and secondary growth of UiO-66 crystals was performed. The impact of temp. and no. of growths was analyzed through powder X-ray diffraction, SEM, and Fourier transform IR spectroscopy. A membrane that underwent three growth cycles at 100 °C was further characterized for potential uses as a gas membrane through inert gas permeation studies and nitrogen porosimetry.
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    Liu, C.; Wang, J.; Li, J.; Liu, J.; Wang, C.; Sun, X.; Shen, J.; Han, W.; Wang, L. Electrospun ZIF-Based Hierarchical Carbon Fiber as an Efficient Electrocatalyst for the Oxygen Reduction Reaction. J. Mater. Chem. A 2017, 5, 1211– 1220,  DOI: 10.1039/C6TA09193H
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    Electrospun ZIF-based hierarchical carbon fiber as an efficient electrocatalyst for the oxygen reduction reaction
    Liu, Chao; Wang, Jing; Li, Jiansheng; Liu, Jizi; Wang, Chaohai; Sun, Xiuyun; Shen, Jinyou; Han, Weiqing; Wang, Lianjun
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2017), 5 (3), 1211-1220CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    The inherently granular nature of nitrogen and metal co-doped carbons derived from metal-org. frameworks (MOFs) hinders their practical application in the oxygen redn. reaction (ORR). In this work, we have developed a novel N, Co-contg. MOF-based hierarchical carbon fiber as an ORR catalyst. The products (ZCP-CFs) are synthesized by the incorporation of a Zn, Co-zeolitic imidazolate framework (Zn, Co-ZIF) with electrospun Co2+/poly(acrylonitrile) fiber, followed by carbonization and acid leaching treatment. The effects of the pyrolysis temp. and precursor on the ORR performance of the final samples were systematically studied. The results indicated that the material prepd. at 900 °C (ZCP-CFs-9) was identified as the best ORR catalyst in the series of samples. Further comparison among samples obtained from different catalyst precursors also demonstrated the superior performance of ZCP-CFs-9, with its more pos. half-wave potential (-0.135 V vs. Ag/AgCl), higher diffusion-limited and kinetic-limiting currents and higher selectivity (no. of electrons transferred n = ∼3.97) than Zn, Co-ZIF derived carbon and Zn, Co-ZIF free carbon fiber. Notably, the ZCP-CFs-9 catalyst exhibited very close activity to a com. Pt/C catalyst with better durability and stronger tolerance to methanol crossover. The remarkable ORR performance may be ascribed to its unique structure, such as its large surface area and hierarchical porosity, the dispersed and protected Co nanoparticles and N functionalized carbon framework, as well as the abundant graphitic carbon and its 1D fibrous structure. Considering the diversity of MOFs and electrospinnable polymer precursors, this strategy may be further extended to other MOF-based carbon fibers for energy storage and conversion.
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  30. 30
    Yang, F.; Efome, J. E.; Rana, D.; Matsuura, T.; Lan, C. Metal–Organic Frameworks Supported on Nanofiber for Desalination by Direct Contact Membrane Distillation. ACS Appl. Mater. Interfaces 2018, 10, 11251– 11260,  DOI: 10.1021/acsami.8b01371
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    30
    Metal-Organic Frameworks Supported on Nanofiber for Desalination by Direct Contact Membrane Distillation
    Yang, Fan; Efome, Johnson E.; Rana, Dipak; Matsuura, Takeshi; Lan, Christopher
    ACS Applied Materials & Interfaces (2018), 10 (13), 11251-11260CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Among other applications, metal-org. frameworks (MOFs) are slowly gaining grounds as fillers for desalination composite membranes. In this study, superhydrophobic poly(vinylidene fluoride) nanofibrous membranes were fabricated with MOF (iron 1,3,5-benzenetricarboxylate) loading of up to 5 wt % via electrospinning on a nonwoven substrate. To improve the attachment of nanofibers onto the substrate, a substrate pretreatment method called "solvent basing" was employed. The iron content in the nanofiber, measured by energy-dispersive X-ray spectroscopy, increased proportionally with the increase of the MOF concn. in the spinning dope, indicating a uniform distribution of MOF in the nanofiber. The water contact angle increased up to 138.06 ± 2.18° upon the incorporation of 5 wt % MOF, and a liq. entry pressure of 82.73 kPa could be maintained, making the membrane useful for direct contact membrane distn. expts. The membrane was stable for the entire operating period of 5 h, exhibiting 2.87 kg/m2·h of water vapor flux and 99.99% NaCl (35 g/L) rejection when the feed and permeate temp. were 48 and 16 °C, resp. Immobilization of MOF on nanofibers with the enhanced attachment was proven by inductively coupled mass spectrometry anal., by which no Fe2+ could be found in the permeate to the detection limit of ppt.
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    Meilikhov, M.; Yusenko, K.; Schollmeyer, E.; Mayer, C.; Buschmann, H.-J.; Fischer, R. A. Stepwise Deposition of Metal Organic Frameworks on Flexible Synthetic Polymer Surfaces. Dalton Trans. 2011, 40, 4838– 4841,  DOI: 10.1039/c0dt01820a
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    Stepwise deposition of metal organic frameworks on flexible synthetic polymer surfaces
    Meilikhov, Mikhail; Yusenko, Kirill; Schollmeyer, Eckhardt; Mayer, Christian; Buschmann, Hans-Juergen; Fischer, Roland A.
    Dalton Transactions (2011), 40 (18), 4838-4841CODEN: DTARAF; ISSN:1477-9226. (Royal Society of Chemistry)
    Thin films of [Cu3(btc)2]n (btc = 1,3,5-benzenetricarboxylate) metal org. framework were deposited in a stepwise manner on surfaces of flexible org. polymers. The thickness of films can be precisely controlled. The deposition of the first cycles was monitored by UV-vis spectroscopy. The porosity was proven by the adsorption of pyrazine, which was monitored by FT-IR and thermogravimetric anal. The deposition of MOF thin films on flexible polymer surfaces might be a new path for the fabrication of functional materials for different applications, such as protection layers for working clothes and gas sepn. materials in the textile industry.
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    da Silva Pinto, M.; Sierra-Avila, C. A.; Hinestroza, J. P. In Situ Synthesis of a Cu-BTC Metal–Organic Framework (MOF 199) onto Cellulosic Fibrous Substrates: Cotton. Cellulose 2012, 19, 1771– 1779,  DOI: 10.1007/s10570-012-9752-y
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    32
    In situ synthesis of a Cu-BTC metal-organic framework (MOF 199) onto cellulosic fibrous substrates: cotton
    da Silva Pinto, Marcia; Sierra-Avila, Cesar Augusto; Hinestroza, Juan P.
    Cellulose (Dordrecht, Netherlands) (2012), 19 (5), 1771-1779CODEN: CELLE8; ISSN:0969-0239. (Springer)
    A mechanism for chem. attachment and growth of a Cu-BTC Metal-Org. Framework, also known as MOF-199 or HKUST-1, onto cellulosic substrates is reported. Four different exptl. procedures were attempted in order to elucidate the role of carboxylate groups on the anionic cellulose's surface. The order of addn. of Cu(OAc)2-copper acetate, BTH3, 1,3,5-benzenetricarboxylic acid and TEA-Triethylamine was found to be a crit. factor for the attachment and growth of the MOF-199 crystals onto anionic cellulose. The presence of MOF-199 crystals was probed using XRD and XPS spectra and a strong chem. interaction to the carboxymethylated cellulose fibers was confirmed by intense and vigorous washing of the specimens with water, DMF and methanol. Based on the recognized ability of MOF-199 to capture gases and toxic chems., combined with the availability of cellulose-based fibrous materials, the described procedure provides the basis for future fabrication of functionalized fibers and active filtration media.
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    Bechelany, M.; Drobek, M.; Vallicari, C.; Abou Chaaya, A.; Julbe, A.; Miele, P. Highly Crystalline MOF-Based Materials Grown on Electrospun Nanofibers. Nanoscale 2015, 7, 5794– 5802,  DOI: 10.1039/C4NR06640E
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    Highly crystalline MOF-based materials grown on electrospun nanofibers
    Bechelany, M.; Drobek, M.; Vallicari, C.; Abou Chaaya, A.; Julbe, A.; Miele, P.
    Nanoscale (2015), 7 (13), 5794-5802CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
    Supported Metal Org. Frameworks (MOFs) with a high sp. surface area are of great interest for applications in gas storage, sepn., sensing, and catalysis. In the present work we report the synthesis of a novel composite architecture of MOF materials supported on a flexible mat of electrospun nanofibers. The system, based on three-dimensional interwoven nanofibers, was designed by using a low-cost and scalable multistep synthesis protocol involving a combination of electrospinning and low-temp. at. layer deposition of oxide materials, and their subsequent solvothermal conversion under either conventional or microwave-assisted heating. This highly versatile approach allows the prodn. of different types of supported MOF crystals with controlled sizes, morphol., orientation and high accessibility.
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    Liu, C.; Wu, Y.-N.; Morlay, C.; Gu, Y.; Gebremariam, B.; Yuan, X.; Li, F. General Deposition of Metal–Organic Frameworks on Highly Adaptive Organic–Inorganic Hybrid Electrospun Fibrous Substrates. ACS Appl. Mater. Interfaces 2016, 8, 2552– 2561,  DOI: 10.1021/acsami.5b10078
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    General Deposition of Metal-Organic Frameworks on Highly Adaptive Organic-Inorganic Hybrid Electrospun Fibrous Substrates
    Liu, Chang; Wu, Yi-nan; Morlay, Catherine; Gu, Yifan; Gebremariam, Binyam; Yuan, Xiao; Li, Fengting
    ACS Applied Materials & Interfaces (2016), 8 (4), 2552-2561CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Org.-inorg. hybrid electrospun fibrous mats have been used as support materials to study the deposition of various MOF particles. HKUST-1 and MIL-53(Al) were produced through solvothermal method, while ZIF-8 and MIL-88B(Fe) were prepd. using microwave-induced heating method. The synthesis procedure for both methods were simple and effective because the hybrid nanofibrous mats showed considerable affinity to MOF particles and could be used without addnl. modifications. The obtained MOF composites exhibited effective incorporation between MOF particles and the porous substrates. MIL-53(Al) composite was applied as fibrous sorbent and showed enhanced adsorption capacity and removal rate, as well as easier operation, compared with the powd. sample. Moreover, MIL-53(Al) composite was easier to be regenerated compared with powder form.
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    Abbasi, A. R.; Akhbari, K.; Morsali, A. Dense Coating of Surface Mounted CuBTC Metal–Organic Framework Nanostructures on Silk Fibers, Prepared by Layer-by-Layer Method under Ultrasound Irradiation with Antibacterial Activity. Ultrason. Sonochem. 2012, 19, 846– 852,  DOI: 10.1016/j.ultsonch.2011.11.016
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    Dense coating of surface mounted CuBTC Metal-Organic Framework nanostructures on silk fibers, prepared by layer-by-layer method under ultrasound irradiation with antibacterial activity
    Abbasi, Amir Reza; Akhbari, Kamran; Morsali, Ali
    Ultrasonics Sonochemistry (2012), 19 (4), 846-852CODEN: ULSOER; ISSN:1350-4177. (Elsevier B.V.)
    The growth of Cu3(BTC)2 (BTC = 1,3,5-benzenetricarboxylate), also known as CuBTC and HKUST-1, Metal-Org. Framework (MOF) nanostructures on silk fibers were achieved by layer-by-layer technique in alternating bath of Cu(OAc)2·2H2O and H3BTC solns. under ultrasound irradn. The effect of pH, reaction time, ultrasound irradn. and sequential dipping steps in growth of the CuBTC Metal-Org. Framework nanostructures has been studied. These systems depicted a decrease in the size accompanying a decrease in the sequential dipping steps. In addn., dense coating of silk fibers with CuBTC MOF results in decrease the emission intensity of silk fibers. The silk fibers contg. CuBTC Metal-Org. Framework exhibited high antibacterial activity against Escherichia coli and Staphylococcus aureus. The samples were characterized with powder X-ray diffraction (XRD), Fourier transform IR spectroscopy (FTIR) spectra and SEM. XRD analyses indicated that the prepd. CuBTC MOF nanostructures on silk fibers were cryst.
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    Horcajada, P.; Serre, C.; Vallet-Regí, M.; Sebban, M.; Taulelle, F.; Férey, G. Metal–Organic Frameworks as Efficient Materials for Drug Delivery. Angew. Chem., Int. Ed. 2006, 45, 5974– 5978,  DOI: 10.1002/anie.200601878
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    Metal-organic frameworks as efficient materials for drug delivery
    Horcajada, Patricia; Serre, Christian; Vallet-Regi, Maria; Sebban, Muriel; Taulelle, Francis; Ferey, Gerard
    Angewandte Chemie, International Edition (2006), 45 (36), 5974-5978CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The metal carboxylates MIL-100 and MIL-101 (MIL = Materials of Institut Lavoisier) act as porous matrixes for drug-delivery systems using ibuprofen as a model substrate. Very large amts. of the drug could be incorporated, up to an unprecedented capacity of 1.4 g of drug per g of porous solid for MIL-101, and the total release of ibuprofen was achieved under physiol. conditions in 3 (MIL-100) and 6 days (MIL-101).
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    Quirós, J.; Boltes, K.; Aguado, S.; de Villoria, R. G.; Vilatela, J. J.; Rosal, R. Antimicrobial Metal–Organic Frameworks Incorporated into Electrospun Fibers. Chem. Eng. J. 2015, 262, 189– 197,  DOI: 10.1016/j.cej.2014.09.104
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    Antimicrobial metal-organic frameworks incorporated into electrospun fibers
    Quiros, Jennifer; Boltes, Karina; Aguado, Sonia; de Villoria, Roberto Guzman; Vilatela, Juan Jose; Rosal, Roberto
    Chemical Engineering Journal (Amsterdam, Netherlands) (2015), 262 (), 189-197CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
    The objective of this paper is to present a new class of polylactic acid (PLA) fibers contg. cobalt-based metal org. frameworks (MOF). The material used was Co-SIM-1, a cobalt-based substituted imidazolate. Composite mats were prepd. by electrospinning PLA with a suspension of polyvinylpyrrolidone-stabilized Co-SIM-1. MOF particles formed aggregate of a small no. of primary particles that, after electrospun, became completely embedded inside polymeric fibers. The dispersion of particles was better for lower loadings, for which the relative amt. of metal released to culture media was also higher. The antimicrobial activity of composite mats was assessed using SEM images, fluorescence microscopy, direct plate reading of fluorescent stains and plate count of colony forming units among other. The microorganisms used in this study were Pseudomonas putida and Staphylococcus aureus. Fluorescence techniques allowed recording viable and damaged cells directly on mat surface and in the culture media embedding the fibers. The results showed higher sensitivity of S. aureus to cobalt-contg. fibers, with a redn. in colony forming units of up to 60% with respect to PLA mats. The results also showed the presence of viable but non-culturable microorganisms, which fail to form colonies but yield a pos. signal to viable cell staining. Cobalt-based MOF included in electrospun mats provide antibacterial activity suitable to be used to prep. membranes for various biomedical applications.
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    Gao, M.; Zeng, L.; Nie, J.; Ma, G. Polymer–Metal–Organic Framework Core–Shell Framework Nanofibers via Electrospinning and Their Gas Adsorption Activities. RSC Adv. 2016, 6, 7078– 7085,  DOI: 10.1039/C5RA23147G
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    Polymer-metal-organic framework core-shell framework nanofibers via electrospinning and their gas adsorption activities
    Gao, Ming; Zeng, Lingwang; Nie, Jun; Ma, Guiping
    RSC Advances (2016), 6 (9), 7078-7085CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
    In this study, we have fabricated of Polyacrylonitrile/Zeoliticimidazolate frameworks (PAN@ZIF-8) core-shell nanofibers by combining electrospinning techniques and the MOF synthesis method. In the first step, 2MI ligand was dispersed on PAN by using electrospinning, and then 2MI was made to coordinate Zn2+ ions derived from a zinc acetate soln. In the second step, the nanofiber mats were immersed in a ZIF-8 seed soln., and continuous and compact ZIF-8 was formed on the PAN surface by a second round of crystal growth. Analyses of XPS results and of SEM and TEM images revealed the core-shell structure of PAN@ZIF-8 nanofibers, and showed them to have a uniform nanoshell but a variety of crystal diams. In addn., the core-shell PAN@ZIF-8 nanofibers were found to display unique properties such as a stable and flexible structure and an excellent gas adsorption capability. Our findings suggest that the core-shell PAN@ZIF-8 nanofiber mats may form a good filter material because of their gas absorption properties and because of the structural flexibility and stability of ZIF-8.
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    Zhang, C.-L.; Lu, B.-R.; Cao, F.-H.; Wu, Z.-Y.; Zhang, W.; Cong, H.-P.; Yu, S.-H. Electrospun Metal-Organic Framework Nanoparticle Fibers and Their Derived Electrocatalysts for Oxygen Reduction Reaction. Nano Energy 2019, 55, 226– 233,  DOI: 10.1016/j.nanoen.2018.10.029
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    Electrospun metal-organic framework nanoparticle fibers and their derived electrocatalysts for oxygen reduction reaction
    Zhang, Chuan-Ling; Lu, Bing-Rong; Cao, Fu-Hu; Wu, Zhen-Yu; Zhang, Wang; Cong, Huai-Ping; Yu, Shu-Hong
    Nano Energy (2019), 55 (), 226-233CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
    The rational design of assembled metal-org. frameworks (MOFs) derived carbon materials with rapid mass transport properties and stable porous structure is highly desirable yet a great challenge to date. In this work, MOFs-derived Co/N-doped porous carbon fibers with high electrochem. performance can be prepd. simply by carbonizing MOFs nanofibers, which were fabricated by the electrospinning-assisted assembly of bimetallic zeolitic imidazolate framework nanoparticles (BMZIFs) based on ZIF-8 and ZIF-67. The effects of assembly and Zn/Co ratios on the oxygen redn. reaction (ORR) performances of the electrospun fibers derivs. were systematically studied. As expected, compared to the non-electrospun samples, such doped porous carbon nanofibers exhibited excellent electrocatalytic performances without any etching or other activating processes, and the sample with the molar ratio of Zn: Co= 5:1 even showed comparable ORR performance with the com. Pt/C catalyst under the same conditions. The high catalytic performances root in the dense assembly of MOFs within the electrospun fibers, which was beneficial to endow the derivs. with the high surface area as well as uniform N and Co doping. Besides, the one-dimensional porous structure significantly promoted the mass transfer and exposure of active sites.
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    McCarthy, D. L.; Liu, J.; Dwyer, D. B.; Troiano, J. L.; Boyer, S. M.; DeCoste, J. B.; Bernier, W. E.; Jones, W. E., Jr. Electrospun Metal–Organic Framework Polymer Composites for the Catalytic Degradation of Methyl Paraoxon. New J. Chem. 2017, 41, 8748– 8753,  DOI: 10.1039/C7NJ00525C
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    Electrospun metal-organic framework polymer composites for the catalytic degradation of methyl paraoxon
    McCarthy, Danielle L.; Liu, Jian; Dwyer, Derek B.; Troiano, Jennifer L.; Boyer, Steven M.; DeCoste, Jared B.; Bernier, William E.; Jones, Jr, Wayne E.
    New Journal of Chemistry (2017), 41 (17), 8748-8753CODEN: NJCHE5; ISSN:1144-0546. (Royal Society of Chemistry)
    Current world events involving chem. warfare agents have resulted in the need for developing a novel engineered material for the decompn. of the nerve agents contg. toxic P-F or P-C≡N bond as seen in G-agents and P-S bond as seen in VX. Engineered composites consisting of electrospun PMMA/Ti(OH)4/UiO-66 were fabricated and employed in the degrdn. of Me paraoxon, a chem. warfare agent simulant. UiO-66 and other Zr based metal-org. frameworks have previously demonstrated their ability to catalytically hydrolyze the phosphonate ester bond. In this study, the PMMA/Ti(OH)4/UiO-66 composite has been found to decrease the half-life of the simulant Me paraoxon to only 29 min with only a fraction of the MOF material, compared to 45 min for pure UiO-66. We conclude that the dispersion of UiO-66 particles on the engineered fibers allow for improved diffusion of the analyte into the pores. This is turn gives promise to other engineered forms of MOFs for improving the catalytic degrdn. of organophosphates.
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    Chui, S. S.-Y.; Lo, S. M.-F.; Charmant, J. P. H.; Orpen, G. A.; Williams, I. D. A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]N. Science 1999, 283, 1148– 1150,  DOI: 10.1126/science.283.5405.1148
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    A chemically functionalizable nanoporous material [Cu3(TMA)2(H2O)3]n
    Chui, Stephen S.-Y.; Lo, Samuel M.-F.; Charmant, Jonathan P. H.; Orpen, A. Guy; Williams, Ian D.
    Science (Washington, D. C.) (1999), 283 (5405), 1148-1150CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
    Although zeolites and related materials combine nanoporosity with high thermal stability, they are difficult to modify or derivatize in a systematic way. A highly porous metal coordination polymer [Cu3(TMA)2(H2O)3]n (TMA is benzene-1,3,5-tricarboxylate) was formed in 80% yield. It has interconnected [Cu2(O2CR)4] units (R is an arom. ring), which create a three-dimensional system of channels with a pore size of 1 nm and an accessible porosity of ∼40% in the solid. Unlike zeolites, the channel linings can be chem. functionalized; for example, the aqua ligands can be replaced by pyridines. TGA and high-temp. single-crystal diffractometry indicate that the framework is stable up to 240°.
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    Park, K. S.; Ni, Z.; Cote, A. P.; Choi, J. Y.; Huang, R.; Uribe-Romo, F. J.; Chae, H. K.; O’Keeffe, M.; Yaghi, O. M. Exceptional Chemical and Thermal Stability of Zeolitic Imidazolate Frameworks. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 10186– 10191,  DOI: 10.1073/pnas.0602439103
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    Exceptional chemical and thermal stability of zeolitic imidazolate frameworks
    Park, Kyo Sung; Ni, Zheng; Cote, Adrien P.; Choi, Jae Yong; Huang, Rudan; Uribe-Romo, Fernando J.; Chae, Hee K.; O'Keeffe, Michael; Yaghi, Omar M.
    Proceedings of the National Academy of Sciences of the United States of America (2006), 103 (27), 10186-10191CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
    Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) were synthesized as crystals by copolymn. of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, resp. One example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chem. stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m2/g), high thermal stability (up to 550°), and remarkable chem. resistance to boiling alk. H2O and org. solvents.
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    Huang, X.-C.; Lin, Y.-Y.; Zhang, J.-P.; Chen, X.-M. Ligand-Directed Strategy for Zeolite-Type Metal–Organic Frameworks: Zinc(II) Imidazolates with Unusual Zeolitic Topologies. Angew. Chem., Int. Ed. 2006, 45, 1557– 1559,  DOI: 10.1002/anie.200503778
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    Ligand-directed strategy for zeolite-type metal-organic frameworks: zinc(II) imidazolates with unusual zeolitic topologies
    Huang, Xiao-Chun; Lin, Yan-Yong; Zhang, Jie-Peng; Chen, Xiao-Ming
    Angewandte Chemie, International Edition (2006), 45 (10), 1557-1559CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Thermally robust porous metal-org. frameworks (MOFs) with zeolitic topologies were constructed by means of a ligand-directed strategy involving mol. tailoring of simple bridging imidazolates with coordinatively unimportant substituents. This led to the isolation of three new MOFs having unusually high symmetries, intriguing topologies such as the supercage shown in the picture, and high thermal stability. Crystal structures of the metal-org. framework compds. are described.
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    Stock, N.; Biswas, S. Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites. Chem. Rev. 2011, 112, 933– 969,  DOI: 10.1021/cr200304e
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    Lee, Y.-R.; Kim, J.; Ahn, W.-S. Synthesis of Metal-Organic Frameworks: A Mini Review. Korean J. Chem. Eng. 2013, 30, 1667– 1680,  DOI: 10.1007/s11814-013-0140-6
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    Synthesis of metal-organic frameworks: A mini review
    Lee, Yu-Ri; Kim, Jun; Ahn, Wha-Seung
    Korean Journal of Chemical Engineering (2013), 30 (9), 1667-1680CODEN: KJCHE6; ISSN:0256-1115. (Springer)
    A review. Metal org. frameworks (MOFs) are porous cryst. materials of one-, two-, or three-dimensional networks constructed from metal ions/clusters and multidentate org. linkers via coordination bonding, which are emerging as an important group of materials for energy storage, CO2 adsorption, alkane/alkene sepn., and catalysis. To introduce newcomers in chem. engineering discipline to the rapidly expanding MOF research works, this review presents a brief introduction to the currently available MOFs synthesis methods. Starting from the conventional solvothermal/hydrothermal synthesis, microwave-assisted, sonochem., electrochem., mechanochem., ionothermal, drygel conversion, and microfluidic synthesis methods will be presented. Examples will be limited to those representative MOF structures that can be synthesized using common org. ligands of 1,4-benzenedicarboxylic acid (and its functionalized forms) and 1,3,5-benzenetricarboxylic acid, in conjunction with metal nodes of Zn2+, Cu2+, Cr3+, Al3+, Fe3+ and Zr4+. Synthesis of widely-investigated zeolitic imidazolate framework (ZIF) structure, ZIF-8 is also included.
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    Wendorff, J. H.; Agarwal, S.; Greiner, A. Electrospinning: Materials, Processing, and Applications; John Wiley & Sons, Incorporated: Weinheim, 2012.
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    Shahmiri, M.; Ibrahim, N. A.; Shayesteh, F.; Asim, N.; Motallebi, N. Preparation of PVP-Coated Copper Oxide Nanosheets as Antibacterial and Antifungal Agents. J. Mater. Res. 2013, 28, 3109– 3118,  DOI: 10.1557/jmr.2013.316
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    Preparation of PVP-coated copper oxide nanosheets as antibacterial and antifungal agents
    Shahmiri, Mahdi; Ibrahim, Nor Azowa; Shayesteh, Fatemeh; Asim, Nilofar; Motallebi, Nabi
    Journal of Materials Research (2013), 28 (22), 3109-3118CODEN: JMREEE; ISSN:2044-5326. (Cambridge University Press)
