CCSD(T) study on the structures and chemical bonds of AnO molecules (An = Bk–Lr)

The molecular geometries and dissociation energies of AnO (An = Bk–Lr) molecules were first obtained at thecoupled-cluster single-, double-, and perturbative triple-excitations [CCSD(T)] level of theory. Four hybrid functionals,B3LYP, M06-2X, TPSSh, and PBE0, were also employed in the calculations for the sake of comparison. In comparison ofthe CCSD(T) results, B3LYP, TPSSh, and PBE0 functionals can obtain more appropriate results than M06-2X and MP2.The analyses on molecular orbitals show that the 7s, 6d, and 5f atomic orbitals of actinide (An) atoms participate in thebonding of An–O bonds. The partial covalent nature between An and O atoms is revealed by QTAIM analyses.     

Distribution dependent stochastic differential equations

Due to their intrinsic link with nonlinear Fokker-Planck equations and many other applications, distribution dependent stochastic differential equations (DDSDEs) have been intensively investigated. In this paper, we summarize some recent progresses in the study of DDSDEs, which include the correspondence of weak solutions and nonlinear Fokker-Planck equations, the well-posedness, regularity estimates, exponential ergodicity, long time large deviations, and comparison theorems.     

Virtual Field Characterization for Ratcheting Effect Under Cyclic Loading

Experimental Mechanics - Ratcheting is an important mechanical behavior of metals and alloys, which is caused by the repeated accumulations of tensile and compressive strain in circle load....     

富晶格位错的多孔铋纳米花高效电还原二氧化碳制甲酸盐※

二氧化碳转化已成为现今世界研究的热点. 本工作采用原位电化学转化的策略, 将简单溶剂热法合成的层状甲酸氧铋纳米花(BiOCOOH NFs)还原为带有大量晶格位错的多孔铋纳米花(p-Bi NFs). 研究结果表明, p-Bi NFs电催化二氧化碳转化为甲酸盐具有较小的过电位(436 mV). 在–1.8 V(相对饱和甘汞电极, vs. SCE)时, 甲酸盐的分电流密度(j_formate)高达24.4 mA•cm^-2, 法拉第效率(FE_formate)为96.7%, 且在超过500 mV的宽电位窗口内FE_formate超过90%, 并具有很好的稳定性. 该催化剂的高催化性能可归因于前驱体晶格坍塌和重构而形成特殊的多孔粗糙的微纳多级结构, 其表面富含晶格位错和缺陷等高本征活性位, 且具有较强的电子传递能力. 本研究为设计合成高性能的电催化二氧化碳还原产甲酸催化剂提供了新的思路.     

The Synergistic Photocatalytic Effect of H3PW12O40 and Pt Nanoparticles Comodified UiO-66-NH2 on the Reduction of Aqueous Cr(VI) under Original pH

Kinetics and Catalysis - A ternary synergistic photocatalyst H3PW12O40/Pt/UiO-66-NH2 was successfully fabricated for the first time through a simple solvothermal synthetic strategy. We found that...     

High-efficient surface tailoring via reverse atom transfer radical polymerization and reversible addition-fragmentation chain-transfer polymerization in an aqueous system initiated by a monocenter redox pair

The commonly used multi-center initiation methods always lead to the formation of quantities of homopolymer in the surface tailoring based on reverse atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. In this study, a monocenter redox pair constructed of silica bearing tert-butyl hydroperoxide groups and ascorbic acid (SiO₂-TBHP/AsAc) was applied to substitute the commonly used initiation method of R-supported RAFT grafting polymerization. All the propagating radicals were restricted on the surface of solid particles during the whole procedure theoretically, resulting in a higher grafting efficiency of 95.1% combined with the “controllable” feature at 10 h. This redox pair was also used to initiate the reverse ATRP in miniemulsion successfully with a grafting efficiency of 86.3% at 10 h. The grafting efficiency obtained under this monocenter initiation method was significantly higher than that of the frequently reported surface modification by reverse ATRP and RAFT polymerization. In addition, the high-efficient surface tailoring was traced and confirmed by nuclear magnetic resonance, Fourier transform infrared, X-ray photoelectron spectroscopy, thermogravimetric analysis, transmission electron microscopy, and other analysis tests. The advantage of this monocenter redox pair will open a new avenue for the potential “high-efficient” surface tailoring of various materials.     

