Multiwalled Nanotubes Formed by Catanionic Mixtures of Drug Amphiphiles
- Yi-An Lin ,
- Andrew G. Cheetham ,
- Pengcheng Zhang ,
- Yu-Chuan Ou ,
- Yuguo Li ,
- Guanshu Liu ,
- Daniel Hermida-Merino ,
- Ian W. Hamley , and
- Honggang Cui
Abstract

Mixing of oppositely charged amphiphilic molecules (catanionic mixing) offers an attractive strategy to produce morphologies different from those formed by individual molecules. We report here on the use of catanionic mixing of anticancer drug amphiphiles to construct multiwalled nanotubes containing a fixed and high drug loading. We found that the molecular mixing ratio, the solvent composition, the overall drug concentrations, as well as the molecular design of the studied amphiphiles are all important experimental parameters contributing to the tubular morphology. We believe these results demonstrate the remarkable potential that anticancer drugs could offer to self-assemble into discrete nanostructures and also provide important insight into the formation mechanism of nanotubes by catanionic mixtures. Our preliminary animal studies reveal that the CPT nanotubes show significantly prolonged retention time in the tumor site after intratumoral injection.
Figure 1

Figure 1. (a) Chemical structures and schematic representations of qCPT-Sup35-K2 and qCPT-Sup35-E2. (b–d) Schematic representations and TEM micrographs of the supramolecular structures formed by qCPT-Sup35-K2, qCPT-Sup35-E2, and the CAM of the two DAs. Both qCPT-Sup35-K2 (b) and qCPT-Sup35-E2 (c) formed single filaments in 1:1 MeCN/H2O after the materials had been previously treated with HFIP. The widths of the single filaments measured from TEM are 5.7 ± 0.9 nm, and 5.9 ± 0.9 nm for qCPT-Sup35-K2 and qCPT-Sup35-E2, respectively. (d–f) The CAM of qCPT-Sup35 (mixing ratio 1:3) results in the almost exclusive formation of tubular structures in 1:1 MeCN/H2O. The tubular size measured from cryo-TEM imaging is 123 ± 28 nm. Total concentration for all samples = 400 μM.
Results and Discussion
Catanionic Assembly
Figure 2

Figure 2. TEM and cryo-TEM micrographs of the qCPT-Sup35 CAM with a mixing ratio of 1:3 at 400 μM in 1:1 MeCN/H2O. (a, b) Bending of the tubular structures (indicated by the red arrows) and the direct observation of the multiwalled nature of the tubules (labeled with blue arrows) in cryo-TEM imaging. (c, d) Undulation of the tube widths is commonly observed in regions where overlapping occurs. All bars = 200 nm.
Morphology Characterization
Figure 3

Figure 3. (a, b) Cryo-TEM micrographs of qCPT-Sup35 CAMs with a mixing ratio of 1:1 (a) and 3:1 (b) at 400 μM in 1:1 MeCN/H2O. All bars = 500 nm. (c) Zeta potential measurements of the qCPT-Sup35 CAMs with different mixing ratios. Data are presented as mean ± s.d. (d) CD spectra of the 1:3 qCPT-Sup35 CAM, and individual DAs in 1:1 MeCN/H2O. All spectra were obtained from 400 μM solutions that were diluted to 50 μM immediately prior to measurement.
Nanotube Assembly Pathways
Figure 4

Figure 4. TEM micrographs of the intermediate structures of the 1:3 qCPT-Sup35 CAM in 1:1 MeCN/H2O, unless stated otherwise. (a, b) Clusters of belts and helical ribbons are the dominant structures at 10 μM (a) and 50 μM (b). (c) Multilayer helical ribbon at 50 μM. (d) An intermediate multiwall tubular structure in a 100 μM solution, showing a tubular structure wrapped with another layer of belt. (e, f) Similar intermediate structures, such as multilayer helical ribbons and intermediate multiwall tubular structures in 3:1 MeCN/H2O, where the materials exhibited limited solubility. Bulk concentration = 400 μM.
Role of Molecular Design
Figure 5

Figure 5. Proposed mechanism of the tubule formation by qCPT-Sup35 CAMs. (a) Schematic illustration of the effect of packing parameter of qCPT-Sup35 and dCPT-Sup35 on the formation of ion pairs and the resulting supramolecular morphology of corresponding catanionic mixtures. (b) The formation of the multiwall nanotubes by CAMs of qCPT-Sup35 is the cumulative result of three occurrences: 1D elongation, formation of multilayers, and bilayer extension from helical ribbons. The CAM of qCPT-Sup35 formed bilayers, where the direction of lateral bilayer extension is perpendicular to the orientation of the intermolecular hydrogen bonds.
Figure 6

Figure 6. In vivo NIRF imaging of CT26 tumor-bearing mice. The heat maps display the distribution of Cy7.5 labeled CAM nanotubes of qCPT-Sup35 (a) and free Cy7.5 (b) after intratumoral injection.
In Vivo Evaluation
Conclusion
Materials and Methods
Peptide Synthesis
Synthesis of 4-(Pyridin-2-yldisulfanyl)butanoic Acid
Synthesis of Camptothecin-4-(pyridin-2-yldisulfanyl)butanoate (CPT-buSS-Pyr)
Syntheses of the DAs and Purification
Calibration of the Concentration
Preparation of the Catanonic Mixtures (CAMs)
Transmission Electron Microscopy (TEM)
Cryogenic-Transmission Electron Microscopy (Cryo-TEM)
Circular Dichroism Spectroscopy
where [θ] represents the molar ellipticity, θ is the measured ellipticity in deg, c is the concentration of the DAs in dmol·cm–3, and l is the light path length of the cuvette in cm.Zeta Potential Measurements
Animal Model
Near-IR Imaging in Vivo
Supporting Information
Additional molecular characterization, spectroscopic studies, and additional TEM images. This material is available free of charge via the Internet at http://pubs.acs.org.
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.
Acknowledgment
We acknowledge financial support from the National Science Foundation (DMR 1255281) and the National Institutes of Health for funding Y.L. (R25CA153952) and A.C. (T-32CA130840). G.L. acknowledges the financial support from National Institutes of Health (R21EB015609). We also acknowledge JHU Integrated Imaging Center (IIC) for TEM imaging, Prof. K. Hristova (JHU MSE) for the use of the CD spectropolarimeter, and the NSF (NSF CHE-0840463) for the purchase of a mass spectrometer at the the JHU Department of Chemistry.
References
This article references 67 other publications.
- 1Hill, J. P.; Jin, W. S.; Kosaka, A.; Fukushima, T.; Ichihara, H.; Shimomura, T.; Ito, K.; Hashizume, T.; Ishii, N.; Aida, T. Self-Assembled Hexa-peri-hexabenzocoronene Graphitic Nanotube Science 2004, 304, 1481– 1483[Crossref], [PubMed], [CAS], Google Scholar1https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXksVGmsLc%253D&md5=eb42b19b58780709a3aed8fe3dc27fb5Self-assembled hexa-peri-hexabenzocoronene graphitic nanotubeHill, Jonathan P.; Jin, Wusong; Kosaka, Atsuko; Fukushima, Takanori; Ichihara, Hideki; Shimomura, Takeshi; Ito, Kohzo; Hashizume, Tomihiro; Ishii, Noriyuki; Aida, TakuzoScience (Washington, DC, United States) (2004), 304 (5676), 1481-1483CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)An amphiphilic hexa-peri-hexabenzocoronene self-assembles to form a π-electronic, discrete nanotubular object. The object was characterized by an aspect ratio >1000 and has a uniform, 14-nm-wide, open-ended hollow space, which is an order of magnitude larger than those of C nanotubes. The wall is 3 nm thick and consists of helical arrays of the π-stacked graphene mol., whose exterior and interior surfaces are covered by hydrophilic triethylene glycol chains. The graphitic nanotube is redox active, and a single piece of the nanotube across 180-nm-gap electrodes shows, upon oxidn., an elec. cond. of 2.5MΩs at 285 K. This family of molecularly engineered graphite with a 1-dimensional tubular shape and a chem. accessible surface constitutes an important step toward mol. electronics.
- 2Iijima, S. Helical Microtubules of Graphitic Carbon Nature 1991, 354, 56– 58[Crossref], [CAS], Google Scholar2https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK38Xmt1Ojtg%253D%253D&md5=ab9fd03bc14a16606749af946bac86bfHelical microtubules of graphitic carbonIijima, SumioNature (London, United Kingdom) (1991), 354 (6348), 56-8CODEN: NATUAS; ISSN:0028-0836.The prepn. of a novel type of finite C structure consisting of needle-like tubes is reported. Produced using an arc-discharge evapn. method similar to that used for fullerenes synthesis, the needles grow at the neg. end of the electrode used for the arc discharge. Electron microscopy reveals that each needle comprises coaxial tubes of graphitic sheets, ranging from 2 to ∼50. On each tube, the C-atom hexagons are arranged in a helical fashion about the needle axis. The helical pitch varies from needle to needle and from tube to tube within a single needle. This helical structure may aid growth. The formation of these needles, ranging from a few to a few tens of nanometers in diam., suggests that engineering of C structures should be possible on scales considerably greater than those relevant to the fullerenes.
- 3Treacy, M. M. J.; Ebbesen, T. W.; Gibson, J. M. Exceptionally High Young’s Modulus Observed for Individual Carbon Nanotubes Nature 1996, 381, 678– 680Google ScholarThere is no corresponding record for this reference.
- 4Mitchison, T.; Kirschner, M. Dynamic Instability of Microtubule Growth Nature 1984, 312, 237– 242[Crossref], [PubMed], [CAS], Google Scholar4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2MXhvF2jsQ%253D%253D&md5=2c8244aca07fd3b65f76da5580cf6c48Dynamic instability of microtubule growthMitchison, Tim; Kirschner, MarcNature (London, United Kingdom) (1984), 312 (5991), 237-42CODEN: NATUAS; ISSN:0028-0836.Microtubules placed in a tubulin soln. just about the steady-state concn. of 14 μM showed a steady increase in length with no change in no. of microtubules. At lower tubulin concns. (7.5 μM), the no. of microtubules decreased with time, whereas the mean length of microtubules still increased somewhat. Axonemes could nucleate growth of microtubules well below the steady-state concn. of tubulin. At steady state (14 μM tubulin), when the net polymer mass remained const., a steady increase in mean microtubule length still occurred, whereas the no. of microtubules decreased steadily. This was attributed to depolymn. of some microtubules, which provided tubulin monomers for growth of other microtubules. The transition of microtubules between growing and shrinking phases was evidently rare. Possibly growing microtubules have GTP-liganded caps, whereas shrinking ones do not. A new model for microtubule assembly is proposed based on these findings.
- 5Hamley, I. W. Peptide Nanotubes Angew. Chem. Int. Ed. 2014, 53, 6866– 6881[Crossref], [PubMed], [CAS], Google Scholar5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXps1ygu70%253D&md5=d9be9db7fbfc18f939964c6d3c4c5bf6Peptide NanotubesHamley, Ian W.Angewandte Chemie, International Edition (2014), 53 (27), 6866-6881CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. The self-assembly of different classes of peptide, including cyclic peptides, amyloid peptides and surfactant-like peptides into nanotube structures is reviewed. The modes of self-assembly are discussed. Addnl., applications in bionanotechnol. and synthetic materials science are summarized.
- 6Zhang, W.; Jin, W. S.; Fukushima, T.; Saeki, A.; Seki, S.; Aida, T. Supramolecular Linear Heterojunction Composed of Graphite-Like Semiconducting Nanotubular Segments Science 2011, 334, 340– 343[Crossref], [PubMed], [CAS], Google Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhtlahsr%252FJ&md5=e9580703a3d80af81f712fc9596382c3Supramolecular Linear Heterojunction Composed of Graphite-Like Semiconducting Nanotubular SegmentsZhang, Wei; Jin, Wusong; Fukushima, Takanori; Saeki, Akinori; Seki, Shu; Aida, TakuzoScience (Washington, DC, United States) (2011), 334 (6054), 340-343CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)One-dimensionally connected org. nanostructures with dissimilar semiconducting properties are expected to provide a reliable platform in understanding the behaviors of photocarriers, which are important for the development of efficient photon-to-elec. energy conversion systems. Although bottom-up supramol. approaches are considered promising for the realization of such nanoscale heterojunctions, the dynamic nature of mol. assembly is problematic. We report a semiconducting nanoscale org. heterojunction, demonstrated by stepwise nanotubular coassembly of two strategically designed mol. graphenes. The dissimilar nanotubular segments, thus connected noncovalently, were electronically communicable with one another over the heterojunction interface and displayed characteristic excitation energy transfer and charge transport properties not present in a mixt. of the corresponding homotropically assembled nanotubes.
- 7Adler-Abramovich, L.; Aronov, D.; Beker, P.; Yevnin, M.; Stempler, S.; Buzhansky, L.; Rosenman, G.; Gazit, E. Self-Assembled Arrays of Peptide Nanotubes by Vapour Deposition Nat. Nanotechnol. 2009, 4, 849– 854[Crossref], [PubMed], [CAS], Google Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhsFagsrnK&md5=d5ecdffefece40280cebd107065cbb59Self-assembled arrays of peptide nanotubes by vapour depositionAdler-Abramovich, Lihi; Aronov, Daniel; Beker, Peter; Yevnin, Maya; Stempler, Shiri; Buzhansky, Ludmila; Rosenman, Gil; Gazit, EhudNature Nanotechnology (2009), 4 (12), 849-854CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)The use of bionanostructures in real-world applications will require precise control over biomol. self-assembly and the ability to scale up prodn. of these materials. A significant challenge is to control the formation of large, homogeneous arrays of bionanostructures on macroscopic surfaces. Previously, bionanostructure formation has been based on the spontaneous growth of heterogenic populations in bulk soln. Here, we demonstrate the self-assembly of large arrays of arom. peptide nanotubes using vapor deposition methods. This approach allows the length and d. of the nanotubes to be fine-tuned by carefully controlling the supply of the building blocks from the gas phase. Furthermore, we show that the nanotube arrays can be used to develop high-surface-area electrodes for energy storage applications, highly hydrophobic self-cleaning surfaces and microfluidic chips.
- 8Gazit, E. Self-Assembled Peptide Nanostructures: The Design of Molecular Building Blocks and Their Technological Utilization Chem. Soc. Rev. 2007, 36, 1263– 1269[Crossref], [PubMed], [CAS], Google Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXnsVChurY%253D&md5=7dc68e71f2dc63208a366b677856e85fSelf-assembled peptide nanostructures: The design of molecular building blocks and their technological utilizationGazit, EhudChemical Society Reviews (2007), 36 (8), 1263-1269CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. The process and applications of peptide self-assembly into nanotubes, nanospheres, nanofibrils, nanotapes, and other ordered structures at the nano-scale are discussed in this tutorial review. The formation of well-ordered nanostructures by a process of self-assocn. represents the essence of modern nanotechnol. Such self-assembled structures can be formed by a variety of building blocks, both org. and inorg. Of the org. building blocks, peptides are among the most useful ones. Peptides possess the biocompatibility and chem. diversity that are found in proteins, yet they are much more stable and robust and can be readily synthesized on a large scale. Short peptides can spontaneously assoc. to form nanotubes, nanospheres, nanofibrils, nanotapes, and other ordered structures at the nano-scale. Peptides can also form macroscopic assemblies such as hydrogels with nano-scale order. The application of peptide building blocks in biosensors, tissue engineering, and the development of antibacterial agents has already been demonstrated.
- 9Ashkenasy, N.; Horne, W. S.; Ghadiri, M. R. Design of Self-Assembling Peptide Nanotubes with Delocalized Electronic States Small 2006, 2, 99– 102[Crossref], [PubMed], [CAS], Google Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXhtlWqsrjP&md5=984d38ecb81cf1fdaf7037f5af4215e9Design of self-assembling peptide nanotubes with delocalized electronic statesAshkenasy, Nurit; Horne, W. Seth; Ghadiri, M. RezaSmall (2006), 2 (1), 99-102CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)An eight-residue cyclic DL-α-peptide bearing four cationic 1,4,5,8-naphthalenetetracarboxylic diimide (NDI) side chains that undergoes redox-triggered self-assembly in aq. soln. into peptide nanotubes in described. Using this approach, isolated peptide nanotubes hundreds of nanometers in length can be obtained and adsorbed on solid surfaces. The long-range supramol. order afforded by the directed backbone hydrogen bonding interactions in self-assembling cyclic DL-α-peptide nanotubes can provide a facile method for the prepn. of a new class of synthetic biomaterials that exhibit extended charge delocalized states.
- 10Zhang, J.; Liu, X.; Blume, R.; Zhang, A. H.; Schlogl, R.; Su, D. S. Surface-Modified Carbon Nanotubes Catalyze Oxidative Dehydrogenation of n-Butane Science 2008, 322, 73– 77[Crossref], [PubMed], [CAS], Google Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhtFyhurfP&md5=702a3916692a10b61da5e7d52452ac03Surface-Modified Carbon Nanotubes Catalyze Oxidative Dehydrogenation of n-ButaneZhang, Jian; Liu, Xi; Blume, Raoul; Zhang, Aihua; Schloegl, Robert; Su, Dang ShengScience (Washington, DC, United States) (2008), 322 (5898), 73-77CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Butenes and butadiene, which are useful intermediates for the synthesis of polymers and other compds., are synthesized traditionally by oxidative dehydrogenation (ODH) of n-butane over complex metal oxides. Such catalysts require high O2/butane ratios to maintain the activity, which leads to unwanted product oxidn. We show that carbon nanotubes with modified surface functionality brought about by oxidn. in concn. HNO3 efficiently catalyze the oxidative dehydrogenation of n-butane to butenes, esp. butadiene. For low O2/butane ratios, a high selectivity to alkenes was achieved for periods as long as 100 h. This process is mildly catalyzed by ketonic C=O groups and occurs via a combination of parallel and sequential oxidn. steps. A small amt. of phosphorus greatly improved the selectivity by suppressing the combustion of hydrocarbons.
- 11Schnur, J. M. Lipid Tubules - A Paradigm for Molecularly Engineered Structures Science 1993, 262, 1669– 1676Google ScholarThere is no corresponding record for this reference.
- 12Margulis-Goshen, K.; di Gregorio, M. C.; Pavel, N. V.; Abezgauz, L.; Danino, D.; Tato, J. V.; Tellini, V. H. S.; Magdassi, S.; Galantini, L. Drug-Loaded Nanoparticles and Supramolecular Nanotubes Formed from A Volatile Microemulsion with Bile Salt Derivatives Phys. Chem. Chem. Phys. 2013, 15, 6016– 6024Google ScholarThere is no corresponding record for this reference.
- 13Stewart, S.; Liu, G. Block Copolymer Nanotubes Angew. Chem. Int. Ed. 2000, 112, 348– 352Google ScholarThere is no corresponding record for this reference.
- 14Lara, C.; Handschin, S.; Mezzenga, R. Towards Lysozyme Nanotube and 3D Hybrid Self-Assembly Nanoscale 2013, 5, 7197– 7201Google ScholarThere is no corresponding record for this reference.
- 15Shimizu, T.; Masuda, M.; Minamikawa, H. Supramolecular Nanotube Architectures Based on Amphiphilic Molecules Chem. Rev. 2005, 105, 1401– 1443[ACS Full Text
], [CAS], Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXisFWrtrs%253D&md5=b2c17e4ab967a44faa74786ea5cc5f95Supramolecular Nanotube Architectures Based on Amphiphilic MoleculesShimizu, Toshimi; Masuda, Mitsutoshi; Minamikawa, HiroyukiChemical Reviews (Washington, DC, United States) (2005), 105 (4), 1401-1443CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. We here present the principle of chiral self-assembly for the formation of lipid nanotube, its prepn. methods, application possibilities, and novel properties. - 16Raez, J.; Manners, I.; Winnik, M. A. Nanotubes from The Self-Assembly of Asymmetric Crystalline-Coil Poly(Ferrocenylsilane-Siloxane) Block Copolymers J. Am. Chem. Soc. 2002, 124, 10381– 10395
- 17Hamley, I. W. Nanoshells and Nanotubes from Block Copolymers Soft Matter 2005, 1, 36– 43Google ScholarThere is no corresponding record for this reference.
