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The diffusion of polystyrene (PS) polymer chains from a hydroxy (-OH)-terminated Si surface with different grafting densities φG is studied based on all-atom simulation. Our particular attention is paid to the impact of the attractive substrate on the diffusive and configurational properties of PS. Our simulation results uncover a very novel and unexpected modification to polymer diffusion with the increment of φG, namely, the diffusion is slowed down most significantly from a substrate with moderate grafting densities, while in lower or full grafting cases, the diffusive dynamics is even facilitated rather than retarded. The underlying mechanism is investigated in terms of energy and conformational change in detail. Surprisingly, we obtain a consistent scenario for diffusion. Under moderate grafting densities, the energy required to be overcome for diffusion is relatively large. In addition, PS chains are more likely to be in a stretched configuration subject to a slower relaxation. These facts can account for the hindered diffusion. While under lower or full grafting densities, the energy required for diffusion becomes even smaller than the ungrafted situation. Also, PS chains prefer a shrinking configuration undergoing faster relaxation. Consequently, the diffusion of PS is reasonably promoted.

The mechanism of the hetero-Diels-Alder reaction of butadiene with benzaldehyde catalyzed by chiral N,NЈ-dioxide/ In(OTf) 3 complexes was studied theoretically by using density functional theory (DFT) and model system. The computational results indicate that the catalyzed reaction proceeded through a concerted mechanism via a highly zwitterionic transition state. The lowest energy barrier was 11.8 kJ mol -1 , which is 63.0 kJ mol -1 lower than that of the uncatalyzed reaction. The results indicate that the endo approach is advantageous over the exo approach, because exo transitions states suffer from more steric hindrance than the endo transitions states as a result of interactions among the substrates,

A theoretical framework based on a generalized Langevin equation with fractional Gaussian noise is presented to describe the looping kinetics of chains in polymer solutions. Particular attention is paid to quantitatively revealing crowding effects on the loop formation rate in terms of microviscosity and collapse. By the aid of empirical relations for these two crowding associated physical quantities, we explicitly investigate the relationship between the looping rate and polymer concentration, the degree of polymerization, and system parameters. According to our analysis, the dependence of the looping rate on the crowder volume fraction exhibits three typical regimes: monotonic decreasing, a non-monotonic trend and monotonic increasing. We reveal that these non-trivial behaviors can be attributed to the competition between the two opposing factors of viscosity-associated inhibition and collapse-induced facilitation of loop formation. We apply our theory to analyze the kinetics of single-stranded DNA hairpin base pairing in polyethylene glycol solutions. The theoretical results can reproduce the experimental data on the closing rate of hairpins quantitatively to a certain degree with reasonable fitting parameters. The unexpected increase of the closing rate upon the addition of increasing amounts of polymer is well rationalised. Such good agreements clearly demonstrate the validity of our theory, appropriately addressing the very role of crowding effects in the relevant kinetics.