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11.
Yulong Kuang Hui Cao Haidi Tang Junhong Chew Wei Chen Xiangcheng Shi Jie Wu 《Chemical science》2020,11(33):8912
Deuterium labelled compounds are of significant importance in chemical mechanism investigations, mass spectrometric studies, diagnoses of drug metabolisms, and pharmaceutical discovery. Herein, we report an efficient hydrogen deuterium exchange reaction using deuterium oxide (D2O) as the deuterium source, enabled by merging a tetra-n-butylammonium decatungstate (TBADT) hydrogen atom transfer photocatalyst and a thiol catalyst under light irradiation at 390 nm. This deuteration protocol is effective with formyl C–H bonds and a wide range of hydridic C(sp3)–H bonds (e.g. α-oxy, α-thioxy, α-amino, benzylic, and unactivated tertiary C(sp3)–H bonds). It has been successfully applied to the high incorporation of deuterium in 38 feedstock chemicals, 15 pharmaceutical compounds, and 6 drug precursors. Sequential deuteration between formyl C–H bonds of aldehydes and other activated hydridic C(sp3)–H bonds can be achieved in a selective manner.A selective hydrogen deuterium exchange reaction with formyl C–H bonds and a wide range of hydridic C(sp3)–H bonds has been achieved by merging tetra-n-butylammonium decatungstate photocatalyst and a thiol catalyst under 390 nm light irradiation. 相似文献
12.
Peirong Chen Ly May Chew Aleksander Kostka Kunpeng Xie Martin Muhler Wei Xia 《Journal of Energy Chemistry》2013,22(2):312-320
Oxygen- and nitrogen-functionalized carbon nanotubes (OCNTs and NCNTs) were applied as metal-free catalysts in selective olefin hydrogenation. A series of NCNTs was synthesized by NH3 post-treatment of OCNTs. Temperature-programmed desorption, N2 physisorption, Raman spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the surface properties of OCNTs and NCNTs, aiming at a detailed analysis of the type and amount of oxygen- and nitrogen-containing groups as well as surface defects. The gas-phase treatments applied for oxygen and nitrogen functionalization at elevated temperatures up to 600 °C led to the increase of surface defects, but did not cause structural damages in the bulk. NCNTs showed a clearly higher activity than the pristine CNTs and OCNTs in the hydrogenation of 1,5-cyclooctadiene, and also the selectivity to cyclooctene was higher. The favorable catalytic properties are ascribed to the nitrogen-containing surface functional groups as well as surface defects related to nitrogen species. In contrast, oxygen-containing surface groups and the surface defects caused by oxygen species did not show clear contribution to the hydrogenation catalysis. 相似文献
13.
A convenient and sustainable synthesis of pyrazolo[1,5-a]quinazolin-5(4H)-ones and [1,2,4]triazolo[1,5-a]quinazolin-5(4H)-one through copper-catalyzed cascade reactions of 2-bromobenzoates with 1H-pyrazol-5-amines or 1H-1,2,4-triazol-5-amine under ligand-free conditions in water is presented. It is notable that aqueous medium turned out to be crucial for the chemoselective formation of the title compounds. Compared with literature protocols, this new method showed advantages such as simple and sustainable procedure, commercially available starting materials, and convenient reuse of the reaction medium together with the copper catalyst. 相似文献
14.
通过实验,采用荧光光谱法研究了对二甲氨基偶氮苯邻羧酸(JJR)与脱氧核糖核酸(DNA)结合反应的特征.由Stern-Volmer方程和双倒数曲线Lineweaver-Burk方程获得了反应的猝灭常数Ksv=1×106~2×106 L/mol、结合常数KA≈0.5×106 mol/L以及对猝灭的类型做出了推断.通过热力学参数、离子强度实验讨论并得到它们以氢键、嵌插入、范德华力等几种方式作用.该反应的最佳实验条件为pH值控制在6.1左右;加入顺序为JJR+DNA+(B-R)适宜反应体系;线性范围在0~100 mg/L之间. 相似文献
15.
16.
Bis(tert-butylperoxy)iodobenzene, generated in situ by the reaction between diacetoxyl iodobenzene (DIB) and tert-butyl hydroperoxide (TBHP), was used in the oxidative transformation of primary azides to nitriles, and secondary azides to ketones. 相似文献
17.
以细胞色素c(Cyt c)为碱性蛋白质模型,建立了毛细管电泳评价Cyt c与3种不同链长的单链脱氧核糖核酸(ssDNA)库相互作用的评价方法,研究了离子强度对Cyt c与ssDNA库相互作用的影响。比较了Cyt c与含有20、40和60个随机碱基序列的3种不同链长的ssDNA库的作用及基于未涂层毛细管和涂层毛细管的毛细管区带电泳方法。因碱性蛋白质在未涂层毛细管管壁上存在吸附,因此利用未涂层毛细管区带电泳不能区别3种ssDNA库与其作用的差异。利用涂层毛细管电泳法,在压力辅助的反向电压下,根据游离ssDNA库的峰面积变化可比较3种ssDNA库与细胞色素c的相互作用差异。结果表明,含有20个随机寡核苷酸链长的ssDNA库与Cty c的作用最强。此外,NaCl浓度显著影响Cyt c与ssDNA60库的作用。在优化的实验条件下,0.02 mol/L NaCl有利于两者的相互作用。调节盐浓度可抑制非特异性静电作用,能提高碱性蛋白质适配体的单轮筛选效率。利用未涂层毛细管电泳分析复合物及游离ssDNA库的峰面积变化,可优化有利复合物形成的盐浓度。 相似文献
18.
Xinying Zhang Xiaoyan Li Xuesen Fan Xia Wang Dongfang Li Guirong Qu Jianji Wang 《Molecular diversity》2009,13(1):57-61
One-pot multi-component reactions of aldehydes, cyanothioacetamide and malononitrile promoted by ionic liquid proved to be
an efficient way for the synthesis of thiopyran derivatives. Without any added catalyst, both aromatic and aliphatic aldehydes
participated in this reaction smoothly. As an application of this method, a pyrimidine nucleoside-thiopyran chimera with potential
biological activities was obtained in high yield from 5-formyl-2’-deoxyuridine. In addition, the ionic liquid used can be
easily recovered and effectively reused for at least 5 times.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
19.
20.
A unified boundary integral equation (BIE) is developed for the scattering of elastic and acoustic waves. Traditionally, the elastic and acoustic wave problems are solved separately with different BIEs. The elastic wave case is represented in a vector BIE with the traction and displacement vectors as unknowns whereas the acoustic wave case is governed by a scalar BIE with velocity potential or pressure as unknowns. Although these two waves can be unified in the form of a partial differential equation, the unified form in its BIE counterpart has not been reported. In this work, we derive the unified BIE for these two waves and then show that the acoustic wave case can be derived from this BIE by introducing a shielding loss for small shear modulus approximation; hence only one code needs to be maintained for both elastic and acoustic wave scattering. We also derive the asymptotic Green's tensor for zero shear modulus and solve the corresponding vector equation. We employ the method of moments, which has been widely used in electromagnetics, as a numerical tool to solve the BIEs involved. Our numerical experiments show that it can also be used robustly in elastodynamics and acoustics. 相似文献