Intermolecular And Surface Forces

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

Carbon nanotubes and graphene are some of the most intensively explored carbon allotropes in materials science. This interest mainly resides in their unique properties with electrical conductivities as high as 104 S cm−1, thermal conductivities as high as 5000 W m−1 K and superior mechanical properties with elastic moduli on the order of 1 TPa for both of them. The possibility to translate the individual properties of these monodimensional (e.g. carbon nanotubes) and bidimensional (e.g. graphene) building units into two-dimensional free-standing thick and thin films has paved the way for using these allotropes in a number of applications (including photocatalysis, electrochemistry, electronics and optoelectronics, among others) as well as for the preparation of biological and chemical sensors. More recently and while recognizing the tremendous interest of these two-dimensional structures, researchers are noticing that the performance of certain devices can experience a significant enhancement by the use of three-dimensional architectures and/or aerogels because of the increase of active material per projected area. This is obviously the case as long as the nanometre-sized building units remain accessible so that the concept of hierarchical three-dimensional organization is critical to guarantee the mass transport and, as consequence, performance enhancement. Thus, this review aims to describe the different synthetic processes used for preparation of these three-dimensional architectures and/or aerogels containing either any or both allotropes, and the different fields of application in which the particular structure of these materials provided a significant enhancement in the efficacy as compared to their two-dimensional analogues or even opened the path to novel applications. The unprecedented compilation of information from both CNT- and graphene-based three-dimensional architectures and/or aerogels in a single revision is also of interest because it allows a straightforward comparison between the particular features provided by each allotrope.

Three dimensional macroporous architectures and aerogels built of carbon nanotubes and/or graphene: synthesis and applications

The classical Poisson-Boltzmann (PB) theory of electrolytes assumes a dilute solution of point charges with mean-field electrostatic forces. Even for very dilute solutions, however, it predicts absurdly large ion concentrations (exceeding close packing) for surface potentials of only a few tenths of a volt, which are often exceeded, e.g. in microfluidic pumps and electrochemical sensors. Since the 1950s, several modifications of the PB equation have been proposed to account for the finite size of ions in equilibrium, but in this two-part series, we consider steric effects on diffuse charge dynamics (in the absence of electro-osmotic flow). In this first part, we review the literature and analyze two simple models for the charging of a thin double layer, which must form a condensed layer of close-packed ions near the surface at high voltage. A surprising prediction is that the differential capacitance typically varies non-monotonically with the applied voltage, and thus so does the response time of an electrolytic system. In PB theory, the capacitance blows up exponentially with voltage, but steric effects actually cause it to decrease above a threshold voltage where ions become crowded near the surface. Other nonlinear effects in PB theory are also strongly suppressed by steric effects: The net salt adsorption by the double layers in response to the applied voltage is greatly reduced, and so is the tangential "surface conduction" in the diffuse layer, to the point that it can often be neglected compared to bulk conduction (small Dukhin number).

Steric effects in the dynamics of electrolytes at large applied voltages: I. Double-layer charging

This review discusses one-dimensional supramolecular polymers that form in aqueous media. First, naturally occurring supramolecular polymers are described, in particular, amyloid fibrils, actin filaments, and microtubules. Their structural, thermodynamic, kinetic, and nanomechanical properties are highlighted, as well as their importance for the advancement of biologically inspired supramolecular polymer materials. Second, five classes of synthetic supramolecular polymers are described: systems based on (1) hydrogen-bond motifs, (2) large π-conjugated surfaces, (3) host–guest interactions, (4) peptides, and (5) DNA. We focus on recent studies that address key challenges in the field, providing mechanistic understanding, rational polymer design, important functionality, robustness, or unusual thermodynamic and kinetic properties.

Supramolecular Polymers in Aqueous Media

Integration into a soft material of all the molecular components necessary to generate storable fuels is an interesting target in supramolecular chemistry. The concept is inspired by the internal structure of photosynthetic organelles, such as plant chloroplasts, which colocalize molecules involved in light absorption, charge transport and catalysis to create chemical bonds using light energy. We report here on the light-driven production of hydrogen inside a hydrogel scaffold built by the supramolecular self-assembly of a perylene monoimide amphiphile. The charged ribbons formed can electrostatically attract a nickel-based catalyst, and electrolyte screening promotes gelation. We found the emergent phenomenon that screening by the catalyst or the electrolytes led to two-dimensional crystallization of the chromophore assemblies and enhanced the electronic coupling among the molecules. Photocatalytic production of hydrogen is observed in the three-dimensional environment of the hydrogel scaffold and the material is easily placed on surfaces or in the pores of solid supports.

/pdf/self-assembling-hydrogel-scaffolds-for-photocatalytic-3b6fo62jia.pdf

Self-assembling hydrogel scaffolds for photocatalytic hydrogen production.

