Physical properties of hierarchically ordered self-assembled planar and spherical membranes

Carvajal, Daniel; Bitton, Ronit; Mantei, Jason R.; Velichko, Yuri S.; Stupp, Samuel I.; Shull, Kenneth R.

doi:10.1039/b923903k

Cited by 54 publications

(105 citation statements)

References 39 publications

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“…As the Ca 2 þ concentration gradient is high at the diffusion front, it is energetically favorable for the highly charged PBDT molecules to orient parallel to the diffusion front, which ensures more complexation. A similar result was reported by Capito et al and Carvajal et al, 58,59 who dropped aqueous solutions of peptide amphiphiles with positive charges into polyanion solution; the partial charge screening of the peptide amphiphiles led them to self-assemble into fibrous bundles aligned parallel to the liquid-liquid interface.…”

Section: Synthesis Of Physical Hydrogels With Centimeter-scale Anisotsupporting

confidence: 69%

Hydrogels with a macroscopic-scale liquid crystal structure by self-assembly of a semi-rigid polyion complex

Kurokawa

Gong

2012

Polym J

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Designing hydrogels with self-assembled or self-organized structures has become an attractive field of research because these hydrogels usually have robust functions and promising applications, such as in artificial tissues and optical sensors. However, the self-organized structures developed in synthetic hydrogels via molecular self-assembly are generally limited to the submicrometer or micrometer level, which is far from the related scale achieved in biological tissues. Therefore, it is desirable to create macroscopically ordered structures in hydrogels; these structures should greatly improve the material's functionalities, such as their optical properties. In this review, we generally introduce our recent studies on the synthesis of hydrogels with macroscopic-scale liquid crystal structures based on the self-assembly of a semi-rigid polyanion, poly(2,2 0 -disulfonyl-4,4 0 -benzidine terephthalamide) (PBDT). Upon electrostatic interaction with multivalent cations or polycations, PBDT molecules form semi-rigid complexes or mesoscopic bundles that further self-assemble into macroscopic organized structures and are frozen by the subsequent gelation process. We have developed physical hydrogels with centimeter-scale anisotropic structures, polycationic hydrogels with millimeter-scale cylindrically symmetric structures and plate gels with cubic-packed concentric domains. This work should contribute to the development of macroscopic self-organized structures in hydrogel materials with specific functions.

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Section: Synthesis Of Physical Hydrogels With Centimeter-scale Anisotsupporting

confidence: 69%

Hydrogels with a macroscopic-scale liquid crystal structure by self-assembly of a semi-rigid polyion complex

Kurokawa

Gong

2012

Polym J

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“…In this way, a closed membrane is formed that entraps the PA solution inside it and leaves the ELP solution outside. Self-assembled membranes formed at the interface between a solution of linear polyelectrolytes and a solution of either oppositely charged PAs [18][19][20][21][22] or surfactant molecules 23 have been reported. However, in our system, within the first minute of formation and on contact with any surface, the membrane spontaneously, yet controllably, adheres, focally opens and seals to the surface (Fig.…”

Section: Resultsmentioning

confidence: 99%

Co-assembly, spatiotemporal control and morphogenesis of a hybrid protein–peptide system