    Copper oxide (CuO) nanosheets synthesized in polyvinylpyrrolidone (PVP) were characterized with respect to antimicrobial activity by quick pptn. method. Different sizes and shapes of CuO nanosheets were obtained by simple variations of PVP concns. The x-ray diffraction results revealed the formation of pure-phase CuO with monoclinic structure. Transmission electron microscopy anal. showed that the av. ratio of length to width of these nanosheets increased with increasing PVP concns. Due to the quantum size effect, CuO nanosheets exhibit a blue shift in the UV-visible spectra. Field emission SEM results showed that as the concn. of PVP increased, well-defined morphologies were formed on the surface of the products. Energy dispersive anal. of x-ray clearly confirmed the presence of Cu and O with an at. ratio of 1:1. Fourier transform IR spectroscopy results showed that C=O in PVP coordinated with CuO and formed a protective layer. The mechanism of the reaction was also discussed. CuO nanosheets in suspension showed activity against a range of bacterial pathogens and fungi with min. bactericidal concns. (MBCs) ranging from 100 to 5000 μg/mL. The extent of the inhibition zones and the MBCs was found to be size-dependent.
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  48. 48
    Diao, S.; Wang, Y.; Jin, H. Electronucleation Mechanism of Copper in Wastewater by Controlled Electrodeposition Analysis. RSC Adv. 2020, 10, 38683– 38694,  DOI: 10.1039/D0RA07380F
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    Electronucleation mechanism of copper in wastewater by controlled electrodeposition analysis
    Diao, Shuzhi; Wang, Yiyong; Jin, Hui
    RSC Advances (2020), 10 (63), 38683-38694CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
    In order to improve the efficiency of copper deposition in wastewater contg. the surfactant polyvinylpyrrolidone (PVP) and reveal the mechanism of copper crystals, a controlled electrodeposition process was developed using a low-cost stainless steel cathode and investigated using chronoamperometry (CA), electrochem. impedance spectroscopy (EIS) and IR spectroscopy (IR). The theor. anal. was verified by fitting them to exptl. curves and calcg. the kinetic parameters of the deposition process. The exptl. results showed that Cu(PVP)2 was formed by the reaction between the CO bond of PVP and Cu2++. When powd., redn. of Cu2++ in the Cu(PVP)2 structure was promoted, a pos.-charged PVP-coating layer was formed on the surface of the copper crystal nuclei to inhibit the growth of the copper powder. At a potential of -0.2 V, the electrodeposition crystn. curve of copper changed from progressive nucleation to instantaneous nucleation. The kinetic parameters of the deposition process were calcd. by fitting the exptl. curves to verify the correctness of the theor. anal. The EIS tests showed that removing the powder reduced the resistance of the org. solvent (PVP) film on the electrode surface and the charge transfer resistance during copper deposition. According to particle size anal., removing the powder could reduce the growth energy of copper powder on the electrode surface, increase the area of the active part on the electrode surface, increase the current efficiency of copper powder to 84.2%, and control dust. The size of copper powder reached up to around 900 nm.
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  49. 49
    Soltani, N.; Saion, E.; Erfani, M.; Rezaee, K.; Bahmanrokh, G.; Drummen, G. P. C.; Bahrami, A.; Hussein, M. Z. Influence of the Polyvinyl Pyrrolidone Concentration on Particle Size and Dispersion of ZnS Nanoparticles Synthesized by Microwave Irradiation. Int. J. Mol. Sci. 2012, 13, 12412– 12427,  DOI: 10.3390/ijms131012412
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    Influence of the polyvinylpyrrolidone concentration on particle size and dispersion of ZnS nanoparticles synthesized by microwave irradiation
    Soltani, Nayereh; Saion, Elias; Erfani, Maryam; Rezaee, Khadijeh; Bahmanrokh, Ghazaleh; Drummen, Gregor P. C.; Bahrami, Afarin; Hussein, Mohd. Zobi
    International Journal of Molecular Sciences (2012), 13 (), 12412-12427CODEN: IJMCFK; ISSN:1422-0067. (MDPI AG)
    ZnS semiconductor nanoparticles were prepd. in an aq. soln. of polyvinyl pyrrolidone via a simple microwave irradn. method. The effect of the polymer concn. and the type of sulfur source on the particle size and dispersion of the final ZnS nanoparticle product was carefully examd. Microwave heating generally occurs by two main mechanisms: dipolar polarization of water and ionic conduction of precursors. The introduction of the polymer affects the heating rate by restriction of the rotational motion of dipole mols. and immobilization of ions. The presence of the polymer strongly affects the nucleation and growth rates of the ZnS nanoparticles and therefore dets. the av. particle size and the dispersion. PVP adsorbed on the surface of the ZnS nanoparticles by interaction of the C-N and C=O with the nanoparticle's surface, thereby affording protection from agglomeration by steric hindrance. Generally, with increasing PVP concn., monodispersed colloidal solns. were obtained and at the optimal PVP concn. (5%), sufficiently small size and narrow size distributions were obtained from both Na2S and thioacetamide sulfur sources. Finally, the sulfur source directly influences the reaction mechanism and the final particle morphol., as well as the av. size.
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    Ameloot, R.; Gobechiya, E.; Uji-i, H.; Martens, J. A.; Hofkens, J.; Alaerts, L.; Sels, B. F.; De Vos, D. E. Direct Patterning of Oriented Metal-Organic Framework Crystals via Control over Crystallization Kinetics in Clear Precursor Solutions. Adv. Mater. 2010, 22, 2685– 2688,  DOI: 10.1002/adma.200903867
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    50
    Direct Patterning of Oriented Metal-Organic Framework Crystals via Control over Crystallization Kinetics in Clear Precursor Solutions
    Ameloot, Rob; Gobechiya, Elena; Uji-i, Hiroshi; Martens, Johan A.; Hofkens, Johan; Alaerts, Luc; Sels, Bert F.; De Vos, Dirk E.
    Advanced Materials (Weinheim, Germany) (2010), 22 (24), 2685-2688CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A concept of metal-org. framework (MOF) processing based on the use of stable precursor soln. of the MOF primary building blocks is proposed. Crystal nucleation, growth, and morphol. of Cu3(BTC)2 crystals and the effect of the solvent on these processes were studied (BTC = 1,3,5-benzenetricarboxylate). Cu3(BTC)2 crystals were grown from clear precursor soln. using patterned template.
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    Cravillon, J.; Münzer, S.; Lohmeier, S.-J.; Feldhoff, A.; Huber, K.; Wiebcke, M. Rapid Room-Temperature Synthesis and Characterization of Nanocrystals of a Prototypical Zeolitic Imidazolate Framework. Chem. Mater. 2009, 21, 1410– 1412,  DOI: 10.1021/cm900166h
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    Rapid Room-Temperature Synthesis and Characterization of Nanocrystals of a Prototypical Zeolitic Imidazolate Framework
    Cravillon, Janosch; Munzer, Simon; Lohmeier, Sven-Jare; Feldhoff, Armin; Huber, Klaus; Wiebcke, Michael
    Chemistry of Materials (2009), 21 (8), 1410-1412CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    Simply reacting Zn(NO3)2·6H2O with an excess of 2-methylimidazole in methanol at room temp. yields well-shaped nanocrystals of ZIF-8 with a narrow size distribution. The rapid growth has been monitored by time-resolved static light scattering. Nanoscale ZIF-8 powder is microporous and thermally stable up to ca. 200°.
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    Zhuang, J.-L.; Ceglarek, D.; Pethuraj, S.; Terfort, A. Rapid Room-Temperature Synthesis of Metal-Organic Framework HKUST-1 Crystals in Bulk and as Oriented and Patterned Thin Films. Adv. Funct. Mater. 2011, 21, 1442– 1447,  DOI: 10.1002/adfm.201002529
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    Rapid Room-Temperature Synthesis of Metal-Organic Framework HKUST-1 Crystals in Bulk and as Oriented and Patterned Thin Films
    Zhuang, Jin-Liang; Ceglarek, Doris; Pethuraj, Sangeetha; Terfort, Andreas
    Advanced Functional Materials (2011), 21 (8), 1442-1447CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Whereas the prepn. of defined metal-org. framework (MOF) materials via hydrothermal or diffusion methods typically requires hours to days, the simple pptn. route opens the access to the known HKUST-1 frameworks within minutes. Crucial for the formation of a well-defined, cryst. material is the choice of suitable pptg. solvents, with methanol and ethanol being the most favorable ones. This approach could be extended to the formation of dense, surface-mounted MOF films (so-called SURMOFs), in particular if the surfaces are decorated with suitable binding groups by formation of self-assembled monolayers (SAMs). By combination with micro-contact printing (μCP), patterned SURMOFs became accessible, in which the pptg. solvent is decisive on the formation of either spatially restricted films or single particles.
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    Wang, M.; Fang, D.; Wang, N.; Jiang, S.; Nie, J.; Yu, Q.; Ma, G. Preparation of PVDF/PVP Core–Shell Nanofibers Mats via Homogeneous Electrospinning. Polymer 2014, 55, 2188– 2196,  DOI: 10.1016/j.polymer.2014.02.035
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    Preparation of PVDF/PVP core-shell nanofibers mats via homogeneous electrospinning
    Wang, Meice; Fang, Dawei; Wang, Nannan; Jiang, Shan; Nie, Jun; Yu, Qiang; Ma, Guiping
    Polymer (2014), 55 (9), 2188-2196CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)
    The polyvinylpyrrolidone (PVP)/poly(vinylidene fluoride) (PVDF) core-shell nanofiber mats with superhydrophobic surface have been prepd. via electrospinning its homogeneous blending solns., and the formation of the core-shell structure was achieved by the thermal induced phase sepn. assisted with the low surface tension of PVDF. The electrospinnability of the blending solns. was also investigated by varying the blending ratio of the PVP and PVDF, and it enhanced with the increase of PVP content. SEM and TEM results showed that the fibers size was varied in the range of 100 nm-600 nm with smooth surface and core-shell structure. The compn. of the shell layer was detd. by the XPS anal., and further confirmed by water contact angle (WCA) testing. As the fraction of PVDF exceeding PVP in the electrospinning solns., the nanofiber mats showed superhydrophobic property with the WCA above 120°. It indicated that the PVDF was concd. in the shell layer of the fibers. X-Ray diffraction (XRD) and attenuated total reflection IR spectroscopy (ATR-IR) anal. indicated that the PVDF was aggregated with the β-phase crystallite as dominant crystallite. The nanofiber mats with the gas breathability and watertightness ability due to the porous structure and superhydrophobic would be potential applied in wound healing.
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    Niu, Q.; Zeng, L.; Mu, X.; Nie, J.; Ma, G. Preparation and Characterization of Core-Shell Nanofibers by Electrospinning Combined with in Situ UV Photopolymerization. J. Ind. Eng. Chem. 2016, 34, 337– 343,  DOI: 10.1016/j.jiec.2015.12.006
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    54
    Preparation and characterization of core-shell nanofibers by electrospinning combined with in situ UV photopolymerization
    Niu, Qijian; Zeng, Lingwang; Mu, Xueyan; Nie, Jun; Ma, Guiping
    Journal of Industrial and Engineering Chemistry (Amsterdam, Netherlands) (2016), 34 (), 337-343CODEN: JIECFI; ISSN:1226-086X. (Elsevier B.V.)
    The objective of this work is to demonstrate the feasibility of prepn. of core-shell nanofibers by electrospinning combined with in situ UV photopolymn. The thiol-ene monomer with Si atom and the initiator can migrate to the surface with the evapn. of the solvent during the process of electrospinning, which caused phase sepn. due to the great migration ability of small mol. and low surface energy. Then photo induced polymn. and crosslinking reaction took place simultaneously during the electrospinning process, which formed shell of the nanofibers. The morphol. and structure of electrospun nanofibers were investigated by SEM and TEM. The compn. of the shell layer was detd. by ATR-IR and XPS. Moreover, the nanofiber mats were tested by WCA test, and the hydrophobic ability of PVP nanofibers was improved because of the protection of the shell layer with Si atom. The most important thing is that the technol. which combined electrospinning with in situ photopolymn. provides a simple method for prepn. of core-shell nanofibers.
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    Niu, C.; Meng, J.; Wang, X.; Han, C.; Yan, M.; Zhao, K.; Xu, X.; Ren, W.; Zhao, Y.; Xu, L.; Zhang, Q.; Zhao, D.; Mai, L. General Synthesis of Complex Nanotubes by Gradient Electrospinning and Controlled Pyrolysis. Nat. Commun. 2015, 6, 7402,  DOI: 10.1038/ncomms8402
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    General synthesis of complex nanotubes by gradient electrospinning and controlled pyrolysis
    Niu Chaojiang; Meng Jiashen; Wang Xuanpeng; Han Chunhua; Yan Mengyu; Zhao Kangning; Xu Xiaoming; Ren Wenhao; Zhang Qingjie; Zhao Dongyuan; Mai Liqiang; Zhao Yunlong; Xu Lin
    Nature communications (2015), 6 (), 7402 ISSN:.
    Nanowires and nanotubes have been the focus of considerable efforts in energy storage and solar energy conversion because of their unique properties. However, owing to the limitations of synthetic methods, most inorganic nanotubes, especially for multi-element oxides and binary-metal oxides, have been rarely fabricated. Here we design a gradient electrospinning and controlled pyrolysis method to synthesize various controllable 1D nanostructures, including mesoporous nanotubes, pea-like nanotubes and continuous nanowires. The key point of this method is the gradient distribution of low-/middle-/high-molecular-weight poly(vinyl alcohol) during the electrospinning process. This simple technique is extended to various inorganic multi-element oxides, binary-metal oxides and single-metal oxides. Among them, Li3V2(PO4)3, Na0.7Fe0.7Mn0.3O2 and Co3O4 mesoporous nanotubes exhibit ultrastable electrochemical performance when used in lithium-ion batteries, sodium-ion batteries and supercapacitors, respectively. We believe that a wide range of new materials available from our composition gradient electrospinning and pyrolysis methodology may lead to further developments in research on 1D systems.
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    Liang, W.; Wied, P.; Carraro, F.; Sumby, C. J.; Nidetzky, B.; Tsung, C.-K.; Falcaro, P.; Doonan, C. J. Metal–Organic Framework-Based Enzyme Biocomposites. Chem. Rev. 2021, 121, 1077– 1129,  DOI: 10.1021/acs.chemrev.0c01029
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    Metal-Organic Framework-Based Enzyme Biocomposites
    Liang, Weibin; Wied, Peter; Carraro, Francesco; Sumby, Christopher J.; Nidetzky, Bernd; Tsung, Chia-Kuang; Falcaro, Paolo; Doonan, Christian J.
    Chemical Reviews (Washington, DC, United States) (2021), 121 (3), 1077-1129CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. Because of their efficiency, selectivity, and environmental sustainability, there are significant opportunities for enzymes in chem. synthesis and biotechnol. However, as the three-dimensional active structure of enzymes is predominantly maintained by weaker noncovalent interactions, thermal, pH, and chem. stressors can modify or eliminate activity. Metal-org. frameworks (MOFs), which are extended porous network materials assembled by a bottom-up building block approach from metal-based nodes and org. linkers, can be used to afford protection to enzymes. The self-assembled structures of MOFs can be used to encase an enzyme in a process called encapsulation when the MOF is synthesized in the presence of the biomol. Alternatively, enzymes can be infiltrated into mesoporous MOF structures or surface bound via covalent or noncovalent processes. Integration of MOF materials and enzymes in this way affords protection and allows the enzyme to maintain activity in challenge conditions (e.g., denaturing agents, elevated temp., non-native pH, and org. solvents). In addn. to forming simple enzyme/MOF biocomposites, other materials can be introduced to the composites to improve recovery or facilitate advanced applications in sensing and fuel cell technol. This review canvasses enzyme protection via encapsulation, pore infiltration, and surface adsorption and summarizes strategies to form multicomponent composites. Also, given that enzyme/MOF biocomposites straddle materials chem. and enzymol., this review provides an assessment of the characterization methodologies used for MOF-immobilized enzymes and identifies some key parameters to facilitate development of the field.
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    Huang, S.; Kou, X.; Shen, J.; Chen, G.; Ouyang, G. “Armor-Plating” Enzymes with Metal–Organic Frameworks (MOFs). Angew. Chem., Int. Ed. 2020, 59, 8786– 8798,  DOI: 10.1002/anie.201916474
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    "Armor-Plating" Enzymes with Metal-Organic Frameworks (MOFs)
    Huang, Siming; Kou, Xiaoxue; Shen, Jun; Chen, Guosheng; Ouyang, Gangfeng
    Angewandte Chemie, International Edition (2020), 59 (23), 8786-8798CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. Cell-free enzymic catalysis (CFEC) is an emerging biotechnol. that enable the biol. transformations in complex natural networks to be imitated. This biomimetic approach allows industrial products such as biofuels and biochem. to be manufd. in a green manner. Nevertheless, the main challenge in CFEC is the poor stability, which restricts the effectiveness and lifetime of enzymes in sophisticated applications. Immobilization of the enzymes within solid carriers is considered an efficient strategy for addressing these obstacles. Specifically, putting an "armor-like" porous metal-org. framework (MOF) exoskeleton tightly around the enzymes not only shields the enzymes against external stimulus, but also allows the selective transport of guests through the accessible porous network. Herein we present the concept of this biotechnol. of MOF-entrapped enzymes and its cutting-edge applications.
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    Majewski, M. B.; Howarth, A. J.; Li, P.; Wasielewski, M. R.; Hupp, J. T.; Farha, O. K. Enzyme Encapsulation in Metal–Organic Frameworks for Applications in Catalysis. CrystEngComm 2017, 19, 4082– 4091,  DOI: 10.1039/C7CE00022G
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    Enzyme encapsulation in metal-organic frameworks for applications in catalysis
    Majewski, Marek B.; Howarth, Ashlee J.; Li, Peng; Wasielewski, Michael R.; Hupp, Joseph T.; Farha, Omar K.
    CrystEngComm (2017), 19 (29), 4082-4091CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
    A review. Enzymes are natural catalysts which are highly selective and efficient. Given that enzymes have very intricate and delicate structures, they need to be stabilized and protected by a support material if they are to be used under challenging catalytic conditions. This highlight focuses on the use of metal-org. frameworks as supports for enzyme encapsulation and subsequent catalytic applications. De novo and post-synthetic methods of encapsulation are discussed and the relative catalytic activities of the enzyme@MOF composites vs. free enzymes are highlighted.
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    Xia, H.; Li, N.; Zhong, X.; Jiang, Y. Metal-Organic Frameworks: A Potential Platform for Enzyme Immobilization and Related Applications. Front. Bioeng. Biotechnol. 2020, 8, 695,  DOI: 10.3389/fbioe.2020.00695
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    Metal-Organic Frameworks: A Potential Platform for Enzyme Immobilization and Related Applications
    Xia Huan; Li Na; Zhong Xue; Jiang Yanbin
    Frontiers in bioengineering and biotechnology (2020), 8 (), 695 ISSN:2296-4185.
    Enzymes, as natural catalysts with remarkable catalytic activity and high region-selectivities, hold great promise in industrial catalysis. However, applications of enzymatic transformation are hampered by the fragility of enzymes in harsh conditions. Recently, metal-organic frameworks (MOFs), due to their high stability and available structural properties, have emerged as a promising platform for enzyme immobilization. Synthetic strategies of enzyme-MOF composites mainly including surface immobilization, covalent linkage, pore entrapment and in situ synthesis. Compared with free enzymes, most immobilized enzymes exhibit enhanced resistance against solvents and high temperatures. Besides, MOFs serving as matrixes for enzyme immobilization show extraordinary superiority in many aspects compared with other supporting materials. The advantages of using MOFs to support enzymes are discussed. To obtain a high enzyme loading capacity and to reduce the diffusion resistance of reactants and products during the reaction, the mesoporous MOFs have been designed and constructed. This review also covers the applications of enzyme-MOF composites in bio-sensing and detection, bio-catalysis, and cancer therapy, which is concerned with interdisciplinary nano-chemistry, material science and medical chemistry. Finally, some perspectives on reservation or enhancement of bio-catalytic activity of enzyme-MOF composites and the future of enzyme immobilization strategies are discussed.
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    Liang, K.; Ricco, R.; Doherty, C. M.; Styles, M. J.; Bell, S.; Kirby, N.; Mudie, S.; Haylock, D.; Hill, A. J.; Doonan, C. J.; Falcaro, P. Biomimetic Mineralization of Metal-Organic Frameworks as Protective Coatings for Biomacromolecules. Nat. Commun. 2015, 6, 7240,  DOI: 10.1038/ncomms8240
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    Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules
    Liang, Kang; Ricco, Raffaele; Doherty, Cara M.; Styles, Mark J.; Bell, Stephen; Kirby, Nigel; Mudie, Stephen; Haylock, David; Hill, Anita J.; Doonan, Christian J.; Falcaro, Paolo
    Nature Communications (2015), 6 (), 7240CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)
    Enhancing the robustness of functional biomacromols. is a crit. challenge in biotechnol., which if addressed would enhance their use in pharmaceuticals, chem. processing and biostorage. Here we report a novel method, inspired by natural biomineralization processes, which provides unprecedented protection of biomacromols. by encapsulating them within a class of porous materials termed metal-org. frameworks. We show that proteins, enzymes and DNA rapidly induce the formation of protective metal-org. framework coatings under physiol. conditions by concg. the framework building blocks and facilitating crystn. around the biomacromols. The resulting biocomposite is stable under conditions that would normally decomp. many biol. macromols. For example, urease and horseradish peroxidase protected within a metal-org. framework shell are found to retain bioactivity after being treated at 80 °C and boiled in DMF (153 °C), resp. This rapid, low-cost biomimetic mineralization process gives rise to new possibilities for the exploitation of biomacromols.
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    Pisklak, T. J.; Macías, M.; Coutinho, D. H.; Huang, R. S.; Balkus, K. J., Jr. Hybrid Materials for Immobilization of MP-11 Catalyst. Top. Catal. 2006, 38, 269– 278,  DOI: 10.1007/s11244-006-0025-6
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    Hybrid materials for immobilization of MP-11 catalyst
    Pisklak, Thomas J.; Macias, Minedys; Coutinho, Decio H.; Huang, Rita S.; Balkus, Kenneth J., Jr.
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    Enzyme immobilization in hierarchically porous metal-org. frameworks (HP-MOFs) has attracted extensive attention in biocatalysis and contaminant biodegrdn. However, the small-dimension mesopores and micropores on the exterior of MOFs are incompatible with large-sized enzymes, thus limiting the further enhancement of mass transfer efficiency and enzyme accessibility. Herein, we encapsulated horseradish peroxidase (HRP) in highly ordered macro-micropore zeolitic imidazolate framework-8, in which the encapsulated enzyme not only fully preserved its catalytic activity, but also exhibited long-term stability, recyclability, low leakage, and resistance to chelating compds. Through enzyme immobilization, we significantly enhanced the biodegrdn. process of hazardous dyes probably as a result of the pre-concn. of the dye reactant for the combination of enzymes and MOFs. This work shows the great potential of constructing highly functional biocatalysts in three-dimensional ordered macro-micropore MOFs with enhanced mass diffusion efficiency, which is promising for applications to biodegrdn. of all sorts of other org. pollutants in water resources.
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    RSC Advances (2017), 7 (34), 21205-21213CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
    Magnetic multi-enzyme nanosystems have been prepd. via co-pptn. of enzymes and metal-org. framework HKUST-1 precursors in the presence of magnetic Fe3O4 nanoparticles. The spatial co-localization of two enzymes was achieved using a layer-by-layer positional assembly strategy. Glucose oxidase (GOx) and horseradish peroxidase (HRP) were used as the model enzymes for cascade biocatalysis. By controlling the spatial positions of enzymes, three bienzyme nanosystems GOx@HRP@HKUST-1@Fe3O4, GOx-HRP@HKUST-1@Fe3O4 and HRP@GOx@HKUST-1@Fe3O4 were prepd. in which GOx and HRP contg. layers were in close proximity, either encapsulated in the HKUST-1 inner layer, or immobilized on the HKUST-1 outer shell, or randomly distributed in the two MOF layers. Their properties were characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform IR spectroscopy, X-ray diffraction, thermal gravimetric anal., and zeta potential measurements. The highest activity was obsd. at pH = 6 and a temp. of 20°C. Thanks to the favorable positioning of enzymes, the GOx@HRP@HKUST-1@Fe3O4 nanosystem revealed superior kinetics with a Michaelis const. Km = 0.8 mmol L-1 and the max. reaction rate Vmax = 11.3μmol L-1 min-1. The enzyme-HKUST-1 conjugates exhibited remarkably high operational stability compared to the free enzymes. This work provides a facile and versatile approach to spatially organized multienzyme systems with well-defined nanostructures and greatly enhanced the overall biocatalytic efficiency.
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    Cui, Jiandong; Feng, Yuxiao; Jia, Shiru
    Chemical Engineering Journal (Amsterdam, Netherlands) (2018), 351 (), 506-514CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
    Metal-org. frameworks (MOFs) have recently emerged as a promising candidate for the immobilization of enzymes due to their diversified structures and porosity. However, it is difficult to handle and fully recover the enzyme-MOF composites from the reaction medium due to their nanometer size and good dispersity in solvents, which limits their practical applications. Here, a novel enzyme-MOF composite with both highly stable and easily reusable features was prepd. via encapsulating catalase/ZIF-8 nanocrystals into large mesoporous silica layer (silica@CAT/ZIF-8). This immobilized system exhibited high activity recovery (81%). The silica layer around the catalase/ZIF-8 particles provided a "shield" to protect from biol. and chem. degrdn. for enzyme. As a result, the silica@CAT/ZIF-8 composites exhibited higher stability against proteolytic agent and extreme conditions (such as low pH) than that of conventional catalase/ZIF-8 composites. More importantly, the micrometer-sized silica@CAT/ZIF-8 can be easily repeatedly used without obvious activity loss. The silica@CAT/ZIF-8 composites still remained 50% of their original activity after 10 cycles, whereas the conventional catalase/ZIF-8 composites only retained 7% of their original activity after 5 cycles. These results demonstrated that this approach could be an efficient strategy to prep. enzyme-ZIF-8 composite with both high stability and excellent recyclability.
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  • Abstract