- 18Kralj-Iglic, V.; Iglic, A.; Gomiscek, G.; Sevsek, F.; Arrigler, V.; Hagerstrand, H. Microtubes and Nanotubes of A Phospholipid Bilayer Membrane J. Phys. A: Math. Gen. 2002, 35, 1533– 1549[Crossref], [CAS], Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD38Xit1entLw%253D&md5=30ed9f6c74fedb0a722370da2d7b5e1eMicrotubes and nanotubes of a phospholipid bilayer membraneKralj-Iglic, Veronika; Iglic, Ales; Gomiscek, Gregor; Sevsek, France; Arrigler, Vesna; Hagerstrand, HenryJournal of Physics A: Mathematical and General (2002), 35 (7), 1533-1549CODEN: JPHAC5; ISSN:0305-4470. (Institute of Physics Publishing)We propose a theory describing the stable structure of a phospholipid bilayer in pure water involving a spherical mother vesicle with long thin tubular protrusion. It is considered that the phospholipid mols. are in general anisotropic with respect to the axis normal to the membrane and can orient in the plane of the membrane if the curvature field is strongly anisotropic. Taking this into account, the membrane free energy is derived starting from a single-mol. energy and using methods of statistical mechanics. By linking the description on the microscopic level with the continuum theory of elasticity we recover the expression for the membrane bending energy and obtain an addnl. (deviatoric) contribution due to the orientational ordering of the phospholipid mols. It is shown that the deviatoric contribution may considerably decrease the phospholipid vesicle membrane free energy if the vesicle involves regions where the difference between the two principal curvatures is large (thin cylindrical protrusions and/or thin finite necks) and thereby yields a possible explanation for the stability of the long thin tubular protrusions of the phospholipid bilayer vesicles. We report on the expt. exhibiting a stable shape of the spherical phospholipid vesicle with a long thin tubular protrusion in pure water.
- 19Spector, M. S.; Singh, A.; Messersmith, P. B.; Schnur, J. M. Chiral Self-Assembly of Nanotubules and Ribbons from Phospholipid Mixtures Nano Lett. 2001, 1, 375– 378
- 20Thomas, B. N.; Safinya, C. R.; Plano, R. J.; Clark, N. A. Lipid Tubule Self-Assembly - Length Dependence on Cooling Rate Through A First-Order Phase-Transition Science 1995, 267, 1635– 1638Google ScholarThere is no corresponding record for this reference.
- 21Yager, P.; Schoen, P. E. Formation of Tubules by a Polymerizable Surfactant Mol. Cryst. Liq. Cryst. 1984, 106, 371– 381[Crossref], [CAS], Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2cXksFSnsbY%253D&md5=20ab0684ed7aa7e656644164d2181f9bFormation of tubules by a polymerizable surfactantYager, Paul; Schoen, Paul E.Molecular Crystals and Liquid Crystals (1984), 106 (3-4), 371-81CODEN: MCLCA5; ISSN:0026-8941.The phospholipid 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine, in which both fatty acyl chains contain polymerizable diacetylenic units, has been studied with regard to its behavior in aq. dispersion before and after polymn. The monomeric lipid may be dispersed in distd. water above its chain melting transition temp., but, contrary to previous reports, it does not stay in the liposomal form on subsequent redn. of the temp. Microscopic observation shows formation of structures resembling so-called cochleate cylinders, except that these cylinders are water-filled. These tubules reversibly convert to liposomal form on heating above the monomer chain melting temp. However, on polymn. with UV light, the cylinders are locked in and no morphol. changes are obsd. on heating. These unique structures may represent a new class of orientable polymers.
- 22Terech, P.; de Geyer, A.; Struth, B.; Talmon, Y. Self-Assembled Monodisperse Steroid Nanotubes in Water Adv. Mater. 2002, 14, 495– 498Google ScholarThere is no corresponding record for this reference.
- 23Lu, K.; Jacob, J.; Thiyagarajan, P.; Conticello, V. P.; Lynn, D. G. Exploiting Amyloid Fibril Lamination for Nanotube Self-Assembly J. Am. Chem. Soc. 2003, 125, 6391– 6393[ACS Full Text
], [CAS], Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXjtlKisL4%253D&md5=ab1b3a940aeed7523963742e387a4367Exploiting Amyloid Fibril Lamination for Nanotube Self-AssemblyLu, Kun; Jacob, Jaby; Thiyagarajan, Pappannan; Conticello, Vincent P.; Lynn, David G.Journal of the American Chemical Society (2003), 125 (21), 6391-6393CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Fundamental questions about the relative arrangement of the β-sheet arrays within amyloid fibrils remain central to both its structure and the mechanism of self-assembly. Recent computational analyses suggested that sheet-to-sheet lamination was limited by the length of the strand. On the basis of this hypothesis, a short seven-residue segment of the Alzheimer's disease-related Aβ peptide, Aβ(16-22), was allowed to self-assemble under conditions that maintained the basic amphiphilic character of Aβ. Indeed, the no. increased over 20-fold to 130 laminates, giving homogeneous bilayer structures that supercoil into long robust nanotubes. Small-angle neutron scattering and x-ray scattering defined the outer and inner radii of the nanotubes in soln. to contain a 44-nm inner cavity with 4-nm-thick walls. At. force microscopy and TEM images further confirmed these homogeneous arrays of solvent-filled nanotubes arising from a flat rectangular bilayer, 130 nm wide × 4 nm thick, with each bilayer leaflet composed of laminated β-sheets. The corresponding backbone H-bonds are along the long axis, and β-sheet lamination defines the 130-nm bilayer width. This bilayer coils to give the final nanotube. Such robust and persistent self-assembling nanotubes with pos. charged surfaces of very different inner and outer curvature now offer a unique, robust, and easily accessible scaffold for nanotechnol. - 24Childers, W. S.; Mehta, A. K.; Ni, R.; Taylor, J. V.; Lynn, D. G. Peptides Organized as Bilayer Membranes Angew. Chem. Int. Ed. 2010, 49, 4104– 4107Google ScholarThere is no corresponding record for this reference.
- 25Hartgerink, J. D.; Granja, J. R.; Milligan, R. A.; Ghadiri, M. R. Self-Assembling Peptide Nanotubes J. Am. Chem. Soc. 1996, 118, 43– 50[ACS Full Text
], [CAS], Google Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28XltVGjsw%253D%253D&md5=30a5183ccbf3ebc1776a892fbe030da9Self-Assembling Peptide NanotubesHartgerink, Jeffrey D.; Granja, Juan R.; Milligan, Ronald A.; Ghadiri, M. RezaJournal of the American Chemical Society (1996), 118 (1), 43-50CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The general design criteria and synthesis of four new peptide-based solid-state tubular array structures are described. Peptide nanotubes, which are extended tubular β-sheet-like structures, are constructed by the self-assembly of flat, ring-shaped peptide subunits made up of alternating D- and L-amino acid residues. Peptide self-assembly is directed by the formation of an extensive network of intersubunit hydrogen bonds. In the crystal structures, nanotubes are stabilized by intertubular hydrophobic packing interactions. Peptide nanotubes exhibit good mech. and thermal stabilities in water and are stable for long periods of times in most common org. solvents including DMF and DMSO. The remarkable stability of peptide nanotubes can be attributed to the highly cooperative nature of the noncovalent interactions throughout the crystal lattice. Nanotube structures were characterized by cryoelectron microscopy, electron diffraction, Fourier-transform IR spectroscopy, and crystal structure modeling. This study also serves to exemplify the predictive structural aspects of the peptide self-assembly process. - 26Adamcik, J.; Castelletto, V.; Bolisetty, S.; Hamley, I. W.; Mezzenga, R. Direct Observation of Time-Resolved Polymorphic States in the Self-Assembly of End-Capped Heptapeptides Angew. Chem. Int. Ed. 2011, 50, 5495– 5498Google ScholarThere is no corresponding record for this reference.
- 27Middleton, D. A.; Madine, J.; Castelletto, V.; Hamley, I. W. Insights into the Molecular Architecture of a Peptide Nanotube Using FTIR and Solid-State NMR Spectroscopic Measurements on an Aligned Sample Angew. Chem. Int. Ed. 2013, 52, 10537– 10540Google ScholarThere is no corresponding record for this reference.
- 28Ziserman, L.; Lee, H. Y.; Raghavan, S. R.; Mor, A.; Danino, D. Unraveling the Mechanism of Nanotube Formation by Chiral Self-Assembly of Amphiphiles J. Am. Chem. Soc. 2011, 133, 2511– 2517
- 29Huang, Z.; Kang, S. K.; Banno, M.; Yamaguchi, T.; Lee, D.; Seok, C.; Yashima, E.; Lee, M. Pulsating Tubules from Noncovalent Macrocycles Science 2012, 337, 1521– 1526[Crossref], [PubMed], [CAS], Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtlGrtbbL&md5=faca70ea6f368aa0b84c60552fdfd8f9Pulsating Tubules from Noncovalent MacrocyclesHuang, Zhegang; Kang, Seong-Kyun; Banno, Motonori; Yamaguchi, Tomoko; Lee, Dongseon; Seok, Chaok; Yashima, Eiji; Lee, MyongsooScience (Washington, DC, United States) (2012), 337 (6101), 1521-1526CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Despite recent advances in synthetic nanometer-scale tubular assembly, conferral of dynamic response characteristics to the tubules remains a challenge. Here, we report on supramol. nanotubules that undergo a reversible contraction-expansion motion accompanied by an inversion of helical chirality. Bent-shaped arom. amphiphiles self-assemble into hexameric macrocycles in aq. soln., forming chiral tubules by spontaneous one-dimensional stacking with a mutual rotation in the same direction. The adjacent arom. segments within the hexameric macrocycles reversibly slide along one another in response to external triggers, resulting in pulsating motions of the tubules accompanied by a chiral inversion. The arom. interior of the self-assembled tubules encapsulates hydrophobic guests such as carbon-60 (C60). Using a thermal trigger, we could regulate the C60-C60 interactions through the pulsating motion of the tubules.
- 30Ghadiri, M. R.; Granja, J. R.; Milligan, R. A.; McRee, D. E.; Khazanovich, N. Self-Assembling Organic Nanotubes Based on a Cyclic Peptide Architecture Nature 1993, 366, 324– 327[Crossref], [PubMed], [CAS], Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXhtVOksLw%253D&md5=8077abd61a375136ebc6b10c9e7e892aSelf-assembling organic nanotubes based on a cyclic peptide architectureGhadiri, M. Reza; Granja, Juan R.; Milligan, Ronald A.; McRee, Duncan E.; Khazanovich, NinaNature (London, United Kingdom) (1993), 366 (6453), 324-7CODEN: NATUAS; ISSN:0028-0836.The design, synthesis, and characterization of a new class of org. nanotubes based on rationally designed cyclic peptides, e.g. cyclo(D-Ala-Glu-D-Ala-Gln-D-Ala-Glu-D-Ala-Gln), is reported. When protonated, the cyclopeptides crystallize into tubular structures hundreds of nanometers long, with internal diams. of 7-8Å. Support for the proposed tubular structures is provided by electron microscopy, electron diffraction, Fourier-transform IR, and mol. modeling. The tubes are open-ended, with uniform shape and internal diam. It is anticipated that the may have possible applications in inclusion chem., catalysis, mol. electronics, and mol. sepn. technol.
- 31Zhao, F.; Ma, M. L.; Xu, B. Molecular Hydrogels of Therapeutic Agents Chem. Soc. Rev. 2009, 38, 883– 891[Crossref], [PubMed], [CAS], Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXjsFaju7c%253D&md5=003b6bad079d11e744ab1b680f724017Molecular hydrogels of therapeutic agentsZhao, Fan; Ma, Man Lung; Xu, BingChemical Society Reviews (2009), 38 (4), 883-891CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. This tutorial review aims to introduce a new kind of biomaterials-mol. hydrogels of therapeutic agents. Based on the mol. self-assembly in water, it is possible to transform therapeutic agents into analogs that form hydrogels without compromising their pharmacol. efficacy. This transformation can be beneficial in three aspects: (i) the therapeutic agents become "self-deliverable" in the form of hydrogels; (ii) the self-assembly of hydrogelators of drugs might confer new and useful properties such as multivalency or high local densities; (iii) the exploration of mol. hydrogels of drugs may ultimately lead to bioactive mols. that have dual or multiple roles. By summarizing the reports on the mol. hydrogels made from clin. used drugs or other bioactive mols., this article presents representative mol. hydrogels of therapeutics and outlines the promises and challenges for developing this new class of biomaterials.
- 32Cheetham, A. G.; Ou, Y. C.; Zhang, P. C.; Cui, H. G. Linker-Determined Drug Release Mechanism of Free Camptothecin from Self-Assembling Drug Amphiphiles Chem. Commun. 2014, 50, 6039– 6042[Crossref], [PubMed], [CAS], Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXnslegsLs%253D&md5=e8756d1cb7b3c6dc62f920935a533528Linker-determined drug release mechanism of free camptothecin from self-assembling drug amphiphilesCheetham, Andrew G.; Ou, Yu-Chuan; Zhang, Pengcheng; Cui, HonggangChemical Communications (Cambridge, United Kingdom) (2014), 50 (45), 6039-6042CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)We report here that the release mechanism of free camptothecin from self-assembling drug amphiphiles can be regulated by use of different linker groups. Our results highlight the significance of the linker group of drug amphiphiles on the drug release efficiency and their consequent in vitro efficacy.
- 33Cheetham, A. G.; Zhang, P. C.; Lin, L. Y.; Lin, R.; Cui, H. Synthesis and Self-Assembly of A Mikto-Arm Star Dual Drug Amphiphile Containing Both Paclitaxel and Camptothecin J. Mater. Chem. B 2014, 2, 7316– 7326[Crossref], [PubMed], [CAS], Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsVCrtLvN&md5=a42a59b1244377d4acfdb9fd7fdf6dbeSynthesis and self-assembly of a mikto-arm star dual drug amphiphile containing both paclitaxel and camptothecinCheetham, A. G.; Zhang, P.; Lin, Y.-A.; Lin, R.; Cui, H.Journal of Materials Chemistry B: Materials for Biology and Medicine (2014), 2 (42), 7316-7326CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)Self-assembly of anticancer therapeutics into discrete nanostructures provides an innovative way to develop a self-delivering nanomedicine with a high, quant. drug loading. We report here the synthesis and assembly of a mikto-arm star dual drug amphiphile (DA) contg. both a bulky paclitaxel (PTX) and a planar camptothecin (CPT). The two anti-cancer drugs of interest were stochastically conjugated to a β-sheet forming peptide (Sup35) and under physiol.-relevant conditions the dual DA could spontaneously assoc. into supramol. filaments with a fixed 41% total drug loading (29% PTX and 12% CPT). Transmission electron microscopy imaging and CD spectroscopy studies reveal that the bulkiness of the PTX, as well as the π-π interaction preference between the CPT units, has a significant impact on the assembly kinetics, mol. level packing, and nanostructure morphol. and stability. We found that the DA contg. two PTX units assembled into non-filamentous micelle-like structures, in contrast to the filamentous structures formed by the hetero dual DA and the DA contg. two CPTs. The hetero dual DA was found to effectively release the two anticancer agents, exhibiting superior cytotoxicity against PTX-resistant cervical cancer cells. The presented work offers a potential method to generate well-defined filamentous nanostructures and provides the basis for a future combination therapy platform.
- 34Cheetham, A. G.; Zhang, P. C.; Lin, Y.-A.; Lock, L. L.; Cui, H. G. Supramolecular Nanostructures Formed by Anticancer Drug Assembly J. Am. Chem. Soc. 2013, 135, 2907– 2910[ACS Full Text
], [CAS], Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhvVymsbc%253D&md5=59ef9bc13c8a82ed9727a9d989baa959Supramolecular Nanostructures Formed by Anticancer Drug AssemblyCheetham, Andrew G.; Zhang, Pengcheng; Lin, Yi-an; Lock, Lye Lin; Cui, HonggangJournal of the American Chemical Society (2013), 135 (8), 2907-2910CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)We report here a supramol. strategy to directly assemble the small mol. hydrophobic anticancer drug camptothecin (CPT) into discrete, stable, well-defined nanostructures with a high and quant. drug loading. Depending on the no. of CPTs in the mol. design, the resulting nanostructures can be either nanofibers or nanotubes, and have a fixed CPT loading content ranging from 23% to 38%. We found that formation of nanostructures provides protection for both the CPT drug and the biodegradable linker from the external environment and thus offers a mechanism for controlled release of CPT. Under tumor-relevant conditions, these drug nanostructures can release the bioactive form of CPT and show in vitro efficacy against a no. of cancer cell lines. This strategy can be extended to construct nanostructures of other types of anticancer drugs and thus presents new opportunities for the development of self-delivering drugs for cancer therapeutics. - 35Lin, R.; Cheetham, A. G.; Zhang, P. C.; Lin, Y. A.; Cui, H. G. Supramolecular filaments containing a fixed 41% paclitaxel loading Chem. Commun. 2013, 49, 4968– 4970[Crossref], [PubMed], [CAS], Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXmvFyqsr4%253D&md5=25bdb30bcabf36cfe3a1d689979dfb1fSupramolecular filaments containing a fixed 41% paclitaxel loadingLin, Ran; Cheetham, Andrew G.; Zhang, Pengcheng; Lin, Yi-an; Cui, HonggangChemical Communications (Cambridge, United Kingdom) (2013), 49 (43), 4968-4970CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)We report here the self-assembly of a rationally designed paclitaxel drug amphiphile into well-defined supramol. filaments that possess a fixed 41% paclitaxel loading. These filaments can exert effective cytotoxicity against a no. of cell lines comparable to that of free paclitaxel.
- 36MacKay, J. A.; Chen, M. N.; McDaniel, J. R.; Liu, W. G.; Simnick, A. J.; Chilkoti, A. Self-Assembling Chimeric Polypeptide-Doxorubicin Conjugate Nanoparticles That Abolish Tumours after A Single Injection Nat. Mater. 2009, 8, 993– 999[Crossref], [PubMed], [CAS], Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BD1MjotFSgsg%253D%253D&md5=ba61975d7929e6a9fa86b3b3dcc18319Self-assembling chimeric polypeptide-doxorubicin conjugate nanoparticles that abolish tumours after a single injectionMacKay J Andrew; Chen Mingnan; McDaniel Jonathan R; Liu Wenge; Simnick Andrew J; Chilkoti AshutoshNature materials (2009), 8 (12), 993-9 ISSN:1476-1122.New strategies to self-assemble biocompatible materials into nanoscale, drug-loaded packages with improved therapeutic efficacy are needed for nanomedicine. To address this need, we developed artificial recombinant chimeric polypeptides (CPs) that spontaneously self-assemble into sub-100-nm-sized, near-monodisperse nanoparticles on conjugation of diverse hydrophobic molecules, including chemotherapeutics. These CPs consist of a biodegradable polypeptide that is attached to a short Cys-rich segment. Covalent modification of the Cys residues with a structurally diverse set of hydrophobic small molecules, including chemotherapeutics, leads to spontaneous formation of nanoparticles over a range of CP compositions and molecular weights. When used to deliver chemotherapeutics to a murine cancer model, CP nanoparticles have a fourfold higher maximum tolerated dose than free drug, and induce nearly complete tumour regression after a single dose. This simple strategy can promote co-assembly of drugs, imaging agents and targeting moieties into multifunctional nanomedicines.
- 37Li, X. Y.; Yang, C. B.; Zhang, Z. L.; Wu, Z. D.; Deng, Y.; Liang, G. L.; Yang, Z. M.; Chen, H. Folic Acid as A Versatile Motif to Construct Molecular Hydrogelators through Conjugations with Hydrophobic Therapeutic Agents J. Mater. Chem. 2012, 22, 21838– 21840Google ScholarThere is no corresponding record for this reference.
- 38Duncan, R. Polymer Conjugates as Anticancer Nanomedicines Nat. Rev. Cancer 2006, 6, 688– 701[Crossref], [PubMed], [CAS], Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XosVOmsLY%253D&md5=467349c6d177a8fdd8002d677139bf31Polymer conjugates as anticancer nanomedicinesDuncan, RuthNature Reviews Cancer (2006), 6 (9), 688-701CODEN: NRCAC4; ISSN:1474-175X. (Nature Publishing Group)A review. The transfer of polymer-protein conjugates into routine clin. use, and the clin. development of polymer-anticancer-drug conjugates, both as single agents and as components of combination therapy, is establishing polymer therapeutics as one of the first classes of anticancer nanomedicines. There is growing optimism that ever more sophisticated polymer-based vectors will be a significant addn. to the armory currently used for cancer therapy.
- 39Branco, M. C.; Schneider, J. P. Self-Assembling Materials for Therapeutic Delivery Acta Biomater. 2009, 5, 817– 831[Crossref], [PubMed], [CAS], Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXksF2qu7g%253D&md5=e2fa065e82a37e522ec4525c3996e4a4Self-assembling materials for therapeutic deliveryBranco, Monica C.; Schneider, Joel P.Acta Biomaterialia (2009), 5 (3), 817-831CODEN: ABCICB; ISSN:1742-7061. (Elsevier Ltd.)A review. A growing no. of medications must be administered through parenteral delivery, i.e., i.v., i.m., or s.c. injection, to ensure effectiveness of the therapeutic. For some therapeutics, the use of delivery vehicles in conjunction with this delivery mechanism can improve drug efficacy and patient compliance. Macromol. self-assembly has been exploited recently to engineer materials for the encapsulation and controlled delivery of therapeutics. Self-assembled materials offer the advantages of conventional crosslinked materials normally used for release, but also provide the ability to tailor specific bulk material properties, such as release profiles, at the mol. level via monomer design. As a result, the design of materials from the "bottom up" approach has generated a variety of supramol. devices for biomedical applications. This review provides an overview of self-assembling mols., their resultant structures, and their use in therapeutic delivery. It highlights the current progress in the design of polymer- and peptide-based self-assembled materials.
