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231.
Prof. Dr. Fa-Guang Zhang Xue-Qi Wang Yin Zhou Hong-Song Shi Zhe Feng Prof. Dr. Jun-An Ma Prof. Dr. Ilan Marek 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15378-15396
Remote functionalization reactions have the power to transform a C−H (or C−C) bond at a distant position from a functional group. This Review summarizes recent advances and key breakthroughs in remote fluorination, trifluoromethylation, difluoromethylation, trifluoromethylthiolation, and fluoroalkenylation reactions. Several powerful strategies have emerged to control the reactivity and distal selectivity such as the undirected radical approach, the 1,5-hydrogen atom transfer, the metal migration, the use of distant directing groups, and the ring-opening reactions. These unconventional and predictable C−H (and C−C) functionalization transformations should allow for the preparation of a wide range of otherwise-difficult-to-access alkyl, aromatic, heteroaromatic, and structurally complex fluorides. 相似文献
232.
Deliang Kong Lihua Guo Meng Tian Shumiao Zhang Zhenzhen Tian Huayun Yang Ye Tian Zhe Liu 《应用有机金属化学》2019,33(1)
Fifteen organometallic Ir(III) half‐sandwich complexes ( 1A – 5C ) having the general formula [(η5‐Cpx)Ir(N^N)Cl]PF6 (Cpx = Cp*, tetramethyl(phenyl)cyclopentadienyl (Cpxph) or tetramethyl(biphenyl)cyclopentadienyl (Cpxbiph); N^N = diamine) have been synthesized and characterized. The molecular structure of 1A was determined using single‐crystal X‐ray diffraction analysis. The hydrolysis of 1A – 5C was monitored using UV–visible spectra. Complexes 3A – 3C showed catalytic activity for the oxidation of NADH to NAD+, where 3C showed the highest turnover number of 29.9 within 450 min. Cytotoxicity examination by MTT assay was carried out against two human cancer cell lines (HeLa and A549) after 24 or 48 h drug treatment. The complexes showed high potency, where the most potent complex ( 3C ; IC50 = 3.4 μM) was six times more active than cisplatin against A549 cells after 24 h drug exposure. Cytotoxic potency towards A549 cells increased with phenyl substitution on Cp ring: Cpxbiph > Cpxph > Cp*. In addition, the biological studies showed that 3C caused cell apoptosis and cell cycle arrest at G1 phase in A549 cancer cells. Moreover, 3C increased the level of reactive oxygen species markedly after 24 h, which may provide an important basis for killing cancer cells. Confocal laser scanning microscopy was used to track 3C in A549 cells. The cellular localization experiment showed that 3C targeted lysosomes and caused lysosomal damage. 相似文献
233.
Jing He Mohan Yu Maofu Pang Yanqing Fan Zhe Lian Dr. Ying Wang Prof. Wenguang Wang Prof. Yajun Liu Prof. Hua Jiang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(13):e202103832
Structural designs combining cycloparaphenylenes (CPPs) backbone with planar chiral [2.2]paracyclophane ([2.2]PCP) lead to optical-active chiral macrocycles with intriguing properties. X-ray crystal analysis revealed aesthetic necklace-shaped structures and size-dependent packages with long-range channels. The macrocycles exhibit unique photophysical properties with high fluorescence quantum yield of up to 82 %, and the fluorescent color varies with ring size. In addition, size-dependent chiroptical properties with moderately large CPL dissymmetry factor of 10−3 and CPL brightness in the range of 30–40 M−1 cm−1 were observed. 相似文献
234.
