A multi-scale framework for predicting α-cyclodextrin assembly on polyethylene glycol axles.

Controlling the distribution of rings on polymer axles, such as α-cyclodextrin (αCD) on polyethylene glycol (PEG), is paramount in imparting robust mechanical properties to slide-ring gels and polyrotaxane-based networks. Previous experiments demonstrated that the functionalization of polymer ends could modulate the coverage of αCDs on PEG. To explore the design rule, we propose a multi-scale framework for predicting αCD assembly on bare and functionalized PEG.

Kinetics and Thermodynamics of Reactions Involving Criegee Intermediates: An Assessment of Density Functional Theory and Ab Initio Methods Through Comparison with CCSDT(Q)/CBS Data.

Reactions involving Criegee intermediates (CIs, R R COO) are important in atmospheric ozonolysis models. In recent years, density functional theory (DFT) and CCSD(T)-based ab initio methods are increasingly being used for modeling reaction profiles involving CIs. We obtain highly accurate CCSDT(Q)/CBS reaction energies and barrier heights for ring-closing reactions involving atmospherically important CIs (R /R = H, Me, OH, OMe, F, CN, cyclopropene, ethylene, acetaldehyde, and acrolein).