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261.
Phosphate Monoester Hydrolysis by Trinuclear Alkaline Phosphatase; DFT Study of Transition States and Reaction Mechanism 下载免费PDF全文
Alkaline phosphatase (AP) is a trinuclear metalloenzyme that catalyzes the hydrolysis of a broad range of phosphate monoesters to form inorganic phosphate and alcohol (or phenol). In this paper, by using density functional theory with a model based on a crystal structure, the AP‐catalyzed hydrolysis of phosphate monoesters is investigated by calculating two substrates, that is, methyl and p‐nitrophenyl phosphates, which represent alkyl and aryl phosphates, respectively. The calculations confirm that the AP reaction employs a “ping‐pong” mechanism involving two chemical displacement steps, that is, the displacement of the substrate leaving group by a Ser102 alkoxide and the hydrolysis of the phosphoseryl intermediate by a Zn2‐bound hydroxide. Both displacement steps proceed via a concerted associative pathway no matter which substrate is used. Other mechanistic aspects are also studied. Comparison of our calculations with linear free energy relationships experiments shows good agreement. 相似文献
262.
采用全原子分子动力学模拟方法研究了纤连蛋白(FN)在金红石表面、23%石墨烯覆盖率的金红石表面、92%石墨烯覆盖率的金红石表面、石墨表面的吸附行为.模拟结果表明:FN在金红石表面吸附不稳定.通过石墨烯修饰二氧化钛表面可降低金红石表面的亲水性;当表面含有石墨烯层时,FN都将稳定地吸附在表面上.在23%石墨烯覆盖率的金红石表面上,FN的特异性识别位点朝向溶液而有利于整合素识别.DSSP分析结果显示在40 ns的分子动力学模拟过程中,FN的七个β-折叠结构在所有体系中均没有发生太大变化.由于有石墨烯层存在,表面附近水分子层密度减小.FN的表面吸附能随着表面石墨烯覆盖率的增加而增大.石墨烯修饰能加强二氧化钛表面对蛋白质的吸附.本工作可以为移植体修饰生物材料设计与开发提供参考. 相似文献
263.
Dunhua Hong Taisong Pan Dayu Feng Zhenlong Huang Feiyi Liao XiaoMei Li Yin Zhang Min Gao 《Journal of Sol-Gel Science and Technology》2014,71(3):464-469
(LaBa)Co2O5+δ (LBCO) thin films were successfully fabricated on Si (001) substrates by polymer-assisted deposition method. Microstructures were examined by X-ray diffraction technique, which confirmed the films were a single phase, pseudo cubic structure. The electrical transport properties of the films were investigated by the temperature dependence of films resistance, which suggested that LBCO films have typical semiconductor properties. After circle tests, the oxygen–hydrogen response rate did not show obvious variation in the specific temperature environment of 580 °C. This demonstrates that the LBCO thin films have a superior stability in both oxygen and hydrogen (6 % H2, 94 % N2) environment. Simultaneously, the drastic changes of films resistance (from ~106 to ~102 Ω) with the switch of redox (O2–H2) environment within such a short time (~2.2 s) indicated that LBCO films have an excellent oxygen sensitive property and extraordinary fast surface exchange rate. 相似文献
264.
Zheng Li Lingcong Jiao Yunhai Sun Zeying He Dr. Zhonglin Wei Prof. Wei-Wei Liao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(18):7333-7337
An unprecedented electrochemical trifluoromethylation/SO2 insertion/cyclization process has been achieved in an undivided cell in an atom-economic fashion. The protocol relies on tandem cyclization of N-cyanamide alkenes by using Langlois’ reagent as a source of both CF3 and SO2 under direct anodically oxidative conditions, in which two C−C bonds, two C−X bonds (N−S and S−C), and two rings were formed in a single operation. This transformation enabled efficient construction of various trifluoromethylated cyclic N-sulfonylimines from readily accessible materials. 相似文献
265.
