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

The science and technology of ultracapacitors are reviewed for a number of electrode materials, including carbon, mixed metal oxides, and conducting polymers. More work has been done using microporous carbons than with the other materials and most of the commercially available devices use carbon electrodes and an organic electrolytes. The energy density of these devices is 3¯5 Wh/kg with a power density of 300¯500 W/kg for high efficiency (90¯95%) charge/discharges. Projections of future developments using carbon indicate that energy densities of 10 Wh/kg or higher are likely with power densities of 1¯2 kW/kg. A key problem in the fabrication of these advanced devices is the bonding of the thin electrodes to a current collector such the contact resistance is less than 0.1 cm2. Special attention is given in the paper to comparing the power density characteristics of ultracapacitors and batteries. The comparisons should be made at the same charge/discharge efficiency.

Ultracapacitors: Why, How, and Where is the Technology

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

Transition metal carbides and nitrides (MXenes), a family of two-dimensional (2D) inorganic compounds, are materials composed of a few atomic layers of transition metal carbides, nitrides, or carbonitrides. Ti3C2, the first 2D layered MXene, was isolated in 2011. This material, which is a layered bulk material analogous to graphite, was derived from its 3D phase, Ti3AlC2 MAX. Since then, material scientists have either determined or predicted the stable phases of >200 different MXenes based on combinations of various transition metals such as Ti, Mo, V, Cr, and their alloys with C and N. Extensive experimental and theoretical studies have shown their exciting potential for energy conversion and electrochemical storage. To this end, we comprehensively summarize the current advances in MXene research. We begin by reviewing the structure types and morphologies and their fabrication routes. The review then discusses the mechanical, electrical, optical, and electrochemical properties of MXenes. The focus then turns to their exciting potential in energy storage and conversion. Energy storage applications include electrodes in rechargeable lithium- and sodium-ion batteries, lithium-sulfur batteries, and supercapacitors. In terms of energy conversion, photocatalytic fuel production, such as hydrogen evolution from water splitting, and carbon dioxide reduction are presented. The potential of MXenes for the photocatalytic degradation of organic pollutants in water, such as dye waste, is also addressed, along with their promise as catalysts for ammonium synthesis from nitrogen. Finally, their application potential is summarized.

Applications of 2D MXenes in energy conversion and storage systems

Thiourea (TU), a commercially available laboratory chemical, has been discovered to introduce metallogelation when reacted with copper(II) chloride in aqueous medium. The chemistry involves the reduction of Cu(II) to Cu(I) with concomitant oxidation of thiourea to dithiobisformamidinium dichloride. The gel formation is triggered through metal–ligand complexation, i.e., Cu(I)-TU coordination and extensive hydrogen bonding interactions involving thiourea, the disulfide product, water, and chloride ions. Entangled network morphology of the gel selectively develops in water, maybe for its superior hydrogen-bonding ability, as accounted from Kamlet–Taft solvent parameters. Complete and systematic chemical analyses demonstrate the importance of both Cu(I) and chloride ions as the key ingredients in the metal–organic coordination gel framework. The gel is highly fluorescent. Again, exclusive presence of Cu(I) metal centers in the gel structure makes the gel redox-responsive and therefore it shows reversible gel–...

Redox-Switchable Copper(I) Metallogel: A Metal–Organic Material for Selective and Naked-Eye Sensing of Picric Acid

We report the preparation of hierarchically structured fullerene C70 cubes (HFC) composed of mesoporous C70 nanorods with crystalline pore walls. Highly crystalline cubic shape C70 crystals (FC) were grown at a liquid–liquid interface formed between tert-butyl alcohol and C70 solution in mesitylene. HFCs were then prepared by washing with isopropanol of the FC at 25 °C. The growth directions and diameters of C70 nanorods could be controlled by varying washing conditions. HFCs perform as an excellent sensing system for vapor-phase aromatic solvents due to their easy diffusion through the mesoporous architecture and strong π–π interactions with the sp2 carbon-rich pore walls. Moreover, HFCs offer an enhanced electrochemically active surface area resulting in an energy storage capacity 1 order of magnitude greater than pristine C70 and fullerene C70 cubes not containing mesoporous nanorods.

Hierarchically Structured Fullerene C70 Cube for Sensing Volatile Aromatic Solvent Vapors

The last twenty years have witnessed increasing research activity in the area of supramolecular chemistry of 1 : 1 co-assembly of melamine (M)–cyanuric acid (CA), since the historic discovery of the M·CA aggregate in crystal form and its structural analysis by Wang and his coworkers in 1990. Its useful chemical structure and fascinating H-bonding interaction sites distinguish M and its analogous derivatives as scaffolding components in the field of supramolecular chemistry to develop desired nano-to-micro scaled architecture. To date, M-based supramolecular assemblies are known in diverse forms which include fascinating nano- to micromorphological structures, molecular guest boxes, small molecular gels, membrane, sensor and liquid crystal development, polymeric scaffolds etc. In this review, we have covered the development of M and its derivatives, encompassing both nano/micro-ordered structures and advanced functional materials.

Supramolecular assembly of melamine and its derivatives: nanostructures to functional materials

A new and facile approach for synthesizing graphene quantum dots (GQDs) using sono-Fenton reaction in an aqueous dispersion of graphene oxide (GO) is reported. The transmission electron microscopy (TEM) micrographs of GQDs indicate its average diameter as ∼5.6 ± 1.4 nm having a lattice parameter of 0.24 nm. GQDs are used to fabricate composites (PG) with a water-soluble polymer, polythiophene-g-poly[(diethylene glycol methyl ether methacrylate)-co-poly(N,N-dimethylaminoethyl methacrylate)] [PT-g-P(MeO2MA-co-DMAEMA), P]. TEM micrographs indicate that both P and PG possess distinct core–shell morphology and the average particle size of P (0.16 ± 0.08 μm) increases in PG (0.95 ± 0.45 μm). Fourier transform infrared and X-ray photoelectron spectrometry spectra suggest an interaction between −OH and −COOH groups of GQDs and −NMe2 groups of P. A decrease of the intensity ratio of Raman D and G bands (ID/IG) is noticed during GQD and PG formation. In contrast to GO, GQDs do not exhibit any absorption peak for it...

Graphene quantum dots from a facile sono-Fenton reaction and its hybrid with a polythiophene graft copolymer toward photovoltaic application.

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...

Partha Bairi

Papers

Redox-Switchable Copper(I) Metallogel: A Metal–Organic Material for Selective and Naked-Eye Sensing of Picric Acid

Hierarchically Structured Fullerene C70 Cube for Sensing Volatile Aromatic Solvent Vapors

Supramolecular assembly of melamine and its derivatives: nanostructures to functional materials

Graphene quantum dots from a facile sono-Fenton reaction and its hybrid with a polythiophene graft copolymer toward photovoltaic application.

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