- 40Aida, T.; Meijer, E. W.; Stupp, S. I. Functional Supramolecular Polymers Science 2012, 335, 813– 817[Crossref], [PubMed], [CAS], Google Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XitFGquro%253D&md5=65127aa5a199aa9136a8ce66e8cbd448Functional Supramolecular PolymersAida, T.; Meijer, E. W.; Stupp, S. I.Science (Washington, DC, United States) (2012), 335 (6070), 813-817CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)A review. Supramol. polymers can be random and entangled coils with the mech. properties of plastics and elastomers, but with great capacity for processability, recycling, and self-healing due to their reversible monomer-to-polymer transitions. At the other extreme, supramol. polymers can be formed by self-assembly among designed subunits to yield shape-persistent and highly ordered filaments. The use of strong and directional interactions among mol. subunits can achieve not only rich dynamic behavior but also high degrees of internal order that are not known in ordinary polymers. They can resemble, for example, the ordered and dynamic one-dimensional supramol. assemblies of the cell cytoskeleton and possess useful biol. and electronic functions.
- 41Tu, R. S.; Tirrell, M. Bottom-up Design of Biomimetic Assemblies Adv. Drug. Deliver. Rev. 2004, 56, 1537– 1563Google ScholarThere is no corresponding record for this reference.
- 42Zhang, Y.; Kuang, Y.; Gao, Y. A.; Xu, B. Versatile Small-Molecule Motifs for Self-Assembly in Water and the Formation of Biofunctional Supramolecular Hydrogels Langmuir 2011, 27, 529– 537[ACS Full Text
], [CAS], Google Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXosVOqu7s%253D&md5=edd3aff3d30a5300b70abe9524dfbf8cVersatile Small-Molecule Motifs for Self-Assembly in Water and the Formation of Biofunctional Supramolecular HydrogelsZhang, Ye; Kuang, Yi; Gao, Yuan; Xu, BingLangmuir (2011), 27 (2), 529-537CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)This feature article introduces new structural motifs (referred as "samogen") that serve as the building blocks of hydrogelators for mol. self-assembly in water to result in a series of supramol. hydrogels. Using a compd. that consists of two phenylalanine residues and a naphthyl group (also abbreviated as NapFF) as an example of the samogens, we demonstrated the ability of the samogens to convert bioactive mols. into mol. hydrogelators that self-assemble in water to result in nanofibers. By briefly summarizing the properties and applications (e.g., wound healing, drug delivery, controlling cell fate, typing bacteria, and catalysis) of these mol. hydrogelators derived from the samogens, we intend to illustrate the basic requirements and promises of the small-mol. hydrogelators for applications in chem., materials science, and biomedicine. - 43Ulijn, R. V.; Smith, A. M. Designing Peptide Based Nanomaterials Chem. Soc. Rev. 2008, 37, 664– 675[Crossref], [PubMed], [CAS], Google Scholar43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXjs12hsbo%253D&md5=d6c7d3ab82107b9bd914ad6c1a4d279dDesigning peptide based nanomaterialsUlijn, Rein V.; Smith, Andrew M.Chemical Society Reviews (2008), 37 (4), 664-675CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. This tutorial review looks at the design rules that allow peptides to be exploited as building bloc for the assembly nanomaterials. These design rules are either derived by copying nature (α-helix, β-sheet) or may exploit entirely new designs based on peptide derivs. (peptide amphiphiles, π-stacking systems). The authors will examine the features that can be introduced to allow self-assembly to be controlled and directed by application of an externally applied stimulus, such as pH, light or enzyme action. Lastly the applications of designed self-assembly peptide systems in biotechnol. (3D cell culture, biosensing) and technol. (nanoelectronics, templating) will be examd.
- 44Toft, D. J.; Moyer, T. J.; Standley, S. M.; Ruff, Y.; Ugolkov, A.; Stupp, S. I.; Cryns, V. L. Coassembled Cytotoxic and Pegylated Peptide Amphiphiles Form Filamentous Nanostructures with Potent Antitumor Activity in Models of Breast Cancer ACS Nano 2012, 6, 7956– 7965[ACS Full Text
], [CAS], Google Scholar44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xht1OksLzK&md5=2eb410a5e46a57106ca5060bd0ed866dCoassembled Cytotoxic and Pegylated Peptide Amphiphiles Form Filamentous Nanostructures with Potent Antitumor Activity in Models of Breast CancerToft, Daniel J.; Moyer, Tyson J.; Standley, Stephany M.; Ruff, Yves; Ugolkov, Andrey; Stupp, Samuel I.; Cryns, Vincent L.ACS Nano (2012), 6 (9), 7956-7965CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)Self-assembled peptide amphiphiles (PAs) consisting of hydrophobic, hydrogen-bonding, and charged hydrophilic domains form cylindrical nanofibers in physiol. conditions and allow for the presentation of a high d. of bioactive epitopes on the nanofiber surface. We report here on the use of PAs to form multifunctional nanostructures with tumoricidal activity. The combination of a cationic, membrane-lytic PA coassembled with a serum-protective, pegylated PA was shown to self-assemble into nanofibers. Addn. of the pegylated PA to the nanostructure substantially limited degrdn. of the cytolytic PA by the protease trypsin, with an 8-fold increase in the amt. of intact PA obsd. after digestion. At the same time, addn. of up to 50% pegylated PA to the nanofibers did not decrease the in vitro cytotoxicity of the cytolytic PA. Using a fluorescent tag covalently attached to PA nanofibers we were able to track the biodistribution in plasma and tissues of tumor-bearing mice over time after i.p. administration of the nanoscale filaments. Using an orthotopic mouse xenograft model of breast cancer, systemic administration of the cytotoxic pegylated nanostructures significantly reduced tumor cell proliferation and overall tumor growth, demonstrating the potential of multifunctional PA nanostructures as versatile cancer therapeutics. - 45Behanna, H. A.; Donners, J. J. J. M.; Gordon, A. C.; Stupp, S. I. Coassembly of Amphiphiles with Opposite Peptide Polarities into Nanofibers J. Am. Chem. Soc. 2005, 127, 1193– 1200[ACS Full Text
], [CAS], Google Scholar45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXitlGhtA%253D%253D&md5=4b39410a654d95b7e8e64a491b6c4c3eCoassembly of Amphiphiles with Opposite Peptide Polarities into NanofibersBehanna, Heather A.; Donners, Jack J. J. M.; Gordon, Alex C.; Stupp, Samuel I.Journal of the American Chemical Society (2005), 127 (4), 1193-1200CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The design, synthesis, and characterization of "reverse" peptide amphiphiles (PAs) with free N-termini is described. Use of an unnatural amino acid modified with a fatty acid tail allows for the synthesis of this new class of PA mols. The mixing of these mols. with complementary ones contg. a free C-terminus results in coassembled structures, as demonstrated by CD and NOE/NMR spectroscopy. These assemblies show unusual thermal stability when compared to assemblies composed of only one type of PA mol. This class of reverse PAs has made it possible to create biol. significant assemblies with free N-terminal peptide sequences, which were previously inaccessible, including those derived from phage display methodologies. - 46Mata, A.; Geng, Y.; Henrikson, K. J.; Aparicio, C.; Stock, S. R.; Satcher, R. L.; Stupp, S. I. Bone Regeneration Mediated by Biomimetic Mineralization of A Nanofiber Matrix Biomaterials 2010, 31, 6004– 6012[Crossref], [PubMed], [CAS], Google Scholar46https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXnslamt7g%253D&md5=31b506ca096d15e5545c810d5ddf4424Bone regeneration mediated by biomimetic mineralization of a nanofiber matrixMata, Alvaro; Geng, Yanbiao; Henrikson, Karl J.; Aparicio, Conrado; Stock, Stuart R.; Satcher, Robert L.; Stupp, Samuel I.Biomaterials (2010), 31 (23), 6004-6012CODEN: BIMADU; ISSN:0142-9612. (Elsevier Ltd.)Rapid bone regeneration within a three-dimensional defect without the use of bone grafts, exogenous growth factors, or cells remains a major challenge. We report here on the use of self-assembling peptide nanostructured gels to promote bone regeneration that have the capacity to mineralize in biomimetic fashion. The main mol. design was the use of phosphoserine residues in the sequence of a peptide amphiphile known to nucleate hydroxyapatite crystals on the surfaces of nanofibers. We tested the system in a rat femoral crit.-size defect by placing pre-assembled nanofiber gels in a 5 mm gap and analyzed bone formation with micro-computed tomog. and histol. We found within 4 wk significantly higher bone formation relative to controls lacking phosphorylated residues and comparable bone formation to that obsd. in animals treated with a clin. used allogenic bone matrix.
- 47Hamley, I. W.; Dehsorkhi, A.; Castelletto, V. Coassembly in Binary Mixtures of Peptide Amphiphiles Containing Oppositely Charged Residues Langmuir 2013, 29, 5050– 5059[ACS Full Text
], [CAS], Google Scholar47https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXkslWlu7o%253D&md5=f166a49d6cc6d94e145d84832163889bCoassembly in Binary Mixtures of Peptide Amphiphiles Containing Oppositely Charged ResiduesHamley, I. W.; Dehsorkhi, A.; Castelletto, V.Langmuir (2013), 29 (16), 5050-5059CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)The self-assembly in water of designed peptide amphiphile (PA) C16-ETTES contg. two anionic residues and its mixts. with C16-KTTKS contg. two cationic residues was studied. Multiple spectroscopy, microscopy, and scattering techniques were used to examine ordering extending from the β-sheet structures up to the fibrillar aggregate structure. The peptide amphiphiles both comprise a hexadecyl alkyl chain and a charged pentapeptide headgroup contg. two charged residues. For C16-ETTES, the crit. aggregation concn. was detd. by fluorescence expts. FTIR and CD spectroscopy were used to examine β-sheet formation. TEM revealed highly extended tape nanostructures with some striped regions corresponding to bilayer structures viewed edge-on. Small-angle x-ray scattering showed a main 5.3 nm bilayer spacing along with a 3. nm spacing. These spacings are assigned resp. to predominant hydrated bilayers and a fraction of dehydrated bilayers. Signs of cooperative self-assembly are obsd. in the mixts., including reduced bundling of peptide amphiphile aggregates (extended tape structures) and enhanced β-sheet formation. - 48Kaler, E. W.; Herrington, K. L.; Murthy, A. K.; Zasadzinski, J. A. N. Phase-Behavior and Structures of Mixtures of Anionic and Cationic Surfactants J. Phys. Chem. 1992, 96, 6698– 6707
- 49Marques, E. F.; Regev, O.; Khan, A.; Miguel, M. D.; Lindman, B. Vesicle Formation and General Phase Behavior in the Catanionic Mixture SDS-DDAB-Water. The Anionic-Rich Side Phys. Chem. B 1998, 102, 6746– 6758[ACS Full Text
], [CAS], Google Scholar49https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1cXltVegt7o%253D&md5=b84c598a9350f6ecf5a9454782b70cf1Vesicle Formation and General Phase Behavior in the Catanionic Mixture SDS-DDAB-Water. The Anionic-Rich SideMarques, Eduardo F.; Regev, Oren; Khan, Ali; Da Graca Miguel, Maria; Lindman, BjoernJournal of Physical Chemistry B (1998), 102 (35), 6746-6758CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)Catanionic mixts. are aq. mixts. of oppositely charged surfactants which display novel phase behavior and interfacial properties in comparison with those of the individual surfactants. One phase behavior property is the ability of these systems to spontaneously form stable vesicles at high diln. The phase behavior of the mixt. sodium dodecyl sulfate (SDS) - didodecyldimethylammonium bromide (DDAB) in water has been studied in detail, and two regions of isotropic vesicular phases (anionic-rich and cationic-rich) were identified. Cryo-transmission electron microscopy allowed direct visualization of relatively small and polydisperse unilamellar vesicles on the SDS-rich side. Monitoring of the microstructure evolution from mixed micelles to vesicles as the surfactant mixing ratio is varied toward equimolarity was also obtained. Further information was provided by water self-diffusion measurements by pulsed field gradient spin-echo NMR. Water mols. can be in fast or slow exchange between the inside and outside of the vesicle with respect to the exptl. time scale, depending on membrane permeability and vesicle size. For the SDS-rich vesicles, a slow-diffusing component of very low molar fraction obsd. for the echo decays was traced down to very large vesicles in soln. Light microscopy confirmed the presence of vesicles of several microns in diam. Thus, polydispersity seems to be an inherent feature of the system. - 50Tondre, C.; Caillet, C. Properties of the Amphiphilic Films in Mixed Cationic/Anionic Vesicles: A Comprehensive View from A Literature Analysis Adv. Colloid Interface Sci. 2001, 93, 115– 134Google ScholarThere is no corresponding record for this reference.
- 51Leung, C. Y.; Palmer, L. C.; Qiao, B. F.; Kewalramani, S.; Sknepnek, R.; Newcomb, C. J.; Greenfield, M. A.; Vernizzi, G.; Stupp, S. I.; Bedzyk, M. J.; de la Cruz, M. O. Molecular Crystallization Controlled by pH Regulates Mesoscopic Membrane Morphology ACS Nano 2012, 6, 10901– 10909
- 52Dubois, M.; Deme, B.; Gulik-Krzywicki, T.; Dedieu, J. C.; Vautrin, C.; Desert, S.; Perez, E.; Zemb, T. Self-Assembly of Regular Hollow Icosahedra in Salt-Free Catanionic Solutions Nature 2001, 411, 672– 675[Crossref], [PubMed], [CAS], Google Scholar52https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXksF2htL0%253D&md5=e41d5bb789b3747506e4794cf3cb8dd3Self-assembly of regular hollow icosahedra in salt-free catanionic solutionsDubois, Monique; Deme, Bruno; Gulik-Krzywicki, Thaddee; Dedieu, Jean-Claude; Vautrin, Claire; Desert, Sylvan; Perez, Emile; Zemb, ThomasNature (London, United Kingdom) (2001), 411 (6838), 672-675CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)Self-assembled structures having a regular hollow icosahedral form (such as those obsd. for proteins of virus capsids) can occur as a result of biomineralization processes, but are extremely rare in mineral crystallites. Compact icosahedra made from a boron oxide have been reported, but equiv. structures made of synthetic org. components such as surfactants have not hitherto been obsd. It is, however, well known that lipids, as well as mixts. of anionic and cationic single chain surfactants can readily form bilayers that can adopt a variety of distinct geometric forms: they can fold into soft vesicles or random bilayers (the so-called sponge phase) or form ordered stacks of flat or undulating membranes. Here we show that in salt-free mixts. of anionic and cationic surfactants, such bilayers can self-assemble into hollow aggregates with a regular icosahedral shape. These aggregates are stabilized by the presence of pores located at the vertices of the icosahedra. The resulting structure have a size of about one micrometer and mass of about 1010 daltons, making them larger than any known icosahedral protein assembly or virus capsid. We expect the combination of wall rigidity and holes at vertices of these icosahedral aggregates to be of practical value for controlled drug or DNA release.
- 53Zemb, T.; Dubois, M.; Deme, B.; Gulik-Krzywicki, T. Self-Assembly of Flat Nanodiscs in Salt-Free Catanionic Surfactant Solutions Science 1999, 283, 816– 819[Crossref], [PubMed], [CAS], Google Scholar53https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1MXhtFShsLw%253D&md5=e9498ce86594265aa35f211c32ab30a3Self-assembly of flat nanodiscs in salt-free cationic surfactant solutionsZemb, Th.; Dubois, M.; Deme, B.; Gulik-Krzywicki, Th.Science (Washington, D. C.) (1999), 283 (5403), 816-819CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Disks of finite size are a very rare form of stable surfactant self-assembly. It is shown that mixing of two oppositely charged single-chain surfactants can produce rigid nanodiscs as well as swollen lamellar liq. crystals with frozen bilayers. The crucial requirement for obtaining nanodisc self-assembly is the use of H+ and OH- as counterions. These counterions then form water and lower the cond. to 10 microsiemens per cm. In the case of cationic component excess, a dil. soln. of nanodiscs is in thermodn. equil. with a lamellar phase. The diam. of the cationic nanodiscs is continuously adjustable from a few micrometers to 30 nm, with the pos. charge located mainly around the edges.
- 54Manghisi, N.; Leggio, C.; Jover, A.; Meijide, F.; Pavel, N. V.; Tellini, V. H. S.; Tato, J. V.; Agostino, R. G.; Galantini, L. Catanionic Tubules with Tunable Charge Angew. Chem. Int. Ed. 2010, 49, 6604– 6607Google ScholarThere is no corresponding record for this reference.
- 55Nelson, R.; Sawaya, M. R.; Balbirnie, M.; Madsen, A. O.; Riekel, C.; Grothe, R.; Eisenberg, D. Structure of the Cross-[Beta] Spine of Amyloid-Like Fibrils Nature 2005, 435, 773– 778Google ScholarThere is no corresponding record for this reference.
- 56Cui, H.; Hodgdon, T. K.; Kaler, E. W.; Abezgauz, L.; Danino, D.; Lubovsky, M.; Talmon, Y.; Pochan, D. J. Elucidating the Assembled Structure of Amphiphiles in Solution via Cryogenic Transmission Electron Microscopy Soft Matter 2007, 3, 945– 955[Crossref], [PubMed], [CAS], Google Scholar56https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXnslGkur8%253D&md5=6c021ddb07165fd54ba77526e711ba55Elucidating the assembled structure of amphiphiles in solution via cryogenic transmission electron microscopyCui, Honggang; Hodgdon, Travis K.; Kaler, Eric W.; Abezgauz, Ludmila; Danino, Dganit; Lubovsky, Maya; Talmon, Yeshayahu; Pochan, Darrin J.Soft Matter (2007), 3 (8), 945-955CODEN: SMOABF; ISSN:1744-683X. (Royal Society of Chemistry)A review. For the past twenty years, significant progress was made in both developing cryogenic transmission electron microscopy (cryo-TEM) technol. and understanding assembled behavior of amphiphilic mols. Cryo-TEM can provide high-resoln. images of complex fluids in a near in situ state. Samples embedded in a thin layer of vitrified solvent do not exhibit artifacts that would normally occur when using chem. fixation or staining-and-drying techniques. Cryo-TEM was useful in imaging biol. mols. in aq. solns. Cryo-TEM has become a powerful tool in the study of in situ-assembled structures of amphiphiles in soln. as a complementary tool to small-angle x-ray and neutron scattering, light scattering, rheol. measurements, and NMR. The application of cryo-TEM in the study of assembled behavior of amphiphilic block copolymers, hydrogels, and other complex soft systems continues to emerge. In this context, the usage of cryo-TEM in the field of amphiphilic complex fluids and self-assembled nanomaterials is briefly reviewed, and its unique role in exploring the nature of assembled structure in liq. suspension is highlighted.
- 57Helfrich, W.; Prost, J. Intrinsic Bending Force In Anisotropic Membranes Made of Chiral Molecules Phys. Rev. A 1988, 38, 3065– 3068Google ScholarThere is no corresponding record for this reference.
- 58Selinger, J. V.; Spector, M. S.; Schnur, J. M. Theory of Self-Assembled Tubules and Helical Ribbons J. Phys. Chem. B 2001, 105, 7157– 7169[ACS Full Text
], [CAS], Google Scholar58https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXks1Sgurw%253D&md5=e1be35c60c89069255bec682a98525eeTheory of Self-Assembled Tubules and Helical RibbonsSelinger, Jonathan V.; Spector, Mark S.; Schnur, Joel M.Journal of Physical Chemistry B (2001), 105 (30), 7157-7169CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)A review with 64 refs. Many types of amphiphilic mols. self-assemble in soln. to form cylindrical tubules and helical ribbons. Some examples include diacetylenic lipids, amide amphiphiles, bile, and diblock copolymers. Researchers have proposed a variety of models to explain the formation of these high-curvature structures. These models can be divided into two broad categories: models based on the chiral elastic properties of membranes, and models based on other effects, including electrostatic interactions, elasticity of orientational order, and spontaneous curvature. In this paper, we review the range of theor. approaches and compare them with relevant expts. We argue that the category of models based on chiral elastic properties provides the most likely explanation of current exptl. results, and we propose further theor. and exptl. research to give a more detailed test of these models. - 59Israelachvili, J. N. Intermolecular and Surface Forces, 3rd ed.; Elsevier: New York, 2011.