et al. 2015

Self Cite

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ature uses self-assembly to create a widespread variety of complex structures with elaborate geometries and outstanding properties 1 such as hierarchical order, adaptability, selfhealing and bioactivity. Developing new bioinspired processes based on dynamic self-assembly could facilitate the fabrication of synthetic three-dimensional (3D) materials with enhanced complexity, dynamic properties and functionality 2 . Proteins are particularly attractive building blocks because of their versatility and biofunctionality 3 . Elastin-like polypeptides (ELPs) 4 are recombinant proteins that have generated great interest 5 as a result of their modular structure, bioactivity, ease of design and production, and the possibility to create robust and elastic materials 5,6 . ELPs allow for a tunable molecular design 7 and are based on the tropoelastin recurrent motif Val-Pro-Gly-X-Gly (VPGXG), in which X is any amino acid other than proline 7 . This repeating pentapeptide provides ELPs with a thermoresponsive behaviour. Below a critical transition temperature (T t ), the ELP molecule undergoes a reversible-phase transition wherein the protein is soluble in aqueous solution and becomes highly solvated, surrounded by clatharate-like water structures. Above the T t , the hydrophobic domains dehydrate and the protein chain hydrophobically collapses and aggregates to form a phaseseparated state 8 .The use of natural and synthetic proteins to create functional materials has been hindered by the difficulty in controlling their conformation and nanoscale assembly with the precision required to form macroscopic materials. This limitation has driven the development of simpler and more-predictable peptide-based materials 9,10 . Peptide amphiphiles (PAs), for example, are synthetic molecules that can self-assemble into nanofibres and create functional 3D hydrogels that emulate the fibrous architecture of the extracellular matrix (ECM) 11,12 . Nonetheless, most peptide and/or protein materials are formed through equilibrium-based self-assembly approaches that are capable of generating stable supramolecular structures, but with limited hierarchy and spatiotemporal control, which has hindered their functionality 2 .Novel approaches based on the dynamic self-assembly of inorganic building blocks [13][14][15] , actin self-organization 16 and the combination of top-down processes with peptide self-assembly have been reported recently 17 . In particular, Stupp and co-workers have described a self-assembling membrane system obtained through strong electrostatic interactions between PAs and oppositely charged polysaccharides 18 . However, the possibility to exploit the unique structural and functional properties of proteins to create dynamic hierarchical materials remains an elusive target. In this study, we attempt to overcome this hurdle by using self-assembling peptides to promote protein conformational changes and guide their assembly into complex, yet functional, materials. We report the discovery and development of a protein/peptide system t...

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“…They cited a 11 recent paper detailing how a membranes could be formed from spreading a peptide amphiphile solution 12 upon hyaluronan (an anionic long-branched polysaccharide) solution. [79] Here, although the authors focus 13 centred more upon the membrane mechanical properties than a need to discern mesostructure, they 14 nevertheless demonstrated that a microstructure orientated normal to the interface could result from 15 interfacial assembly, without a support, at the liquid-liquid interface. Schacht et al [80] interface.…”

Section: Polymer-surfactant Films Formed At Liquid-liquid Interfacesmentioning

confidence: 99%

Solid mesostructured polymer–surfactant films at the air–liquid interface

Pegg

Eastoe

2015

Advances in Colloid and Interface Science

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General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available: http://www.bristol.ac.uk/pure/about/ebr-terms Solid, Mesostructured Polymer-Surfactant Films Formed at the Air-Liquid Interface self-supporting films comprising surfactant micelles encased with a polymer hydrogel-surfactant-polymer 6 films, that can be grown spontaneously at the air-liquid interface. These films can be prepared with defined 7 and controllable mesostructures. Addition of a siliconalkoxide to polymer-surfactant mixtures allowed for 8 the growth of mesostructured hybrid polymer-surfactant silica films that retained film geometry after 9 calcination and exhibit superior mechanical properties to typically brittle inorganic films. Growing films at 10 the air-liquid interface provides the most rapid and simple means to prepare ordered solid inorganic films 11 and to date the only method to form mesostructure films thick enough (up to several hundred microns) to be 12 removed from the interface. Applications of these films could range from catalysis to encapsulation of 13 hydrophobic species and drug delivery. Film properties and mesostructure are sensitive to surfactant 14 structure, polymer properties and polymer-surfactant phase behaviour: herein it will be shown in particular 15 how the film mesostructure can be tailored by directing these parameters and some interesting analogies will 16 be drawn with more familiar mesostructure silica materials.

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Physical properties of hierarchically ordered self-assembled planar and spherical membranes

Cited by 54 publications

References 39 publications

Hydrogels with a macroscopic-scale liquid crystal structure by self-assembly of a semi-rigid polyion complex

Hydrogels with a macroscopic-scale liquid crystal structure by self-assembly of a semi-rigid polyion complex

Co-assembly, spatiotemporal control and morphogenesis of a hybrid protein–peptide system

Solid mesostructured polymer–surfactant films at the air–liquid interface

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