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    Figure 1

    Figure 1. (a) Schematic illustration of the core–shell architecture for the fabrication of the MOF fiber mesh. The core solution (in green) contains PVP + MOF precursors (Cu(NO3)2·3H2O and BTC for HKUST-1; Zn(O2CCH3)2·2H2O and Hmim for ZIF-8), and the shell solution (in blue) contains PLGA. The two solutions are injected simultaneously to achieve a core–shell structure (left). After the fabrication of the fibers, they are flushed with ethanol vapor, inducing the growth of the MOF crystals (right). (b) Molecular structures of the precursors of the two MOFs: HKUST-1 precursors (left) and ZIF-8 precursors (right).

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    Figure 2

    Figure 2. (a) Electrospun mesh of fibers containing HKUST-1 precursors before (left) and after (right) exposure to ethanol. (b) The growth of the HKUST-1 crystals is clearly seen when comparing a single fiber before (left) and after (right) exposure to ethanol. (c) Obtained XRD pattern (top) in comparison to the theoretical pattern for HKUST-1 (bottom). The inset shows a zoom-in of the obtained HKUST-1 crystals.

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    Figure 3

    Figure 3. (a) Electrospun mesh of fibers containing ZIF-8 precursors before (left) and after (right) exposure to ethanol. (b) The growth of the ZIF-8 crystals is clearly seen when comparing a single fiber before (left) and after (right) exposure to ethanol. (c) Obtained XRD pattern (top) in comparison to the theoretical pattern for ZIF-8 (bottom). The inset shows a zoom-in of the obtained ZIF-8 crystals.

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    Figure 4

    Figure 4. Upon stretching of an HKUST-1 embedded fiber, initially, the polymeric fiber extends (a), leading to the formation of fractures in the external crystal layer (b). Eventually, the polymer fiber backbone is torn, revealing an embedded crystal shell wrapping the polymeric fiber backbone (c).

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    Figure 5

    Figure 5. (a) XPS spectra of the fibers before (black) and after (red) exposure to ethanol vapor. The peak assignment is reported above the peaks, indicating the emergence of copper and nitrogen on the surface after the exposure. (b) Schematic illustration of the proposed growth scheme. At the first stage, the precursors are positioned only at the core. As the ethanol vapor penetrates the fiber, the precursors diffuse toward the surface (stage 2), and once the ethanol concentration increases enough in the fibers, the growth process begins, and MOF crystals are formed on the surface of the fibers (stage 3).

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    Figure 6

    Figure 6. (a) A 12 cm × 7 cm nonwoven mesh fabric of HKUST-1 fibers after exposure to ethanol vapor can go through (b) rolling and (c, d) folding without tearing of the fibers or apparent release of the embedded MOF crystals.

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    Figure 7

    Figure 7. Tensile strength for HKUST-1 fabrics before (purple) and after (green) exposure to ethanol vapor. Average value for each set of samples is depicted as a black triangle marker in the center of mass of each set. Ellipsoids are guidance to the eye.

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    Figure 8

    Figure 8. (a) Catalysis of Amplex Red to resorufin by HRP. (b) Resorufin emission intensity as a function of time for a ZIF-8 mesh that was exposed to ethanol and was not soaked in HRP solution (black, squares), a mesh that was not exposed to ethanol but was soaked with HRP (red circles), and a mesh that was exposed to ethanol and was soaked in HRP solution (blue triangles). All measurements were performed with meshes of similar fiber densities and with similar concentrations of reagents. (c) Similar experiment repeated with HKUST-1 meshes.