- 60Adamcik, J.; Mezzenga, R. Adjustable Twisting Periodic Pitch of Amyloid Fibrils Soft Matter 2011, 7, 5437– 5443[Crossref], [CAS], Google Scholar60https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXmsVCqtL8%253D&md5=07e92b337f9c6e8b433ed41e9a1b0fa0Adjustable twisting periodic pitch of amyloid fibrilsAdamcik, Jozef; Mezzenga, RaffaeleSoft Matter (2011), 7 (11), 5437-5443CODEN: SMOABF; ISSN:1744-683X. (Royal Society of Chemistry)We present compelling exptl. evidence supported by theor. arguments demonstrating that the periodic twisting pitch in protein amyloid fibrils arises from the fine balance between competing electrostatic energy and torsional elastic energy stored along the fibrils contour length. To construct the present picture we have used increasing ionic strengths to progressively screen the electrostatic interactions and obsd. the corresponding pitch variations in mature β-lactoglobulin amyloid fibrils using single-mol. at. force microscopy (AFM). Because the ionic strength is changed after fibrils formation, this does not affect the mechanism by which fibrils grow up to their mature structure. For each individual population of the multi-stranded fibrils family, the pitch is found to increase systematically with the salt content, leading to the gradual untwisting of the fibrils and to the establishment of a controllable pitch up to virtually infinite values.
- 61Adamcik, J.; Mezzenga, R. Proteins Fibrils from a Polymer Physics Perspective Macromolecules 2012, 45, 1137– 1150[ACS Full Text
], [CAS], Google Scholar61https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhs1GltrjJ&md5=d1317aae7dbbbf181e97b27ffa7a3934Proteins Fibrils from a Polymer Physics PerspectiveAdamcik, Jozef; Mezzenga, RaffaeleMacromolecules (Washington, DC, United States) (2012), 45 (3), 1137-1150CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)A review. Protein fibrils resulting from assembly of proteins or peptides into long, insol., highly ordered fibrillar structures are emerging as one of the fastest growing scientific areas, since interest in these systems spans disciplines as broad and diverse as medicine, biol., soft condensed matter, nanotechnol., and materials science. Since the discovery of the implication of protein amyloid fibrils in neurodegenerative diseases, to their more recent applications in high-performance materials, the understanding of these intriguing macromol. assemblies has been steadily widening and deepening. Thus, the precise characterization of structural, phys., and mech. properties of protein fibrils is the first crit. step toward our understanding of these systems not only in the context of biol. and medicine but also in nanotechnol. and advanced biomaterials applications. In this Perspective we wish to discuss how polymer and colloidal science concepts can be efficiently used to unravel very useful information on the mechanisms of formation, structure, and phys. properties of protein fibrils and want to show, through available examples, how a soft condensed matter perspective can shed light into these fascinating systems. - 62Usov, I.; Adamcik, J.; Mezzenga, R. Polymorphism Complexity and Handedness Inversion in Serum Albumin Amyloid Fibrils ACS Nano 2013, 7, 10465– 10474
- 63Adamcik, J.; Lara, C.; Usov, I.; Jeong, J. S.; Ruggeri, F. S.; Dietler, G.; Lashuel, H. A.; Hamley, I. W.; Mezzenga, R. Measurement of Intrinsic Properties of Amyloid Fibrils by the Peak Force QNM Method Nanoscale 2012, 4, 4426– 4429[Crossref], [PubMed], [CAS], Google Scholar63https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtVSqt7rJ&md5=50a0998477ba555f78ba8dd8676faf0eMeasurement of intrinsic properties of amyloid fibrils by the peak force QNM methodAdamcik, Jozef; Lara, Cecile; Usov, Ivan; Jeong, Jae Sun; Ruggeri, Francesco S.; Dietler, Giovanni; Lashuel, Hilal A.; Hamley, Ian W.; Mezzenga, RaffaeleNanoscale (2012), 4 (15), 4426-4429CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)We report the investigation of the mech. properties of different types of amyloid fibrils by the peak force quant. nanomech. (PF-QNM) technique. We demonstrate that this technique correctly measures the Young's modulus independent of the polymorphic state and the cross-sectional structural details of the fibrils, and the authors show that values for amyloid fibrils assembled from heptapeptides, α-synuclein, Aβ(1-42), insulin, β-lactoglobulin, lysozyme, ovalbumin, Tau protein and bovine serum albumin all fall in the range of 2-4 GPa.
- 64Usov, I.; Mezzenga, R. Correlation between Nanomechanics and Polymorphic Conformations in Amyloid Fibrils ACS Nano 2014, 8, 11035– 11041[ACS Full Text
], [CAS], Google Scholar64https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhs1Oiu77P&md5=02a6bbb6de225e80563371270efa9e06Correlation between Nanomechanics and Polymorphic Conformations in Amyloid FibrilsUsov, Ivan; Mezzenga, RaffaeleACS Nano (2014), 8 (11), 11035-11041CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)Amyloid fibrils occur in diverse morphologies, but how polymorphism affects the resulting mech. properties is still not fully appreciated. Using formalisms from the theory of elasticity, we propose an original way of averaging the second area moment of inertia for non-axisym. fibrils, which constitutes the great majority of amyloid fibrils. By following this approach, we derive theor. expressions for the bending properties of the most common polymorphic forms of amyloid fibrils (twisted ribbons, helical ribbons, and nanotubes), and we benchmark the predictions to exptl. cases. These results not only allow an accurate estn. of the amyloid fibrils' elastic moduli but also bring insight into the structure-property relationships in the nanomechanics of amyloid systems, such as in the closure of helical ribbons into nanotubes. - 65Geng, Y.; Dalhaimer, P.; Cai, S. S.; Tsai, R.; Tewari, M.; Minko, T.; Discher, D. E. Shape Effects of Filaments versus Spherical Particles in Flow and Drug Delivery Nat. Nanotechnol. 2007, 2, 249– 255[Crossref], [PubMed], [CAS], Google Scholar65https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXktVGgsbs%253D&md5=e93d8a9b11bf2a6cc2c5e970aa37a433Shape effects of filaments versus spherical particles in flow and drug deliveryGeng, Yan; Dalhaimer, Paul; Cai, Shenshen; Tsai, Richard; Tewari, Manorama; Minko, Tamara; Discher, Dennis E.Nature Nanotechnology (2007), 2 (4), 249-255CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)Interaction of spherical particles with cells and within animals was studied extensively, but the effects of shape have received little attention. Here the authors use highly stable, polymer micelle assemblies known as filomicelles to compare the transport and trafficking of flexible filaments with spheres of similar chem. In rodents, filomicelles persisted in the circulation up to one week after i.v. injection. This is about ten times longer than their spherical counterparts and is more persistent than any known synthetic nanoparticle. Under fluid flow conditions, spheres and short filomicelles are taken up by cells more readily than longer filaments because the latter are extended by the flow. Preliminary results further demonstrate that filomicelles can effectively deliver the anticancer drug paclitaxel and shrink human-derived tumors in mice. Although these findings show that long-circulating vehicles need not be nanospheres, they also lead insight into possible shape effects of natural filamentous viruses.
- 66Jiang, S. Y.; Cao, Z. Q. Ultralow-Fouling, Functionalizable, and Hydrolyzable Zwitterionic Materials and Their Derivatives for Biological Applications Adv. Mater. 2010, 22, 920– 932Google ScholarThere is no corresponding record for this reference.
- 67Dubikovskaya, E. A.; Thorne, S. H.; Pillow, T. H.; Contag, C. H.; Wender, P. A. Overcoming multidrug resistance of small-molecule therapeutics through conjugation with releasable octaarginine transporters Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 12128– 12133[Crossref], [PubMed], [CAS], Google Scholar67https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhtVOhtrzN&md5=0f8f068576e4304d23d0ac0bfecb5a7dOvercoming multidrug resistance of small-molecule therapeutics through conjugation with releasable octaarginine transportersDubikovskaya, Elena A.; Thorne, Steve H.; Pillow, Thomas H.; Contag, Christopher H.; Wender, Paul A.Proceedings of the National Academy of Sciences of the United States of America (2008), 105 (34), 12128-12133CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)Many cancer therapeutic agents elicit resistance that renders them ineffective and often produces cross-resistance to other drugs. One of the most common mechanisms of resistance involves P-glycoprotein (Pgp)-mediated drug efflux. To address this problem, new agents have been sought that are less prone to inducing resistance and less likely to serve as substrates for Pgp efflux. An alternative to this approach is to deliver established agents as mol. transporter conjugates into cells through a mechanism that circumvents Pgp-mediated efflux and allows for release of free drug only after cell entry. Here we report that the widely used chemotherapeutic agent Taxol, ineffective against Taxol-resistant human ovarian cancer cell lines, can be incorporated into a releasable octaarginine conjugate that is effective against the same Taxol-resistant cell lines. It is significant that the ability of the Taxol conjugates to overcome Taxol resistance is obsd. both in cell culture and in animal models of ovarian cancer. The generality and mechanistic basis for this effect were also explored with coelenterazine, a Pgp substrate. Although coelenterazine itself does not enter cells because of Pgp efflux, its octaarginine conjugate does so readily. This approach shows generality for overcoming the multidrug resistance elicited by small-mol. cancer chemotherapeutics and could improve the prognosis for many patients with cancer and fundamentally alter search strategies for novel therapeutic agents that are effective against resistant disease.
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- Minxi Hu, Ping Huang, Yao Wang, Yue Su, Linzhu Zhou, Xinyuan Zhu, and Deyue Yan . Synergistic Combination Chemotherapy of Camptothecin and Floxuridine through Self-Assembly of Amphiphilic Drug–Drug Conjugate. Bioconjugate Chemistry 2015, 26 (12) , 2497-2506. https://doi.org/10.1021/acs.bioconjchem.5b00513
- Xuyu Tan, Ben B. Li, Xueguang Lu, Fei Jia, Clarissa Santori, Priyanka Menon, Hui Li, Bohan Zhang, Jean J. Zhao, and Ke Zhang . Light-Triggered, Self-Immolative Nucleic Acid-Drug Nanostructures. Journal of the American Chemical Society 2015, 137 (19) , 6112-6115. https://doi.org/10.1021/jacs.5b00795
- Lye Lin Lock, Zidu Tang, Daniel Keith, Claudia Reyes, and Honggang Cui . Enzyme-Specific Doxorubicin Drug Beacon as Drug-Resistant Theranostic Molecular Probes. ACS Macro Letters 2015, 4 (5) , 552-555. https://doi.org/10.1021/acsmacrolett.5b00170
- Ian W. Hamley, Ashkan Dehsorkhi, Valeria Castelletto, Merlin N. M. Walter, Che J. Connon, Mehedi Reza, and Janne Ruokolainen . Self-Assembly and Collagen-Stimulating Activity of a Peptide Amphiphile Incorporating a Peptide Sequence from Lumican. Langmuir 2015, 31 (15) , 4490-4495. https://doi.org/10.1021/acs.langmuir.5b00057
- Yan Wang, Xiaoyuan Zhang, Keming Wan, Nan Zhou, Gang Wei, Zhiqiang Su. Supramolecular peptide nano-assemblies for cancer diagnosis and therapy: from molecular design to material synthesis and function-specific applications. Journal of Nanobiotechnology 2021, 19 (1) https://doi.org/10.1186/s12951-021-00999-x
- Yurong Zhao, Limin Zhang, Xing Zhou, Hai Xu, Xingfan Li, Dong Wang, Cuixia Chen, Jiqian Wang, Li Wang, Wenxin Wang. Tuning the Shell Structure of Peptide Nanotubes with Sodium Tartrate: from Monolayer to Bilayer. Journal of Colloid and Interface Science 2021, 24 https://doi.org/10.1016/j.jcis.2021.10.023
- Mingyang Ji, Zhaoyang Liu. Construction of spatially organized, peptide/peptide derivative containing nanocomposites. Materials Advances 2021, 2 (18) , 5803-5823. https://doi.org/10.1039/D1MA00400J
- Kathrin Siegl, Luba Kolik‐Shmuel, Mingming Zhang, Sylvain Prévost, Kalanit Vishnia, Amram Mor, Marie‐Sousai Appavou, Charl J. Jafta, Dganit Danino, Michael Gradzielski. Directed Assembly of Multi‐Walled Nanotubes and Nanoribbons of Amino Acid Amphiphiles Using a Layer‐by‐Layer Approach. Chemistry – A European Journal 2021, 27 (23) , 6904-6910. https://doi.org/10.1002/chem.202005331
- Valeria Castelletto, Jani Seitsonen, Janne Ruokolainen, Ian W. Hamley. Alpha helical surfactant-like peptides self-assemble into pH-dependent nanostructures. Soft Matter 2021, 17 (11) , 3096-3104. https://doi.org/10.1039/D0SM02095H
- Yi Lai, Fenglin Li, Zhifeng Zou, Madiha Saeed, Zhiai Xu, Haijun Yu. Bio-inspired amyloid polypeptides: From self-assembly to nanostructure design and biotechnological applications. Applied Materials Today 2021, 22 , 100966. https://doi.org/10.1016/j.apmt.2021.100966
- Yurong Zhao, Xuzhi Hu, Limin Zhang, Dong Wang, Stephen M. King, Sarah E. Rogers, Jiqian Wang, Jian R. Lu, Hai Xu. Monolayer wall nanotubes self-assembled from short peptide bolaamphiphiles. Journal of Colloid and Interface Science 2021, 583 , 553-562. https://doi.org/10.1016/j.jcis.2020.09.023
- Phu K. Tang, Anjela Manandhar, William Hu, Myungshim Kang, Sharon M. Loverde. The interaction of supramolecular anticancer drug amphiphiles with phospholipid membranes. Nanoscale Advances 2021, 3 (2) , 370-382. https://doi.org/10.1039/D0NA00697A
- Paula Schiapparelli, Montserrat Lara-Velazquez, Rawan Al-kharboosh, Hao Su, Honggang Cui, Alfredo Quinones-Hinojosa. Strategies to Modulate the Blood-Brain Barrier for Directed Brain Tumor Targeting. 2021,,, 79-108. https://doi.org/10.1007/978-1-0716-1052-7_3
- Li Huang, Shaojing Zhao, Fang Fang, Ting Xu, Minhuan Lan, Jinfeng Zhang. Advances and perspectives in carrier-free nanodrugs for cancer chemo-monotherapy and combination therapy. Biomaterials 2021, 268 , 120557. https://doi.org/10.1016/j.biomaterials.2020.120557
- Jingjing Wang, Ying Qian, Liu Xu, Yurou Shao, Hu Zhang, Fanli Shi, Jiaxin Chen, Siqi Cui, Xiaoyan Chen, Dongwei Zhu, Rongfeng Hu, Zhipeng Chen. Hyaluronic acid-shelled, peptide drug conjugate-cored nanomedicine for the treatment of hepatocellular carcinoma. Materials Science and Engineering: C 2020, 117 , 111261. https://doi.org/10.1016/j.msec.2020.111261
- Bradford Paik, Cesar Calero-Rubio, Jee Young Lee, Xinqiao Jia, Kristi L. Kiick, Christopher J. Roberts. Characterizing aggregate growth and morphology of alanine-rich polypeptides as a function of sequence chemistry and solution temperature from scattering, spectroscopy, and microscopy. Biophysical Chemistry 2020, 267 , 106481. https://doi.org/10.1016/j.bpc.2020.106481
- Zhengyu Deng, Shiyong Liu. Controlled drug delivery with nanoassemblies of redox-responsive prodrug and polyprodrug amphiphiles. Journal of Controlled Release 2020, 326 , 276-296. https://doi.org/10.1016/j.jconrel.2020.07.010
- Xiaoli Zhang, Tian Zhang, Xianbin Ma, Yajun Wang, Yi Lu, Die Jia, Xiaohua Huang, Jiucun Chen, Zhigang Xu, Feiqiu Wen. The design and synthesis of dextran-doxorubicin prodrug-based pH-sensitive drug delivery system for improving chemotherapy efficacy. Asian Journal of Pharmaceutical Sciences 2020, 15 (5) , 605-616. https://doi.org/10.1016/j.ajps.2019.10.001
- Zhiren Wang, Jiawei Chen, Nicholas Little, Jianqin Lu. Self-assembling prodrug nanotherapeutics for synergistic tumor targeted drug delivery. Acta Biomaterialia 2020, 111 , 20-28. https://doi.org/10.1016/j.actbio.2020.05.026
- Wei Ran, Xiaoyu Liu, Lu Chang, Ying Cai, Chao Zheng, Jia Liu, Yaping Li, Pengcheng Zhang. Self-assembling mertansine prodrug improves tolerability and efficacy of chemotherapy against metastatic triple-negative breast cancer. Journal of Controlled Release 2020, 318 , 234-245. https://doi.org/10.1016/j.jconrel.2019.12.027
- Yi Zhang, Hong-Yan Cai, Song-Shuang Hu, Jian-Guo Li, Qing-Tao Gong, Wang-Jing Ma, Zi-Yu Liu, Lei Zhang, Lu Zhang, Sui Zhao. Interfacial dilational properties of betaines and sulfonate mixtures: Effects of alkyl chain length. Journal of Dispersion Science and Technology 2020, 41 (2) , 195-206. https://doi.org/10.1080/01932691.2018.1561305
- Christian Helbing, Klaus D. Jandt. Novel protein and peptide nanofibrous structures via supramolecular co-assembly. 2020,,, 69-97. https://doi.org/10.1016/B978-0-08-102850-6.00004-8
- Soumi Das, Kamalesh Verma, Vikash K. Dubey, Lal Mohan Kundu. Fabrication of nanoparticles from a synthesized peptide amphiphile as a versatile therapeutic cargo for high antiproliferative activity in tumor cells. Bioorganic Chemistry 2020, 94 , 103440. https://doi.org/10.1016/j.bioorg.2019.103440
- Tian Zhang, Yajun Wang, Xianbin Ma, Cuilan Hou, Shuangyu Lv, Die Jia, Yi Lu, Peng Xue, Yuejun Kang, Zhigang Xu. A bottlebrush-architectured dextran polyprodrug as an acidity-responsive vector for enhanced chemotherapy efficiency. Biomaterials Science 2020, 8 (1) , 473-484. https://doi.org/10.1039/C9BM01692A
- Zhenghong Chen, Pingping Zhang, Yimeng Sun, Ce Wang, Baocai Xu. Interfacial Dilational Rheology of Sodium Lauryl Glycine and Mixtures with Conventional Surfactants. Journal of Surfactants and Detergents 2019, 22 (6) , 1477-1485. https://doi.org/10.1002/jsde.12312
- Zakharova, Pashirova, Doktorovova, Fernandes, Sanchez-Lopez, Silva, Souto, Souto. Cationic Surfactants: Self-Assembly, Structure-Activity Correlation and Their Biological Applications. International Journal of Molecular Sciences 2019, 20 (22) , 5534. https://doi.org/10.3390/ijms20225534
- Shaofeng Lou, Xinmou Wang, Zhilin Yu, Linqi Shi. Peptide Tectonics: Encoded Structural Complementarity Dictates Programmable Self‐Assembly. Advanced Science 2019, 6 (13) , 1802043. https://doi.org/10.1002/advs.201802043
- Tao Zhang, Chong Ma, Tingting Sun, Zhigang Xie. Unadulterated BODIPY nanoparticles for biomedical applications. Coordination Chemistry Reviews 2019, 390 , 76-85. https://doi.org/10.1016/j.ccr.2019.04.001
- Yanyi Wang, Jiahua Pu, Bolin An, Timothy K. Lu, Chao Zhong. Emerging Paradigms for Synthetic Design of Functional Amyloids. Journal of Molecular Biology 2018, 430 (20) , 3720-3734. https://doi.org/10.1016/j.jmb.2018.04.012
