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871.
The integration technology of hydrogen preparation–hydrogen storage not only can utilize hydrogen energy efficiently but also can improve the selectivity of the electrode maximally. In the present work, the structure and composition of the PtNi catalyst was characterized by X-ray diffraction (XRD); and its electrochemical properties, morphology, and surface binding energy were analyzed by cyclic voltammetry (CV) and linear scanning voltammetry (LSV), scanning electron microscopy equipped with energy-dispersive spectrometry (SEM-EDS), and X-ray photoelectron spectroscopy (XPS), respectively. The effects of different acid etching treatments (e.g., etching time, etchant concentration, and etching temperature) on the structure and surface active sites were investigated by the orthogonal experiment. The experimental results reveal that after etching with 0.5 mol/L of perchloric acid for 0.5 h at 60°C, the electrode weight loss of the PtNi catalyst is mainly attributed to the large loss of Ni atoms in film layer. This results in the reduced alloy phase in film layer and the appearance of Pt characteristic diffraction peak. The relative content of Pt on the surface of the film electrode increases significantly, and the total number of active sites also increases correspondingly. The binding energy of Pt4f7/2 decreases by 0.19 eV, and the number of active sites involved in hydrogen release decreases, indicative of the reduced promotion effect of the PtNi catalyst on hydrogen release. 相似文献
872.
A quantification method for imatinib (IM), its major metabolite N-desmethyl imatinib (NDI), and a degradation by-product was developed using CE–MS combined with an online concentration technique. The use of multiple reaction monitoring (MRM)–MS/MS further improved the sensitivity of this technology. Liquid–liquid extraction (LLE) using tertiary butyl methyl ether yielded high recovery and reproducibility for the pretreatment of serum samples. The recovery rate exceeded 83% for all three analytes, and was 90% for IM. To improve quantification results, a conductivity-induced online analyte concentration technique, field-amplified sample stacking (FASS), was used. The S/N ratios were improved at least 10-fold when compared with conventional capillary zone electrophoresis. The detection limits were 0.2 ng/mL for IM, 0.4 ng/mL for NDI, and 4 ng/mL for the degradation by-product. These results are superior to those previously obtained by other reported methods. The new method was validated in terms of its selectivity, intra- and interday repeatability and accuracy, and sample storage stability, following the guidelines issued by the European Medicines Agency. Considering the convenient pretreatment procedure (LLE), superior sensitivity, and fast analysis speed (<15 min), this method can be useful in the determination of imatinib levels in blood. 相似文献
873.
Dandan Jiang Mingxing Fu Yajun Zhang Qianqian Li Kai Guo Yanhui Yang Lili Zhao 《Journal of computational chemistry》2020,41(4):279-289
Density functional theory (DFT) calculations were performed to gain insight into the mechanism of the nickel-catalyzed hydrocyanation of terminal alkynes with Zn(CN)2 and water to exclusively generate the branched nitrile with excellent Markovnikov selectivity. After precatalyst activation to give the LNi(0) active species, the transformation proceeds via the following steps: (1) oxidative addition of H2O to the LNi(0) provides the intermediate LNi(II)H(OH); (2) ligand exchange of LNi(II)H(OH) with Zn(CN)2 gives the intermediate LNi(II)H(CN); (3) alkyne insertion to the LNi(II)H(CN) forms the alkenyl nickel complex, followed by the reductive elimination step reaching the final product. This mechanism is kinetically and thermodynamically more favorable than that of the experimental proposed ones. On the basis of the experimental observations, more water molecules cannot further improve the reaction as it has also been rationalized. Furthermore, the origin of the high regioselectivity of the product, the variable effectiveness of the metal mediator as function of ligands, as well as the high yield of the alkyl-substituted alkynes substrates, is analyzed in detail. © 2019 Wiley Periodicals, Inc. 相似文献
874.
Litao Zhao Fanghong Luo Anting Wang Jing Zhang Yuanhang Wang Liangtao Zhao Zhaoyan Wang Qiaosheng Pu 《Electrophoresis》2020,41(15):1273-1279
Mutations in the potassium channel genes may be linked to the development of epilepsy and affect the blood potassium levels. Therefore, accurate determination of potassium in the blood will be critical to diagnose the cause of epilepsy. CE is a competent technique for the fast detection of multiple ions, but complicated matrices of a blood sample may cause significant variation of migration times and the peak shape. In this work, a procedure for rapid stabilization of the capillary inner surface through preflushing of a blood sample was employed. The process takes only 40 min for a capillary and then it can be used for more than 2 weeks. No pretreatment of the blood sample or other surface modification of the capillary is needed for the analysis. The RSDs of the migration time and peak area were reduced to 1.5 and 5.1% from 12.6 and 14.5%, respectively. The proposed method has been successfully applied to the determination of the potassium contents in the blood sample of patients with epilepsy at different stages. The recoveries of potassium ions in these blood samples are in a range from 86.5 to 104.5%. 相似文献
875.