Characterization of diterpene metabolism in rats with ingestion of seed products from Euphorbia lathyris L. (Semen Euphorbiae and Semen Euphorbiae Pulveratum) using UHPLC-Q-Exactive MS

Previous pharmacological studies have indicated that diterpenoids are the primary effective chemical cluster in the seeds of Euphorbia lathyris L. The seed products are used in traditional Chinese medicine in the forms of Semen Euphorbiae (SE) and Semen Euphorbiae Pulveratum (SEP). However, the metabolism of the plant's diterpenoids has not been well elucidated, which means that the in vivo metabolite products have not been identified. The current study screened the physiological metabolites of six diterpenes [Euphorbia factor L₁ (L1), L₂ (L2), L₃ (L3), L_7a (L7a), L_7b (L7b), and L₈ (L8)] in feces and urine of rats after oral administration of SE and SEP using UHPLC-Q-Exactive MS. A total of 22 metabolites were detected in feces and 8 in urine, indicating that the major elimination route of diterpenoids is via the colon. Hydrolysis, methylation, and glucuronidation served as the primary metabolic pathways of these diterpenoids. In sum, this study contributed to the elucidation of new metabolites and metabolic pathways of SE and SEP, and the new chemical identities can be used to guide further pharmacokinetic studies.     

Chemical Composition and Antifungal Activity of Essential Oil from the Roots of Tinomiscium petiolare

Chemistry of Natural Compounds -     

Injectable Micromotor@Hydrogel System for Antibacterial Therapy

The drug delivery system based on nano/micromotors has become a research hot spot in recent years. However, naked micromotors may be ruptured or passivated under the complex biological environment, which will result in the leakage of drugs in advance or limited self-propulsion performance. Herein, an injectable micromotor@hydrogel drug delivery system to protect micromotors from the external environment is proposed. The micromotors were prepared through layer-by-layer assembly technology. The asymmetric decomposition of hydrogen peroxide catalyzed by the locally distributed platinum nanoparticles enabled efficient propulsion of the micromotors in low concentration of hydrogen peroxide. In order to protect micromotors, they were loaded into the Schiff base hydrogel. The micromotor@hydrogel system can be injected directly into the lesion to release micromotors in response to the environment, reducing external influence on micromotors and improving the sustained-release effect. Erythromycin (Ery) loaded into the micromotors and the micromotor@hydrogel system demonstrated excellent antibacterial effect. Micromotors released from the hydrogel underwent enhanced diffusion in the surroundings of bacteria without addition of exogenous hydrogen peroxide, which was manifested by their appearance in edge of the inhibition zone. The proposed micromotor@hydrogel drug delivery system offers a new strategy for the treatment of bacterial infections.     

Bicomponent Cocatalyst Decoration on Flux-assisted CaTaO2N Single Crystals for Photocatalytic CO2 Reduction under Visible Light

Cubic-like CaTaO₂N photocatalysts with high crystallinity and uniform particle size were successfully prepared by the flux-assisted nitridation method. The growth of CaTaO₂N single crystals under different synthesis conditions was systematically investigated to understand the effects of the crystallinity and optical property on photocatalytic performance of CO₂ reduction. Moreover, the modification of CaTaO₂N single crystals with core-shell Ni−Ag bicomponent cocatalyst by two-step decoration process gave a 2.4 times higher amount of CO evolution than the deposition of sole Ag cocatalyst, because of the synergistic effects of bicomponent cocatalyst on the interfacial electron transfer and surface catalytic process. This study provides a valuable way to construct high-crystalline photocatalysts with effective bicomponent cocatalyst for visible-light-driven CO₂ reduction with H₂O.