- Meili Hou, Yong-E Gao, Xiaoxiao Shi, Shuang Bai, Xiaoqian Ma, Baosheng Li, Bo Xiao, Peng Xue, Yuejun Kang, Zhigang Xu. Methotrexate-based amphiphilic prodrug nanoaggregates for co-administration of multiple therapeutics and synergistic cancer therapy. Acta Biomaterialia 2018, 77 , 228-239. https://doi.org/10.1016/j.actbio.2018.07.014
- Dganit Danino, Edward H. Egelman. Direct imaging and computational cryo-electron microscopy of ribbons and nanotubes. Current Opinion in Colloid & Interface Science 2018, 34 , 100-113. https://doi.org/10.1016/j.cocis.2018.05.002
- Lucia Y. Zakharova, Tatiana N. Pashirova, Ana R. Fernandes, Slavomira Doktorovova, Carlos Martins-Gomes, Amélia M. Silva, Eliana B. Souto. Self-assembled quaternary ammonium surfactants for pharmaceuticals and biotechnology. 2018,,, 601-618. https://doi.org/10.1016/B978-0-12-813663-8.00014-2
- Pengcheng Zhang, Yonggang Cui, Caleb F. Anderson, Chunli Zhang, Yaping Li, Rongfu Wang, Honggang Cui. Peptide-based nanoprobes for molecular imaging and disease diagnostics. Chemical Society Reviews 2018, 47 (10) , 3490-3529. https://doi.org/10.1039/C7CS00793K
- Seyed Ali Eghtesadi, Marjan Alsadat Kashfipour, Xinyu Sun, Wei Zhang, Robert Scott Lillard, Stephen Z. D. Cheng, Tianbo Liu. Hierarchical self-assembly of zwitterionic dendrimer–anionic surfactant complexes into multiple stimuli-responsive dynamic nanotubes. Nanoscale 2018, 10 (3) , 1411-1419. https://doi.org/10.1039/C7NR07950H
- Xiaoxiao Shi, Shuang Bai, Cangjie Yang, Xiaoqian Ma, Meili Hou, Jiucun Chen, Peng Xue, Chang Ming Li, Yuejun Kang, Zhigang Xu. Improving the carrier stability and drug loading of unimolecular micelle-based nanotherapeutics for acid-activated drug delivery and enhanced antitumor therapy. Journal of Materials Chemistry B 2018, 6 (35) , 5549-5561. https://doi.org/10.1039/C8TB01384E
- Rami Walid Chakroun, Pengcheng Zhang, Ran Lin, Paula Schiapparelli, Alfredo Quinones‐Hinojosa, Honggang Cui. Nanotherapeutic systems for local treatment of brain tumors. WIREs Nanomedicine and Nanobiotechnology 2018, 10 (1) https://doi.org/10.1002/wnan.1479
- Rongliang Wu, Jun Liu, Xinlong Qiu, Manli Deng. Molecular dynamics simulation of the nanofibrils formed by amyloid-based peptide amphiphiles. Molecular Simulation 2017, 43 (13-16) , 1227-1239. https://doi.org/10.1080/08927022.2017.1321758
- Hao Su, Yuzhu Wang, Caleb F. Anderson, Jin Mo Koo, Han Wang, Honggang Cui. Recent progress in exploiting small molecule peptides as supramolecular hydrogelators. Chinese Journal of Polymer Science 2017, 35 (10) , 1194-1211. https://doi.org/10.1007/s10118-017-1998-2
- Wang Ma, Hao Su, Andrew G. Cheetham, Weifang Zhang, Yuzhu Wang, QuanCheng Kan, Honggang Cui. Synergistic antitumor activity of a self-assembling camptothecin and capecitabine hybrid prodrug for improved efficacy. Journal of Controlled Release 2017, 263 , 102-111. https://doi.org/10.1016/j.jconrel.2017.01.015
- Durga Dharmadana, Nicholas P. Reynolds, Charlotte E. Conn, Céline Valéry. Molecular interactions of amyloid nanofibrils with biological aggregation modifiers: implications for cytotoxicity mechanisms and biomaterial design. Interface Focus 2017, 7 (4) , 20160160. https://doi.org/10.1098/rsfs.2016.0160
- Darija Domazet Jurašin, Suzana Šegota, Vida Čadež, Atiđa Selmani, Maja Dutour Sikirć. Recent Advances in Catanionic Mixtures. 2017,,https://doi.org/10.5772/67998
- Huaimin Wang, Zhaoqianqi Feng, Alvin Lu, Yujie Jiang, Hao Wu, Bing Xu. Instant Hydrogelation Inspired by Inflammasomes. Angewandte Chemie 2017, 129 (26) , 7687-7691. https://doi.org/10.1002/ange.201702783
- Huaimin Wang, Zhaoqianqi Feng, Alvin Lu, Yujie Jiang, Hao Wu, Bing Xu. Instant Hydrogelation Inspired by Inflammasomes. Angewandte Chemie International Edition 2017, 56 (26) , 7579-7583. https://doi.org/10.1002/anie.201702783
- Zhanfeng Wang, Miao Zhuang, Tingting Sun, Xin Wang, Zhigang Xie. Self-assembly of glutamic acid linked paclitaxel dimers into nanoparticles for chemotherapy. Bioorganic & Medicinal Chemistry Letters 2017, 27 (11) , 2493-2496. https://doi.org/10.1016/j.bmcl.2017.03.101
- Andrew G Cheetham, Yi-an Lin, Ran Lin, Honggang Cui. Molecular design and synthesis of self-assembling camptothecin drug amphiphiles. Acta Pharmacologica Sinica 2017, 38 (6) , 874-884. https://doi.org/10.1038/aps.2016.151
- Pablo Botella, Eva Rivero-Buceta. Safe approaches for camptothecin delivery: Structural analogues and nanomedicines. Journal of Controlled Release 2017, 247 , 28-54. https://doi.org/10.1016/j.jconrel.2016.12.023
- Yin Wang, Andrew G. Cheetham, Garren Angacian, Hao Su, Lisi Xie, Honggang Cui. Peptide–drug conjugates as effective prodrug strategies for targeted delivery. Advanced Drug Delivery Reviews 2017, 110-111 , 112-126. https://doi.org/10.1016/j.addr.2016.06.015
- M. Gubitosi, A. D'Annibale, K. Schillén, U. Olsson, N. V. Pavel, L. Galantini. On the stability of lithocholate derivative supramolecular tubules. RSC Advances 2017, 7 (1) , 512-517. https://doi.org/10.1039/C6RA26092F
- Si-Yong Qin, Ai-Qing Zhang, Si-Xue Cheng, Lei Rong, Xian-Zheng Zhang. Drug self-delivery systems for cancer therapy. Biomaterials 2017, 112 , 234-247. https://doi.org/10.1016/j.biomaterials.2016.10.016
- Zhigang Xu, Meili Hou, Xiaoxiao Shi, Yong-E. Gao, Peng Xue, Shiying Liu, Yuejun Kang. Rapidly cell-penetrating and reductive milieu-responsive nanoaggregates assembled from an amphiphilic folate-camptothecin prodrug for enhanced drug delivery and controlled release. Biomaterials Science 2017, 5 (3) , 444-454. https://doi.org/10.1039/C6BM00800C
- M. C. di Gregorio, M. Gubitosi, L. Travaglini, N. V. Pavel, A. Jover, F. Meijide, J. Vázquez Tato, S. Sennato, K. Schillén, F. Tranchini, S. De Santis, G. Masci, L. Galantini. Supramolecular assembly of a thermoresponsive steroidal surfactant with an oppositely charged thermoresponsive block copolymer. Physical Chemistry Chemical Physics 2017, 19 (2) , 1504-1515. https://doi.org/10.1039/C6CP05665B
- Gang Wei, Zhiqiang Su, Nicholas P. Reynolds, Paolo Arosio, Ian W. Hamley, Ehud Gazit, Raffaele Mezzenga. Self-assembling peptide and protein amyloids: from structure to tailored function in nanotechnology. Chemical Society Reviews 2017, 46 (15) , 4661-4708. https://doi.org/10.1039/C6CS00542J
- Meili Hou, Peng Xue, Yong-E. Gao, Xiaoqian Ma, Shuang Bai, Yuejun Kang, Zhigang Xu. Gemcitabine–camptothecin conjugates: a hybrid prodrug for controlled drug release and synergistic therapeutics. Biomaterials Science 2017, 5 (9) , 1889-1897. https://doi.org/10.1039/C7BM00382J
- Mingyang Ji, Brian Daniels, Aileen Shieh, David A. Modarelli, Jon R. Parquette. Controlling the length of self-assembled nanotubes by sonication followed by polymer wrapping. Chemical Communications 2017, 53 (95) , 12806-12809. https://doi.org/10.1039/C7CC07418B
- Matthew J. Webber, Robert Langer. Drug delivery by supramolecular design. Chemical Society Reviews 2017, 46 (21) , 6600-6620. https://doi.org/10.1039/C7CS00391A
- Andrew G. Cheetham, Rami W. Chakroun, Wang Ma, Honggang Cui. Self-assembling prodrugs. Chem. Soc. Rev. 2017, 46 (21) , 6638-6663. https://doi.org/10.1039/C7CS00521K
- Yan Wen, Wei Zhang, Ningqiang Gong, Yi-Feng Wang, Hong-Bo Guo, Weisheng Guo, Paul C. Wang, Xing-Jie Liang. Carrier-free, self-assembled pure drug nanorods composed of 10-hydroxycamptothecin and chlorin e6 for combinatorial chemo-photodynamic antitumor therapy in vivo. Nanoscale 2017, 9 (38) , 14347-14356. https://doi.org/10.1039/C7NR03129G
- Zijun Zhou, Jingzhe Yan, Tingting Sun, Xin Wang, Zhigang Xie. Nanoprodrug of retinoic acid-modified paclitaxel. Organic & Biomolecular Chemistry 2017, 15 (45) , 9611-9615. https://doi.org/10.1039/C7OB02553J
- Tingting Sun, Wenhai Lin, Wei Zhang, Zhigang Xie. Self-Assembly of Amphiphilic Drug-Dye Conjugates into Nanoparticles for Imaging and Chemotherapy. Chemistry - An Asian Journal 2016, 11 (22) , 3174-3177. https://doi.org/10.1002/asia.201601206
- Yang Hu, Ran Lin, Kunal Patel, Andrew G. Cheetham, Chengyou Kan, Honggang Cui. Spatiotemporal control of the creation and immolation of peptide assemblies. Coordination Chemistry Reviews 2016, 320-321 , 2-17. https://doi.org/10.1016/j.ccr.2016.02.014
- Weiju Hao, Tian Xia, Yazhuo Shang, Shouhong Xu, Honglai Liu. Characterization and release kinetics of liposomes inserted by pH-responsive bola-polymer. Colloid and Polymer Science 2016, 294 (7) , 1107-1116. https://doi.org/10.1007/s00396-016-3871-1
- Frank Versluis, Jan H. van Esch, Rienk Eelkema. Synthetic Self-Assembled Materials in Biological Environments. Advanced Materials 2016, 28 (23) , 4576-4592. https://doi.org/10.1002/adma.201505025
- Yuan Sun, Aileen Shieh, Se Hye Kim, Samantha King, Anne Kim, Hui-Lung Sun, Carlo M. Croce, Jon R. Parquette. The self-assembly of a camptothecin-lysine nanotube. Bioorganic & Medicinal Chemistry Letters 2016, 26 (12) , 2834-2838. https://doi.org/10.1016/j.bmcl.2016.04.056
- Wang Ma, Andrew G. Cheetham, Honggang Cui. Building nanostructures with drugs. Nano Today 2016, 11 (1) , 13-30. https://doi.org/10.1016/j.nantod.2015.11.003
- Siteng Wang, Hongping Deng, Ping Huang, Pei Sun, Xiaohua Huang, Yue Su, Xinyuan Zhu, Jian Shen, Deyue Yan. Real-time self-tracking of an anticancer small molecule nanodrug based on colorful fluorescence variations. RSC Advances 2016, 6 (15) , 12472-12478. https://doi.org/10.1039/C5RA24273H
- Monika Rani, Lovika Moudgil, Baljinder Singh, Akshey Kaushal, Anu Mittal, G. S. S. Saini, S. K. Tripathi, Gurinder Singh, Aman Kaura. Understanding the mechanism of replacement of citrate from the surface of gold nanoparticles by amino acids: a theoretical and experimental investigation and their biological application. RSC Advances 2016, 6 (21) , 17373-17383. https://doi.org/10.1039/C5RA26502A
- Huyeon Choi, M. T. Jeena, L. Palanikumar, Yoojeong Jeong, Sooham Park, Eunji Lee, Ja-Hyoung Ryu. The HA-incorporated nanostructure of a peptide–drug amphiphile for targeted anticancer drug delivery. Chemical Communications 2016, 52 (32) , 5637-5640. https://doi.org/10.1039/C6CC00200E
- Xiaoqing Ji, Chunhuan Shi, Nuannuan Li, Kaiming Wang, Zhonghao Li, Yuxia Luan. Catanionic drug-derivative nano-objects constructed by chlorambucil and its derivative for efficient leukaemia therapy. Colloids and Surfaces B: Biointerfaces 2015, 136 , 1081-1088. https://doi.org/10.1016/j.colsurfb.2015.11.016
- Hao Su, Jin Mo Koo, Honggang Cui. One-component nanomedicine. Journal of Controlled Release 2015, 219 , 383-395. https://doi.org/10.1016/j.jconrel.2015.09.056
- Seelam Prasanthkumar, Wei Zhang, Wusong Jin, Takanori Fukushima, Takuzo Aida. Selective Synthesis of Single- and Multi-Walled Supramolecular Nanotubes by Using Solvophobic/Solvophilic Controls: Stepwise Radial Growth via “Coil-on-Tube” Intermediates. Angewandte Chemie 2015, 127 (38) , 11320-11324. https://doi.org/10.1002/ange.201505806
- Seelam Prasanthkumar, Wei Zhang, Wusong Jin, Takanori Fukushima, Takuzo Aida. Selective Synthesis of Single- and Multi-Walled Supramolecular Nanotubes by Using Solvophobic/Solvophilic Controls: Stepwise Radial Growth via “Coil-on-Tube” Intermediates. Angewandte Chemie International Edition 2015, 54 (38) , 11168-11172. https://doi.org/10.1002/anie.201505806
- Si-Yong Qin, Meng-Yun Peng, Lei Rong, Bin Li, Shi-Bo Wang, Si-Xue Cheng, Ren-Xi Zhuo, Xian-Zheng Zhang. Self-defensive nano-assemblies from camptothecin-based antitumor drugs. Regenerative Biomaterials 2015, 2 (3) , 159-166. https://doi.org/10.1093/rb/rbv011
- Marta Gubitosi, Leana Travaglini, Maria Chiara di Gregorio, Nicolae V. Pavel, José Vázquez Tato, Simona Sennato, Ulf Olsson, Karin Schillén, Luciano Galantini. Tailoring Supramolecular Nanotubes by Bile Salt Based Surfactant Mixtures. Angewandte Chemie 2015, 127 (24) , 7124-7127. https://doi.org/10.1002/ange.201500445
- Marta Gubitosi, Leana Travaglini, Maria Chiara di Gregorio, Nicolae V. Pavel, José Vázquez Tato, Simona Sennato, Ulf Olsson, Karin Schillén, Luciano Galantini. Tailoring Supramolecular Nanotubes by Bile Salt Based Surfactant Mixtures. Angewandte Chemie International Edition 2015, 54 (24) , 7018-7021. https://doi.org/10.1002/anie.201500445
- Guoqin Chen, Jiaxin Chen, Qicai Liu, Caiwen Ou, Jie Gao. Enzymatic formation of a meta-stable supramolecular hydrogel for 3D cell culture. RSC Advances 2015, 5 (39) , 30675-30678. https://doi.org/10.1039/C5RA02449H
- Ashkan Dehsorkhi, Ricardo M. Gouveia, Andrew M. Smith, Ian W. Hamley, Valeria Castelletto, Che J. Connon, Mehedi Reza, Janne Ruokolainen. Self-assembly of a dual functional bioactive peptide amphiphile incorporating both matrix metalloprotease substrate and cell adhesion motifs. Soft Matter 2015, 11 (16) , 3115-3124. https://doi.org/10.1039/C5SM00459D
Abstract

Figure 1

Figure 1. (a) Chemical structures and schematic representations of qCPT-Sup35-K2 and qCPT-Sup35-E2. (b–d) Schematic representations and TEM micrographs of the supramolecular structures formed by qCPT-Sup35-K2, qCPT-Sup35-E2, and the CAM of the two DAs. Both qCPT-Sup35-K2 (b) and qCPT-Sup35-E2 (c) formed single filaments in 1:1 MeCN/H2O after the materials had been previously treated with HFIP. The widths of the single filaments measured from TEM are 5.7 ± 0.9 nm, and 5.9 ± 0.9 nm for qCPT-Sup35-K2 and qCPT-Sup35-E2, respectively. (d–f) The CAM of qCPT-Sup35 (mixing ratio 1:3) results in the almost exclusive formation of tubular structures in 1:1 MeCN/H2O. The tubular size measured from cryo-TEM imaging is 123 ± 28 nm. Total concentration for all samples = 400 μM.
Figure 2

Figure 2. TEM and cryo-TEM micrographs of the qCPT-Sup35 CAM with a mixing ratio of 1:3 at 400 μM in 1:1 MeCN/H2O. (a, b) Bending of the tubular structures (indicated by the red arrows) and the direct observation of the multiwalled nature of the tubules (labeled with blue arrows) in cryo-TEM imaging. (c, d) Undulation of the tube widths is commonly observed in regions where overlapping occurs. All bars = 200 nm.
Figure 3

Figure 3. (a, b) Cryo-TEM micrographs of qCPT-Sup35 CAMs with a mixing ratio of 1:1 (a) and 3:1 (b) at 400 μM in 1:1 MeCN/H2O. All bars = 500 nm. (c) Zeta potential measurements of the qCPT-Sup35 CAMs with different mixing ratios. Data are presented as mean ± s.d. (d) CD spectra of the 1:3 qCPT-Sup35 CAM, and individual DAs in 1:1 MeCN/H2O. All spectra were obtained from 400 μM solutions that were diluted to 50 μM immediately prior to measurement.
Figure 4

Figure 4. TEM micrographs of the intermediate structures of the 1:3 qCPT-Sup35 CAM in 1:1 MeCN/H2O, unless stated otherwise. (a, b) Clusters of belts and helical ribbons are the dominant structures at 10 μM (a) and 50 μM (b). (c) Multilayer helical ribbon at 50 μM. (d) An intermediate multiwall tubular structure in a 100 μM solution, showing a tubular structure wrapped with another layer of belt. (e, f) Similar intermediate structures, such as multilayer helical ribbons and intermediate multiwall tubular structures in 3:1 MeCN/H2O, where the materials exhibited limited solubility. Bulk concentration = 400 μM.
Figure 5

Figure 5. Proposed mechanism of the tubule formation by qCPT-Sup35 CAMs. (a) Schematic illustration of the effect of packing parameter of qCPT-Sup35 and dCPT-Sup35 on the formation of ion pairs and the resulting supramolecular morphology of corresponding catanionic mixtures. (b) The formation of the multiwall nanotubes by CAMs of qCPT-Sup35 is the cumulative result of three occurrences: 1D elongation, formation of multilayers, and bilayer extension from helical ribbons. The CAM of qCPT-Sup35 formed bilayers, where the direction of lateral bilayer extension is perpendicular to the orientation of the intermolecular hydrogen bonds.
Figure 6

Figure 6. In vivo NIRF imaging of CT26 tumor-bearing mice. The heat maps display the distribution of Cy7.5 labeled CAM nanotubes of qCPT-Sup35 (a) and free Cy7.5 (b) after intratumoral injection.
References
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- 1Hill, J. P.; Jin, W. S.; Kosaka, A.; Fukushima, T.; Ichihara, H.; Shimomura, T.; Ito, K.; Hashizume, T.; Ishii, N.; Aida, T. Self-Assembled Hexa-peri-hexabenzocoronene Graphitic Nanotube Science 2004, 304, 1481– 1483[Crossref], [PubMed], [CAS], Google Scholar1https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXksVGmsLc%253D&md5=eb42b19b58780709a3aed8fe3dc27fb5Self-assembled hexa-peri-hexabenzocoronene graphitic nanotubeHill, Jonathan P.; Jin, Wusong; Kosaka, Atsuko; Fukushima, Takanori; Ichihara, Hideki; Shimomura, Takeshi; Ito, Kohzo; Hashizume, Tomihiro; Ishii, Noriyuki; Aida, TakuzoScience (Washington, DC, United States) (2004), 304 (5676), 1481-1483CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)An amphiphilic hexa-peri-hexabenzocoronene self-assembles to form a π-electronic, discrete nanotubular object. The object was characterized by an aspect ratio >1000 and has a uniform, 14-nm-wide, open-ended hollow space, which is an order of magnitude larger than those of C nanotubes. The wall is 3 nm thick and consists of helical arrays of the π-stacked graphene mol., whose exterior and interior surfaces are covered by hydrophilic triethylene glycol chains. The graphitic nanotube is redox active, and a single piece of the nanotube across 180-nm-gap electrodes shows, upon oxidn., an elec. cond. of 2.5MΩs at 285 K. This family of molecularly engineered graphite with a 1-dimensional tubular shape and a chem. accessible surface constitutes an important step toward mol. electronics.
- 2Iijima, S. Helical Microtubules of Graphitic Carbon Nature 1991, 354, 56– 58[Crossref], [CAS], Google Scholar2https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK38Xmt1Ojtg%253D%253D&md5=ab9fd03bc14a16606749af946bac86bfHelical microtubules of graphitic carbonIijima, SumioNature (London, United Kingdom) (1991), 354 (6348), 56-8CODEN: NATUAS; ISSN:0028-0836.The prepn. of a novel type of finite C structure consisting of needle-like tubes is reported. Produced using an arc-discharge evapn. method similar to that used for fullerenes synthesis, the needles grow at the neg. end of the electrode used for the arc discharge. Electron microscopy reveals that each needle comprises coaxial tubes of graphitic sheets, ranging from 2 to ∼50. On each tube, the C-atom hexagons are arranged in a helical fashion about the needle axis. The helical pitch varies from needle to needle and from tube to tube within a single needle. This helical structure may aid growth. The formation of these needles, ranging from a few to a few tens of nanometers in diam., suggests that engineering of C structures should be possible on scales considerably greater than those relevant to the fullerenes.