The remarkable electronic properties of graphene and related two-dimensional (2D) materials result from the confinement of electrons within the material. Similarly, the interstitial space between 2D materials can enable the 2D confinement of ions and electrolytes and alter their transport. Many different 2D sheets can be obtained by exfoliation of natural layered materials ( 1 ), and an exfoliation-reconstruction strategy can convert powders of layered materials into continuous, robust bulk forms in which lamellar nanochannels occupy a substantial volume fraction (up to several tens of percent). Nanofluidics, which enables the manipulation of confined ions and electrolytes, has applications in electrochemical energy conversion and storage, biosensing, and water purification.

http://science.sciencemag.org/content/sci/351/6280/1395.full.pdf

Two-dimensional nanofluidics

Exfoliated two-dimensional (2D) sheets can readily stack to form flexible, free-standing films with lamellar microstructure. The interlayer spaces in such lamellar films form a percolated network of molecularly sized, 2D nanochannels that could be used to regulate molecular transport. Here we report self-assembled clay-based 2D nanofluidic channels with surface charge-governed proton conductivity. Proton conductivity of these 2D channels exceeds that of acid solution for concentrations up to 0.1 M, and remains stable as the reservoir concentration is varied by orders of magnitude. Proton transport occurs through a Grotthuss mechanism, with activation energy and mobility of 0.19 eV and 1.2 × 10(-3) cm(2) V(-1) s(-1), respectively. Vermiculite nanochannels exhibit extraordinary thermal stability, maintaining their proton conduction functions even after annealing at 500 °C in air. The ease of constructing massive arrays of stable 2D nanochannels without lithography should prove useful to the study of confined ionic transport, and will enable new ionic device designs.

/pdf/self-assembled-two-dimensional-nanofluidic-proton-channels-3zaio1wea3.pdf

Self-assembled two-dimensional nanofluidic proton channels with high thermal stability

Ultrafine particles are often used as lubricant additives because they are capable of entering tribological contacts to reduce friction and protect surfaces from wear. They tend to be more stable than molecular additives under high thermal and mechanical stresses during rubbing. It is highly desirable for these particles to remain well dispersed in oil without relying on molecular ligands. Borrowing from the analogy that pieces of paper that are crumpled do not readily stick to each other (unlike flat sheets), we expect that ultrafine particles resembling miniaturized crumpled paper balls should self-disperse in oil and could act like nanoscale ball bearings to reduce friction and wear. Here we report the use of crumpled graphene balls as a high-performance additive that can significantly improve the lubrication properties of polyalphaolefin base oil. The tribological performance of crumpled graphene balls is only weakly dependent on their concentration in oil and readily exceeds that of other carbon additives such as graphite, reduced graphene oxide, and carbon black. Notably, polyalphaolefin base oil with only 0.01-0.1 wt % of crumpled graphene balls outperforms a fully formulated commercial lubricant in terms of friction and wear reduction.

https://www.pnas.org/content/pnas/113/6/1528.full.pdf

Self-dispersed crumpled graphene balls in oil for friction and wear reduction.

Light harvesting supramolecular assemblies are potentially useful structures as components of solar-to-fuel conversion materials. The development of these functional constructs requires an understanding of optimal packing modes for chromophores. We investigated here assembly in water and the photocatalytic function of perylene monoimide chromophore amphiphiles with different alkyl linker lengths separating their hydrophobic core and the hydrophilic carboxylate headgroup. We found that these chromophore amphiphiles (CAs) self-assemble into charged nanostructures of increasing aspect ratio as the linker length is increased. The addition of salt to screen the charged nanostructures induced the formation of hydrogels and led to internal crystallization within some of the nanostructures. For linker lengths up to seven methylenes, the CAs were found to pack into 2D crystalline unit cells within ribbon-shaped nanostructures, whereas the nine methylene CAs assembled into long nanofibers without crystalline molecular packing. At the same time, the different molecular packing arrangements after charge screening led to different absorbance spectra, despite the identical electronic properties of all PMI amphiphiles. While the crystalline CAs formed electronically coupled H-aggregates, only CAs with intermediate linker lengths showed evidence of high intermolecular orbital overlap. Photocatalytic hydrogen production using a nickel-based catalyst was observed in all hydrogels, with the highest turnovers observed for CA gels having intermediate linker lengths. We conclude that the improved photocatalytic performance of the hydrogels formed by supramolecular assemblies of the intermediate linker CA molecules likely arises from improved exciton splitting efficiencies due to their higher orbital overlap.

/pdf/supramolecular-packing-controls-h2-photocatalysis-in-31n025va7s.pdf

Andrew R. Koltonow

Papers

Self-assembling hydrogel scaffolds for photocatalytic hydrogen production.

Two-dimensional nanofluidics

Self-assembled two-dimensional nanofluidic proton channels with high thermal stability

Self-dispersed crumpled graphene balls in oil for friction and wear reduction.

Supramolecular Packing Controls H2 Photocatalysis in Chromophore Amphiphile Hydrogels