Molecular self-assembly is the spontaneous association of molecules under equilibrium conditions into stable, structurally well-defined aggregates joined by noncovalent bonds. Molecular self-assembly is ubiquitous in biological systems and underlies the formation of a wide variety of complex biological structures. Understanding self-assembly and the associated noncovalent interactions that connect complementary interacting molecular surfaces in biological aggregates is a central concern in structural biochemistry. Self-assembly is also emerging as a new strategy in chemical synthesis, with the potential of generating nonbiological structures with dimensions of 1 to 10(2) nanometers (with molecular weights of 10(4) to 10(10) daltons). Structures in the upper part of this range of sizes are presently inaccessible through chemical synthesis, and the ability to prepare them would open a route to structures comparable in size (and perhaps complementary in function) to those that can be prepared by microlithography and other techniques of microfabrication.

Molecular self-assembly and nanochemistry: A chemical strategy for the synthesis of nanostructures

Functional π-Gelators and Their Applications

In this review we intend to provide a relatively comprehensive summary of the work of supramolecular hydrogelators after 2004 and to put emphasis particularly on the applications of supramolecular hydrogels/hydrogelators as molecular biomaterials. After a brief introduction of methods for generating supramolecular hydrogels, we discuss supramolecular hydrogelators on the basis of their categories, such as small organic molecules, coordination complexes, peptides, nucleobases, and saccharides. Following molecular design, we focus on various potential applications of supramolecular hydrogels as molecular biomaterials, classified by their applications in cell cultures, tissue engineering, cell behavior, imaging, and unique applications of hydrogelators. Particularly, we discuss the applications of supramolecular hydrogelators after they form supramolecular assemblies but prior to reaching the critical gelation concentration because this subject is less explored but may hold equally great promise for helping ...

Supramolecular Hydrogelators and Hydrogels: From Soft Matter to Molecular Biomaterials

https://www.pnas.org/content/pnas/90/5/1635.full.pdf

Supramolecular chemistry.

Solar desalination is a promising method for large-scale water purification by utilizing sustainable energy. However, current high-rate solar evaporation often relies on optical concentration due to the diffusion of natural sunlight, which leads to inadequate energy supply. Here we demonstrate a hydrogel-based solar evaporator that is capable of generating vapor at a high rate of ∼2.5 kg m−2 h−1 under one sun irradiation (1 kW m−2), among the best values reported in the literature. Such highly efficient solar evaporation is achieved by a hybrid hydrogel composed of a hydrophilic polymer framework (polyvinyl alcohol, PVA) and solar absorber (reduced graphene oxide, rGO), which has internal capillary channels. The PVA can greatly facilitate the water evaporation owing to the reduced water evaporation enthalpy in the hydrogel network. The rGO penetrating into the polymeric network enables efficient energy utilization. The capillary channels sustain an adequate water supply for continuous solar vapor generation at a high rate. This hydrogel-based solar evaporator also exhibits promising antifouling properties, enabling long-term water desalination without recycling. The high-efficiency hydrogel-based solar vapor generators open significant opportunities to enhance solar water evaporation performance and reduce the cost of solar desalination systems.

A hydrogel-based antifouling solar evaporator for highly efficient water desalination

Conducting polymer hydrogels (CPHs) emerge as excellent functional materials, as they harness the advantages of conducting polymers with the mechanical properties and continuous 3D nanostructures of hydrogels. This bicomponent organization results in soft, all-organic, conducting micro-/nanostructures with multifarious material applications. However, the application of CPHs as functional materials for biomedical applications is currently limited due to the necessity to combine the features of biocompatibility, self-healing, and fine-tuning of the mechanical properties. To overcome this issue, we choose to combine a protected dipeptide as the supramolecular gelator, owing to its intrinsic biocompatibility and excellent gelation ability, with the conductive polymer polyaniline (PAni), which was polymerized in situ. Thus, a two-component, all-organic, conducting hydrogel was formed. Spectroscopic evidence reveals the formation of the emeraldine salt form of PAni by intrinsic doping. The composite hydrogel is...

A Self-Healing, All-Organic, Conducting, Composite Peptide Hydrogel as Pressure Sensor and Electrogenic Cell Soft Substrate.

