Pentaerithrityl Tetranitrate

In this work, we present simulations of the optical rotation (OR) for five molecular crystals at density functional theory level with periodic boundary conditions (DFT‐PBC). Calculations are compared with experimental measurements and show semi‐quantitative agreement with experimental data for three of the crystals: tartatic acid, benzil, and pentaerythritol. For the other two crystals, aspartic acid and glutamic acid, the calculated data are in qualitative agreement with, but two orders of magnitude smaller than, the experimental data. We provide some arguments that support the theoretical predictions and suggest that the experiments should be revisited. We also find that the position of H centers provided in experimental X‐ray data is not sufficiently reliable for simulating OR, and better results are obtained when H atoms are allowed to relax while keeping heavier elements fixed at the experimental positions. Comparison with molecular cluster calculations with a better functional and a larger basis set indicate that the role of intermolecular interactions (reproduced with the PBC technique) is as or more important than the choice of model chemistry. Despite the current limitations in the level of theory that can be employed, these simulations provide a promising avenue to investigate the effect of intermolecular interactions on this sensitive electronic property of molecules and materials.

Hierarchically porous monoliths with satisfactory properties have been employed in diverse fields, especially separation. In this study, pentafluorophenyl acrylate (PFPA), pentaerythritol tetraacrylate (PETA) and trimethylolpropane tris(3-mercaptopropionate) (TTMP) were selected as precursors to fabricate a novel monolithic column by thermally initiated polymerization in the presence of a binary porogenic system containing tetrahydrofuran and 1-propanol. The fabricated poly(PFPA-co-PETA-co-TTMP) monolithic column revealed excellent permeability and mechanical stability. Additionally, baseline separation of the mixture of small molecules can be achieved, involving alkylbenzene and fluorobenzene in chromatographic assessment, and the theoretical plate number is up to 60,500 plates/m for butylbenzene with a linear velocity of 0.14 mm/s. Tryptic digest of HeLa as an analyte was used to investigate the possibility of the poly(PFPA-co-PETA-co-TTMP) monolith in biological separation by cLC-MS/MS. Moreover, benefiting from the existence of pentafluorophenyl groups, the cucurbit[8]uril (CB[8]) could be modified on the prepared poly(PFPA-co-PETA-co-TTMP) monolith through host-guest interaction to obtain poly(PFPA-co-PETA-co-TTMP)-CB[8] monolith. It could be observed that significant changes in retention behavior of analytes appeared after immobilizing CB[8] on the monolith. It offered an innovative approach by utilizing host-guest interaction to fabricate monolithic columns with different chromatographic behaviors.