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  • References

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      Hybrid porous solids: past, present, future
      Ferey, Gerard
      Chemical Society Reviews (2008), 37 (1), 191-214CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. This crit. review will be of interest to the experts in porous solids (including catalysis), but also solid state chemists and physicists. It presents the state-of-the-art on hybrid porous solids, their advantages, their new routes of synthesis, the structural concepts useful for their 'design', aiming at reaching very large pores. Their dynamic properties and the possibility of predicting their structure are described. The large tunability of the pore size leads to unprecedented properties and applications. They concern adsorption of species, storage and delivery and the phys. properties of the dense phases. (323 refs.).
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    2. 2
      Davis, M. E. Ordered Porous Materials for Emerging Applications. Nature 2002, 417, 813– 821,  DOI: 10.1038/nature00785
      2
      Ordered porous materials for emerging applications
      Davis, Mark E.
      Nature (London, United Kingdom) (2002), 417 (6891), 813-821CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
      A review. "Space,the final frontier. "This preamble to a well-known television series captures the challenge encountered not only in space travel adventures, but also in the field of porous materials, which aims to control the size, shape and uniformity of the porous space and the atoms and mols. that define it. The past decade has seen significant advances in the ability to fabricate new porous solids with ordered structures from a wide range of different materials. This has resulted in materials with unusual properties and broadened their application range beyond the traditional use as catalysts and adsorbents. In fact, porous materials now seem set to contribute to developments in areas ranging from microelectronics to medical diagnosis.
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    3. 3
      Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J. Reticular Synthesis and the Design of New Materials. Nature 2003, 423, 705– 714,  DOI: 10.1038/nature01650
      3
      Reticular synthesis and the design of new materials
      Yaghi, Omar M.; O'Keeffe, Michael; Ockwig, Nathan W.; Chae, Hee K.; Eddaoudi, Mohamed; Kim, Jaheon
      Nature (London, United Kingdom) (2003), 423 (6941), 705-714CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
      A review. The long-standing challenge of designing and constructing new cryst. solid-state materials from mol. building blocks is just beginning to be addressed with success. A conceptual approach that requires the use of secondary building units to direct the assembly of ordered frameworks epitomizes this process: the authors call this approach reticular synthesis. This chem. has yielded materials designed to have predetd. structures, compns. and properties. In particular, highly porous frameworks held together by strong metal-O-C bonds and with exceptionally large surface area and capacity for gas storage were prepd. and their pore metrics systematically varied and functionalized.
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    4. 4
      Kitagawa, S.; Kitaura, R.; Noro, S. I. Functional Porous Coordination Polymers. Angew. Chem., Int. Ed. 2004, 43, 2334– 2375,  DOI: 10.1002/anie.200300610
      4
      Functional porous coordination polymers
      Kitagawa, Susumu; Kitaura, Ryo; Noro, Shin-ichiro
      Angewandte Chemie, International Edition (2004), 43 (18), 2334-2375CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Discussion concs. on three aspects of coordination polymers: (1) the use of crystal engineering to construct porous frameworks from connectors and linkers (nano-space engineering), (2) characterizing and cataloging the porous properties by functions for storage, exchange, sepn., etc., and (3) the next generation of porous functions based on dynamic crystal transformations caused by guest mols. or phys. stimuli. The authors' aim is to present the state of the art chem. and physics of and in the micropores of porous coordination polymers.
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    5. 5
      James, S. L. Metal-Organic Frameworks. Chem. Soc. Rev. 2003, 32, 276– 288,  DOI: 10.1039/b200393g
      5
      Metal-organic frameworks
      James, Stuart L.
      Chemical Society Reviews (2003), 32 (5), 276-288CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. Metal-org. frameworks are a recently-identified class of porous polymeric material, consisting of metal ions linked together by org. bridging ligands, and are a new development on the interface between mol. coordination chem. and materials science. A range of novel structures was prepd. which feature amongst the largest pores known for cryst. compds., very high sorption capacities and complex sorption behavior not seen in aluminosilicate zeolites. The development of synthetic approaches to these materials and studies of their properties are reviewed.
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    6. 6
      Chen, B.; Xiang, S.; Qian, G. Metal–Organic Frameworks with Functional Pores for Recognition of Small Molecules. Acc. Chem. Res. 2010, 43, 1115– 1124,  DOI: 10.1021/ar100023y
      6
      Metal-Organic Frameworks with Functional Pores for Recognition of Small Molecules
      Chen, Banglin; Xiang, Shengchang; Qian, Guodong
      Accounts of Chemical Research (2010), 43 (8), 1115-1124CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
      A review. Mol. recognition, an important process in biol. and chem. systems, governs the diverse functions of a variety of enzymes and unique properties of some synthetic receptors. Because mol. recognition is based on weak interactions between receptors and substrates, the design and assembly of synthetic receptors to mimic biol. systems and the development of novel materials to discriminate different substrates for selective recognition of specific mols. has proved challenging. The extensive research on synthetic receptors for mol. recognition, particularly on noncovalent complexes self-assembled by hydrogen bonding and metal-org. coordination, has revealed some underlying principles. In particular, these studies have demonstrated that the shapes of the supramol. receptors play significant roles in their specific and selective recognition of substrates: receptors can offer concave surfaces that complement their convex targets. This Account describes our research to develop a synthetic mol. recognition platform using porous metal-org. frameworks (MOFs). These materials contain functional pores to direct their specific and unique recognition of small mols. through several types of interactions: van der Waals interactions of the framework surface with the substrate, metal-substrate interactions, and hydrogen bonding of the framework surface with the substrate. These materials have potential applications for gas storage, sepn., and sensing. We demonstrate a simple strategy to construct a primitive cubic net of interpenetrated microporous MOFs from the self-assembly of the paddle-wheel clusters M2(CO2)4 (M = Cu2+, Zn2+, and Co2+) with two types of org. dicarboxylic acid and pillar bidentate linkers. This efficient method allows us to rationally tune the micropores to size-exclusively sort different small gas mols., leading to the highly selective sepn. and purifn. of gases. By optimizing the strong interactions between open metal sites within porous MOFs and gas mols. such as hydrogen and acetylene, we have developed several MOF materials with extraordinary acetylene storage capacity at room temp. We have also immobilized Lewis acidic and basic sites into luminescent porous MOFs to recognize and sense neutral and ionic species. Using the strategy to systematically immobilize different open metal sites within porous MOFs from the metallo-ligand precursors, we have developed the first microporous mixed-metal-org. framework (M'MOF) with enhanced affinity for hydrogen mols., which successfully sepd. D2 from H2 using kinetic isotope quantum mol. sieving. Because we can functionalize the pores to direct their specific recognition of small mols., the emerging porous MOFs serve as novel functional materials for gas storage, sepn., heterogeneous catalysis, and sensing.
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    7. 7
      Czaja, A. U.; Trukhan, N.; Müller, U. Industrial Applications of Metal–Organic Frameworks. Chem. Soc. Rev. 2009, 38, 1284– 1293,  DOI: 10.1039/b804680h
      7
      Industrial applications of metal-organic frameworks
      Czaja, Alexander U.; Trukhan, Natalia; Muller, Ulrich
      Chemical Society Reviews (2009), 38 (5), 1284-1293CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. New materials are prerequisite for major breakthrough applications affecting the daily life, and therefore are pivotal for the chem. industry. Metal-org. frameworks (MOFs) constitute an emerging class of materials useful in gas storage, gas purifn., and sepn. applications as well as heterogeneous catalysis. They not only offer higher surface areas and the potential for enhanced activity than currently used materials like base metal oxides, but also provide shape/size selectivity which is important both for sepns. and catalysis. In this crit. review an overview of the potential applications of MOFs in the chem. industry is presented. Furthermore, the synthesis and characterization of the materials are briefly discussed from the industrial perspective.
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    8. 8
      Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The Chemistry and Applications of Metal-Organic Frameworks. Science 2013, 341, 1230444,  DOI: 10.1126/science.1230444
      8
      The chemistry and applications of metal-organic frameworks
      Furukawa Hiroyasu; Cordova Kyle E; O'Keeffe Michael; Yaghi Omar M
      Science (New York, N.Y.) (2013), 341 (6149), 1230444 ISSN:.
      Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.
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    9. 9
      Falcaro, P.; Ricco, R.; Doherty, C. M.; Liang, K.; Hill, A. J.; Styles, M. J. MOF Positioning Technology and Device Fabrication. Chem. Soc. Rev. 2014, 43, 5513– 5560,  DOI: 10.1039/C4CS00089G
      9
      MOF positioning technology and device fabrication
      Falcaro, Paolo; Ricco, Raffaele; Doherty, Cara M.; Liang, Kang; Hill, Anita J.; Styles, Mark J.
      Chemical Society Reviews (2014), 43 (16), 5513-5560CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review of current technologies that enable the precise positioning of MOFs onto different platforms. Metal org. frameworks (MOFs) offer the highest surface areas per g of any known material. As such, they epitomize resource productivity in uses where sp. surface area is crit., such as adsorption, storage, filtration and catalysis. However, the ability to control the position of MOFs is also crucial for their use in devices for applications such as sensing, delivery, sequestration, mol. transport, electronics, energy prodn., optics, bioreactors and catalysis. Methods for permanent localization, dynamic localization, and spatial control of functional materials within MOF crystals are described. Finally, examples of devices in which the control of MOF position and functionalization will play a major technol. role are presented.
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    10. 10
      Furukawa, S.; Reboul, J.; Diring, S.; Sumida, K.; Kitagawa, S. Structuring of Metal-Organic Frameworks at the Mesoscopic/Macroscopic Scale. Chem. Soc. Rev. 2014, 43, 5700– 5734,  DOI: 10.1039/C4CS00106K
      10
      Structuring of metal-organic frameworks at the mesoscopic/macroscopic scale
      Furukawa, Shuhei; Reboul, Julien; Diring, Stephane; Sumida, Kenji; Kitagawa, Susumu
      Chemical Society Reviews (2014), 43 (16), 5700-5734CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. The assembly of metal ions with org. ligands through the formation of coordination bonds gives cryst. framework materials, known as metal-org. frameworks (MOFs), which recently emerged as a new class of porous materials. Besides the structural designability of MOFs at the mol. length scale, the researchers in this field very recently made important advances in creating more complex architectures at the mesoscopic/macroscopic scale, in which MOF nanocrystals were used as building units to construct higher-order superstructures. The structuring of MOFs in such a hierarchical order certainly opens a new opportunity to improve the material performance via design of the phys. form rather than altering the chem. component. This review highlights these superstructures and their applications by categorizing them into four dimensionalities, zero-dimensional (0D), 1-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) superstructures. Because the key issue for structuring of MOFs is to spatially control the nucleation process in desired locations, this review conceptually categorizes the available synthetic methodologies from the viewpoint of the reaction system.
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    11. 11
      Luo, Y.; Ahmad, M.; Schug, A.; Tsotsalas, M. Rising Up: Hierarchical Metal–Organic Frameworks in Experiments and Simulations. Adv. Mater. 2019, 31, 1901744,  DOI: 10.1002/adma.201901744
      There is no corresponding record for this reference.
    12. 12
      Zhuang, J.-L.; Ar, D.; Yu, X.-J.; Liu, J.-X.; Terfort, A. Patterned Deposition of Metal-Organic Frameworks onto Plastic, Paper, and Textile Substrates by Inkjet Printing of a Precursor Solution. Adv. Mater. 2013, 25, 4631– 4635,  DOI: 10.1002/adma.201301626
      12
      Patterned Deposition of Metal-Organic Frameworks onto Plastic, Paper, and Textile Substrates by Inkjet Printing of a Precursor Solution
      Zhuang, Jin-Liang; Ar, Deniz; Yu, Xiu-Jun; Liu, Jin-Xuan; Terfort, Andreas
      Advanced Materials (Weinheim, Germany) (2013), 25 (33), 4631-4635CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The authors have developed a new, facile, and precursor-based strategy for the growth of surface-attached metal-org. frameworks (SURMOFs) on various flexible substrates (plastics, papers, and textiles) by using the inkjet-printing technic. This unique method allows one to fabricate large area, high d., and laterally patterned SURMOFs (including gradients) in a low cost, time-efficient way. The printed HKUST-1 films are characterized by a hierarchical, surfactant-free pore structure, which makes them promising materials for gas capture and heterogeneous catalysis, since the diffusion of guest mols. becomes facilitated. HKUST-1 SURMOFs printed on textiles are able to capture several hazardous gases and indicate this process by a unique color change, which might be useful for personal protection applications. The high accessible pore vol. of HKUST-1 films was confirmed by QCM measurements and resulted in excellent adsorption properties for several hazardous gases. To demonstrate the generality of this approach, the authors also printed patterns of an MOF from a completely different family, [Zn2[adc]2(dabco)2] (adc = 9,10-anthracenedicarboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane).
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    13. 13
      Shekhah, O.; Liu, J.; Fischer, R. A.; Wöll, C. MOF Thin Films: Existing and Future Applications. Chem. Soc. Rev. 2011, 40, 1081– 1106,  DOI: 10.1039/c0cs00147c
      13
      MOF thin films: existing and future applications
      Shekhah, O.; Liu, J.; Fischer, R. A.; Woell, Ch.
      Chemical Society Reviews (2011), 40 (2), 1081-1106CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. The applications and potentials of thin film coatings of metal-org. frameworks (MOFs) supported on various substrates are discussed in this crit. review. Because the demand for fabricating such porous coatings is rather obvious, in the past years several synthesis schemes were developed for the prepn. of thin porous MOF films. Although this is an emerging field seeing a rapid development a no. of different applications on MOF films were either already demonstrated or are proposed. This review focuses on the fabrication of continuous, thin porous films, either supported on solid substrates or as free-standing membranes. The availability of such two-dimensional types of porous coatings opened the door for a no. of new perspectives for functionalizing surfaces. Also for the porous materials themselves, the availability of a solid support to which the MOF-films are rigidly (in a mech. sense) anchored provides access to applications not available for the typical MOF powders with particle sizes of a few μm. The authors will also address some of the potential and applications of thin films in different fields like luminescence, QCM-based sensors, optoelectronics, gas sepn. and catalysis. A sep. chapter was devoted to the delamination of MOF thin films and discusses the potential to use them as free-standing membranes or as nanocontainers. The review also demonstrates the possibility of using MOF thin films as model systems for detailed studies on MOF-related phenomena, e.g. adsorption and diffusion of small mols. into MOFs as well as the formation mechanism of MOFs (101 refs.).
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    14. 14
      Park, J.; Oh, M. Construction of Flexible Metal–Organic Framework (MOF) Papers through MOF Growth on Filter Paper and Their Selective Dye Capture. Nanoscale 2017, 9, 12850– 12854,  DOI: 10.1039/C7NR04113F
      14
      Construction of flexible metal-organic framework (MOF) papers through MOF growth on filter paper and their selective dye capture
      Park, Jeehyun; Oh, Moonhyun
      Nanoscale (2017), 9 (35), 12850-12854CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
      The conjugation of metal-org. frameworks (MOFs) with other materials is an excellent strategy for the prodn. of advanced materials having desired properties and so appropriate applicability. In particular, the integration of MOFs with a flexible paper is expected to form valuable materials in sepn. technol. Here authors report a simple method for the generation of MOF papers through the compact and uniform growth of MOF nanoparticles on the cellulose surface of a carboxymethylated filter paper. The resulting MOF papers show a selective capture ability for neg. charged org. dyes and they can be used for dye sepn. through simple filtration of a dye soln. on the MOF papers. In addn., MOF papers can be reused after a simple washing process without losing their effective dye capture ability.
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    15. 15
      Zanchetta, E.; Malfatti, L.; Ricco, R.; Styles, M. J.; Lisi, F.; Coghlan, C. J.; Doonan, C. J.; Hill, A. J.; Brusatin, G.; Falcaro, P. ZnO as an Efficient Nucleating Agent for Rapid, Room Temperature Synthesis and Patterning of Zn-Based Metal–Organic Frameworks. Chem. Mater. 2015, 27, 690– 699,  DOI: 10.1021/cm502882a
      15
      ZnO as an Efficient Nucleating Agent for Rapid, Room Temperature Synthesis and Patterning of Zn-Based Metal-Organic Frameworks
      Zanchetta, Erika; Malfatti, Luca; Ricco, Raffaele; Styles, Mark J.; Lisi, Fabio; Coghlan, Campbell J.; Doonan, Christian J.; Hill, Anita J.; Brusatin, Giovanna; Falcaro, Paolo
      Chemistry of Materials (2015), 27 (3), 690-699CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      The use of ZnO particles as efficient agents for seeding, growing, and precisely positioning metal-org. frameworks (MOFs) is described. Ceramic seeds were successfully used for the prepn. of Zn-based MOFs with a no. of different carboxylic acids: terephthalic acid, 2-aminoterephthalic acid, 1,3,5-benzenetricarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 4,4'-biphenyldicarboxylic acid. In situ synchrotron small-angle x-ray scattering and electron microscopy expts. were employed to det. the effect of the concn. of ZnO nanoparticles, temp., and time on MOF growth. Under optimized conditions, MOF crystals form in several minutes. This unprecedented capacity to seed MOF formation was used to control the growth of crystals in precise locations. Accordingly, the authors employed this seeding technique to position porous MOF crystals on paper strips (lateral flow), or within glass and PDMS microchannels (120 μm width and 100 μm height). ZnO nanoparticles are versatile seeding agents for the growth of porous crystals in a no. of different microfluidic platforms.