A porous 3D folic acid(F)-polyaniline(PANI) hybrid hydrogel (F-PANI), produced by in situ polymerization of aniline, exhibit highest compressive stress(15.1 kPa), 3D hierarchical network morphology with BET surface area 236 m2/g. Here PANI is present in emeraldine salt(ES) state which facilitates excellent adsorption of anionic pollutants. It exhibits an extremely high adsorption capacity for Cr(VI) and during adsorption Cr(VI) is reduced to Cr(III).The electrical impedance spectra of the Cr(VI) adsorbed xerogel, support the conversion of PANI chains from ES to pernigraniline base(PB) making the xerogel more resistive. It also selectively adsorbs anionic dyes, the adsorption capacity increases with decrease of pH. Both the adsorption data are found to be well explained through pseudo-second-order kinetic model and they obey Langmuir adsorption isotherm. F-PANI2 showed high adsorption capacities selectively towards anionic pollutants e.g. Cr(VI), eosine yellow, rose bengal, methyl orange and low adsorption...

Folic Acid-Polyaniline Hybrid Hydrogel for Adsorption/Reduction of Chromium (VI) and Selective Adsorption of Anionic Dye from Water

The misfolding of proteins and peptides potentially leads to a conformation transition from an α-helix or random coil to β-sheet-rich fibril structures, which are associated with various amyloid degenerative disorders. Inhibition of the β-sheet aggregate formation and control of the structural transition could therefore attenuate the development of amyloid-associated diseases. However, the structural transitions of proteins and peptides are extraordinarily complex processes that are still not fully understood and thus challenging to manipulate. To simplify this complexity, herein, the effect of metal ions on the inhibition of amyloid-like β-sheet dipeptide self-assembly is investigated. By changing the type and ratio of the metal ion/dipeptide mixture, structural transformation is achieved from a β-sheet to a superhelix or random coil, as confirmed by experimental results and computational studies. Furthermore, the obtained supramolecular metallogel exhibits excellent in vitro DNA binding and diffusion capability due to the positive charge of the metal/dipeptide complex. This work may facilitate the understanding of the role of metal ions in inhibiting amyloid formation and broaden the future applications of supramolecular metallogels in three-dimensional (3D) DNA biochip, cell culture, and drug delivery.

Metal-Ion Modulated Structural Transformation of Amyloid-Like Dipeptide Supramolecular Self-Assembly.

A coassembled light-harvesting hydrogel of melamine (M), 6,7-dimethoxy-2,4[1H, 3H]-quinazolinedione (Q) with riboflavin (R), is used to produce a white-light-emitting hydrogel (W-gel) by mixing with the dye rhodamine B (RhB) in a requisite proportion. Addition of R to the Q solution causes both static and dynamic quenching to the emission of Q as evident from the Stern–Volmer plot and the emission of R shows a gradual increase in intensity. On addition of RhB to an aqueous solution of R, fluorescence resonance energy transfer (FRET) occurs, showing an emission peak at 581 nm. In a solution of constant molar ratio of Q and R, addition of RhB causes a quenching of emission of R with no effect on the emission of Q, indicating that the energy transfer takes place only between R and RhB. In the MQR coassembled hydrogel containing RhB, the gel melting temperature is lower than those of MQ and MQR gel, but the storage modulus remains almost unaffected. The oscillatory stress experiment indicates a gradual decrea...

Co-assembled white-light-emitting hydrogel of melamine.

Amino acids are the simplest biological building blocks capable of forming discreet nanostructures by supramolecular self-assembly. The understanding of the process of organization of amino acid nanostructures is of fundamental importance for the study of metabolic diseases as well as for materials science applications. Although peptide self-assembled structures have been the topic of many review articles, much less attention has been devoted to the ability of amino acid building blocks, both natural and synthetic, to form ordered assemblies with defined architectures and notable physical properties, by the process of self-association. Herein, we try to shed light on amino acid based nanostructures, their fabrication and implications. We discuss self-assembled nanostructures, including hydrogels with nanoscale order, obtained from both modified and unmodified single amino acids. We also envision some future prospects in this emerging field.

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Priyadarshi Chakraborty

Papers

A Self-Healing, All-Organic, Conducting, Composite Peptide Hydrogel as Pressure Sensor and Electrogenic Cell Soft Substrate.

Folic Acid-Polyaniline Hybrid Hydrogel for Adsorption/Reduction of Chromium (VI) and Selective Adsorption of Anionic Dye from Water

Metal-Ion Modulated Structural Transformation of Amyloid-Like Dipeptide Supramolecular Self-Assembly.

Co-assembled white-light-emitting hydrogel of melamine.

Amino Acid Based Self-assembled Nanostructures: Complex Structures from Remarkably Simple Building Blocks