Rational Design of Cyclometalated Iridium(III) Complexes for Three-Photon Phosphorescence Bioimaging
Dr. Chengzhi Jin Fengyin Liang Dr. Jinquan Wang Dr. Lili Wang Dr. Jiangping Liu Xinxing Liao Dr. Thomas W. Rees Bo Yuan Prof. Dr. Hui Wang Prof. Dr. Yong Shen Prof. Dr. Zhong Pei Prof. Dr. Liangnian Ji Prof. Dr. Hui Chao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16121-16125
Compared to 2PE (two-photon excitation) microscopy, 3PE microscopy has superior spatial resolution, deeper tissue penetration, and less defocused interference. The design of suitable agents with a large Stokes shift, good three-photon absorption (3PA), subcellular targeting, and fluorescence lifetime imaging (FLIM) properties, is challenging. Now, two IrIII complexes (3PAIr1 and 3PAIr2) were developed as efficient three-photon phosphorescence (3PP) agents. Calculations reveal that the introduction of a new group to the molecular scaffold confers a quadruple promotion in three-photon transition probability. Confocal and lifetime imaging of mitochondria using IrIII complexes as 3PP agents is shown. The complexes exhibit low working concentration (50 nm ), fast uptake (5 min), and low threshold for three-photon excitation power (0.5 mW at 980 nm). The impressive tissue penetration depth (ca. 450 μm) allowed the 3D imaging and reconstruction of brain vasculature from a living specimen. 相似文献
266.
Jiann-Jyh Huang Yu-Hsiang Lin Chun-Liang Lai Sheng-Chuan Yang Shu Fu Lin Ju-Ying Yang Hung-Jyun Huang Chiawei Liu Win-Yin Wei Shih-Hsien Chuang Chao-Cheng Chiang Ying-Shuen E. Lee Chu-Bin Liao Ching Yuh Chern 《中国化学会会志》2020,67(3):422-429
In this study, we reported the inhibition profiles of 4′-acylpyrrole–5-fluoroindolin-2-one 3 with a C-3′ side chain for VEGFR2, PDGFR-β, and FGFR-1 protein kinases. The pyrrole-fused cyclohexanone moiety provided 3 with the best potency to inhibit the three kinases, and the C-3′ side chains contributed to the different inhibition profiles of 3 . Compound 3b with a C-3′ 2-carboxylethyl side chain showed good potency for the three kinase (IC50: 25–260 nM), and compound 3g with a N,N-dialkyl-2-carbamoylethyl side chain was more active for VEGFR2 (IC50: 59 nM) and PDGFR-β (IC50: 16 nM) than FGFR-1 (IC50: 1.7 μM). The C-3′ 3-(dialkylamino)propyl side chain accomplished 3h – j as selective PDGFR-β inhibitors (IC50: 7.8–13 nM). Compound 3b was further investigated and found potent to inhibit VEGF- and FGF-dependent cell proliferation with moderate in vivo anticancer activity. Results from docking simulations revealed that the interactions of 3b with VEGFR2 and FGFR-1 which could account for the different inhibition profiles of 3 . 相似文献
267.
We report two anion-templated Ag40 clusters, [Ag40(E)4(SO4){S2P(OEt)2}24](PF6)6 (E = S, 1 ; Se, 2 ). The anionic templates were generated in situ from the decomposition of dithiophosphate (dtp) ligands. The extrusion of sulfur undergoes disproportionation reactions to generate sulfide and sulfate anions, which provide the source of templates in the subsequent cluster assembly reactions. Two Ag40 clusters display high similarity in their structures. The sulfide (selenide) anions and the central sulfate anion reveal a six-coordinate and a rare dodecametallic dodecaconnective pattern, respectively. Four near-equivalent [Ag10(E){S2P(OEt)2}6]2+ motifs were assembled via the connection of central sulfate anion to construct Ag40 clusters. The cluster cation, [Ag40(E)4(SO4){S2P(OEt)2}24]6+, displayed in T symmetry, is unprecedented in anion-templated silver clusters. 相似文献
268.
In this study,two new dendronized nonlinear optical(NLO)polymers were synthesized with high FTC chromophore loading density by introduction of high generation chromophore dendrons on the side chains.Due to their suitable molecular weights,both of them possessed good solubility in common solvents.They also inherited the advantages of dendrimers(large NLO coefficient),especially for PG2 whose NLO coefficient d33 value was as high as 282 pm·V^–1.Also,PG2 had a good temporal stability with 80%of its maximum value being retained at the temperature as high as 129℃. 相似文献
269.
ABSTRACTWe demonstrate a spatially and electrically tunable random lasing based on polymer-stabilized blue phase liquid crystal (PS-BPLC)-wedged cell. The spatially tunable random lasers can be obtained from the laser dye-doped PS-BPLC-wedged cell through changing the pump positions, where the emission wavelength of the random laser can be tuned due to the thickness gradient of the wedged cell, which affects the scattering mean free path. Additionally, applying different electric fields can also tune the laser emission wavelength. The changing of refractive index due to the Kerr effect leads to a change in the scattering mean free path, resulting in shift of lasing wavelength. This PS-BPLC-wedged cell device has a great potential in applications of speckle-free imaging, document coding, biomedicine and other photonic devices. 相似文献
270.