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    16. 16
      Neufeld, M. J.; Harding, J. L.; Reynolds, M. M. Immobilization of Metal-Organic Framework Copper(II) Benzene-1,3,5-Tricarboxylate (CuBTC) onto Cotton Fabric as a Nitric Oxide Release Catalyst. ACS Appl. Mater. Interfaces 2015, 7, 26742– 26750,  DOI: 10.1021/acsami.5b08773
      16
      Immobilization of Metal-Organic Framework Copper(II) Benzene-1,3,5-tricarboxylate (CuBTC) onto Cotton Fabric as a Nitric Oxide Release Catalyst
      Neufeld, Megan J.; Harding, Jacqueline L.; Reynolds, Melissa M.
      ACS Applied Materials & Interfaces (2015), 7 (48), 26742-26750CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Immobilization of metal-org. frameworks (MOFs) onto flexible polymeric substrates as secondary supports expands the versatility of MOFs for surface coatings for the development of functional materials. In this work, we demonstrate the deposition of copper(II) benzene-1,3,5-tricarboxylate (CuBTC) crystals directly onto the surface of carboxyl-functionalized cotton capable of generating the therapeutic bioagent nitric oxide (NO) from endogenous sources. Characterization of the CuBTC-cotton material by XRD, ATR-IR, and UV-vis indicate that CuBTC is successfully immobilized on the cotton fabric. In addn., SEM imaging reveals excellent surface coverage with well-defined CuBTC crystals. Subsequently, the CuBTC-cotton material was evaluated as a supported heterogeneous catalyst for the generation of NO using S-nitrosocysteamine as the substrate. The resulting reactivity is consistent with the activity obsd. for unsupported CuBTC particles. Overall, this work demonstrates deposition of MOFs onto a flexible polymeric material with excellent coverage as well as catalytic NO release from S-nitrosocysteamine at therapeutic levels.
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    17. 17
      Ma, K.; Islamoglu, T.; Chen, Z.; Li, P.; Wasson, M. C.; Chen, Y.; Wang, Y.; Peterson, G. W.; Xin, J. H.; Farha, O. K. Scalable and Template-Free Aqueous Synthesis of Zirconium-Based Metal-Organic Framework Coating on Textile Fiber. J. Am. Chem. Soc. 2019, 141, 15626– 15633,  DOI: 10.1021/jacs.9b07301
      17
      Scalable and Template-Free Aqueous Synthesis of Zirconium-Based Metal-Organic Framework Coating on Textile Fiber
      Ma, Kaikai; Islamoglu, Timur; Chen, Zhijie; Li, Peng; Wasson, Megan C.; Chen, Yongwei; Wang, Yuanfeng; Peterson, Gregory W.; Xin, John H.; Farha, Omar K.
      Journal of the American Chemical Society (2019), 141 (39), 15626-15633CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Organophosphonate-based nerve agents, such as VX, Sarin (GB), and Soman (GD), are among the most toxic chems. to humankind. Recently, we have shown that Zr-based metal-org. frameworks (Zr-MOFs) can effectively catalyze the hydrolysis of these toxic chems. for diminishing their toxicity. On the other hand, utilizing these materials in powder form is not practical, and developing scalable and economical processes for integrating these materials onto fibers is crucial for protective gear. Herein, we report a scalable, template-free, and aq. soln.-based synthesis strategy for the prodn. of Zr-MOF-coated textiles. Among all MOF/fiber composites reported to date, the MOF-808/polyester fibers exhibit the highest rates of nerve agent hydrolysis. Moreover, such highly porous fiber composites display significantly higher protection time compared to that of its parent fabric for a mustard gas simulant, 2-chloroethyl Et sulfide (CEES). A decreased diffusion rate of toxic chems. through the MOF layer can provide time needed for the destruction of the harmful species.
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    18. 18
      Cao, R.; Chen, Z.; Chen, Y.; Idrees, K. B.; Hanna, S. L.; Wang, X.; Goetjen, T. A.; Sun, Q.; Islamoglu, T.; Farha, O. K. Benign Integration of a Zn-Azolate Metal–Organic Framework onto Textile Fiber for Ammonia Capture. ACS Appl. Mater. Interfaces 2020, 12, 47747– 47753,  DOI: 10.1021/acsami.0c14316
      18
      Benign Integration of a Zn-Azolate Metal-Organic Framework onto Textile Fiber for Ammonia Capture
      Cao, Ran; Chen, Zhijie; Chen, Yongwei; Idrees, Karam B.; Hanna, Sylvia L.; Wang, Xingjie; Goetjen, Timothy A.; Sun, Qijun; Islamoglu, Timur; Farha, Omar K.
      ACS Applied Materials & Interfaces (2020), 12 (42), 47747-47753CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Ammonia (NH3) exposure has a serious impact on human health because of its toxic and corrosive nature. Therefore, efficient personal protective equipment (PPE) such as masks is necessary to eliminate and mitigate NH3 exposure risks. Because economically and environmentally viable conditions are of interest for large-scale manuf. of PPE, we herein report a benign procedure to synthesize a Zn-azolate metal-org. framework (MOF), MFU-4, for NH3 capture. The surface area and morphol. of MFU-4 obtained in alc. solvents at room temp. is consistent with that of traditionally synthesized MFU-4 in N,N-dimethylformamide at 140 °C. In addn. to its large NH3 uptake capacity at 1 bar (17.7 mmol/g), MFU-4 shows outstanding performance in capturing NH3 at low concn. (10.8 mmol/g at 0.05 bar). Furthermore, the mild synthetic conditions implemented make it facile to immobilize MFU-4 onto cotton textile fiber. Enhanced NH3 capture ability of the MFU-4/fiber composite was also attributed to the well-exposed MOF particles. The benign synthetic MFU-4 procedure, high NH3 uptake, and easy integration onto fiber pave the way toward implementation of similar materials in PPE.
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    19. 19
      Ma, K.; Wang, Y.; Chen, Z.; Islamoglu, T.; Lai, C.; Wang, X.; Fei, B.; Farha, O. K.; Xin, J. H. Facile and Scalable Coating of Metal–Organic Frameworks on Fibrous Substrates by a Coordination Replication Method at Room Temperature. ACS Appl. Mater. Interfaces 2019, 11, 22714– 22721,  DOI: 10.1021/acsami.9b04780
      19
      Facile and Scalable Coating of Metal-Organic Frameworks on Fibrous Substrates by a Coordination Replication Method at Room Temperature
      Ma, Kaikai; Wang, Yuanfeng; Chen, Zhijie; Islamoglu, Timur; Lai, Chuilin; Wang, Xiaowen; Fei, Bin; Farha, Omar K.; Xin, John H.
      ACS Applied Materials & Interfaces (2019), 11 (25), 22714-22721CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Coating of metal-org. frameworks (MOFs) on flexible substrates is a crucial technol. for applications such as purifn./sepn., sensing, and catalysis. In this work, a facile coordination replication strategy was developed to coat various MOFs onto flexible fibrous materials where a dense layer of an insol. precursor template, such as a layered hydroxide salt, was first deposited onto a fiber substrate via a mild interfacial reaction and then rapidly transformed into a MOF coating in a ligand soln. at room temp. Spatiotemporal harmonization of solid precursor dissoln. and MOF crystn. enabled precise replication of the precursor layer morphol. to form a continuous MOF coating composed of intergrown crystals. The resulting flexible, highly robust, and processable fibrous MOF/textile composites demonstrated tremendous potential for industrially relevant applications such as continuous removal of the organosulfur compd. dibenzothiophene from simulated gasoline and ammonia capture. This rapid, versatile, eco-friendly, and scalable MOF coating process at room temp. gives rise to new possibilities for prepg. MOF-coated functional materials.
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    20. 20
      Rubin, H. N.; Neufeld, B. H.; Reynolds, M. M. Surface-Anchored Metal-Organic Framework-Cotton Material for Tunable Antibacterial Copper Delivery. ACS Appl. Mater. Interfaces 2018, 10, 15189– 15199,  DOI: 10.1021/acsami.7b19455
      20
      Surface-anchored metal-organic framework-cotton material for tunable antibacterial copper delivery
      Rubin, Heather N.; Neufeld, Bella H.; Reynolds, Melissa M.
      ACS Applied Materials & Interfaces (2018), 10 (17), 15189-15199CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      In the present study, a new copper metal-org. framework (MOF)-cotton material was strategically fabricated to exploit its antibacterial properties for postsynthetic modification (PSM) to introduce a free amine to tune the physicochem. properties of the material. A modified methodol. for carboxymethylation of natural cotton was utilized to enhance the no. of nucleation sites for the MOF growth. Subsequently, MOF Cu3(NH2BTC)2 was synthesized into a homogenous surface-supported film via a layer-by-layer dip-coating process. The resultant materials contained uniformly distributed 1 μm × 1 μm octahedral MOF crystals around each carboxymethylated fiber. Importantly, the accessible free amine of the MOF ligand allowed for the PSM of the MOF-cotton surface with valeric anhydride, yielding 23.5 ± 2.2% modified. The Cu2+ ion-releasing performance of the materials was probed under biol. conditions per submersion in complex media at 37 °C. Indeed, PSM induces a change in the copper flux of the material over the first 6 h. The materials continue to slowly release Cu2+ ions beyond 24 h tested at a flux of 0.22 ± 0.003 μmol·cm-2·h-1 with the unmodified MOF-cotton and at 0.25 ± 0.004 μmol·cm-2·h-1 with the modified MOF-cotton. The antibacterial activity of the material was explored using Escherichia coli by testing the planktonic and attached bacteria under a variety of conditions. MOF-cotton materials elicit antibacterial effects, yielding a 4-log redn. or greater, after 24 h of exposure. Addnl., the MOF-cotton materials inhibit the attachment of bacteria, under both dry and wet conditions. A material of this type would be ideal for clothing, bandages, and other textile applications. As such, this work serves as a precedence toward developing uniform, tunable MOF-composite textile materials that can kill bacteria and prevent the attachment of bacteria to the surface.
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    21. 21
      Ma, K.; Idrees, K. B.; Son, F. A.; Maldonado, R.; Wasson, M. C.; Zhang, X.; Wang, X.; Shehayeb, E.; Merhi, A.; Kaafarani, B. R.; Islamoglu, T.; Xin, J. H.; Farha, O. K. Fiber Composites of Metal-Organic Frameworks. Chem. Mater. 2020, 32, 7120– 7140,  DOI: 10.1021/acs.chemmater.0c02379
      21
      Fiber Composites of Metal-Organic Frameworks
      Ma, Kaikai; Idrees, Karam B.; Son, Florencia A.; Maldonado, Rodrigo; Wasson, Megan C.; Zhang, Xuan; Wang, Xingjie; Shehayeb, Elissa; Merhi, Areej; Kaafarani, Bilal R.; Islamoglu, Timur; Xin, John H.; Farha, Omar K.
      Chemistry of Materials (2020), 32 (17), 7120-7140CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      A review. The high chem. and structural diversity of metal-org. frameworks (MOFs), which are porous cryst. materials, has attracted significant academic and industrial interest. However, the poor processability of MOF powders limits their full potential in practical applications. Toward this end, MOF-based composite materials increase the framework robustness and subsequent utility. Among these hybrid materials, MOF composites prepd. on com. available textile fibers offer the high flexibility needed for important applications-such as heterogeneous catalysis, chem. sensing, pollutant removal, and drug release-while maintaining the functional properties of MOFs. The ability to further tailor these composites' shapes for incorporation into industrial equipment increases their potential in applications such as adsorption devices and protective gears. In this Review, we summarize recently reported MOF/fiber fabrication methods and applications. Our discussion on the advancements and remaining issues of these prodn. methods segues into several highlighted applications of MOF/fiber composites, esp. within adsorption devices and protective gears.
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    22. 22
      Liu, M.; Cai, N.; Chan, V.; Yu, F. Development and Applications of MOFs Derivative One-Dimensional Nanofibers via Electrospinning:A Mini-Review. Nanomaterials 2019, 9, 1306,  DOI: 10.3390/nano9091306
      22
      Development and applications of MOFs derivative one-dimensional nanofibers via electrospinning: a mini-review
      Liu, Mingming; Cai, Ning; Chan, Vincent; Yu, Faquan
      Nanomaterials (2019), 9 (9), 1306CODEN: NANOKO; ISSN:2079-4991. (MDPI AG)
      Metal org. frameworks (MOFs) have been exploited for various applications in science and engineering due to the possibility of forming di erent mesoscopic frameworks and pore structures. To date, further development of MOFs for practical applications in areas such as energy storage and conversion have encountered tremendous challenge owing to the unitary porous structure (almost filled entirely with micropores) and conventional morphol. (e.g., sphere, polyhedron, and rod shape). More recently, one-dimensional (1D) MOFs/nanofibers composites emerged as a new mol. system with highly engineered novel structures for tailored applications. In this mini-review, the recent progress in the development of MOFs-based 1D nanofibers via electrospinning will be elaborated. In particular, the promising applications and underlying mol. mechanism of electrospun MOF-derived carbon nanofibers are primarily focused and analyzed here. This review is instrumental in providing certain guiding principles for the prepn. and structural anal. of MOFs/electrospun nanofibers (M-NFs) composites and electrospun MOF-derived nanomaterials.
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    23. 23
      Chang, Z.; Zeng, J. Immobilization Seeding Layers Using Precursor for Fabricating Core-Shell Polyimide/Cu-BTC Hierarchical Nanofibers with High Gas Separation and Adsorption of Methylene Blue from Aqueous Solution. Macromol. Chem. Phys. 2016, 217, 1007– 1013,  DOI: 10.1002/macp.201500327
      23
      Immobilization Seeding Layers Using Precursor for Fabricating Core-Shell Polyimide/Cu-BTC Hierarchical Nanofibers with High Gas Separation and Adsorption of Methylene Blue from Aqueous Solution
      Chang, Zhenjun; Zeng, Jing
      Macromolecular Chemistry and Physics (2016), 217 (8), 1007-1013CODEN: MCHPES; ISSN:1022-1352. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Metal-org. frameworks (MOFs), also known as porous coordination polymers, are a class of cryst. porous materials consisting of metal ion nodes held together by multitopic org. ligands. Among MOFs, Cu-BTC is a well-studied benchmark MOF. In practical applications, supported porous and stable MOFs on the surface of nanofibers, which provide a high sp. surface area and prevent aggregation of the microstructure, may be very useful. This paper reports a facile strategy for the synthesis of core-shell polyimide/Cu-BTC hierarchical nanofibers by combining electrospinning, step-by-step seeding, and hydrothermal process. The Cu-BTC nanocrystals can be well immobilized onto the surface of polyimide nanofibers. The hierarchical nanofibers exhibited high gas sepn. and adsorption of methylene blue from aq. soln.
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    24. 24
      Ostermann, R.; Cravillon, J.; Weidmann, C.; Wiebcke, M.; Smarsly, B. M. Metal-organic framework nanofibers viaelectrospinning. Chem. Commun. 2011, 47, 442– 444,  DOI: 10.1039/C0CC02271C
      24
      Metal-organic framework nanofibers via electrospinning
      Ostermann, Rainer; Cravillon, Janosch; Weidmann, Christoph; Wiebcke, Michael; Smarsly, Bernd M.
      Chemical Communications (Cambridge, United Kingdom) (2011), 47 (1), 442-444CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      A hierarchical system of highly porous nanofibers was prepd. by electrospinning MOF (metal-org. framework) nanoparticles with suitable carrier polymers. Nitrogen adsorption proved the MOF nanoparticles to be fully accessible inside the polymeric fibers.
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    25. 25
      Wu, Y.; Li, F.; Liu, H.; Zhu, W.; Teng, M.; Jiang, Y.; Li, W.; Xu, D.; He, D.; Hannam, P.; Li, G. Electrospun Fibrous Mats as Skeletons to Produce Free-Standing MOF Membranes. J. Mater. Chem. 2012, 22, 16971– 16978,  DOI: 10.1039/c2jm32570e
      25
      Electrospun fibrous mats as skeletons to produce free-standing MOF membranes
      Wu, Yi-nan; Li, Fengting; Liu, Huimin; Zhu, Wei; Teng, Minmin; Jiang, Yin; Li, Weina; Xu, Dan; He, Dehua; Hannam, Phillip; Li, Guangtao
      Journal of Materials Chemistry (2012), 22 (33), 16971-16978CODEN: JMACEP; ISSN:0959-9428. (Royal Society of Chemistry)
      Nanofibrous mats produced by electrospinning are ideal porous substrates for developing chem. systems due to their high sp. surface area, large porosity, and enormous structural and chem. tunability. The authors report the fabrication of free-standing MOF membranes using electrospun nanofibrous mats as skeletons, and demonstrate the great potential of such nonwoven fiber mats as a new type of porous support in MOF research field. Direct deposition and seeded secondary growth approaches could be used to produce MOF materials within different nanofibrous skeletons, indicating that the developed method of generating MOF membranes has a remarkable flexibility. The characterizations performed show that the resulting products combine the unique properties of both electrospun nanofibers and MOFs, and can be regarded as a new class of hierarchically nanostructured functional materials.
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    26. 26
      Rose, M.; Böhringer, B.; Jolly, M.; Fischer, R.; Kaskel, S. MOF Processing by Electrospinning for Functional Textiles. Adv. Eng. Mater. 2011, 13, 356– 360,  DOI: 10.1002/adem.201000246
      26
      MOF Processing by Electrospinning for Functional Textiles
      Rose, Marcus; Boehringer, Bertram; Jolly, Marc; Fischer, Roland; Kaskel, Stefan
      Advanced Engineering Materials (2011), 13 (4), 356-360CODEN: AENMFY; ISSN:1438-1656. (Wiley-VCH Verlag GmbH & Co. KGaA)
      We present the use of electrospinning for the immobilization of metal-org. framework particles in fibers and the prodn. of homogeneous textile-like layers. HKUST-1 and MIL-100(Fe) are stable during the electrospinning process from a suspension. Excellent high loadings of up to 80 wt% of MOF in the polymeric fibers are achieved. The total accessibility of the inner surface is guaranteed for adsorption processes due to very small fiber diams. in comparison to the particle size. This method provides the know-how for the immobilization of MOFs on flexible, textile-like substrates. Applications such as gas purifn. or removal of toxic compds. in protective clothing are conceivable.
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    27. 27
      Ren, J.; Musyoka, N. M.; Annamalai, P.; Langmi, H. W.; North, B. C.; Mathe, M. Electrospun MOF Nanofibers as Hydrogen Storage Media. Int. J. Hydrogen Energy 2015, 40, 9382– 9387,  DOI: 10.1016/j.ijhydene.2015.05.088
      27
      Electrospun MOF nanofibers as hydrogen storage media
      Ren, Jianwei; Musyoka, Nicholas M.; Annamalai, Perushini; Langmi, Henrietta W.; North, Brian C.; Mathe, Mkhulu
      International Journal of Hydrogen Energy (2015), 40 (30), 9382-9387CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)
      In this study, Zr-MOF and Cr-MOF were chosen as representatives of the developed MOFs in our lab. and were incorporated into electrospun nanofibers. The obtained MOF nanofibers composites were evaluated as hydrogen storage media. The results showed that the incorporation of vacuum degassing was able to create visible porosity in and/or on the PAN nanofibers and the MOF nanocrystals inside the polymeric nanofibers were fully accessible by N2 and H2 gases. With 20 wt.% loading of MOF nanocrystals, the composites were able to achieve over 50% of the H2 uptake capacity of individual MOF nanocrystals. In addn., the composites also showed good thermal stabilities.
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    28. 28
      Armstrong, M. R.; Arredondo, K. Y. Y.; Liu, C.-Y.; Stevens, J. E.; Mayhob, A.; Shan, B.; Senthilnathan, S.; Balzer, C. J.; Mu, B. UiO-66 MOF and Poly(Vinyl Cinnamate) Nanofiber Composite Membranes Synthesized by a Facile Three-Stage Process. Ind. Eng. Chem. Res. 2015, 54, 12386– 12392,  DOI: 10.1021/acs.iecr.5b03334
      28
      UiO-66 MOF and Poly(vinyl cinnamate) Nanofiber Composite Membranes Synthesized by a Facile Three-Stage Process
