Understanding the pH-dependent behavior of graphene oxide (GO) aqueous solutions is important to the production of assembled GO or reduced GO films for electronic, optical, and biological applications. We have carried out a comparative experimental and molecular dynamics (MD) simulation study to uncover the mechanisms behind the aggregation and the surface activity of GO at different pH values. At low pH, the carboxyl groups are protonated such that the GO sheets become less hydrophilic and form aggregates. MD simulations further suggest that the aggregates exhibit a GO-water-GO sandwichlike structure and as a result are stable in water instead of precipitating. However, at high pH, the deprotonated carboxyl groups are very hydrophilic such that individual GO sheets prefer to dissolve in bulk water like a regular salt. The GO aggregates formed at low pH are found to be surface-active and do not exhibit characteristic features of surfactant micelles. Our findings suggest that GO does not behave like conventional surfactants in pH 1 and 14 aqueous solutions. The molecular-level understanding of the solution behavior of GO presented here can facilitate and improve the experimental techniques used to synthesize and sort large, uniform GO dispersions in a solution phase.

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Solution-processed hybrid organic-inorganic lead halide perovskites are emerging as one of the most promising candidates for low-cost light-emitting diodes (LEDs). However, due to a small exciton binding energy, it is not yet possible to achieve an efficient electroluminescence within the blue wavelength region at room temperature, as is necessary for full-spectrum light sources. Here, we demonstrate efficient blue LEDs based on the colloidal, quantum-confined 2D perovskites, with precisely controlled stacking down to one-unit-cell thickness (n = 1). A variety of low-k organic host compounds are used to disperse the 2D perovskites, effectively creating a matrix of the dielectric quantum wells, which significantly boosts the exciton binding energy by the dielectric confinement effect. Through the Förster resonance energy transfer, the excitons down-convert and recombine radiatively in the 2D perovskites. We report room-temperature pure green (n = 7-10), sky blue (n = 5), pure blue (n = 3), and deep blue (n = 1) electroluminescence, with record-high external quantum efficiencies in the green-to-blue wavelength region.

Understanding the solution-phase dispersion of pristine, unfunctionalized graphene is important for the production of conducting inks and top-down approaches to electronics. This process can also be used as a higher-quality alternative to chemical vapor deposition. We have developed a theoretical framework that utilizes molecular dynamics simulations and the kinetic theory of colloid aggregation to elucidate the mechanism of stabilization of liquid-phase-exfoliated graphene sheets in N-methylpyrrolidone (NMP), N,N'-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), and water. By calculating the potential of mean force between two solvated graphene sheets using molecular dynamics (MD) simulations, we have found that the dominant barrier hindering the aggregation of graphene is the last layer of confined solvent molecules between the graphene sheets, which results from the strong affinity of the solvent molecules for graphene. The origin of the energy barrier responsible for repelling the sheets is the steric repulsions between solvent molecules and graphene before the desorption of the confined single layer of solvent. We have formulated a kinetic theory of colloid aggregation to model the aggregation of graphene sheets in the liquid phase in order to predict the stability using the potential of mean force. With only one adjustable parameter, the average collision area, which can be estimated from experimental data, our theory can describe the experimentally observed degradation of the single-layer graphene fraction in NMP. We have used these results to rank the potential solvents according to their ability to disperse pristine, unfunctionalized graphene as follows: NMP ≈ DMSO > DMF > GBL > H(2)O. This is consistent with the widespread use of the first three solvents for this purpose.

Molecular recognition is central to the design of therapeutics, chemical catalysis and sensors. Motifs for doing so most commonly involve biological structures such as antibodies and aptamers. The key to such biological recognition consists of a folded and constrained heteropolymer that, via intra-molecular forces, forms a unique three dimensional structure that creates a binding pocket or an interface able to recognize a specific molecule. In this work, we demonstrate that synthetic heteropolymers can be alternatively constrained by adsorption around a nanoparticle, and specifically a single walled carbon nanotube (SWNT), forming a corona phase and resulting in a new form of molecular recognition of specific molecules. The phenomenon is shown to be generic, with new heteropolymer recognition complexes demonstrated for three distinct examples: Riboflavin, l-thyroxine, and estradiol, each predicted using a 2D thermodynamic model of surface interactions. The dissociation constants are continuously tunable by perturbing the chemical structure of the heteropolymer. Moreover, these complexes can be used as new types of spatial-temporal sensors based on modulation of SWNT photoemission in the near-infrared, as we show by tracking riboflavin diffusion in murine macrophages.