- 3Treacy, M. M. J.; Ebbesen, T. W.; Gibson, J. M. Exceptionally High Young’s Modulus Observed for Individual Carbon Nanotubes Nature 1996, 381, 678– 680Google ScholarThere is no corresponding record for this reference.
- 4Mitchison, T.; Kirschner, M. Dynamic Instability of Microtubule Growth Nature 1984, 312, 237– 242[Crossref], [PubMed], [CAS], Google Scholar4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2MXhvF2jsQ%253D%253D&md5=2c8244aca07fd3b65f76da5580cf6c48Dynamic instability of microtubule growthMitchison, Tim; Kirschner, MarcNature (London, United Kingdom) (1984), 312 (5991), 237-42CODEN: NATUAS; ISSN:0028-0836.Microtubules placed in a tubulin soln. just about the steady-state concn. of 14 μM showed a steady increase in length with no change in no. of microtubules. At lower tubulin concns. (7.5 μM), the no. of microtubules decreased with time, whereas the mean length of microtubules still increased somewhat. Axonemes could nucleate growth of microtubules well below the steady-state concn. of tubulin. At steady state (14 μM tubulin), when the net polymer mass remained const., a steady increase in mean microtubule length still occurred, whereas the no. of microtubules decreased steadily. This was attributed to depolymn. of some microtubules, which provided tubulin monomers for growth of other microtubules. The transition of microtubules between growing and shrinking phases was evidently rare. Possibly growing microtubules have GTP-liganded caps, whereas shrinking ones do not. A new model for microtubule assembly is proposed based on these findings.
- 5Hamley, I. W. Peptide Nanotubes Angew. Chem. Int. Ed. 2014, 53, 6866– 6881[Crossref], [PubMed], [CAS], Google Scholar5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXps1ygu70%253D&md5=d9be9db7fbfc18f939964c6d3c4c5bf6Peptide NanotubesHamley, Ian W.Angewandte Chemie, International Edition (2014), 53 (27), 6866-6881CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. The self-assembly of different classes of peptide, including cyclic peptides, amyloid peptides and surfactant-like peptides into nanotube structures is reviewed. The modes of self-assembly are discussed. Addnl., applications in bionanotechnol. and synthetic materials science are summarized.
- 6Zhang, W.; Jin, W. S.; Fukushima, T.; Saeki, A.; Seki, S.; Aida, T. Supramolecular Linear Heterojunction Composed of Graphite-Like Semiconducting Nanotubular Segments Science 2011, 334, 340– 343[Crossref], [PubMed], [CAS], Google Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhtlahsr%252FJ&md5=e9580703a3d80af81f712fc9596382c3Supramolecular Linear Heterojunction Composed of Graphite-Like Semiconducting Nanotubular SegmentsZhang, Wei; Jin, Wusong; Fukushima, Takanori; Saeki, Akinori; Seki, Shu; Aida, TakuzoScience (Washington, DC, United States) (2011), 334 (6054), 340-343CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)One-dimensionally connected org. nanostructures with dissimilar semiconducting properties are expected to provide a reliable platform in understanding the behaviors of photocarriers, which are important for the development of efficient photon-to-elec. energy conversion systems. Although bottom-up supramol. approaches are considered promising for the realization of such nanoscale heterojunctions, the dynamic nature of mol. assembly is problematic. We report a semiconducting nanoscale org. heterojunction, demonstrated by stepwise nanotubular coassembly of two strategically designed mol. graphenes. The dissimilar nanotubular segments, thus connected noncovalently, were electronically communicable with one another over the heterojunction interface and displayed characteristic excitation energy transfer and charge transport properties not present in a mixt. of the corresponding homotropically assembled nanotubes.
- 7Adler-Abramovich, L.; Aronov, D.; Beker, P.; Yevnin, M.; Stempler, S.; Buzhansky, L.; Rosenman, G.; Gazit, E. Self-Assembled Arrays of Peptide Nanotubes by Vapour Deposition Nat. Nanotechnol. 2009, 4, 849– 854[Crossref], [PubMed], [CAS], Google Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhsFagsrnK&md5=d5ecdffefece40280cebd107065cbb59Self-assembled arrays of peptide nanotubes by vapour depositionAdler-Abramovich, Lihi; Aronov, Daniel; Beker, Peter; Yevnin, Maya; Stempler, Shiri; Buzhansky, Ludmila; Rosenman, Gil; Gazit, EhudNature Nanotechnology (2009), 4 (12), 849-854CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)The use of bionanostructures in real-world applications will require precise control over biomol. self-assembly and the ability to scale up prodn. of these materials. A significant challenge is to control the formation of large, homogeneous arrays of bionanostructures on macroscopic surfaces. Previously, bionanostructure formation has been based on the spontaneous growth of heterogenic populations in bulk soln. Here, we demonstrate the self-assembly of large arrays of arom. peptide nanotubes using vapor deposition methods. This approach allows the length and d. of the nanotubes to be fine-tuned by carefully controlling the supply of the building blocks from the gas phase. Furthermore, we show that the nanotube arrays can be used to develop high-surface-area electrodes for energy storage applications, highly hydrophobic self-cleaning surfaces and microfluidic chips.
- 8Gazit, E. Self-Assembled Peptide Nanostructures: The Design of Molecular Building Blocks and Their Technological Utilization Chem. Soc. Rev. 2007, 36, 1263– 1269[Crossref], [PubMed], [CAS], Google Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXnsVChurY%253D&md5=7dc68e71f2dc63208a366b677856e85fSelf-assembled peptide nanostructures: The design of molecular building blocks and their technological utilizationGazit, EhudChemical Society Reviews (2007), 36 (8), 1263-1269CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. The process and applications of peptide self-assembly into nanotubes, nanospheres, nanofibrils, nanotapes, and other ordered structures at the nano-scale are discussed in this tutorial review. The formation of well-ordered nanostructures by a process of self-assocn. represents the essence of modern nanotechnol. Such self-assembled structures can be formed by a variety of building blocks, both org. and inorg. Of the org. building blocks, peptides are among the most useful ones. Peptides possess the biocompatibility and chem. diversity that are found in proteins, yet they are much more stable and robust and can be readily synthesized on a large scale. Short peptides can spontaneously assoc. to form nanotubes, nanospheres, nanofibrils, nanotapes, and other ordered structures at the nano-scale. Peptides can also form macroscopic assemblies such as hydrogels with nano-scale order. The application of peptide building blocks in biosensors, tissue engineering, and the development of antibacterial agents has already been demonstrated.
- 9Ashkenasy, N.; Horne, W. S.; Ghadiri, M. R. Design of Self-Assembling Peptide Nanotubes with Delocalized Electronic States Small 2006, 2, 99– 102[Crossref], [PubMed], [CAS], Google Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXhtlWqsrjP&md5=984d38ecb81cf1fdaf7037f5af4215e9Design of self-assembling peptide nanotubes with delocalized electronic statesAshkenasy, Nurit; Horne, W. Seth; Ghadiri, M. RezaSmall (2006), 2 (1), 99-102CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)An eight-residue cyclic DL-α-peptide bearing four cationic 1,4,5,8-naphthalenetetracarboxylic diimide (NDI) side chains that undergoes redox-triggered self-assembly in aq. soln. into peptide nanotubes in described. Using this approach, isolated peptide nanotubes hundreds of nanometers in length can be obtained and adsorbed on solid surfaces. The long-range supramol. order afforded by the directed backbone hydrogen bonding interactions in self-assembling cyclic DL-α-peptide nanotubes can provide a facile method for the prepn. of a new class of synthetic biomaterials that exhibit extended charge delocalized states.
- 10Zhang, J.; Liu, X.; Blume, R.; Zhang, A. H.; Schlogl, R.; Su, D. S. Surface-Modified Carbon Nanotubes Catalyze Oxidative Dehydrogenation of n-Butane Science 2008, 322, 73– 77[Crossref], [PubMed], [CAS], Google Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhtFyhurfP&md5=702a3916692a10b61da5e7d52452ac03Surface-Modified Carbon Nanotubes Catalyze Oxidative Dehydrogenation of n-ButaneZhang, Jian; Liu, Xi; Blume, Raoul; Zhang, Aihua; Schloegl, Robert; Su, Dang ShengScience (Washington, DC, United States) (2008), 322 (5898), 73-77CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Butenes and butadiene, which are useful intermediates for the synthesis of polymers and other compds., are synthesized traditionally by oxidative dehydrogenation (ODH) of n-butane over complex metal oxides. Such catalysts require high O2/butane ratios to maintain the activity, which leads to unwanted product oxidn. We show that carbon nanotubes with modified surface functionality brought about by oxidn. in concn. HNO3 efficiently catalyze the oxidative dehydrogenation of n-butane to butenes, esp. butadiene. For low O2/butane ratios, a high selectivity to alkenes was achieved for periods as long as 100 h. This process is mildly catalyzed by ketonic C=O groups and occurs via a combination of parallel and sequential oxidn. steps. A small amt. of phosphorus greatly improved the selectivity by suppressing the combustion of hydrocarbons.
- 11Schnur, J. M. Lipid Tubules - A Paradigm for Molecularly Engineered Structures Science 1993, 262, 1669– 1676Google ScholarThere is no corresponding record for this reference.
- 12Margulis-Goshen, K.; di Gregorio, M. C.; Pavel, N. V.; Abezgauz, L.; Danino, D.; Tato, J. V.; Tellini, V. H. S.; Magdassi, S.; Galantini, L. Drug-Loaded Nanoparticles and Supramolecular Nanotubes Formed from A Volatile Microemulsion with Bile Salt Derivatives Phys. Chem. Chem. Phys. 2013, 15, 6016– 6024Google ScholarThere is no corresponding record for this reference.
- 13Stewart, S.; Liu, G. Block Copolymer Nanotubes Angew. Chem. Int. Ed. 2000, 112, 348– 352Google ScholarThere is no corresponding record for this reference.
- 14Lara, C.; Handschin, S.; Mezzenga, R. Towards Lysozyme Nanotube and 3D Hybrid Self-Assembly Nanoscale 2013, 5, 7197– 7201Google ScholarThere is no corresponding record for this reference.
- 15Shimizu, T.; Masuda, M.; Minamikawa, H. Supramolecular Nanotube Architectures Based on Amphiphilic Molecules Chem. Rev. 2005, 105, 1401– 1443[ACS Full Text
], [CAS], Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXisFWrtrs%253D&md5=b2c17e4ab967a44faa74786ea5cc5f95Supramolecular Nanotube Architectures Based on Amphiphilic MoleculesShimizu, Toshimi; Masuda, Mitsutoshi; Minamikawa, HiroyukiChemical Reviews (Washington, DC, United States) (2005), 105 (4), 1401-1443CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. We here present the principle of chiral self-assembly for the formation of lipid nanotube, its prepn. methods, application possibilities, and novel properties. - 16Raez, J.; Manners, I.; Winnik, M. A. Nanotubes from The Self-Assembly of Asymmetric Crystalline-Coil Poly(Ferrocenylsilane-Siloxane) Block Copolymers J. Am. Chem. Soc. 2002, 124, 10381– 10395
- 17Hamley, I. W. Nanoshells and Nanotubes from Block Copolymers Soft Matter 2005, 1, 36– 43Google ScholarThere is no corresponding record for this reference.
- 18Kralj-Iglic, V.; Iglic, A.; Gomiscek, G.; Sevsek, F.; Arrigler, V.; Hagerstrand, H. Microtubes and Nanotubes of A Phospholipid Bilayer Membrane J. Phys. A: Math. Gen. 2002, 35, 1533– 1549[Crossref], [CAS], Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD38Xit1entLw%253D&md5=30ed9f6c74fedb0a722370da2d7b5e1eMicrotubes and nanotubes of a phospholipid bilayer membraneKralj-Iglic, Veronika; Iglic, Ales; Gomiscek, Gregor; Sevsek, France; Arrigler, Vesna; Hagerstrand, HenryJournal of Physics A: Mathematical and General (2002), 35 (7), 1533-1549CODEN: JPHAC5; ISSN:0305-4470. (Institute of Physics Publishing)We propose a theory describing the stable structure of a phospholipid bilayer in pure water involving a spherical mother vesicle with long thin tubular protrusion. It is considered that the phospholipid mols. are in general anisotropic with respect to the axis normal to the membrane and can orient in the plane of the membrane if the curvature field is strongly anisotropic. Taking this into account, the membrane free energy is derived starting from a single-mol. energy and using methods of statistical mechanics. By linking the description on the microscopic level with the continuum theory of elasticity we recover the expression for the membrane bending energy and obtain an addnl. (deviatoric) contribution due to the orientational ordering of the phospholipid mols. It is shown that the deviatoric contribution may considerably decrease the phospholipid vesicle membrane free energy if the vesicle involves regions where the difference between the two principal curvatures is large (thin cylindrical protrusions and/or thin finite necks) and thereby yields a possible explanation for the stability of the long thin tubular protrusions of the phospholipid bilayer vesicles. We report on the expt. exhibiting a stable shape of the spherical phospholipid vesicle with a long thin tubular protrusion in pure water.
- 19Spector, M. S.; Singh, A.; Messersmith, P. B.; Schnur, J. M. Chiral Self-Assembly of Nanotubules and Ribbons from Phospholipid Mixtures Nano Lett. 2001, 1, 375– 378
- 20Thomas, B. N.; Safinya, C. R.; Plano, R. J.; Clark, N. A. Lipid Tubule Self-Assembly - Length Dependence on Cooling Rate Through A First-Order Phase-Transition Science 1995, 267, 1635– 1638Google ScholarThere is no corresponding record for this reference.
- 21Yager, P.; Schoen, P. E. Formation of Tubules by a Polymerizable Surfactant Mol. Cryst. Liq. Cryst. 1984, 106, 371– 381[Crossref], [CAS], Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2cXksFSnsbY%253D&md5=20ab0684ed7aa7e656644164d2181f9bFormation of tubules by a polymerizable surfactantYager, Paul; Schoen, Paul E.Molecular Crystals and Liquid Crystals (1984), 106 (3-4), 371-81CODEN: MCLCA5; ISSN:0026-8941.The phospholipid 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine, in which both fatty acyl chains contain polymerizable diacetylenic units, has been studied with regard to its behavior in aq. dispersion before and after polymn. The monomeric lipid may be dispersed in distd. water above its chain melting transition temp., but, contrary to previous reports, it does not stay in the liposomal form on subsequent redn. of the temp. Microscopic observation shows formation of structures resembling so-called cochleate cylinders, except that these cylinders are water-filled. These tubules reversibly convert to liposomal form on heating above the monomer chain melting temp. However, on polymn. with UV light, the cylinders are locked in and no morphol. changes are obsd. on heating. These unique structures may represent a new class of orientable polymers.
- 22Terech, P.; de Geyer, A.; Struth, B.; Talmon, Y. Self-Assembled Monodisperse Steroid Nanotubes in Water Adv. Mater. 2002, 14, 495– 498Google ScholarThere is no corresponding record for this reference.
- 23Lu, K.; Jacob, J.; Thiyagarajan, P.; Conticello, V. P.; Lynn, D. G. Exploiting Amyloid Fibril Lamination for Nanotube Self-Assembly J. Am. Chem. Soc. 2003, 125, 6391– 6393[ACS Full Text
], [CAS], Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXjtlKisL4%253D&md5=ab1b3a940aeed7523963742e387a4367Exploiting Amyloid Fibril Lamination for Nanotube Self-AssemblyLu, Kun; Jacob, Jaby; Thiyagarajan, Pappannan; Conticello, Vincent P.; Lynn, David G.Journal of the American Chemical Society (2003), 125 (21), 6391-6393CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Fundamental questions about the relative arrangement of the β-sheet arrays within amyloid fibrils remain central to both its structure and the mechanism of self-assembly. Recent computational analyses suggested that sheet-to-sheet lamination was limited by the length of the strand. On the basis of this hypothesis, a short seven-residue segment of the Alzheimer's disease-related Aβ peptide, Aβ(16-22), was allowed to self-assemble under conditions that maintained the basic amphiphilic character of Aβ. Indeed, the no. increased over 20-fold to 130 laminates, giving homogeneous bilayer structures that supercoil into long robust nanotubes. Small-angle neutron scattering and x-ray scattering defined the outer and inner radii of the nanotubes in soln. to contain a 44-nm inner cavity with 4-nm-thick walls. At. force microscopy and TEM images further confirmed these homogeneous arrays of solvent-filled nanotubes arising from a flat rectangular bilayer, 130 nm wide × 4 nm thick, with each bilayer leaflet composed of laminated β-sheets. The corresponding backbone H-bonds are along the long axis, and β-sheet lamination defines the 130-nm bilayer width. This bilayer coils to give the final nanotube. Such robust and persistent self-assembling nanotubes with pos. charged surfaces of very different inner and outer curvature now offer a unique, robust, and easily accessible scaffold for nanotechnol. - 24Childers, W. S.; Mehta, A. K.; Ni, R.; Taylor, J. V.; Lynn, D. G. Peptides Organized as Bilayer Membranes Angew. Chem. Int. Ed. 2010, 49, 4104– 4107Google ScholarThere is no corresponding record for this reference.
- 25Hartgerink, J. D.; Granja, J. R.; Milligan, R. A.; Ghadiri, M. R. Self-Assembling Peptide Nanotubes J. Am. Chem. Soc. 1996, 118, 43– 50[ACS Full Text
], [CAS], Google Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28XltVGjsw%253D%253D&md5=30a5183ccbf3ebc1776a892fbe030da9Self-Assembling Peptide NanotubesHartgerink, Jeffrey D.; Granja, Juan R.; Milligan, Ronald A.; Ghadiri, M. RezaJournal of the American Chemical Society (1996), 118 (1), 43-50CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The general design criteria and synthesis of four new peptide-based solid-state tubular array structures are described. Peptide nanotubes, which are extended tubular β-sheet-like structures, are constructed by the self-assembly of flat, ring-shaped peptide subunits made up of alternating D- and L-amino acid residues. Peptide self-assembly is directed by the formation of an extensive network of intersubunit hydrogen bonds. In the crystal structures, nanotubes are stabilized by intertubular hydrophobic packing interactions. Peptide nanotubes exhibit good mech. and thermal stabilities in water and are stable for long periods of times in most common org. solvents including DMF and DMSO. The remarkable stability of peptide nanotubes can be attributed to the highly cooperative nature of the noncovalent interactions throughout the crystal lattice. Nanotube structures were characterized by cryoelectron microscopy, electron diffraction, Fourier-transform IR spectroscopy, and crystal structure modeling. This study also serves to exemplify the predictive structural aspects of the peptide self-assembly process. - 26Adamcik, J.; Castelletto, V.; Bolisetty, S.; Hamley, I. W.; Mezzenga, R. Direct Observation of Time-Resolved Polymorphic States in the Self-Assembly of End-Capped Heptapeptides Angew. Chem. Int. Ed. 2011, 50, 5495– 5498Google ScholarThere is no corresponding record for this reference.
- 27Middleton, D. A.; Madine, J.; Castelletto, V.; Hamley, I. W. Insights into the Molecular Architecture of a Peptide Nanotube Using FTIR and Solid-State NMR Spectroscopic Measurements on an Aligned Sample Angew. Chem. Int. Ed. 2013, 52, 10537– 10540Google ScholarThere is no corresponding record for this reference.
- 28Ziserman, L.; Lee, H. Y.; Raghavan, S. R.; Mor, A.; Danino, D. Unraveling the Mechanism of Nanotube Formation by Chiral Self-Assembly of Amphiphiles J. Am. Chem. Soc. 2011, 133, 2511– 2517
- 29Huang, Z.; Kang, S. K.; Banno, M.; Yamaguchi, T.; Lee, D.; Seok, C.; Yashima, E.; Lee, M. Pulsating Tubules from Noncovalent Macrocycles Science 2012, 337, 1521– 1526[Crossref], [PubMed], [CAS], Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtlGrtbbL&md5=faca70ea6f368aa0b84c60552fdfd8f9Pulsating Tubules from Noncovalent MacrocyclesHuang, Zhegang; Kang, Seong-Kyun; Banno, Motonori; Yamaguchi, Tomoko; Lee, Dongseon; Seok, Chaok; Yashima, Eiji; Lee, MyongsooScience (Washington, DC, United States) (2012), 337 (6101), 1521-1526CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Despite recent advances in synthetic nanometer-scale tubular assembly, conferral of dynamic response characteristics to the tubules remains a challenge. Here, we report on supramol. nanotubules that undergo a reversible contraction-expansion motion accompanied by an inversion of helical chirality. Bent-shaped arom. amphiphiles self-assemble into hexameric macrocycles in aq. soln., forming chiral tubules by spontaneous one-dimensional stacking with a mutual rotation in the same direction. The adjacent arom. segments within the hexameric macrocycles reversibly slide along one another in response to external triggers, resulting in pulsating motions of the tubules accompanied by a chiral inversion. The arom. interior of the self-assembled tubules encapsulates hydrophobic guests such as carbon-60 (C60). Using a thermal trigger, we could regulate the C60-C60 interactions through the pulsating motion of the tubules.