      Armstrong, Mitchell R.; Arredondo, Korinthia Y. Yuriar; Liu, Chao-Yuan; Stevens, Joshua E.; Mayhob, Alexandre; Shan, Bohan; Senthilnathan, Sethuraman; Balzer, Christopher J.; Mu, Bin
      Industrial & Engineering Chemistry Research (2015), 54 (49), 12386-12392CODEN: IECRED; ISSN:0888-5885. (American Chemical Society)
      Electrospun poly(vinyl cinnamate) (PVCi) nanofibers were cross-linked for varying times to study the impact it has on fiber stability at elevated temps. and in DMF solns. UiO-66 impregnated PVCi was cross-linked, and secondary growth of UiO-66 crystals was performed. The impact of temp. and no. of growths was analyzed through powder X-ray diffraction, SEM, and Fourier transform IR spectroscopy. A membrane that underwent three growth cycles at 100 °C was further characterized for potential uses as a gas membrane through inert gas permeation studies and nitrogen porosimetry.
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    29. 29
      Liu, C.; Wang, J.; Li, J.; Liu, J.; Wang, C.; Sun, X.; Shen, J.; Han, W.; Wang, L. Electrospun ZIF-Based Hierarchical Carbon Fiber as an Efficient Electrocatalyst for the Oxygen Reduction Reaction. J. Mater. Chem. A 2017, 5, 1211– 1220,  DOI: 10.1039/C6TA09193H
      29
      Electrospun ZIF-based hierarchical carbon fiber as an efficient electrocatalyst for the oxygen reduction reaction
      Liu, Chao; Wang, Jing; Li, Jiansheng; Liu, Jizi; Wang, Chaohai; Sun, Xiuyun; Shen, Jinyou; Han, Weiqing; Wang, Lianjun
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2017), 5 (3), 1211-1220CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      The inherently granular nature of nitrogen and metal co-doped carbons derived from metal-org. frameworks (MOFs) hinders their practical application in the oxygen redn. reaction (ORR). In this work, we have developed a novel N, Co-contg. MOF-based hierarchical carbon fiber as an ORR catalyst. The products (ZCP-CFs) are synthesized by the incorporation of a Zn, Co-zeolitic imidazolate framework (Zn, Co-ZIF) with electrospun Co2+/poly(acrylonitrile) fiber, followed by carbonization and acid leaching treatment. The effects of the pyrolysis temp. and precursor on the ORR performance of the final samples were systematically studied. The results indicated that the material prepd. at 900 °C (ZCP-CFs-9) was identified as the best ORR catalyst in the series of samples. Further comparison among samples obtained from different catalyst precursors also demonstrated the superior performance of ZCP-CFs-9, with its more pos. half-wave potential (-0.135 V vs. Ag/AgCl), higher diffusion-limited and kinetic-limiting currents and higher selectivity (no. of electrons transferred n = ∼3.97) than Zn, Co-ZIF derived carbon and Zn, Co-ZIF free carbon fiber. Notably, the ZCP-CFs-9 catalyst exhibited very close activity to a com. Pt/C catalyst with better durability and stronger tolerance to methanol crossover. The remarkable ORR performance may be ascribed to its unique structure, such as its large surface area and hierarchical porosity, the dispersed and protected Co nanoparticles and N functionalized carbon framework, as well as the abundant graphitic carbon and its 1D fibrous structure. Considering the diversity of MOFs and electrospinnable polymer precursors, this strategy may be further extended to other MOF-based carbon fibers for energy storage and conversion.
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    30. 30
      Yang, F.; Efome, J. E.; Rana, D.; Matsuura, T.; Lan, C. Metal–Organic Frameworks Supported on Nanofiber for Desalination by Direct Contact Membrane Distillation. ACS Appl. Mater. Interfaces 2018, 10, 11251– 11260,  DOI: 10.1021/acsami.8b01371
      30
      Metal-Organic Frameworks Supported on Nanofiber for Desalination by Direct Contact Membrane Distillation
      Yang, Fan; Efome, Johnson E.; Rana, Dipak; Matsuura, Takeshi; Lan, Christopher
      ACS Applied Materials & Interfaces (2018), 10 (13), 11251-11260CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Among other applications, metal-org. frameworks (MOFs) are slowly gaining grounds as fillers for desalination composite membranes. In this study, superhydrophobic poly(vinylidene fluoride) nanofibrous membranes were fabricated with MOF (iron 1,3,5-benzenetricarboxylate) loading of up to 5 wt % via electrospinning on a nonwoven substrate. To improve the attachment of nanofibers onto the substrate, a substrate pretreatment method called "solvent basing" was employed. The iron content in the nanofiber, measured by energy-dispersive X-ray spectroscopy, increased proportionally with the increase of the MOF concn. in the spinning dope, indicating a uniform distribution of MOF in the nanofiber. The water contact angle increased up to 138.06 ± 2.18° upon the incorporation of 5 wt % MOF, and a liq. entry pressure of 82.73 kPa could be maintained, making the membrane useful for direct contact membrane distn. expts. The membrane was stable for the entire operating period of 5 h, exhibiting 2.87 kg/m2·h of water vapor flux and 99.99% NaCl (35 g/L) rejection when the feed and permeate temp. were 48 and 16 °C, resp. Immobilization of MOF on nanofibers with the enhanced attachment was proven by inductively coupled mass spectrometry anal., by which no Fe2+ could be found in the permeate to the detection limit of ppt.
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    31. 31
      Meilikhov, M.; Yusenko, K.; Schollmeyer, E.; Mayer, C.; Buschmann, H.-J.; Fischer, R. A. Stepwise Deposition of Metal Organic Frameworks on Flexible Synthetic Polymer Surfaces. Dalton Trans. 2011, 40, 4838– 4841,  DOI: 10.1039/c0dt01820a
      31
      Stepwise deposition of metal organic frameworks on flexible synthetic polymer surfaces
      Meilikhov, Mikhail; Yusenko, Kirill; Schollmeyer, Eckhardt; Mayer, Christian; Buschmann, Hans-Juergen; Fischer, Roland A.
      Dalton Transactions (2011), 40 (18), 4838-4841CODEN: DTARAF; ISSN:1477-9226. (Royal Society of Chemistry)
      Thin films of [Cu3(btc)2]n (btc = 1,3,5-benzenetricarboxylate) metal org. framework were deposited in a stepwise manner on surfaces of flexible org. polymers. The thickness of films can be precisely controlled. The deposition of the first cycles was monitored by UV-vis spectroscopy. The porosity was proven by the adsorption of pyrazine, which was monitored by FT-IR and thermogravimetric anal. The deposition of MOF thin films on flexible polymer surfaces might be a new path for the fabrication of functional materials for different applications, such as protection layers for working clothes and gas sepn. materials in the textile industry.
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    32. 32
      da Silva Pinto, M.; Sierra-Avila, C. A.; Hinestroza, J. P. In Situ Synthesis of a Cu-BTC Metal–Organic Framework (MOF 199) onto Cellulosic Fibrous Substrates: Cotton. Cellulose 2012, 19, 1771– 1779,  DOI: 10.1007/s10570-012-9752-y
      32
      In situ synthesis of a Cu-BTC metal-organic framework (MOF 199) onto cellulosic fibrous substrates: cotton
      da Silva Pinto, Marcia; Sierra-Avila, Cesar Augusto; Hinestroza, Juan P.
      Cellulose (Dordrecht, Netherlands) (2012), 19 (5), 1771-1779CODEN: CELLE8; ISSN:0969-0239. (Springer)
      A mechanism for chem. attachment and growth of a Cu-BTC Metal-Org. Framework, also known as MOF-199 or HKUST-1, onto cellulosic substrates is reported. Four different exptl. procedures were attempted in order to elucidate the role of carboxylate groups on the anionic cellulose's surface. The order of addn. of Cu(OAc)2-copper acetate, BTH3, 1,3,5-benzenetricarboxylic acid and TEA-Triethylamine was found to be a crit. factor for the attachment and growth of the MOF-199 crystals onto anionic cellulose. The presence of MOF-199 crystals was probed using XRD and XPS spectra and a strong chem. interaction to the carboxymethylated cellulose fibers was confirmed by intense and vigorous washing of the specimens with water, DMF and methanol. Based on the recognized ability of MOF-199 to capture gases and toxic chems., combined with the availability of cellulose-based fibrous materials, the described procedure provides the basis for future fabrication of functionalized fibers and active filtration media.
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    33. 33
      Bechelany, M.; Drobek, M.; Vallicari, C.; Abou Chaaya, A.; Julbe, A.; Miele, P. Highly Crystalline MOF-Based Materials Grown on Electrospun Nanofibers. Nanoscale 2015, 7, 5794– 5802,  DOI: 10.1039/C4NR06640E
      33
      Highly crystalline MOF-based materials grown on electrospun nanofibers
      Bechelany, M.; Drobek, M.; Vallicari, C.; Abou Chaaya, A.; Julbe, A.; Miele, P.
      Nanoscale (2015), 7 (13), 5794-5802CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
      Supported Metal Org. Frameworks (MOFs) with a high sp. surface area are of great interest for applications in gas storage, sepn., sensing, and catalysis. In the present work we report the synthesis of a novel composite architecture of MOF materials supported on a flexible mat of electrospun nanofibers. The system, based on three-dimensional interwoven nanofibers, was designed by using a low-cost and scalable multistep synthesis protocol involving a combination of electrospinning and low-temp. at. layer deposition of oxide materials, and their subsequent solvothermal conversion under either conventional or microwave-assisted heating. This highly versatile approach allows the prodn. of different types of supported MOF crystals with controlled sizes, morphol., orientation and high accessibility.
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    34. 34
      Liu, C.; Wu, Y.-N.; Morlay, C.; Gu, Y.; Gebremariam, B.; Yuan, X.; Li, F. General Deposition of Metal–Organic Frameworks on Highly Adaptive Organic–Inorganic Hybrid Electrospun Fibrous Substrates. ACS Appl. Mater. Interfaces 2016, 8, 2552– 2561,  DOI: 10.1021/acsami.5b10078
      34
      General Deposition of Metal-Organic Frameworks on Highly Adaptive Organic-Inorganic Hybrid Electrospun Fibrous Substrates
      Liu, Chang; Wu, Yi-nan; Morlay, Catherine; Gu, Yifan; Gebremariam, Binyam; Yuan, Xiao; Li, Fengting
      ACS Applied Materials & Interfaces (2016), 8 (4), 2552-2561CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Org.-inorg. hybrid electrospun fibrous mats have been used as support materials to study the deposition of various MOF particles. HKUST-1 and MIL-53(Al) were produced through solvothermal method, while ZIF-8 and MIL-88B(Fe) were prepd. using microwave-induced heating method. The synthesis procedure for both methods were simple and effective because the hybrid nanofibrous mats showed considerable affinity to MOF particles and could be used without addnl. modifications. The obtained MOF composites exhibited effective incorporation between MOF particles and the porous substrates. MIL-53(Al) composite was applied as fibrous sorbent and showed enhanced adsorption capacity and removal rate, as well as easier operation, compared with the powd. sample. Moreover, MIL-53(Al) composite was easier to be regenerated compared with powder form.
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    35. 35
      Abbasi, A. R.; Akhbari, K.; Morsali, A. Dense Coating of Surface Mounted CuBTC Metal–Organic Framework Nanostructures on Silk Fibers, Prepared by Layer-by-Layer Method under Ultrasound Irradiation with Antibacterial Activity. Ultrason. Sonochem. 2012, 19, 846– 852,  DOI: 10.1016/j.ultsonch.2011.11.016
      35
      Dense coating of surface mounted CuBTC Metal-Organic Framework nanostructures on silk fibers, prepared by layer-by-layer method under ultrasound irradiation with antibacterial activity
      Abbasi, Amir Reza; Akhbari, Kamran; Morsali, Ali
      Ultrasonics Sonochemistry (2012), 19 (4), 846-852CODEN: ULSOER; ISSN:1350-4177. (Elsevier B.V.)
      The growth of Cu3(BTC)2 (BTC = 1,3,5-benzenetricarboxylate), also known as CuBTC and HKUST-1, Metal-Org. Framework (MOF) nanostructures on silk fibers were achieved by layer-by-layer technique in alternating bath of Cu(OAc)2·2H2O and H3BTC solns. under ultrasound irradn. The effect of pH, reaction time, ultrasound irradn. and sequential dipping steps in growth of the CuBTC Metal-Org. Framework nanostructures has been studied. These systems depicted a decrease in the size accompanying a decrease in the sequential dipping steps. In addn., dense coating of silk fibers with CuBTC MOF results in decrease the emission intensity of silk fibers. The silk fibers contg. CuBTC Metal-Org. Framework exhibited high antibacterial activity against Escherichia coli and Staphylococcus aureus. The samples were characterized with powder X-ray diffraction (XRD), Fourier transform IR spectroscopy (FTIR) spectra and SEM. XRD analyses indicated that the prepd. CuBTC MOF nanostructures on silk fibers were cryst.
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    36. 36
      Horcajada, P.; Serre, C.; Vallet-Regí, M.; Sebban, M.; Taulelle, F.; Férey, G. Metal–Organic Frameworks as Efficient Materials for Drug Delivery. Angew. Chem., Int. Ed. 2006, 45, 5974– 5978,  DOI: 10.1002/anie.200601878
      36
      Metal-organic frameworks as efficient materials for drug delivery
      Horcajada, Patricia; Serre, Christian; Vallet-Regi, Maria; Sebban, Muriel; Taulelle, Francis; Ferey, Gerard
      Angewandte Chemie, International Edition (2006), 45 (36), 5974-5978CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The metal carboxylates MIL-100 and MIL-101 (MIL = Materials of Institut Lavoisier) act as porous matrixes for drug-delivery systems using ibuprofen as a model substrate. Very large amts. of the drug could be incorporated, up to an unprecedented capacity of 1.4 g of drug per g of porous solid for MIL-101, and the total release of ibuprofen was achieved under physiol. conditions in 3 (MIL-100) and 6 days (MIL-101).
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    37. 37
      Quirós, J.; Boltes, K.; Aguado, S.; de Villoria, R. G.; Vilatela, J. J.; Rosal, R. Antimicrobial Metal–Organic Frameworks Incorporated into Electrospun Fibers. Chem. Eng. J. 2015, 262, 189– 197,  DOI: 10.1016/j.cej.2014.09.104
      37
      Antimicrobial metal-organic frameworks incorporated into electrospun fibers
      Quiros, Jennifer; Boltes, Karina; Aguado, Sonia; de Villoria, Roberto Guzman; Vilatela, Juan Jose; Rosal, Roberto
      Chemical Engineering Journal (Amsterdam, Netherlands) (2015), 262 (), 189-197CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
      The objective of this paper is to present a new class of polylactic acid (PLA) fibers contg. cobalt-based metal org. frameworks (MOF). The material used was Co-SIM-1, a cobalt-based substituted imidazolate. Composite mats were prepd. by electrospinning PLA with a suspension of polyvinylpyrrolidone-stabilized Co-SIM-1. MOF particles formed aggregate of a small no. of primary particles that, after electrospun, became completely embedded inside polymeric fibers. The dispersion of particles was better for lower loadings, for which the relative amt. of metal released to culture media was also higher. The antimicrobial activity of composite mats was assessed using SEM images, fluorescence microscopy, direct plate reading of fluorescent stains and plate count of colony forming units among other. The microorganisms used in this study were Pseudomonas putida and Staphylococcus aureus. Fluorescence techniques allowed recording viable and damaged cells directly on mat surface and in the culture media embedding the fibers. The results showed higher sensitivity of S. aureus to cobalt-contg. fibers, with a redn. in colony forming units of up to 60% with respect to PLA mats. The results also showed the presence of viable but non-culturable microorganisms, which fail to form colonies but yield a pos. signal to viable cell staining. Cobalt-based MOF included in electrospun mats provide antibacterial activity suitable to be used to prep. membranes for various biomedical applications.
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    38. 38
      Gao, M.; Zeng, L.; Nie, J.; Ma, G. Polymer–Metal–Organic Framework Core–Shell Framework Nanofibers via Electrospinning and Their Gas Adsorption Activities. RSC Adv. 2016, 6, 7078– 7085,  DOI: 10.1039/C5RA23147G
      38
      Polymer-metal-organic framework core-shell framework nanofibers via electrospinning and their gas adsorption activities
      Gao, Ming; Zeng, Lingwang; Nie, Jun; Ma, Guiping
      RSC Advances (2016), 6 (9), 7078-7085CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
      In this study, we have fabricated of Polyacrylonitrile/Zeoliticimidazolate frameworks (PAN@ZIF-8) core-shell nanofibers by combining electrospinning techniques and the MOF synthesis method. In the first step, 2MI ligand was dispersed on PAN by using electrospinning, and then 2MI was made to coordinate Zn2+ ions derived from a zinc acetate soln. In the second step, the nanofiber mats were immersed in a ZIF-8 seed soln., and continuous and compact ZIF-8 was formed on the PAN surface by a second round of crystal growth. Analyses of XPS results and of SEM and TEM images revealed the core-shell structure of PAN@ZIF-8 nanofibers, and showed them to have a uniform nanoshell but a variety of crystal diams. In addn., the core-shell PAN@ZIF-8 nanofibers were found to display unique properties such as a stable and flexible structure and an excellent gas adsorption capability. Our findings suggest that the core-shell PAN@ZIF-8 nanofiber mats may form a good filter material because of their gas absorption properties and because of the structural flexibility and stability of ZIF-8.
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    39. 39
      Zhang, C.-L.; Lu, B.-R.; Cao, F.-H.; Wu, Z.-Y.; Zhang, W.; Cong, H.-P.; Yu, S.-H. Electrospun Metal-Organic Framework Nanoparticle Fibers and Their Derived Electrocatalysts for Oxygen Reduction Reaction. Nano Energy 2019, 55, 226– 233,  DOI: 10.1016/j.nanoen.2018.10.029
      39
      Electrospun metal-organic framework nanoparticle fibers and their derived electrocatalysts for oxygen reduction reaction
      Zhang, Chuan-Ling; Lu, Bing-Rong; Cao, Fu-Hu; Wu, Zhen-Yu; Zhang, Wang; Cong, Huai-Ping; Yu, Shu-Hong
      Nano Energy (2019), 55 (), 226-233CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
      The rational design of assembled metal-org. frameworks (MOFs) derived carbon materials with rapid mass transport properties and stable porous structure is highly desirable yet a great challenge to date. In this work, MOFs-derived Co/N-doped porous carbon fibers with high electrochem. performance can be prepd. simply by carbonizing MOFs nanofibers, which were fabricated by the electrospinning-assisted assembly of bimetallic zeolitic imidazolate framework nanoparticles (BMZIFs) based on ZIF-8 and ZIF-67. The effects of assembly and Zn/Co ratios on the oxygen redn. reaction (ORR) performances of the electrospun fibers derivs. were systematically studied. As expected, compared to the non-electrospun samples, such doped porous carbon nanofibers exhibited excellent electrocatalytic performances without any etching or other activating processes, and the sample with the molar ratio of Zn: Co= 5:1 even showed comparable ORR performance with the com. Pt/C catalyst under the same conditions. The high catalytic performances root in the dense assembly of MOFs within the electrospun fibers, which was beneficial to endow the derivs. with the high surface area as well as uniform N and Co doping. Besides, the one-dimensional porous structure significantly promoted the mass transfer and exposure of active sites.
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    40. 40
      McCarthy, D. L.; Liu, J.; Dwyer, D. B.; Troiano, J. L.; Boyer, S. M.; DeCoste, J. B.; Bernier, W. E.; Jones, W. E., Jr. Electrospun Metal–Organic Framework Polymer Composites for the Catalytic Degradation of Methyl Paraoxon. New J. Chem. 2017, 41, 8748– 8753,  DOI: 10.1039/C7NJ00525C
      40
      Electrospun metal-organic framework polymer composites for the catalytic degradation of methyl paraoxon
      McCarthy, Danielle L.; Liu, Jian; Dwyer, Derek B.; Troiano, Jennifer L.; Boyer, Steven M.; DeCoste, Jared B.; Bernier, William E.; Jones, Jr, Wayne E.
      New Journal of Chemistry (2017), 41 (17), 8748-8753CODEN: NJCHE5; ISSN:1144-0546. (Royal Society of Chemistry)
