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91.
92.
Thermal- and light-driven diselenide metathesis reactions with different types of diselenides are investigated systematically. Their exchange reaction rates and equilibrium conversions are compared in the aspects of the different diselenide structures, activation conditions and solvents. As a result, the metathesis reactions between diselenide small molecules are demonstrated with high dynamic and sensitive features, which can be broadly tuned by varying the electron affinity and aromaticity of the diselenide substituents and external conditions(e.g., solvent, stimulus mode). The current work thus will not only advance our understanding on diselenide metathesis chemistry, but also promote concrete and impactful studies in selenium-containing materials. 相似文献
93.
The purpose of this paper is to fabricate novel nanoparticles (NPs) from a single disulfide bond-bridged block copolymer poly(hydroxyethyl methacrylate)-S-S-polycaprolactone (PHEMA-S-S-PCL). The novel biomaterial was synthesized by ring-opening polymerization and reversible addition–fragmentation chain transfer polymerization. The cargo-free NPs were fabricated with the solvent evaporation method, and studies on NPs' characterizations were carried out. The hydrogen nuclear magnetic resonance (1H NMR) and Fourier transform infrared spectroscopy spectra confirmed the synthesis of PHEMA-S-S-PCL copolymer. Thermo-gravimetric analysis curves indicated that the obtained PHEMA-S-S-PCL copolymer had good thermostability. Transmission electron microscopy and dynamic light scatter results suggested that the cargo-free NPs were in round shapes with an average diameter of 103.6 ± 0.12 nm. The low critical micelle concentration of cargo-free NPs (7.9 × 10?4 mg/ml) indicated that these NPs would keep their spherical shapes after being attenuated by abundant liquid (e.g., blood or body fluid). Furthermore, these NPs showed high stability at the presence of bovine serum albumin. Therefore, it could be speculated that these NPs would not be absorbed by proteins in blood, and they could be used as a candidate carrier for drug delivery. 相似文献
94.
Delocalized \begin{document}$\pi_3^6$\end{document} Bond in OX\begin{document}$_2$\end{document} (X=Halogen) Molecules 下载免费PDF全文
Yi-han Tang Pu Yang Meng-yuan Chen Yu-ru Wang Jia-xin Wang Jia-wei Xu 《化学物理学报(中文版)》2022,35(3):542-550
OX\begin{document}$_2$\end{document} (X=halogen) molecules was studied theoretically. Calculation results show that delocalized \begin{document}$\pi_3^6$\end{document} bonds exist in their electronic structures and O atoms adopt the sp\begin{document}$^2$\end{document} type of hybridization, which violates the prediction of the valence shell electron pair repulsion theory of sp\begin{document}$^3$\end{document} type. Delocalization stabilization energy is proposed to measure the contribution of delocalized \begin{document}$\pi_3^6$\end{document} bond to energy decrease and proves to bring extra-stability to the molecule. These phenomena can be summarized as a kind of coordinating effect. 相似文献
95.
A Mechanistic Switch in C-H Bond Activation by Elusive Fe\begin{document}$^\text{V}$\end{document} (O)(TAML) Reaction Intermediate: A Theoretical Study 下载免费PDF全文
The divergent behavior of C-H bond oxidations of aliphatic substrates compared to those of aromatic substrates shown in Gupta's experiment was mechanistically studied herein by means of density functional theory calculations. Our calculations reveal that such difference is caused by different reaction mechanisms between two kinds of substrates (the aliphatic cyclohexane, 2, 3-dimethylbutane and the aromatic toluene, ethylbenzene and cumene). For the aliphatic substrates, C-H oxidation by the oxidant Fe\begin{document}$^{\rm{V}}$\end{document} (O)(TAML) is a hydrogen atom transfer process; whereas for the aromatic substrates, C-H oxidation is a proton-coupled electron transfer (PCET) process with a proton transfer character on the transition state, that is, a proton-coupled electron transfer process holding a proton transfer-like transition state (PCET(PT)). This difference is caused by the strong \begin{document}$\pi$\end{document} -\begin{document}$\pi$\end{document} interactions between the tetra-anionic TAML ring and the phenyl ring of the aromatic substrates, which has a "pull" effect to make the electron transfer from substrates to the Fe=O moiety inefficient. 相似文献
96.
过渡金属催化的碳氢官能团化反应具有原子经济性高、区域选择性好和合成路线简短等优点,近年来得到了化学家们的广泛关注,是当前有机合成化学的热门研究领域之一。近几年来,稀土金属催化剂也逐渐被开发应用于该领域,得到优异的结果,同时也表现出一些独特的催化活性。本文综述了稀土金属络合物催化的碳氢官能团化反应,主要包括C-H烷基化反应以及C-Hβ-胺烷基化反应,这些反应为C-C键的构筑提供了新方法。同时本文也针对该领域目前存在的挑战,对未来的研究工作做了展望。 相似文献
97.
Neel Sisodia Monica Miranda Kay L. McGuinness Jay D. Wadhawan Nathan S. Lawrence 《Electroanalysis》2021,33(3):559-562
This work presents the electrochemical response of a 2-(methylthio)phenol glassy carbon based electrode for a promising voltammetric pH sensor in both buffered and low-buffered solutions. Electropolymerization of the redox species was performed with the resulting polymer presenting a Nernstian response in buffered media, with a sensitivity of 51 mV/pH unit. The effectiveness of the sulfhydryl bond to facilitate proton transfer from the bulk solution to the phenol molecules has been confirmed, providing an accurate pH measurement of 8.28 in sea water media, compared to that measured with a calibrated glass pH probe of 8.30. 相似文献
98.
在大学本科一二年级的物理化学教学中,化学动力学章节的学习涉及到对不同时间尺度的认识。本文利用过渡态理论得到的速率常数表达公式,以乙烷分子碳/碳单键旋转和水分子氢键交换的动力学过程为例,对这2个应用实例的动力学过程所发生的时间尺度做出估算。这些时间尺度的估算对于学生理解不同动力学过程的物理图像至关重要,同时也有助于加强学生对重要公式的理解并能够将这些公式在化学体系中灵活运用。 相似文献
99.
Two reduction-cleavable ABA triblock copolymers possessing two disulfide linkages, PMMA-ss-PMEO3MA-ss-PMMA and PDEA-ss-PEO-ss-PDEA were synthesized via facile substitution reactions from homopolymer precursors, where PMMA, PMEO3MA, PDEA, and PEO represent poly(methyl methacrylate), poly(tri(ethylene glycol) monomethyl ether methacrylate, poly(2-(diethylamino)ethyl methacrylate), and poly(ethylene oxide), respectively. Spherical micelles were obtained through supramolecular self-assembly of these two triblock copolymers in aqueous solutions. The resultant micelles with abundant disulfide bonds could serve as soft templates and precisely accommodate gold nanoparticles in the core/shell interface as a result of the formation of Au-S bonds. 相似文献
100.