To analyze the H/D isotope effect on porphine and porphycene molecules including the protonic/deuteronic quantum nature and electron correlation efficiently, the authors have developed the new scheme of the multicomponent hybrid density functional theory [MC_(HF+DFT)]. The optimized geometries of porphine, porphycene, and these deuterated isotopomers by our MC_(HF+DFT) method are in good agreement with the experimental "high-symmetric" structures, contrary to the "low-symmetric" geometries optimized by pure multicomponent Hartree-Fock method. The optimized geometries for HD-porphine and HD-porphycene molecules, in which an inner hydrogen is replaced to a deuterium, are found to be low symmetric. Such drastic geometrical change induces the electronic polarization, and gives rise to the slight dipole moment values in these HD species. Their results clearly indicate that the difference of the nuclear quantum nature between inner proton and inner deuteron directly influences the molecular geometry and electronic structure.
Self-healing materials are highly desirable because they allow products to maintain their performance. Typical stimuli used for self-healing are heat and light, despite being unsuitable for materials used in certain products as heat can damage other components, and light cannot reach materials located within a product or device. To address these issues, here we show a gas-plastic elastomer with an ionically crosslinked silicone network that quickly self-heals damage in the presence of CO
2
gas at normal pressures and room temperature. While a strong elastomer generally exhibits slow self-healing properties, CO
2
effectively softened ionic crosslinks in the proposed elastomer, and network rearrangement was promoted. Consequently, self-healing was dramatically accelerated by ~10-fold. Moreover, self-healing was achieved even at −20 °C in the presence of CO
2
and the original mechanical strength was quickly re-established during the exchange of CO
2
with air.
Sialic acid is a sugar residue present in many biologically significant glycans of mammals, commonly as a terminal α-glycoside. The chemical structure of sialic acid, which features an anomeric center with carboxyl and methylene substituents, poses a challenge for synthesis of the α-glycoside, thus impeding biological and therapeutic studies on sialic acid–containing glycans. We present a robust method for the selective α-glycosidation of sialic acid using macrobicyclized sialic acid donors as synthetic equivalents of structurally constrained oxocarbenium ions to impart stereoselectivity. We demonstrate the power of our method by showcasing broad substrate scope and applicability in the preparation of diverse sialic acid–containing architectures.
The geometric isotope effect (GIE) of sp- (acetylene-water), sp(2)- (ethylene-water), and sp(3)- (methane-water) hybridized intermolecular C-H...O and C-D...O hydrogen bonds has been analyzed at the HF/6-31++G level by using the multicomponent molecular orbital method, which directly takes account of the quantum effect of proton/deuteron. In the acetylene-water case, the elongation of C-H length due to the formation of the hydrogen bond is found to be greater than that of C-D. In contrast to sp-type, the contraction of C-H length in methane-water is smaller than that of C-D. After the formation of hydrogen bonds, the C-H length itself in all complexes is longer than C-D and the H...O distance is shorter than D...O, similar to the GIE of conventional hydrogen bonds. Furthermore, the exponent (alpha) value is decreased with the formation of the hydrogen bond, which indicates the stabilization of intermolecular C-H...O hydrogen bonds as well as conventional hydrogen bonds. In addition, the geometric difference induced by the H/D isotope effect of the intramolecular C-H...O hydrogen bond shows the same tendency as that of intermolecular C-H...O. Our study clearly demonstrates that C-H...O hydrogen bonds can be categorized as typical hydrogen bonds from the viewpoint of GIE, irrespective of the hybridizing state of carbon and inter- or intramolecular hydrogen bond.
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