      Current world events involving chem. warfare agents have resulted in the need for developing a novel engineered material for the decompn. of the nerve agents contg. toxic P-F or P-C≡N bond as seen in G-agents and P-S bond as seen in VX. Engineered composites consisting of electrospun PMMA/Ti(OH)4/UiO-66 were fabricated and employed in the degrdn. of Me paraoxon, a chem. warfare agent simulant. UiO-66 and other Zr based metal-org. frameworks have previously demonstrated their ability to catalytically hydrolyze the phosphonate ester bond. In this study, the PMMA/Ti(OH)4/UiO-66 composite has been found to decrease the half-life of the simulant Me paraoxon to only 29 min with only a fraction of the MOF material, compared to 45 min for pure UiO-66. We conclude that the dispersion of UiO-66 particles on the engineered fibers allow for improved diffusion of the analyte into the pores. This is turn gives promise to other engineered forms of MOFs for improving the catalytic degrdn. of organophosphates.
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    41. 41
      Chui, S. S.-Y.; Lo, S. M.-F.; Charmant, J. P. H.; Orpen, G. A.; Williams, I. D. A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]N. Science 1999, 283, 1148– 1150,  DOI: 10.1126/science.283.5405.1148
      41
      A chemically functionalizable nanoporous material [Cu3(TMA)2(H2O)3]n
      Chui, Stephen S.-Y.; Lo, Samuel M.-F.; Charmant, Jonathan P. H.; Orpen, A. Guy; Williams, Ian D.
      Science (Washington, D. C.) (1999), 283 (5405), 1148-1150CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
      Although zeolites and related materials combine nanoporosity with high thermal stability, they are difficult to modify or derivatize in a systematic way. A highly porous metal coordination polymer [Cu3(TMA)2(H2O)3]n (TMA is benzene-1,3,5-tricarboxylate) was formed in 80% yield. It has interconnected [Cu2(O2CR)4] units (R is an arom. ring), which create a three-dimensional system of channels with a pore size of 1 nm and an accessible porosity of ∼40% in the solid. Unlike zeolites, the channel linings can be chem. functionalized; for example, the aqua ligands can be replaced by pyridines. TGA and high-temp. single-crystal diffractometry indicate that the framework is stable up to 240°.
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    42. 42
      Park, K. S.; Ni, Z.; Cote, A. P.; Choi, J. Y.; Huang, R.; Uribe-Romo, F. J.; Chae, H. K.; O’Keeffe, M.; Yaghi, O. M. Exceptional Chemical and Thermal Stability of Zeolitic Imidazolate Frameworks. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 10186– 10191,  DOI: 10.1073/pnas.0602439103
      42
      Exceptional chemical and thermal stability of zeolitic imidazolate frameworks
      Park, Kyo Sung; Ni, Zheng; Cote, Adrien P.; Choi, Jae Yong; Huang, Rudan; Uribe-Romo, Fernando J.; Chae, Hee K.; O'Keeffe, Michael; Yaghi, Omar M.
      Proceedings of the National Academy of Sciences of the United States of America (2006), 103 (27), 10186-10191CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
      Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) were synthesized as crystals by copolymn. of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, resp. One example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chem. stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m2/g), high thermal stability (up to 550°), and remarkable chem. resistance to boiling alk. H2O and org. solvents.
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    43. 43
      Huang, X.-C.; Lin, Y.-Y.; Zhang, J.-P.; Chen, X.-M. Ligand-Directed Strategy for Zeolite-Type Metal–Organic Frameworks: Zinc(II) Imidazolates with Unusual Zeolitic Topologies. Angew. Chem., Int. Ed. 2006, 45, 1557– 1559,  DOI: 10.1002/anie.200503778
      43
      Ligand-directed strategy for zeolite-type metal-organic frameworks: zinc(II) imidazolates with unusual zeolitic topologies
      Huang, Xiao-Chun; Lin, Yan-Yong; Zhang, Jie-Peng; Chen, Xiao-Ming
      Angewandte Chemie, International Edition (2006), 45 (10), 1557-1559CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Thermally robust porous metal-org. frameworks (MOFs) with zeolitic topologies were constructed by means of a ligand-directed strategy involving mol. tailoring of simple bridging imidazolates with coordinatively unimportant substituents. This led to the isolation of three new MOFs having unusually high symmetries, intriguing topologies such as the supercage shown in the picture, and high thermal stability. Crystal structures of the metal-org. framework compds. are described.
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    44. 44
      Stock, N.; Biswas, S. Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites. Chem. Rev. 2011, 112, 933– 969,  DOI: 10.1021/cr200304e
      There is no corresponding record for this reference.
    45. 45
      Lee, Y.-R.; Kim, J.; Ahn, W.-S. Synthesis of Metal-Organic Frameworks: A Mini Review. Korean J. Chem. Eng. 2013, 30, 1667– 1680,  DOI: 10.1007/s11814-013-0140-6
      45
      Synthesis of metal-organic frameworks: A mini review
      Lee, Yu-Ri; Kim, Jun; Ahn, Wha-Seung
      Korean Journal of Chemical Engineering (2013), 30 (9), 1667-1680CODEN: KJCHE6; ISSN:0256-1115. (Springer)
      A review. Metal org. frameworks (MOFs) are porous cryst. materials of one-, two-, or three-dimensional networks constructed from metal ions/clusters and multidentate org. linkers via coordination bonding, which are emerging as an important group of materials for energy storage, CO2 adsorption, alkane/alkene sepn., and catalysis. To introduce newcomers in chem. engineering discipline to the rapidly expanding MOF research works, this review presents a brief introduction to the currently available MOFs synthesis methods. Starting from the conventional solvothermal/hydrothermal synthesis, microwave-assisted, sonochem., electrochem., mechanochem., ionothermal, drygel conversion, and microfluidic synthesis methods will be presented. Examples will be limited to those representative MOF structures that can be synthesized using common org. ligands of 1,4-benzenedicarboxylic acid (and its functionalized forms) and 1,3,5-benzenetricarboxylic acid, in conjunction with metal nodes of Zn2+, Cu2+, Cr3+, Al3+, Fe3+ and Zr4+. Synthesis of widely-investigated zeolitic imidazolate framework (ZIF) structure, ZIF-8 is also included.
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    46. 46
      Wendorff, J. H.; Agarwal, S.; Greiner, A. Electrospinning: Materials, Processing, and Applications; John Wiley & Sons, Incorporated: Weinheim, 2012.
      There is no corresponding record for this reference.
    47. 47
      Shahmiri, M.; Ibrahim, N. A.; Shayesteh, F.; Asim, N.; Motallebi, N. Preparation of PVP-Coated Copper Oxide Nanosheets as Antibacterial and Antifungal Agents. J. Mater. Res. 2013, 28, 3109– 3118,  DOI: 10.1557/jmr.2013.316
      47
      Preparation of PVP-coated copper oxide nanosheets as antibacterial and antifungal agents
      Shahmiri, Mahdi; Ibrahim, Nor Azowa; Shayesteh, Fatemeh; Asim, Nilofar; Motallebi, Nabi
      Journal of Materials Research (2013), 28 (22), 3109-3118CODEN: JMREEE; ISSN:2044-5326. (Cambridge University Press)
      Copper oxide (CuO) nanosheets synthesized in polyvinylpyrrolidone (PVP) were characterized with respect to antimicrobial activity by quick pptn. method. Different sizes and shapes of CuO nanosheets were obtained by simple variations of PVP concns. The x-ray diffraction results revealed the formation of pure-phase CuO with monoclinic structure. Transmission electron microscopy anal. showed that the av. ratio of length to width of these nanosheets increased with increasing PVP concns. Due to the quantum size effect, CuO nanosheets exhibit a blue shift in the UV-visible spectra. Field emission SEM results showed that as the concn. of PVP increased, well-defined morphologies were formed on the surface of the products. Energy dispersive anal. of x-ray clearly confirmed the presence of Cu and O with an at. ratio of 1:1. Fourier transform IR spectroscopy results showed that C=O in PVP coordinated with CuO and formed a protective layer. The mechanism of the reaction was also discussed. CuO nanosheets in suspension showed activity against a range of bacterial pathogens and fungi with min. bactericidal concns. (MBCs) ranging from 100 to 5000 μg/mL. The extent of the inhibition zones and the MBCs was found to be size-dependent.
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    48. 48
      Diao, S.; Wang, Y.; Jin, H. Electronucleation Mechanism of Copper in Wastewater by Controlled Electrodeposition Analysis. RSC Adv. 2020, 10, 38683– 38694,  DOI: 10.1039/D0RA07380F
      48
      Electronucleation mechanism of copper in wastewater by controlled electrodeposition analysis
      Diao, Shuzhi; Wang, Yiyong; Jin, Hui
      RSC Advances (2020), 10 (63), 38683-38694CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
      In order to improve the efficiency of copper deposition in wastewater contg. the surfactant polyvinylpyrrolidone (PVP) and reveal the mechanism of copper crystals, a controlled electrodeposition process was developed using a low-cost stainless steel cathode and investigated using chronoamperometry (CA), electrochem. impedance spectroscopy (EIS) and IR spectroscopy (IR). The theor. anal. was verified by fitting them to exptl. curves and calcg. the kinetic parameters of the deposition process. The exptl. results showed that Cu(PVP)2 was formed by the reaction between the CO bond of PVP and Cu2++. When powd., redn. of Cu2++ in the Cu(PVP)2 structure was promoted, a pos.-charged PVP-coating layer was formed on the surface of the copper crystal nuclei to inhibit the growth of the copper powder. At a potential of -0.2 V, the electrodeposition crystn. curve of copper changed from progressive nucleation to instantaneous nucleation. The kinetic parameters of the deposition process were calcd. by fitting the exptl. curves to verify the correctness of the theor. anal. The EIS tests showed that removing the powder reduced the resistance of the org. solvent (PVP) film on the electrode surface and the charge transfer resistance during copper deposition. According to particle size anal., removing the powder could reduce the growth energy of copper powder on the electrode surface, increase the area of the active part on the electrode surface, increase the current efficiency of copper powder to 84.2%, and control dust. The size of copper powder reached up to around 900 nm.
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    49. 49
      Soltani, N.; Saion, E.; Erfani, M.; Rezaee, K.; Bahmanrokh, G.; Drummen, G. P. C.; Bahrami, A.; Hussein, M. Z. Influence of the Polyvinyl Pyrrolidone Concentration on Particle Size and Dispersion of ZnS Nanoparticles Synthesized by Microwave Irradiation. Int. J. Mol. Sci. 2012, 13, 12412– 12427,  DOI: 10.3390/ijms131012412
      49
      Influence of the polyvinylpyrrolidone concentration on particle size and dispersion of ZnS nanoparticles synthesized by microwave irradiation
      Soltani, Nayereh; Saion, Elias; Erfani, Maryam; Rezaee, Khadijeh; Bahmanrokh, Ghazaleh; Drummen, Gregor P. C.; Bahrami, Afarin; Hussein, Mohd. Zobi
      International Journal of Molecular Sciences (2012), 13 (), 12412-12427CODEN: IJMCFK; ISSN:1422-0067. (MDPI AG)
      ZnS semiconductor nanoparticles were prepd. in an aq. soln. of polyvinyl pyrrolidone via a simple microwave irradn. method. The effect of the polymer concn. and the type of sulfur source on the particle size and dispersion of the final ZnS nanoparticle product was carefully examd. Microwave heating generally occurs by two main mechanisms: dipolar polarization of water and ionic conduction of precursors. The introduction of the polymer affects the heating rate by restriction of the rotational motion of dipole mols. and immobilization of ions. The presence of the polymer strongly affects the nucleation and growth rates of the ZnS nanoparticles and therefore dets. the av. particle size and the dispersion. PVP adsorbed on the surface of the ZnS nanoparticles by interaction of the C-N and C=O with the nanoparticle's surface, thereby affording protection from agglomeration by steric hindrance. Generally, with increasing PVP concn., monodispersed colloidal solns. were obtained and at the optimal PVP concn. (5%), sufficiently small size and narrow size distributions were obtained from both Na2S and thioacetamide sulfur sources. Finally, the sulfur source directly influences the reaction mechanism and the final particle morphol., as well as the av. size.
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    50. 50
      Ameloot, R.; Gobechiya, E.; Uji-i, H.; Martens, J. A.; Hofkens, J.; Alaerts, L.; Sels, B. F.; De Vos, D. E. Direct Patterning of Oriented Metal-Organic Framework Crystals via Control over Crystallization Kinetics in Clear Precursor Solutions. Adv. Mater. 2010, 22, 2685– 2688,  DOI: 10.1002/adma.200903867
      50
      Direct Patterning of Oriented Metal-Organic Framework Crystals via Control over Crystallization Kinetics in Clear Precursor Solutions
      Ameloot, Rob; Gobechiya, Elena; Uji-i, Hiroshi; Martens, Johan A.; Hofkens, Johan; Alaerts, Luc; Sels, Bert F.; De Vos, Dirk E.
      Advanced Materials (Weinheim, Germany) (2010), 22 (24), 2685-2688CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A concept of metal-org. framework (MOF) processing based on the use of stable precursor soln. of the MOF primary building blocks is proposed. Crystal nucleation, growth, and morphol. of Cu3(BTC)2 crystals and the effect of the solvent on these processes were studied (BTC = 1,3,5-benzenetricarboxylate). Cu3(BTC)2 crystals were grown from clear precursor soln. using patterned template.
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    51. 51
      Cravillon, J.; Münzer, S.; Lohmeier, S.-J.; Feldhoff, A.; Huber, K.; Wiebcke, M. Rapid Room-Temperature Synthesis and Characterization of Nanocrystals of a Prototypical Zeolitic Imidazolate Framework. Chem. Mater. 2009, 21, 1410– 1412,  DOI: 10.1021/cm900166h
      51
      Rapid Room-Temperature Synthesis and Characterization of Nanocrystals of a Prototypical Zeolitic Imidazolate Framework
      Cravillon, Janosch; Munzer, Simon; Lohmeier, Sven-Jare; Feldhoff, Armin; Huber, Klaus; Wiebcke, Michael
      Chemistry of Materials (2009), 21 (8), 1410-1412CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      Simply reacting Zn(NO3)2·6H2O with an excess of 2-methylimidazole in methanol at room temp. yields well-shaped nanocrystals of ZIF-8 with a narrow size distribution. The rapid growth has been monitored by time-resolved static light scattering. Nanoscale ZIF-8 powder is microporous and thermally stable up to ca. 200°.
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    52. 52
      Zhuang, J.-L.; Ceglarek, D.; Pethuraj, S.; Terfort, A. Rapid Room-Temperature Synthesis of Metal-Organic Framework HKUST-1 Crystals in Bulk and as Oriented and Patterned Thin Films. Adv. Funct. Mater. 2011, 21, 1442– 1447,  DOI: 10.1002/adfm.201002529
      52
      Rapid Room-Temperature Synthesis of Metal-Organic Framework HKUST-1 Crystals in Bulk and as Oriented and Patterned Thin Films
      Zhuang, Jin-Liang; Ceglarek, Doris; Pethuraj, Sangeetha; Terfort, Andreas
      Advanced Functional Materials (2011), 21 (8), 1442-1447CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Whereas the prepn. of defined metal-org. framework (MOF) materials via hydrothermal or diffusion methods typically requires hours to days, the simple pptn. route opens the access to the known HKUST-1 frameworks within minutes. Crucial for the formation of a well-defined, cryst. material is the choice of suitable pptg. solvents, with methanol and ethanol being the most favorable ones. This approach could be extended to the formation of dense, surface-mounted MOF films (so-called SURMOFs), in particular if the surfaces are decorated with suitable binding groups by formation of self-assembled monolayers (SAMs). By combination with micro-contact printing (μCP), patterned SURMOFs became accessible, in which the pptg. solvent is decisive on the formation of either spatially restricted films or single particles.
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    53. 53
      Wang, M.; Fang, D.; Wang, N.; Jiang, S.; Nie, J.; Yu, Q.; Ma, G. Preparation of PVDF/PVP Core–Shell Nanofibers Mats via Homogeneous Electrospinning. Polymer 2014, 55, 2188– 2196,  DOI: 10.1016/j.polymer.2014.02.035
      53
      Preparation of PVDF/PVP core-shell nanofibers mats via homogeneous electrospinning
      Wang, Meice; Fang, Dawei; Wang, Nannan; Jiang, Shan; Nie, Jun; Yu, Qiang; Ma, Guiping
      Polymer (2014), 55 (9), 2188-2196CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)
      The polyvinylpyrrolidone (PVP)/poly(vinylidene fluoride) (PVDF) core-shell nanofiber mats with superhydrophobic surface have been prepd. via electrospinning its homogeneous blending solns., and the formation of the core-shell structure was achieved by the thermal induced phase sepn. assisted with the low surface tension of PVDF. The electrospinnability of the blending solns. was also investigated by varying the blending ratio of the PVP and PVDF, and it enhanced with the increase of PVP content. SEM and TEM results showed that the fibers size was varied in the range of 100 nm-600 nm with smooth surface and core-shell structure. The compn. of the shell layer was detd. by the XPS anal., and further confirmed by water contact angle (WCA) testing. As the fraction of PVDF exceeding PVP in the electrospinning solns., the nanofiber mats showed superhydrophobic property with the WCA above 120°. It indicated that the PVDF was concd. in the shell layer of the fibers. X-Ray diffraction (XRD) and attenuated total reflection IR spectroscopy (ATR-IR) anal. indicated that the PVDF was aggregated with the β-phase crystallite as dominant crystallite. The nanofiber mats with the gas breathability and watertightness ability due to the porous structure and superhydrophobic would be potential applied in wound healing.
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    54. 54
      Niu, Q.; Zeng, L.; Mu, X.; Nie, J.; Ma, G. Preparation and Characterization of Core-Shell Nanofibers by Electrospinning Combined with in Situ UV Photopolymerization. J. Ind. Eng. Chem. 2016, 34, 337– 343,  DOI: 10.1016/j.jiec.2015.12.006
      54
      Preparation and characterization of core-shell nanofibers by electrospinning combined with in situ UV photopolymerization
      Niu, Qijian; Zeng, Lingwang; Mu, Xueyan; Nie, Jun; Ma, Guiping
      Journal of Industrial and Engineering Chemistry (Amsterdam, Netherlands) (2016), 34 (), 337-343CODEN: JIECFI; ISSN:1226-086X. (Elsevier B.V.)
      The objective of this work is to demonstrate the feasibility of prepn. of core-shell nanofibers by electrospinning combined with in situ UV photopolymn. The thiol-ene monomer with Si atom and the initiator can migrate to the surface with the evapn. of the solvent during the process of electrospinning, which caused phase sepn. due to the great migration ability of small mol. and low surface energy. Then photo induced polymn. and crosslinking reaction took place simultaneously during the electrospinning process, which formed shell of the nanofibers. The morphol. and structure of electrospun nanofibers were investigated by SEM and TEM. The compn. of the shell layer was detd. by ATR-IR and XPS. Moreover, the nanofiber mats were tested by WCA test, and the hydrophobic ability of PVP nanofibers was improved because of the protection of the shell layer with Si atom. The most important thing is that the technol. which combined electrospinning with in situ photopolymn. provides a simple method for prepn. of core-shell nanofibers.
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    55. 55
      Niu, C.; Meng, J.; Wang, X.; Han, C.; Yan, M.; Zhao, K.; Xu, X.; Ren, W.; Zhao, Y.; Xu, L.; Zhang, Q.; Zhao, D.; Mai, L. General Synthesis of Complex Nanotubes by Gradient Electrospinning and Controlled Pyrolysis. Nat. Commun. 2015, 6, 7402,  DOI: 10.1038/ncomms8402
      55
      General synthesis of complex nanotubes by gradient electrospinning and controlled pyrolysis
      Niu Chaojiang; Meng Jiashen; Wang Xuanpeng; Han Chunhua; Yan Mengyu; Zhao Kangning; Xu Xiaoming; Ren Wenhao; Zhang Qingjie; Zhao Dongyuan; Mai Liqiang; Zhao Yunlong; Xu Lin
      Nature communications (2015), 6 (), 7402 ISSN:.