- 30Ghadiri, M. R.; Granja, J. R.; Milligan, R. A.; McRee, D. E.; Khazanovich, N. Self-Assembling Organic Nanotubes Based on a Cyclic Peptide Architecture Nature 1993, 366, 324– 327[Crossref], [PubMed], [CAS], Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXhtVOksLw%253D&md5=8077abd61a375136ebc6b10c9e7e892aSelf-assembling organic nanotubes based on a cyclic peptide architectureGhadiri, M. Reza; Granja, Juan R.; Milligan, Ronald A.; McRee, Duncan E.; Khazanovich, NinaNature (London, United Kingdom) (1993), 366 (6453), 324-7CODEN: NATUAS; ISSN:0028-0836.The design, synthesis, and characterization of a new class of org. nanotubes based on rationally designed cyclic peptides, e.g. cyclo(D-Ala-Glu-D-Ala-Gln-D-Ala-Glu-D-Ala-Gln), is reported. When protonated, the cyclopeptides crystallize into tubular structures hundreds of nanometers long, with internal diams. of 7-8Å. Support for the proposed tubular structures is provided by electron microscopy, electron diffraction, Fourier-transform IR, and mol. modeling. The tubes are open-ended, with uniform shape and internal diam. It is anticipated that the may have possible applications in inclusion chem., catalysis, mol. electronics, and mol. sepn. technol.
- 31Zhao, F.; Ma, M. L.; Xu, B. Molecular Hydrogels of Therapeutic Agents Chem. Soc. Rev. 2009, 38, 883– 891[Crossref], [PubMed], [CAS], Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXjsFaju7c%253D&md5=003b6bad079d11e744ab1b680f724017Molecular hydrogels of therapeutic agentsZhao, Fan; Ma, Man Lung; Xu, BingChemical Society Reviews (2009), 38 (4), 883-891CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. This tutorial review aims to introduce a new kind of biomaterials-mol. hydrogels of therapeutic agents. Based on the mol. self-assembly in water, it is possible to transform therapeutic agents into analogs that form hydrogels without compromising their pharmacol. efficacy. This transformation can be beneficial in three aspects: (i) the therapeutic agents become "self-deliverable" in the form of hydrogels; (ii) the self-assembly of hydrogelators of drugs might confer new and useful properties such as multivalency or high local densities; (iii) the exploration of mol. hydrogels of drugs may ultimately lead to bioactive mols. that have dual or multiple roles. By summarizing the reports on the mol. hydrogels made from clin. used drugs or other bioactive mols., this article presents representative mol. hydrogels of therapeutics and outlines the promises and challenges for developing this new class of biomaterials.
- 32Cheetham, A. G.; Ou, Y. C.; Zhang, P. C.; Cui, H. G. Linker-Determined Drug Release Mechanism of Free Camptothecin from Self-Assembling Drug Amphiphiles Chem. Commun. 2014, 50, 6039– 6042[Crossref], [PubMed], [CAS], Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXnslegsLs%253D&md5=e8756d1cb7b3c6dc62f920935a533528Linker-determined drug release mechanism of free camptothecin from self-assembling drug amphiphilesCheetham, Andrew G.; Ou, Yu-Chuan; Zhang, Pengcheng; Cui, HonggangChemical Communications (Cambridge, United Kingdom) (2014), 50 (45), 6039-6042CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)We report here that the release mechanism of free camptothecin from self-assembling drug amphiphiles can be regulated by use of different linker groups. Our results highlight the significance of the linker group of drug amphiphiles on the drug release efficiency and their consequent in vitro efficacy.
- 33Cheetham, A. G.; Zhang, P. C.; Lin, L. Y.; Lin, R.; Cui, H. Synthesis and Self-Assembly of A Mikto-Arm Star Dual Drug Amphiphile Containing Both Paclitaxel and Camptothecin J. Mater. Chem. B 2014, 2, 7316– 7326[Crossref], [PubMed], [CAS], Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsVCrtLvN&md5=a42a59b1244377d4acfdb9fd7fdf6dbeSynthesis and self-assembly of a mikto-arm star dual drug amphiphile containing both paclitaxel and camptothecinCheetham, A. G.; Zhang, P.; Lin, Y.-A.; Lin, R.; Cui, H.Journal of Materials Chemistry B: Materials for Biology and Medicine (2014), 2 (42), 7316-7326CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)Self-assembly of anticancer therapeutics into discrete nanostructures provides an innovative way to develop a self-delivering nanomedicine with a high, quant. drug loading. We report here the synthesis and assembly of a mikto-arm star dual drug amphiphile (DA) contg. both a bulky paclitaxel (PTX) and a planar camptothecin (CPT). The two anti-cancer drugs of interest were stochastically conjugated to a β-sheet forming peptide (Sup35) and under physiol.-relevant conditions the dual DA could spontaneously assoc. into supramol. filaments with a fixed 41% total drug loading (29% PTX and 12% CPT). Transmission electron microscopy imaging and CD spectroscopy studies reveal that the bulkiness of the PTX, as well as the π-π interaction preference between the CPT units, has a significant impact on the assembly kinetics, mol. level packing, and nanostructure morphol. and stability. We found that the DA contg. two PTX units assembled into non-filamentous micelle-like structures, in contrast to the filamentous structures formed by the hetero dual DA and the DA contg. two CPTs. The hetero dual DA was found to effectively release the two anticancer agents, exhibiting superior cytotoxicity against PTX-resistant cervical cancer cells. The presented work offers a potential method to generate well-defined filamentous nanostructures and provides the basis for a future combination therapy platform.
- 34Cheetham, A. G.; Zhang, P. C.; Lin, Y.-A.; Lock, L. L.; Cui, H. G. Supramolecular Nanostructures Formed by Anticancer Drug Assembly J. Am. Chem. Soc. 2013, 135, 2907– 2910[ACS Full Text
], [CAS], Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhvVymsbc%253D&md5=59ef9bc13c8a82ed9727a9d989baa959Supramolecular Nanostructures Formed by Anticancer Drug AssemblyCheetham, Andrew G.; Zhang, Pengcheng; Lin, Yi-an; Lock, Lye Lin; Cui, HonggangJournal of the American Chemical Society (2013), 135 (8), 2907-2910CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)We report here a supramol. strategy to directly assemble the small mol. hydrophobic anticancer drug camptothecin (CPT) into discrete, stable, well-defined nanostructures with a high and quant. drug loading. Depending on the no. of CPTs in the mol. design, the resulting nanostructures can be either nanofibers or nanotubes, and have a fixed CPT loading content ranging from 23% to 38%. We found that formation of nanostructures provides protection for both the CPT drug and the biodegradable linker from the external environment and thus offers a mechanism for controlled release of CPT. Under tumor-relevant conditions, these drug nanostructures can release the bioactive form of CPT and show in vitro efficacy against a no. of cancer cell lines. This strategy can be extended to construct nanostructures of other types of anticancer drugs and thus presents new opportunities for the development of self-delivering drugs for cancer therapeutics. - 35Lin, R.; Cheetham, A. G.; Zhang, P. C.; Lin, Y. A.; Cui, H. G. Supramolecular filaments containing a fixed 41% paclitaxel loading Chem. Commun. 2013, 49, 4968– 4970[Crossref], [PubMed], [CAS], Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXmvFyqsr4%253D&md5=25bdb30bcabf36cfe3a1d689979dfb1fSupramolecular filaments containing a fixed 41% paclitaxel loadingLin, Ran; Cheetham, Andrew G.; Zhang, Pengcheng; Lin, Yi-an; Cui, HonggangChemical Communications (Cambridge, United Kingdom) (2013), 49 (43), 4968-4970CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)We report here the self-assembly of a rationally designed paclitaxel drug amphiphile into well-defined supramol. filaments that possess a fixed 41% paclitaxel loading. These filaments can exert effective cytotoxicity against a no. of cell lines comparable to that of free paclitaxel.
- 36MacKay, J. A.; Chen, M. N.; McDaniel, J. R.; Liu, W. G.; Simnick, A. J.; Chilkoti, A. Self-Assembling Chimeric Polypeptide-Doxorubicin Conjugate Nanoparticles That Abolish Tumours after A Single Injection Nat. Mater. 2009, 8, 993– 999[Crossref], [PubMed], [CAS], Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BD1MjotFSgsg%253D%253D&md5=ba61975d7929e6a9fa86b3b3dcc18319Self-assembling chimeric polypeptide-doxorubicin conjugate nanoparticles that abolish tumours after a single injectionMacKay J Andrew; Chen Mingnan; McDaniel Jonathan R; Liu Wenge; Simnick Andrew J; Chilkoti AshutoshNature materials (2009), 8 (12), 993-9 ISSN:1476-1122.New strategies to self-assemble biocompatible materials into nanoscale, drug-loaded packages with improved therapeutic efficacy are needed for nanomedicine. To address this need, we developed artificial recombinant chimeric polypeptides (CPs) that spontaneously self-assemble into sub-100-nm-sized, near-monodisperse nanoparticles on conjugation of diverse hydrophobic molecules, including chemotherapeutics. These CPs consist of a biodegradable polypeptide that is attached to a short Cys-rich segment. Covalent modification of the Cys residues with a structurally diverse set of hydrophobic small molecules, including chemotherapeutics, leads to spontaneous formation of nanoparticles over a range of CP compositions and molecular weights. When used to deliver chemotherapeutics to a murine cancer model, CP nanoparticles have a fourfold higher maximum tolerated dose than free drug, and induce nearly complete tumour regression after a single dose. This simple strategy can promote co-assembly of drugs, imaging agents and targeting moieties into multifunctional nanomedicines.
- 37Li, X. Y.; Yang, C. B.; Zhang, Z. L.; Wu, Z. D.; Deng, Y.; Liang, G. L.; Yang, Z. M.; Chen, H. Folic Acid as A Versatile Motif to Construct Molecular Hydrogelators through Conjugations with Hydrophobic Therapeutic Agents J. Mater. Chem. 2012, 22, 21838– 21840Google ScholarThere is no corresponding record for this reference.
- 38Duncan, R. Polymer Conjugates as Anticancer Nanomedicines Nat. Rev. Cancer 2006, 6, 688– 701[Crossref], [PubMed], [CAS], Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XosVOmsLY%253D&md5=467349c6d177a8fdd8002d677139bf31Polymer conjugates as anticancer nanomedicinesDuncan, RuthNature Reviews Cancer (2006), 6 (9), 688-701CODEN: NRCAC4; ISSN:1474-175X. (Nature Publishing Group)A review. The transfer of polymer-protein conjugates into routine clin. use, and the clin. development of polymer-anticancer-drug conjugates, both as single agents and as components of combination therapy, is establishing polymer therapeutics as one of the first classes of anticancer nanomedicines. There is growing optimism that ever more sophisticated polymer-based vectors will be a significant addn. to the armory currently used for cancer therapy.
- 39Branco, M. C.; Schneider, J. P. Self-Assembling Materials for Therapeutic Delivery Acta Biomater. 2009, 5, 817– 831[Crossref], [PubMed], [CAS], Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXksF2qu7g%253D&md5=e2fa065e82a37e522ec4525c3996e4a4Self-assembling materials for therapeutic deliveryBranco, Monica C.; Schneider, Joel P.Acta Biomaterialia (2009), 5 (3), 817-831CODEN: ABCICB; ISSN:1742-7061. (Elsevier Ltd.)A review. A growing no. of medications must be administered through parenteral delivery, i.e., i.v., i.m., or s.c. injection, to ensure effectiveness of the therapeutic. For some therapeutics, the use of delivery vehicles in conjunction with this delivery mechanism can improve drug efficacy and patient compliance. Macromol. self-assembly has been exploited recently to engineer materials for the encapsulation and controlled delivery of therapeutics. Self-assembled materials offer the advantages of conventional crosslinked materials normally used for release, but also provide the ability to tailor specific bulk material properties, such as release profiles, at the mol. level via monomer design. As a result, the design of materials from the "bottom up" approach has generated a variety of supramol. devices for biomedical applications. This review provides an overview of self-assembling mols., their resultant structures, and their use in therapeutic delivery. It highlights the current progress in the design of polymer- and peptide-based self-assembled materials.
- 40Aida, T.; Meijer, E. W.; Stupp, S. I. Functional Supramolecular Polymers Science 2012, 335, 813– 817[Crossref], [PubMed], [CAS], Google Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XitFGquro%253D&md5=65127aa5a199aa9136a8ce66e8cbd448Functional Supramolecular PolymersAida, T.; Meijer, E. W.; Stupp, S. I.Science (Washington, DC, United States) (2012), 335 (6070), 813-817CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)A review. Supramol. polymers can be random and entangled coils with the mech. properties of plastics and elastomers, but with great capacity for processability, recycling, and self-healing due to their reversible monomer-to-polymer transitions. At the other extreme, supramol. polymers can be formed by self-assembly among designed subunits to yield shape-persistent and highly ordered filaments. The use of strong and directional interactions among mol. subunits can achieve not only rich dynamic behavior but also high degrees of internal order that are not known in ordinary polymers. They can resemble, for example, the ordered and dynamic one-dimensional supramol. assemblies of the cell cytoskeleton and possess useful biol. and electronic functions.
- 41Tu, R. S.; Tirrell, M. Bottom-up Design of Biomimetic Assemblies Adv. Drug. Deliver. Rev. 2004, 56, 1537– 1563Google ScholarThere is no corresponding record for this reference.
- 42Zhang, Y.; Kuang, Y.; Gao, Y. A.; Xu, B. Versatile Small-Molecule Motifs for Self-Assembly in Water and the Formation of Biofunctional Supramolecular Hydrogels Langmuir 2011, 27, 529– 537[ACS Full Text
], [CAS], Google Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXosVOqu7s%253D&md5=edd3aff3d30a5300b70abe9524dfbf8cVersatile Small-Molecule Motifs for Self-Assembly in Water and the Formation of Biofunctional Supramolecular HydrogelsZhang, Ye; Kuang, Yi; Gao, Yuan; Xu, BingLangmuir (2011), 27 (2), 529-537CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)This feature article introduces new structural motifs (referred as "samogen") that serve as the building blocks of hydrogelators for mol. self-assembly in water to result in a series of supramol. hydrogels. Using a compd. that consists of two phenylalanine residues and a naphthyl group (also abbreviated as NapFF) as an example of the samogens, we demonstrated the ability of the samogens to convert bioactive mols. into mol. hydrogelators that self-assemble in water to result in nanofibers. By briefly summarizing the properties and applications (e.g., wound healing, drug delivery, controlling cell fate, typing bacteria, and catalysis) of these mol. hydrogelators derived from the samogens, we intend to illustrate the basic requirements and promises of the small-mol. hydrogelators for applications in chem., materials science, and biomedicine. - 43Ulijn, R. V.; Smith, A. M. Designing Peptide Based Nanomaterials Chem. Soc. Rev. 2008, 37, 664– 675[Crossref], [PubMed], [CAS], Google Scholar43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXjs12hsbo%253D&md5=d6c7d3ab82107b9bd914ad6c1a4d279dDesigning peptide based nanomaterialsUlijn, Rein V.; Smith, Andrew M.Chemical Society Reviews (2008), 37 (4), 664-675CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. This tutorial review looks at the design rules that allow peptides to be exploited as building bloc for the assembly nanomaterials. These design rules are either derived by copying nature (α-helix, β-sheet) or may exploit entirely new designs based on peptide derivs. (peptide amphiphiles, π-stacking systems). The authors will examine the features that can be introduced to allow self-assembly to be controlled and directed by application of an externally applied stimulus, such as pH, light or enzyme action. Lastly the applications of designed self-assembly peptide systems in biotechnol. (3D cell culture, biosensing) and technol. (nanoelectronics, templating) will be examd.
- 44Toft, D. J.; Moyer, T. J.; Standley, S. M.; Ruff, Y.; Ugolkov, A.; Stupp, S. I.; Cryns, V. L. Coassembled Cytotoxic and Pegylated Peptide Amphiphiles Form Filamentous Nanostructures with Potent Antitumor Activity in Models of Breast Cancer ACS Nano 2012, 6, 7956– 7965[ACS Full Text
], [CAS], Google Scholar44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xht1OksLzK&md5=2eb410a5e46a57106ca5060bd0ed866dCoassembled Cytotoxic and Pegylated Peptide Amphiphiles Form Filamentous Nanostructures with Potent Antitumor Activity in Models of Breast CancerToft, Daniel J.; Moyer, Tyson J.; Standley, Stephany M.; Ruff, Yves; Ugolkov, Andrey; Stupp, Samuel I.; Cryns, Vincent L.ACS Nano (2012), 6 (9), 7956-7965CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)Self-assembled peptide amphiphiles (PAs) consisting of hydrophobic, hydrogen-bonding, and charged hydrophilic domains form cylindrical nanofibers in physiol. conditions and allow for the presentation of a high d. of bioactive epitopes on the nanofiber surface. We report here on the use of PAs to form multifunctional nanostructures with tumoricidal activity. The combination of a cationic, membrane-lytic PA coassembled with a serum-protective, pegylated PA was shown to self-assemble into nanofibers. Addn. of the pegylated PA to the nanostructure substantially limited degrdn. of the cytolytic PA by the protease trypsin, with an 8-fold increase in the amt. of intact PA obsd. after digestion. At the same time, addn. of up to 50% pegylated PA to the nanofibers did not decrease the in vitro cytotoxicity of the cytolytic PA. Using a fluorescent tag covalently attached to PA nanofibers we were able to track the biodistribution in plasma and tissues of tumor-bearing mice over time after i.p. administration of the nanoscale filaments. Using an orthotopic mouse xenograft model of breast cancer, systemic administration of the cytotoxic pegylated nanostructures significantly reduced tumor cell proliferation and overall tumor growth, demonstrating the potential of multifunctional PA nanostructures as versatile cancer therapeutics. - 45Behanna, H. A.; Donners, J. J. J. M.; Gordon, A. C.; Stupp, S. I. Coassembly of Amphiphiles with Opposite Peptide Polarities into Nanofibers J. Am. Chem. Soc. 2005, 127, 1193– 1200[ACS Full Text
], [CAS], Google Scholar45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXitlGhtA%253D%253D&md5=4b39410a654d95b7e8e64a491b6c4c3eCoassembly of Amphiphiles with Opposite Peptide Polarities into NanofibersBehanna, Heather A.; Donners, Jack J. J. M.; Gordon, Alex C.; Stupp, Samuel I.Journal of the American Chemical Society (2005), 127 (4), 1193-1200CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The design, synthesis, and characterization of "reverse" peptide amphiphiles (PAs) with free N-termini is described. Use of an unnatural amino acid modified with a fatty acid tail allows for the synthesis of this new class of PA mols. The mixing of these mols. with complementary ones contg. a free C-terminus results in coassembled structures, as demonstrated by CD and NOE/NMR spectroscopy. These assemblies show unusual thermal stability when compared to assemblies composed of only one type of PA mol. This class of reverse PAs has made it possible to create biol. significant assemblies with free N-terminal peptide sequences, which were previously inaccessible, including those derived from phage display methodologies. - 46Mata, A.; Geng, Y.; Henrikson, K. J.; Aparicio, C.; Stock, S. R.; Satcher, R. L.; Stupp, S. I. Bone Regeneration Mediated by Biomimetic Mineralization of A Nanofiber Matrix Biomaterials 2010, 31, 6004– 6012[Crossref], [PubMed], [CAS], Google Scholar46https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXnslamt7g%253D&md5=31b506ca096d15e5545c810d5ddf4424Bone regeneration mediated by biomimetic mineralization of a nanofiber matrixMata, Alvaro; Geng, Yanbiao; Henrikson, Karl J.; Aparicio, Conrado; Stock, Stuart R.; Satcher, Robert L.; Stupp, Samuel I.Biomaterials (2010), 31 (23), 6004-6012CODEN: BIMADU; ISSN:0142-9612. (Elsevier Ltd.)Rapid bone regeneration within a three-dimensional defect without the use of bone grafts, exogenous growth factors, or cells remains a major challenge. We report here on the use of self-assembling peptide nanostructured gels to promote bone regeneration that have the capacity to mineralize in biomimetic fashion. The main mol. design was the use of phosphoserine residues in the sequence of a peptide amphiphile known to nucleate hydroxyapatite crystals on the surfaces of nanofibers. We tested the system in a rat femoral crit.-size defect by placing pre-assembled nanofiber gels in a 5 mm gap and analyzed bone formation with micro-computed tomog. and histol. We found within 4 wk significantly higher bone formation relative to controls lacking phosphorylated residues and comparable bone formation to that obsd. in animals treated with a clin. used allogenic bone matrix.
