We report a single-molecule mechanistic investigation into 2-cyanobenzothiazole (CBT) chemistry within a protein nanoreactor. When simple thiols reacted reversibly with CBT, the thioimidate monoadduct was approximately 80-fold longer-lived than the tetrahedral bisadduct, with important implications for the design of molecular walkers. Irreversible condensation between CBT derivatives and N-terminal cysteine residues has been established as a biocompatible reaction for site-selective biomolecular labeling and imaging. During the reaction between CBT and aminothiols, we resolved two transient intermediates, the thioimidate and the cyclic precursor of the thiazoline product, and determined the rate constants associated with the stepwise condensation, thereby providing critical information for a variety of applications, including the covalent inhibition of protein targets and dynamic combinatorial chemistry. 相似文献
Metal azides have attracted increasing attention as precursors for synthesizing polymeric nitrogen. In this article, we report the amorphous polymerization of nitrogen by compressing cupric azide. The ab initio molecular dynamics simulations show that crystalline cupric azide transforms into a disordered network composed of singly bonded nitrogen at a hydrostatic pressure of 40 GPa and room temperature. The transformation manifests the formation of a π delocalization along the disordered Cu-N network, thus resulting in a semiconductor–metal transition. The estimated heat of formation of the amorphous polymeric nitrogen system is comparable to conventional high-energy-density materials. The amorphization provides an alternative route to the polymerization of nitrogen under moderate conditions. 相似文献
In this paper, a single reaction-diffusion population model with memory effect and the heterogeneity of the environment, equipped with the Neumann boundary, is considered. The global existence of a spatial nonhomogeneous steady state is proved by the method of super and subsolutions, which is linearly stable for relatively small memory-induced diffusion. However, after the memory-induced diffusion rate exceeding a critical value, spatial inhomogeneous periodic solution can be generated through Hopf bifurcation, if the integral of intrinsic growth rate over the domain is negative. Such phenomenon will never happen, if only memory-induced diffusion or spatially heterogeneity is presented, and therefore must be induced by their joint effects. This indicates that the memory-induced diffusion will bring about spatial-temporal patterns in the overall hostile environment. When the integral of intrinsic growth rate over the domain is positive, it turns out that the steady state is still linearly stable. Finally, the possible dynamics of the model is also discussed, if the boundary condition is replaced by Dirichlet condition.
