Lattice density functional theory of molecular diffusion

A density functional theory of diffusion is developed for lattice fluids with molecular flux as a functional of the density distribution. The formalism coincides exactly with the generalized Ono-Kondo density functional theory when there is no gradient of chemical potential, i.e., at equilibrium. Away from equilibrium, it gives Fick's first law in the absence of a potential energy gradient, and it departs from Fickian behavior consistently with the Maxwell-Stefan formulation. The theory is applied to model a nanopore, predicting nonequilibrium phase transitions and the role of surface diffusion in the transport of capillary condensate.     

Adsorption behavior of repulsive molecules

Recently, it has been shown that adsorption of gases on solid surfaces often leads to repulsive forces between adsorbate molecules. In this paper, adsorption of molecules on a one-dimensional lattice is considered for repulsive interactions between adsorbate molecules. Exact adsorption isotherms are calculated and analyzed for finite and infinite chains of active sites (i.e., a one-dimensional lattice). Although the mathematical solution for the one-dimensional lattice is known for attractive and repulsive systems, the effects of intermolecular repulsions on adsorption behavior have not been studied in detail previously. Similarly, though the mathematics for the one-dimensional lattice has been solved for any arbitrary lattice length, the effect of finite size on adsorption isotherms for repulsive adsorbate interactions has never been examined. This paper shows that spatial confinement and strong attraction to active sites can cause compression of an adsorbed phase and that repulsive interactions between adsorbed molecules result in steps in the adsorption isotherms. For higher chemical potentials, the density increases until saturating at the lattice capacity. These steps in the adsorption isotherm have not been observed in previous studies of lattice systems. For small lattices, the adsorption behavior was found to be fundamentally different for even and odd values of lattice length. Lattices with an even number of lattice sites can have two steps in the adsorption isotherm, whereas systems with an odd number of sites only have a single step occurring at a coverage slightly greater than half the lattice capacity.     

Diffusion equation for interacting particles

A new approach to molecular diffusion is developed using density functionals for fluxes and the Metropolis algorithm in the mass balance equation. This procedure results in a new equation for diffusion of interacting particles which has multiple solutions and gives density distributions for coexisting and metastable phases. It is shown that the diffusion of interacting molecules is driven by two variables: the density gradient of molecules and the density of molecule-vacancy pairs ("pseudoparticles").     

Facile and efficient Lewis acid catalyzed synthesis of an asymmetric tetrazine useful for bio-orthogonal click chemistry applications

Bio-orthogonal tetrazine click reactions have recently attracted significant interest for applications spanning biological imaging, cancer targeting, and biomaterials science. Here, we report a simple and efficient two-step scheme for the synthesis of an asymmetric tetrazine molecule containing a carboxylic acid handle for subsequent macromolecular conjugation. Yields as high as 75% were achieved using as little as 0.005 equiv of nickel triflate catalyst, which is a significant improvement over previous methodologies.