- 47Hamley, I. W.; Dehsorkhi, A.; Castelletto, V. Coassembly in Binary Mixtures of Peptide Amphiphiles Containing Oppositely Charged Residues Langmuir 2013, 29, 5050– 5059[ACS Full Text
], [CAS], Google Scholar47https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXkslWlu7o%253D&md5=f166a49d6cc6d94e145d84832163889bCoassembly in Binary Mixtures of Peptide Amphiphiles Containing Oppositely Charged ResiduesHamley, I. W.; Dehsorkhi, A.; Castelletto, V.Langmuir (2013), 29 (16), 5050-5059CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)The self-assembly in water of designed peptide amphiphile (PA) C16-ETTES contg. two anionic residues and its mixts. with C16-KTTKS contg. two cationic residues was studied. Multiple spectroscopy, microscopy, and scattering techniques were used to examine ordering extending from the β-sheet structures up to the fibrillar aggregate structure. The peptide amphiphiles both comprise a hexadecyl alkyl chain and a charged pentapeptide headgroup contg. two charged residues. For C16-ETTES, the crit. aggregation concn. was detd. by fluorescence expts. FTIR and CD spectroscopy were used to examine β-sheet formation. TEM revealed highly extended tape nanostructures with some striped regions corresponding to bilayer structures viewed edge-on. Small-angle x-ray scattering showed a main 5.3 nm bilayer spacing along with a 3. nm spacing. These spacings are assigned resp. to predominant hydrated bilayers and a fraction of dehydrated bilayers. Signs of cooperative self-assembly are obsd. in the mixts., including reduced bundling of peptide amphiphile aggregates (extended tape structures) and enhanced β-sheet formation. - 48Kaler, E. W.; Herrington, K. L.; Murthy, A. K.; Zasadzinski, J. A. N. Phase-Behavior and Structures of Mixtures of Anionic and Cationic Surfactants J. Phys. Chem. 1992, 96, 6698– 6707
- 49Marques, E. F.; Regev, O.; Khan, A.; Miguel, M. D.; Lindman, B. Vesicle Formation and General Phase Behavior in the Catanionic Mixture SDS-DDAB-Water. The Anionic-Rich Side Phys. Chem. B 1998, 102, 6746– 6758[ACS Full Text
], [CAS], Google Scholar49https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1cXltVegt7o%253D&md5=b84c598a9350f6ecf5a9454782b70cf1Vesicle Formation and General Phase Behavior in the Catanionic Mixture SDS-DDAB-Water. The Anionic-Rich SideMarques, Eduardo F.; Regev, Oren; Khan, Ali; Da Graca Miguel, Maria; Lindman, BjoernJournal of Physical Chemistry B (1998), 102 (35), 6746-6758CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)Catanionic mixts. are aq. mixts. of oppositely charged surfactants which display novel phase behavior and interfacial properties in comparison with those of the individual surfactants. One phase behavior property is the ability of these systems to spontaneously form stable vesicles at high diln. The phase behavior of the mixt. sodium dodecyl sulfate (SDS) - didodecyldimethylammonium bromide (DDAB) in water has been studied in detail, and two regions of isotropic vesicular phases (anionic-rich and cationic-rich) were identified. Cryo-transmission electron microscopy allowed direct visualization of relatively small and polydisperse unilamellar vesicles on the SDS-rich side. Monitoring of the microstructure evolution from mixed micelles to vesicles as the surfactant mixing ratio is varied toward equimolarity was also obtained. Further information was provided by water self-diffusion measurements by pulsed field gradient spin-echo NMR. Water mols. can be in fast or slow exchange between the inside and outside of the vesicle with respect to the exptl. time scale, depending on membrane permeability and vesicle size. For the SDS-rich vesicles, a slow-diffusing component of very low molar fraction obsd. for the echo decays was traced down to very large vesicles in soln. Light microscopy confirmed the presence of vesicles of several microns in diam. Thus, polydispersity seems to be an inherent feature of the system. - 50Tondre, C.; Caillet, C. Properties of the Amphiphilic Films in Mixed Cationic/Anionic Vesicles: A Comprehensive View from A Literature Analysis Adv. Colloid Interface Sci. 2001, 93, 115– 134Google ScholarThere is no corresponding record for this reference.
- 51Leung, C. Y.; Palmer, L. C.; Qiao, B. F.; Kewalramani, S.; Sknepnek, R.; Newcomb, C. J.; Greenfield, M. A.; Vernizzi, G.; Stupp, S. I.; Bedzyk, M. J.; de la Cruz, M. O. Molecular Crystallization Controlled by pH Regulates Mesoscopic Membrane Morphology ACS Nano 2012, 6, 10901– 10909
- 52Dubois, M.; Deme, B.; Gulik-Krzywicki, T.; Dedieu, J. C.; Vautrin, C.; Desert, S.; Perez, E.; Zemb, T. Self-Assembly of Regular Hollow Icosahedra in Salt-Free Catanionic Solutions Nature 2001, 411, 672– 675[Crossref], [PubMed], [CAS], Google Scholar52https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXksF2htL0%253D&md5=e41d5bb789b3747506e4794cf3cb8dd3Self-assembly of regular hollow icosahedra in salt-free catanionic solutionsDubois, Monique; Deme, Bruno; Gulik-Krzywicki, Thaddee; Dedieu, Jean-Claude; Vautrin, Claire; Desert, Sylvan; Perez, Emile; Zemb, ThomasNature (London, United Kingdom) (2001), 411 (6838), 672-675CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)Self-assembled structures having a regular hollow icosahedral form (such as those obsd. for proteins of virus capsids) can occur as a result of biomineralization processes, but are extremely rare in mineral crystallites. Compact icosahedra made from a boron oxide have been reported, but equiv. structures made of synthetic org. components such as surfactants have not hitherto been obsd. It is, however, well known that lipids, as well as mixts. of anionic and cationic single chain surfactants can readily form bilayers that can adopt a variety of distinct geometric forms: they can fold into soft vesicles or random bilayers (the so-called sponge phase) or form ordered stacks of flat or undulating membranes. Here we show that in salt-free mixts. of anionic and cationic surfactants, such bilayers can self-assemble into hollow aggregates with a regular icosahedral shape. These aggregates are stabilized by the presence of pores located at the vertices of the icosahedra. The resulting structure have a size of about one micrometer and mass of about 1010 daltons, making them larger than any known icosahedral protein assembly or virus capsid. We expect the combination of wall rigidity and holes at vertices of these icosahedral aggregates to be of practical value for controlled drug or DNA release.
- 53Zemb, T.; Dubois, M.; Deme, B.; Gulik-Krzywicki, T. Self-Assembly of Flat Nanodiscs in Salt-Free Catanionic Surfactant Solutions Science 1999, 283, 816– 819[Crossref], [PubMed], [CAS], Google Scholar53https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1MXhtFShsLw%253D&md5=e9498ce86594265aa35f211c32ab30a3Self-assembly of flat nanodiscs in salt-free cationic surfactant solutionsZemb, Th.; Dubois, M.; Deme, B.; Gulik-Krzywicki, Th.Science (Washington, D. C.) (1999), 283 (5403), 816-819CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Disks of finite size are a very rare form of stable surfactant self-assembly. It is shown that mixing of two oppositely charged single-chain surfactants can produce rigid nanodiscs as well as swollen lamellar liq. crystals with frozen bilayers. The crucial requirement for obtaining nanodisc self-assembly is the use of H+ and OH- as counterions. These counterions then form water and lower the cond. to 10 microsiemens per cm. In the case of cationic component excess, a dil. soln. of nanodiscs is in thermodn. equil. with a lamellar phase. The diam. of the cationic nanodiscs is continuously adjustable from a few micrometers to 30 nm, with the pos. charge located mainly around the edges.
- 54Manghisi, N.; Leggio, C.; Jover, A.; Meijide, F.; Pavel, N. V.; Tellini, V. H. S.; Tato, J. V.; Agostino, R. G.; Galantini, L. Catanionic Tubules with Tunable Charge Angew. Chem. Int. Ed. 2010, 49, 6604– 6607Google ScholarThere is no corresponding record for this reference.
- 55Nelson, R.; Sawaya, M. R.; Balbirnie, M.; Madsen, A. O.; Riekel, C.; Grothe, R.; Eisenberg, D. Structure of the Cross-[Beta] Spine of Amyloid-Like Fibrils Nature 2005, 435, 773– 778Google ScholarThere is no corresponding record for this reference.
- 56Cui, H.; Hodgdon, T. K.; Kaler, E. W.; Abezgauz, L.; Danino, D.; Lubovsky, M.; Talmon, Y.; Pochan, D. J. Elucidating the Assembled Structure of Amphiphiles in Solution via Cryogenic Transmission Electron Microscopy Soft Matter 2007, 3, 945– 955[Crossref], [PubMed], [CAS], Google Scholar56https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXnslGkur8%253D&md5=6c021ddb07165fd54ba77526e711ba55Elucidating the assembled structure of amphiphiles in solution via cryogenic transmission electron microscopyCui, Honggang; Hodgdon, Travis K.; Kaler, Eric W.; Abezgauz, Ludmila; Danino, Dganit; Lubovsky, Maya; Talmon, Yeshayahu; Pochan, Darrin J.Soft Matter (2007), 3 (8), 945-955CODEN: SMOABF; ISSN:1744-683X. (Royal Society of Chemistry)A review. For the past twenty years, significant progress was made in both developing cryogenic transmission electron microscopy (cryo-TEM) technol. and understanding assembled behavior of amphiphilic mols. Cryo-TEM can provide high-resoln. images of complex fluids in a near in situ state. Samples embedded in a thin layer of vitrified solvent do not exhibit artifacts that would normally occur when using chem. fixation or staining-and-drying techniques. Cryo-TEM was useful in imaging biol. mols. in aq. solns. Cryo-TEM has become a powerful tool in the study of in situ-assembled structures of amphiphiles in soln. as a complementary tool to small-angle x-ray and neutron scattering, light scattering, rheol. measurements, and NMR. The application of cryo-TEM in the study of assembled behavior of amphiphilic block copolymers, hydrogels, and other complex soft systems continues to emerge. In this context, the usage of cryo-TEM in the field of amphiphilic complex fluids and self-assembled nanomaterials is briefly reviewed, and its unique role in exploring the nature of assembled structure in liq. suspension is highlighted.
- 57Helfrich, W.; Prost, J. Intrinsic Bending Force In Anisotropic Membranes Made of Chiral Molecules Phys. Rev. A 1988, 38, 3065– 3068Google ScholarThere is no corresponding record for this reference.
- 58Selinger, J. V.; Spector, M. S.; Schnur, J. M. Theory of Self-Assembled Tubules and Helical Ribbons J. Phys. Chem. B 2001, 105, 7157– 7169[ACS Full Text
], [CAS], Google Scholar58https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXks1Sgurw%253D&md5=e1be35c60c89069255bec682a98525eeTheory of Self-Assembled Tubules and Helical RibbonsSelinger, Jonathan V.; Spector, Mark S.; Schnur, Joel M.Journal of Physical Chemistry B (2001), 105 (30), 7157-7169CODEN: JPCBFK; ISSN:1089-5647. (American Chemical Society)A review with 64 refs. Many types of amphiphilic mols. self-assemble in soln. to form cylindrical tubules and helical ribbons. Some examples include diacetylenic lipids, amide amphiphiles, bile, and diblock copolymers. Researchers have proposed a variety of models to explain the formation of these high-curvature structures. These models can be divided into two broad categories: models based on the chiral elastic properties of membranes, and models based on other effects, including electrostatic interactions, elasticity of orientational order, and spontaneous curvature. In this paper, we review the range of theor. approaches and compare them with relevant expts. We argue that the category of models based on chiral elastic properties provides the most likely explanation of current exptl. results, and we propose further theor. and exptl. research to give a more detailed test of these models. - 59Israelachvili, J. N. Intermolecular and Surface Forces, 3rd ed.; Elsevier: New York, 2011.
- 60Adamcik, J.; Mezzenga, R. Adjustable Twisting Periodic Pitch of Amyloid Fibrils Soft Matter 2011, 7, 5437– 5443[Crossref], [CAS], Google Scholar60https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXmsVCqtL8%253D&md5=07e92b337f9c6e8b433ed41e9a1b0fa0Adjustable twisting periodic pitch of amyloid fibrilsAdamcik, Jozef; Mezzenga, RaffaeleSoft Matter (2011), 7 (11), 5437-5443CODEN: SMOABF; ISSN:1744-683X. (Royal Society of Chemistry)We present compelling exptl. evidence supported by theor. arguments demonstrating that the periodic twisting pitch in protein amyloid fibrils arises from the fine balance between competing electrostatic energy and torsional elastic energy stored along the fibrils contour length. To construct the present picture we have used increasing ionic strengths to progressively screen the electrostatic interactions and obsd. the corresponding pitch variations in mature β-lactoglobulin amyloid fibrils using single-mol. at. force microscopy (AFM). Because the ionic strength is changed after fibrils formation, this does not affect the mechanism by which fibrils grow up to their mature structure. For each individual population of the multi-stranded fibrils family, the pitch is found to increase systematically with the salt content, leading to the gradual untwisting of the fibrils and to the establishment of a controllable pitch up to virtually infinite values.
- 61Adamcik, J.; Mezzenga, R. Proteins Fibrils from a Polymer Physics Perspective Macromolecules 2012, 45, 1137– 1150[ACS Full Text
], [CAS], Google Scholar61https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhs1GltrjJ&md5=d1317aae7dbbbf181e97b27ffa7a3934Proteins Fibrils from a Polymer Physics PerspectiveAdamcik, Jozef; Mezzenga, RaffaeleMacromolecules (Washington, DC, United States) (2012), 45 (3), 1137-1150CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)A review. Protein fibrils resulting from assembly of proteins or peptides into long, insol., highly ordered fibrillar structures are emerging as one of the fastest growing scientific areas, since interest in these systems spans disciplines as broad and diverse as medicine, biol., soft condensed matter, nanotechnol., and materials science. Since the discovery of the implication of protein amyloid fibrils in neurodegenerative diseases, to their more recent applications in high-performance materials, the understanding of these intriguing macromol. assemblies has been steadily widening and deepening. Thus, the precise characterization of structural, phys., and mech. properties of protein fibrils is the first crit. step toward our understanding of these systems not only in the context of biol. and medicine but also in nanotechnol. and advanced biomaterials applications. In this Perspective we wish to discuss how polymer and colloidal science concepts can be efficiently used to unravel very useful information on the mechanisms of formation, structure, and phys. properties of protein fibrils and want to show, through available examples, how a soft condensed matter perspective can shed light into these fascinating systems. - 62Usov, I.; Adamcik, J.; Mezzenga, R. Polymorphism Complexity and Handedness Inversion in Serum Albumin Amyloid Fibrils ACS Nano 2013, 7, 10465– 10474
- 63Adamcik, J.; Lara, C.; Usov, I.; Jeong, J. S.; Ruggeri, F. S.; Dietler, G.; Lashuel, H. A.; Hamley, I. W.; Mezzenga, R. Measurement of Intrinsic Properties of Amyloid Fibrils by the Peak Force QNM Method Nanoscale 2012, 4, 4426– 4429[Crossref], [PubMed], [CAS], Google Scholar63https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtVSqt7rJ&md5=50a0998477ba555f78ba8dd8676faf0eMeasurement of intrinsic properties of amyloid fibrils by the peak force QNM methodAdamcik, Jozef; Lara, Cecile; Usov, Ivan; Jeong, Jae Sun; Ruggeri, Francesco S.; Dietler, Giovanni; Lashuel, Hilal A.; Hamley, Ian W.; Mezzenga, RaffaeleNanoscale (2012), 4 (15), 4426-4429CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)We report the investigation of the mech. properties of different types of amyloid fibrils by the peak force quant. nanomech. (PF-QNM) technique. We demonstrate that this technique correctly measures the Young's modulus independent of the polymorphic state and the cross-sectional structural details of the fibrils, and the authors show that values for amyloid fibrils assembled from heptapeptides, α-synuclein, Aβ(1-42), insulin, β-lactoglobulin, lysozyme, ovalbumin, Tau protein and bovine serum albumin all fall in the range of 2-4 GPa.
- 64Usov, I.; Mezzenga, R. Correlation between Nanomechanics and Polymorphic Conformations in Amyloid Fibrils ACS Nano 2014, 8, 11035– 11041[ACS Full Text
], [CAS], Google Scholar64https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhs1Oiu77P&md5=02a6bbb6de225e80563371270efa9e06Correlation between Nanomechanics and Polymorphic Conformations in Amyloid FibrilsUsov, Ivan; Mezzenga, RaffaeleACS Nano (2014), 8 (11), 11035-11041CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)Amyloid fibrils occur in diverse morphologies, but how polymorphism affects the resulting mech. properties is still not fully appreciated. Using formalisms from the theory of elasticity, we propose an original way of averaging the second area moment of inertia for non-axisym. fibrils, which constitutes the great majority of amyloid fibrils. By following this approach, we derive theor. expressions for the bending properties of the most common polymorphic forms of amyloid fibrils (twisted ribbons, helical ribbons, and nanotubes), and we benchmark the predictions to exptl. cases. These results not only allow an accurate estn. of the amyloid fibrils' elastic moduli but also bring insight into the structure-property relationships in the nanomechanics of amyloid systems, such as in the closure of helical ribbons into nanotubes. - 65Geng, Y.; Dalhaimer, P.; Cai, S. S.; Tsai, R.; Tewari, M.; Minko, T.; Discher, D. E. Shape Effects of Filaments versus Spherical Particles in Flow and Drug Delivery Nat. Nanotechnol. 2007, 2, 249– 255[Crossref], [PubMed], [CAS], Google Scholar65https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXktVGgsbs%253D&md5=e93d8a9b11bf2a6cc2c5e970aa37a433Shape effects of filaments versus spherical particles in flow and drug deliveryGeng, Yan; Dalhaimer, Paul; Cai, Shenshen; Tsai, Richard; Tewari, Manorama; Minko, Tamara; Discher, Dennis E.Nature Nanotechnology (2007), 2 (4), 249-255CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)Interaction of spherical particles with cells and within animals was studied extensively, but the effects of shape have received little attention. Here the authors use highly stable, polymer micelle assemblies known as filomicelles to compare the transport and trafficking of flexible filaments with spheres of similar chem. In rodents, filomicelles persisted in the circulation up to one week after i.v. injection. This is about ten times longer than their spherical counterparts and is more persistent than any known synthetic nanoparticle. Under fluid flow conditions, spheres and short filomicelles are taken up by cells more readily than longer filaments because the latter are extended by the flow. Preliminary results further demonstrate that filomicelles can effectively deliver the anticancer drug paclitaxel and shrink human-derived tumors in mice. Although these findings show that long-circulating vehicles need not be nanospheres, they also lead insight into possible shape effects of natural filamentous viruses.
- 66Jiang, S. Y.; Cao, Z. Q. Ultralow-Fouling, Functionalizable, and Hydrolyzable Zwitterionic Materials and Their Derivatives for Biological Applications Adv. Mater. 2010, 22, 920– 932Google ScholarThere is no corresponding record for this reference.
- 67Dubikovskaya, E. A.; Thorne, S. H.; Pillow, T. H.; Contag, C. H.; Wender, P. A. Overcoming multidrug resistance of small-molecule therapeutics through conjugation with releasable octaarginine transporters Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 12128– 12133[Crossref], [PubMed], [CAS], Google Scholar67https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhtVOhtrzN&md5=0f8f068576e4304d23d0ac0bfecb5a7dOvercoming multidrug resistance of small-molecule therapeutics through conjugation with releasable octaarginine transportersDubikovskaya, Elena A.; Thorne, Steve H.; Pillow, Thomas H.; Contag, Christopher H.; Wender, Paul A.Proceedings of the National Academy of Sciences of the United States of America (2008), 105 (34), 12128-12133CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)Many cancer therapeutic agents elicit resistance that renders them ineffective and often produces cross-resistance to other drugs. One of the most common mechanisms of resistance involves P-glycoprotein (Pgp)-mediated drug efflux. To address this problem, new agents have been sought that are less prone to inducing resistance and less likely to serve as substrates for Pgp efflux. An alternative to this approach is to deliver established agents as mol. transporter conjugates into cells through a mechanism that circumvents Pgp-mediated efflux and allows for release of free drug only after cell entry. Here we report that the widely used chemotherapeutic agent Taxol, ineffective against Taxol-resistant human ovarian cancer cell lines, can be incorporated into a releasable octaarginine conjugate that is effective against the same Taxol-resistant cell lines. It is significant that the ability of the Taxol conjugates to overcome Taxol resistance is obsd. both in cell culture and in animal models of ovarian cancer. The generality and mechanistic basis for this effect were also explored with coelenterazine, a Pgp substrate. Although coelenterazine itself does not enter cells because of Pgp efflux, its octaarginine conjugate does so readily. This approach shows generality for overcoming the multidrug resistance elicited by small-mol. cancer chemotherapeutics and could improve the prognosis for many patients with cancer and fundamentally alter search strategies for novel therapeutic agents that are effective against resistant disease.
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