Daoyuan Zheng Yurong Guo Mingxing Zhang Xia Feng Lina Zhu Lijuan Qiu Xiaoning Jin Guangjiu Zhao 《Journal of computational chemistry》2020,41(10):976-985
Organic semiconductors (OSCs) materials are currently under intense investigation because of their potential applications such as organic field-effect transistors, organic photovoltaic devices, and organic light-emitting diodes. Inspired by the selenization strategy can promote anisotropic charge carrier migration, and selenium-containing compounds have been proved to be promising materials as OSCs both for hole and electron transfer. Herein, we now explore the anisotropic transport properties of the series of selenium-containing compounds. For the compound containing Se Se bond, the Se Se bond will break when attaching an electron, thus those compounds cannot act as n-type OSCs. About the different isomer compounds with conjugated structure, the charge transfer will be affected by the stacking of the conjugated structures. The analysis of chemical structure and charge transfer property indicates that Se-containing materials are promising high-performance OSCs and might be used as p-type, n-type, or ambipolar OSCs. Furthermore, the symmetry of the selenium-containing OSCs will affect the type of OSCs. In addition, there is no direct relationship between the R groups with their performance, whether it or not as p-type OSCs or n-types. This work demonstrates the relationship between the optoelectronic function and structure of selenium-containing OSCs materials and hence paves the way to design and improve optoelectronic function of OSCs materials. 相似文献
876.
Given the paramount importance of excited-state relaxation in the photochemical process, excited-state hydrogen bonding interactions and excited-state intramolecular proton transfer (ESIPT) are always hot topics. In this work, we theoretically explore the excited-state dynamical behaviors for a novel 2-(3,5-dichloro-2,6-dihydroxy-phenyl)-benzoxazole-6-carboxylicacid (DDPBC) system. As two intramolecular hydrogen bonds (O1 H2⋯N3 and O4 H5⋯O6) exist in the DDPBC structure, we first check if the double proton transfer form cannot be formed in the S1 state. Then, we explore the changes of geometrical parameters involved in hydrogen bonds, based on which we confirm that the dual intramolecular hydrogen bonds are strengthened on photo-excitation. The O1 H2⋯N3 hydrogen bond particularly plays a more important role in excited state. When it comes to the photo-induced excitation, we find charge transfer and electronic density redistribution around O1 H2 and N3 atom moieties. We verify the ESIPT tendency arising from the O1 H2⋯N3 hydrogen bond. In the analysis of the potential energy curves, along with O1 H2⋯N3 and O4 H5⋯O6, we demonstrate that the ESIPT reaction should occur along with O1 H2⋯N3 rather than O4 H5⋯O6. This work not only clarifies the specific ESIPT mechanism for DDPBC system but also paves the way for further novel applications based on DDPBC structure in the future. 相似文献
877.
878.
BiOBr synthesized by alcoholysis precipitation is used in the preparation of BiPO4/BiOBr composites by adding H3PO4. Pristine BiOBr and a series of BiPO4/BiOBr composites have been successfully synthesized using an entirely room-temperature production process. X-ray powder diffraction, scanning electron microscopy, High-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, UV–vis absorption spectroscopy were used to investigated the bulk structure, surface morphology, element composition and optical properties of the samples. The degradation effect of different proportions of BiPO4/BiOBr composites, BiOBr and BiPO4 on Rhodamine B (RhB) was evaluated under visible LED light irradiation. Compared to pure BiOBr and BiPO4, the as-synthesized BiPO4/BiOBr composites showed enhanced performance, with 30% BiPO4/BiOBr composite showing the best performance, as it could degrade 95.66% of RhB (100 ml, 15 mg/L) within 120 min. The enhanced photocatalytic activity of BiPO4/BiOBr was attributed to the heterojunction formation between BiOBr and BiPO4 and efficient charge separation. 相似文献
879.
AbstractA convenient, rapid H2SO4-promoted regioselective monobromination reaction with N-bromosuccinimide was developed. The desired para-monobrominated or ortho-monobrominated products of phenol derivatives were obtained in good to excellent yields with high selectivity. Regioselective chlorination and iodination were also achieved in the presence of H2SO4 using N-chlorosuccinimide and N-iodosuccinimide, respectively. 相似文献
880.
Zhen Zhang Ying-Lin Gu Zheng-Yang Wang Huan-Nan Wang Yan Zhao Xue-Mei Chu Chun-Yan Zhang Mao-Cai Yan 《Journal of heterocyclic chemistry》2020,57(3):1165-1172
Novel indole amide derivatives C1-C10 were successfully synthesized and characterized by 1H NMR, 13C NMR, IR, MS, and elemental analysis, and their molecular formulas were C14H10N6O, C13H10N4O, C16H13N3O2, C19H14N2O2, C16H11N3OS, C15H13N3O, C12H9N5O, C16H10ClN3OS, C15H17N3O2, and C13H14N2O3, respectively. The primary biological activities of these compounds were evaluated in vitro by the DPPH assay, H2O2-induced oxidative stress injury assay, and cytotoxicity assay. The results indicated that compounds C1, C2, C4, C7, and C9 exhibited DPPH·scavenging ability, while C3, C4, C5, and C8 showed potent growth-inhibitory activities against various human tumor cells, including MDA-MB-231, Hela, A549, and HT29. Interestingly, compound C4 showed potent scavenging effects on the DPPH radical and possessed protective effect on H2O2-induced oxidative stress injury in human neuroblastoma SH-SY5Y cells at low concentrations; however, C4 exhibited significant toxicity against four human tumor cells at a higher concentration in all treatments, and the range of IC50 value was 7.91 to 13.35 μM. 相似文献