      Nanowires and nanotubes have been the focus of considerable efforts in energy storage and solar energy conversion because of their unique properties. However, owing to the limitations of synthetic methods, most inorganic nanotubes, especially for multi-element oxides and binary-metal oxides, have been rarely fabricated. Here we design a gradient electrospinning and controlled pyrolysis method to synthesize various controllable 1D nanostructures, including mesoporous nanotubes, pea-like nanotubes and continuous nanowires. The key point of this method is the gradient distribution of low-/middle-/high-molecular-weight poly(vinyl alcohol) during the electrospinning process. This simple technique is extended to various inorganic multi-element oxides, binary-metal oxides and single-metal oxides. Among them, Li3V2(PO4)3, Na0.7Fe0.7Mn0.3O2 and Co3O4 mesoporous nanotubes exhibit ultrastable electrochemical performance when used in lithium-ion batteries, sodium-ion batteries and supercapacitors, respectively. We believe that a wide range of new materials available from our composition gradient electrospinning and pyrolysis methodology may lead to further developments in research on 1D systems.
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    56. 56
      Liang, W.; Wied, P.; Carraro, F.; Sumby, C. J.; Nidetzky, B.; Tsung, C.-K.; Falcaro, P.; Doonan, C. J. Metal–Organic Framework-Based Enzyme Biocomposites. Chem. Rev. 2021, 121, 1077– 1129,  DOI: 10.1021/acs.chemrev.0c01029
      56
      Metal-Organic Framework-Based Enzyme Biocomposites
      Liang, Weibin; Wied, Peter; Carraro, Francesco; Sumby, Christopher J.; Nidetzky, Bernd; Tsung, Chia-Kuang; Falcaro, Paolo; Doonan, Christian J.
      Chemical Reviews (Washington, DC, United States) (2021), 121 (3), 1077-1129CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. Because of their efficiency, selectivity, and environmental sustainability, there are significant opportunities for enzymes in chem. synthesis and biotechnol. However, as the three-dimensional active structure of enzymes is predominantly maintained by weaker noncovalent interactions, thermal, pH, and chem. stressors can modify or eliminate activity. Metal-org. frameworks (MOFs), which are extended porous network materials assembled by a bottom-up building block approach from metal-based nodes and org. linkers, can be used to afford protection to enzymes. The self-assembled structures of MOFs can be used to encase an enzyme in a process called encapsulation when the MOF is synthesized in the presence of the biomol. Alternatively, enzymes can be infiltrated into mesoporous MOF structures or surface bound via covalent or noncovalent processes. Integration of MOF materials and enzymes in this way affords protection and allows the enzyme to maintain activity in challenge conditions (e.g., denaturing agents, elevated temp., non-native pH, and org. solvents). In addn. to forming simple enzyme/MOF biocomposites, other materials can be introduced to the composites to improve recovery or facilitate advanced applications in sensing and fuel cell technol. This review canvasses enzyme protection via encapsulation, pore infiltration, and surface adsorption and summarizes strategies to form multicomponent composites. Also, given that enzyme/MOF biocomposites straddle materials chem. and enzymol., this review provides an assessment of the characterization methodologies used for MOF-immobilized enzymes and identifies some key parameters to facilitate development of the field.
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    57. 57
      Huang, S.; Kou, X.; Shen, J.; Chen, G.; Ouyang, G. “Armor-Plating” Enzymes with Metal–Organic Frameworks (MOFs). Angew. Chem., Int. Ed. 2020, 59, 8786– 8798,  DOI: 10.1002/anie.201916474
      57
      "Armor-Plating" Enzymes with Metal-Organic Frameworks (MOFs)
      Huang, Siming; Kou, Xiaoxue; Shen, Jun; Chen, Guosheng; Ouyang, Gangfeng
      Angewandte Chemie, International Edition (2020), 59 (23), 8786-8798CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Cell-free enzymic catalysis (CFEC) is an emerging biotechnol. that enable the biol. transformations in complex natural networks to be imitated. This biomimetic approach allows industrial products such as biofuels and biochem. to be manufd. in a green manner. Nevertheless, the main challenge in CFEC is the poor stability, which restricts the effectiveness and lifetime of enzymes in sophisticated applications. Immobilization of the enzymes within solid carriers is considered an efficient strategy for addressing these obstacles. Specifically, putting an "armor-like" porous metal-org. framework (MOF) exoskeleton tightly around the enzymes not only shields the enzymes against external stimulus, but also allows the selective transport of guests through the accessible porous network. Herein we present the concept of this biotechnol. of MOF-entrapped enzymes and its cutting-edge applications.
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    58. 58
      Majewski, M. B.; Howarth, A. J.; Li, P.; Wasielewski, M. R.; Hupp, J. T.; Farha, O. K. Enzyme Encapsulation in Metal–Organic Frameworks for Applications in Catalysis. CrystEngComm 2017, 19, 4082– 4091,  DOI: 10.1039/C7CE00022G
      58
      Enzyme encapsulation in metal-organic frameworks for applications in catalysis
      Majewski, Marek B.; Howarth, Ashlee J.; Li, Peng; Wasielewski, Michael R.; Hupp, Joseph T.; Farha, Omar K.
      CrystEngComm (2017), 19 (29), 4082-4091CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
      A review. Enzymes are natural catalysts which are highly selective and efficient. Given that enzymes have very intricate and delicate structures, they need to be stabilized and protected by a support material if they are to be used under challenging catalytic conditions. This highlight focuses on the use of metal-org. frameworks as supports for enzyme encapsulation and subsequent catalytic applications. De novo and post-synthetic methods of encapsulation are discussed and the relative catalytic activities of the enzyme@MOF composites vs. free enzymes are highlighted.
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    59. 59
      Xia, H.; Li, N.; Zhong, X.; Jiang, Y. Metal-Organic Frameworks: A Potential Platform for Enzyme Immobilization and Related Applications. Front. Bioeng. Biotechnol. 2020, 8, 695,  DOI: 10.3389/fbioe.2020.00695
      59
      Metal-Organic Frameworks: A Potential Platform for Enzyme Immobilization and Related Applications
      Xia Huan; Li Na; Zhong Xue; Jiang Yanbin
      Frontiers in bioengineering and biotechnology (2020), 8 (), 695 ISSN:2296-4185.
      Enzymes, as natural catalysts with remarkable catalytic activity and high region-selectivities, hold great promise in industrial catalysis. However, applications of enzymatic transformation are hampered by the fragility of enzymes in harsh conditions. Recently, metal-organic frameworks (MOFs), due to their high stability and available structural properties, have emerged as a promising platform for enzyme immobilization. Synthetic strategies of enzyme-MOF composites mainly including surface immobilization, covalent linkage, pore entrapment and in situ synthesis. Compared with free enzymes, most immobilized enzymes exhibit enhanced resistance against solvents and high temperatures. Besides, MOFs serving as matrixes for enzyme immobilization show extraordinary superiority in many aspects compared with other supporting materials. The advantages of using MOFs to support enzymes are discussed. To obtain a high enzyme loading capacity and to reduce the diffusion resistance of reactants and products during the reaction, the mesoporous MOFs have been designed and constructed. This review also covers the applications of enzyme-MOF composites in bio-sensing and detection, bio-catalysis, and cancer therapy, which is concerned with interdisciplinary nano-chemistry, material science and medical chemistry. Finally, some perspectives on reservation or enhancement of bio-catalytic activity of enzyme-MOF composites and the future of enzyme immobilization strategies are discussed.
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    60. 60
      Liang, K.; Ricco, R.; Doherty, C. M.; Styles, M. J.; Bell, S.; Kirby, N.; Mudie, S.; Haylock, D.; Hill, A. J.; Doonan, C. J.; Falcaro, P. Biomimetic Mineralization of Metal-Organic Frameworks as Protective Coatings for Biomacromolecules. Nat. Commun. 2015, 6, 7240,  DOI: 10.1038/ncomms8240
      60
      Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules
      Liang, Kang; Ricco, Raffaele; Doherty, Cara M.; Styles, Mark J.; Bell, Stephen; Kirby, Nigel; Mudie, Stephen; Haylock, David; Hill, Anita J.; Doonan, Christian J.; Falcaro, Paolo
      Nature Communications (2015), 6 (), 7240CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)
      Enhancing the robustness of functional biomacromols. is a crit. challenge in biotechnol., which if addressed would enhance their use in pharmaceuticals, chem. processing and biostorage. Here we report a novel method, inspired by natural biomineralization processes, which provides unprecedented protection of biomacromols. by encapsulating them within a class of porous materials termed metal-org. frameworks. We show that proteins, enzymes and DNA rapidly induce the formation of protective metal-org. framework coatings under physiol. conditions by concg. the framework building blocks and facilitating crystn. around the biomacromols. The resulting biocomposite is stable under conditions that would normally decomp. many biol. macromols. For example, urease and horseradish peroxidase protected within a metal-org. framework shell are found to retain bioactivity after being treated at 80 °C and boiled in DMF (153 °C), resp. This rapid, low-cost biomimetic mineralization process gives rise to new possibilities for the exploitation of biomacromols.
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    61. 61
      Pisklak, T. J.; Macías, M.; Coutinho, D. H.; Huang, R. S.; Balkus, K. J., Jr. Hybrid Materials for Immobilization of MP-11 Catalyst. Top. Catal. 2006, 38, 269– 278,  DOI: 10.1007/s11244-006-0025-6
      61
      Hybrid materials for immobilization of MP-11 catalyst
      Pisklak, Thomas J.; Macias, Minedys; Coutinho, Decio H.; Huang, Rita S.; Balkus, Kenneth J., Jr.
      Topics in Catalysis (2006), 38 (4), 269-278CODEN: TOCAFI; ISSN:1022-5528. (Springer)
      Microperoxidase-11 (MP-11) has been immobilized for the first time in hybrid periodic mesoporous organosilica (PMO) materials and in a nanocryst. metal org. framework (MOF). Microperoxidase-11 was phys. absorbed from soln. into the periodic mesoporous organosilica MBS and functionalized derivs. of MBS as well as in the 3-dimensional [Cu(OOC-C6H4-C6H4-COO)·1/2 C6H12N2] n metal org. framework. The conversion of Amplex UltraRed and methylene blue to their resp. oxidn. products by immobilized MP-11 was detd.
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    62. 62
      Zhong, X.; Xia, H.; Huang, W.; Li, Z.; Jiang, Y. Biomimetic Metal-Organic Frameworks Mediated Hybrid Multi-Enzyme Mimic for Tandem Catalysis. Chem. Eng. J. 2020, 381, 122758,  DOI: 10.1016/j.cej.2019.122758
      62
      Biomimetic metal-organic frameworks mediated hybrid multi-enzyme mimic for tandem catalysis
      Zhong, Xue; Xia, Huan; Huang, Wenquan; Li, Zhixian; Jiang, Yanbin
      Chemical Engineering Journal (Amsterdam, Netherlands) (2020), 381 (), 122758CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
      The combination of chemo- and enzyme catalysis for multi-step tandem reactions has presented great challenges for decades. Herein, glucose oxidase (GOx) and a metal-org. framework MOF-545(Fe), which possessed peroxidase-like activity, were combined to construct a mimic multi-enzyme system for tandem catalysis. MOF-545(Fe) not only served as a support for the enzyme immobilization, but also contributed its catalytic activity to cooperate with natural enzymes for the cascade reactions. Based on the prepd. mimic multi-enzyme system GOx@MOF-545(Fe), a colorimetric biosensor for glucose rapid detection was achieved with a low limit of detection (0.28 μM) and high specificity. Meanwhile, due to the protection of MOF-545(Fe), the immobilized enzyme exhibited excellent reusability and stability, e.g. long-term stability, thermal stability and anti-org. solvent stability. After being stored at room temp. for 7 days, the immobilized enzyme retained 92% of activity, while only 40% of activity of free enzyme was retained. And the immobilized enzyme maintained 71% of its initial activity after 5 cycles. This strategy of combining MOF mimics and natural enzymes for tandem catalysis may provide a novel and facile approach to design a highly efficient, stable, functional chemo-enzyme composites catalyst, which holds great promise for applications in biosensing, biopharmaceutical and industrial catalysis.
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    63. 63
      Lyu, F.; Zhang, Y.; Zare, R. N.; Ge, J.; Liu, Z. One-Pot Synthesis of Protein-Embedded Metal–Organic Frameworks with Enhanced Biological Activities. Nano Lett. 2014, 14, 5761– 5765,  DOI: 10.1021/nl5026419
      63
      One-Pot Synthesis of Protein-Embedded Metal-Organic Frameworks with Enhanced Biological Activities
      Lyu, Fengjiao; Zhang, Yifei; Zare, Richard N.; Ge, Jun; Liu, Zheng
      Nano Letters (2014), 14 (10), 5761-5765CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
      Protein mols. were directly embedded in metal-org. frameworks (MOFs) by a copptn. method. The protein mols. majorly embedded on the surface region of MOFs display high biol. activities. As a demonstration of the power of such materials, the resulting Cyt c embedded in ZIF-8 showed a 10-fold increase in peroxidase activity compared to free Cyt c in soln. and thus gave convenient, fast, and highly sensitive detection of trace amts. of explosive org. peroxides in soln.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsFamsrfE&md5=89d9836c8dad3bb84163b0227bac37fb
    64. 64
      Li, S.-F.; Zhai, X.-J.; Zhang, C.; Mo, H.-L.; Zang, S.-Q. Enzyme Immobilization in Highly Ordered Macro–Microporous Metal–Organic Frameworks for Rapid Biodegradation of Hazardous Dyes. Inorg. Chem. Front. 2020, 7, 3146– 3153,  DOI: 10.1039/D0QI00489H
      64
      Enzyme immobilization in highly ordered macro-microporous metal-organic frameworks for rapid biodegradation of hazardous dyes
      Li, Shu-Fan; Zhai, Xue-Jing; Zhang, Chong; Mo, Hui-Lin; Zang, Shuang-Quan
      Inorganic Chemistry Frontiers (2020), 7 (17), 3146-3153CODEN: ICFNAW; ISSN:2052-1553. (Royal Society of Chemistry)
      Enzyme immobilization in hierarchically porous metal-org. frameworks (HP-MOFs) has attracted extensive attention in biocatalysis and contaminant biodegrdn. However, the small-dimension mesopores and micropores on the exterior of MOFs are incompatible with large-sized enzymes, thus limiting the further enhancement of mass transfer efficiency and enzyme accessibility. Herein, we encapsulated horseradish peroxidase (HRP) in highly ordered macro-micropore zeolitic imidazolate framework-8, in which the encapsulated enzyme not only fully preserved its catalytic activity, but also exhibited long-term stability, recyclability, low leakage, and resistance to chelating compds. Through enzyme immobilization, we significantly enhanced the biodegrdn. process of hazardous dyes probably as a result of the pre-concn. of the dye reactant for the combination of enzymes and MOFs. This work shows the great potential of constructing highly functional biocatalysts in three-dimensional ordered macro-micropore MOFs with enhanced mass diffusion efficiency, which is promising for applications to biodegrdn. of all sorts of other org. pollutants in water resources.
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    65. 65
      Chen, S.; Wen, L.; Svec, F.; Tan, T.; Lv, Y. Magnetic Metal–Organic Frameworks as Scaffolds for Spatial Co-Location and Positional Assembly of Multi-Enzyme Systems Enabling Enhanced Cascade Biocatalysis. RSC Adv. 2017, 7, 21205– 21213,  DOI: 10.1039/C7RA02291C
      65
      Magnetic metal-organic frameworks as scaffolds for spatial co-location and positional assembly of multi-enzyme systems enabling enhanced cascade biocatalysis
      Chen, Sijia; Wen, Liyin; Svec, Frantisek; Tan, Tianwei; Lv, Yongqin
      RSC Advances (2017), 7 (34), 21205-21213CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
      Magnetic multi-enzyme nanosystems have been prepd. via co-pptn. of enzymes and metal-org. framework HKUST-1 precursors in the presence of magnetic Fe3O4 nanoparticles. The spatial co-localization of two enzymes was achieved using a layer-by-layer positional assembly strategy. Glucose oxidase (GOx) and horseradish peroxidase (HRP) were used as the model enzymes for cascade biocatalysis. By controlling the spatial positions of enzymes, three bienzyme nanosystems GOx@HRP@HKUST-1@Fe3O4, GOx-HRP@HKUST-1@Fe3O4 and HRP@GOx@HKUST-1@Fe3O4 were prepd. in which GOx and HRP contg. layers were in close proximity, either encapsulated in the HKUST-1 inner layer, or immobilized on the HKUST-1 outer shell, or randomly distributed in the two MOF layers. Their properties were characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform IR spectroscopy, X-ray diffraction, thermal gravimetric anal., and zeta potential measurements. The highest activity was obsd. at pH = 6 and a temp. of 20°C. Thanks to the favorable positioning of enzymes, the GOx@HRP@HKUST-1@Fe3O4 nanosystem revealed superior kinetics with a Michaelis const. Km = 0.8 mmol L-1 and the max. reaction rate Vmax = 11.3μmol L-1 min-1. The enzyme-HKUST-1 conjugates exhibited remarkably high operational stability compared to the free enzymes. This work provides a facile and versatile approach to spatially organized multienzyme systems with well-defined nanostructures and greatly enhanced the overall biocatalytic efficiency.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXmtVeqt7w%253D&md5=82582d74dd2855843122ab44b876b6b5
    66. 66
      Feng, Y.; Zhong, L.; Bilal, M.; Tan, Z.; Hou, Y.; Jia, S.; Cui, J. Enzymes@ZIF-8 Nanocomposites with Protection Nanocoating: Stability and Acid-Resistant Evaluation. Polym. 2018, 11, 27,  DOI: 10.3390/polym11010027
      There is no corresponding record for this reference.
    67. 67
      Cui, J.; Feng, Y.; Jia, S. Silica Encapsulated Catalase@metal-Organic Framework Composite: A Highly Stable and Recyclable Biocatalyst. Chem. Eng. J. 2018, 351, 506– 514,  DOI: 10.1016/j.cej.2018.06.121
      67
      Silica encapsulated catalase@metal-organic framework composite: A highly stable and recyclable biocatalyst
      Cui, Jiandong; Feng, Yuxiao; Jia, Shiru
      Chemical Engineering Journal (Amsterdam, Netherlands) (2018), 351 (), 506-514CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
      Metal-org. frameworks (MOFs) have recently emerged as a promising candidate for the immobilization of enzymes due to their diversified structures and porosity. However, it is difficult to handle and fully recover the enzyme-MOF composites from the reaction medium due to their nanometer size and good dispersity in solvents, which limits their practical applications. Here, a novel enzyme-MOF composite with both highly stable and easily reusable features was prepd. via encapsulating catalase/ZIF-8 nanocrystals into large mesoporous silica layer (silica@CAT/ZIF-8). This immobilized system exhibited high activity recovery (81%). The silica layer around the catalase/ZIF-8 particles provided a "shield" to protect from biol. and chem. degrdn. for enzyme. As a result, the silica@CAT/ZIF-8 composites exhibited higher stability against proteolytic agent and extreme conditions (such as low pH) than that of conventional catalase/ZIF-8 composites. More importantly, the micrometer-sized silica@CAT/ZIF-8 can be easily repeatedly used without obvious activity loss. The silica@CAT/ZIF-8 composites still remained 50% of their original activity after 10 cycles, whereas the conventional catalase/ZIF-8 composites only retained 7% of their original activity after 5 cycles. These results demonstrated that this approach could be an efficient strategy to prep. enzyme-ZIF-8 composite with both high stability and excellent recyclability.
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  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.0c22729.

    • Average diameters of the fibers and the crystals for HKUST-1 and ZIF-8 composite fibers, thermogravimetric analysis (TGA), MOF weight percentage in MOF composite fibers, a cross section of HKUST-1 fiber after exposure to ethanol, mechanically pulled ZIF-8 fiber SEM micrograph, SEM micrographs of a folded HKUST-1 fiber, tensile measurements of HKUST-1 fabrics, and catalase enzyme immobilization on MOF nonwoven meshes (PDF)

    • Mechanical deformation of nonwoven HKUST-1 fabric (Movie S1) (MP4)


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