Xingxing Ge Xicheng Liu Zhenzhen Tian Shujiao Chen Xinyu Liu Lihua Guo Peiwei Gong Baoping Ling Xiang‐Ai Yuan Zhe Liu 《应用有机金属化学》2019,33(11)
Four half‐sandwich rutheniumII (RuII) complexes with triphenylamine‐modifed dipyridine frameworks were synthesized and characterized. The cytotoxicity of target complexes toward A549 (lung cancer cells), HeLa (cervical cancer cells) and HepG2 (hepatoma cells) were obtained by the MTT assay, which were superior to cisplatin with the IC50 values changed from 2.4 ± 0.1 μM to 9.2 ± 2.7 μM. Meanwhile, complexes possess the ability of antimetastasis to cancer cells. RuII complexes could be transported by serum albumin, catalyze the conversion of NADH (the reduced state of nicotinamide‐adenine dinucleotide) to NAD+ and induce the accumulation of reactive oxygen species, which confirmed the antineoplastic mechanism of oxidation. RuII complexes could enter A549 cells followed by a non‐energy dependent cellular uptake mechanism, target lysosomes with the Pearson's colocalization coefficient of 0.75, lead to lysosomal damage, disturb the cell cycle (S phase), and eventually induce apoptosis. The results demonstrate that these RuII complexes are potential anticancer agents with dual functions, including metastasis inhibition and lysosomal damage. 相似文献
235.
Sidra Jabeen Zhe Zeng Mohammednoor Altarawneh Xiangpeng Gao Anam Saeed Bogdan Z. Dlugogorski 《国际化学动力学杂志》2019,51(9):696-710
This contribution investigates thermal decomposition of leucine, as a representative model compound for amino acids in algal biomass. We map out potential energy surface for a wide array of unimolecular and self-condensation reactions operating in the decomposition of leucine. Decarboxylation and dehydration of leucine ensues by eliminating CO2 and –OH, respectively, from the –COOH group attached to the α-carbon. The molecular channel for deamination involves cleavage of NH2 from α-carbon of leucine. The activation energies for direct elimination of CO2, NH3, and H2O from a leucine molecule lie within 20.7 kJ/mol of each other. Activation energies for these decomposition pathways reside below the bond dissociation enthalpy of H–C(α) of 323.1 kJ/mol. The decarboxylation, deamination, and dehydration pathways, via radical-prompted pathways, systematically require lower energy barriers, in reference to closed-shell reaction corridors. Detailed computations at the CBS-QB3 level provide the Arrhenius rate parameters for the unimolecular and bimolecular reactions, and standard enthalpies of formation, standard entropies, and heat capacities for all the products and intermediates. A kinetic analysis of gas-phase reactions, within the context of a plug-flow reactor model, accounts qualitatively for the formation of major products observed experimentally in the thermal degradation of the condensed-phase leucine. Among notable N-containing species, the model predicts the prevailing of NH3 over HCN and HNCO, in addition to corresponding appreciable concentrations of amines, imines, and nitriles. Our detailed kinetic investigation illustrates a negligible contribution of the self-condensation reactions of leucine in the gas phase. 相似文献
236.
Dr. Ying Wang Dr. Wenming Sun Xiaofei Ling Xiangkai Shi Dr. Lanlan Li Prof. Yida Deng Dr. Cuihua An Dr. Xiaopeng Han 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(18):4097-4103
The development of high-efficiency, low-cost, and earth-abundant electrocatalysts for overall water splitting remains a challenge. In this work, Ni-modified MoS2 hybrid catalysts are grown on carbon cloth (Ni-Mo-S@CC) through a one-step hydrothermal treatment. The optimized Ni-Mo-S@CC catalyst shows excellent hydrogen evolution reaction (HER) activity with a low overpotential of 168 mV at a current density of 10 mA cm−2 in 1.0 m KOH, which is lower than those of Ni-Mo-S@CC (1:1), Ni-Mo-S@CC (3:1), and pure MoS2. Significantly, the Ni-Mo-S@CC hybrid catalyst also displays outstanding oxygen evolution reaction (OER) activity with a low overpotential of 320 mV at a current density of 10 mA cm−2, and remarkable long-term stability for 30 h at a constant current density of 10 mA cm−2. Experimental results and theoretical analysis based on density functional theory demonstrate that the excellent electrocatalytic performance can be attributed mainly to the remarkable conductivity, abundant active sites, and synergistic effect of the Ni-doped MoS2. This work sheds light on a unique strategy for the design of high-performance and stable electrocatalysts for water-splitting electrolyzers. 相似文献
237.
Belyaev B. A. Tyurnev V. V. Voloshin A. S. Leksikov An. A. Galeev R. G. Shabanov V. F. 《Doklady Physics》2020,65(9):343-348
Doklady Physics - The design of a multilayer bandpass filter has been investigated, in which each of the half-wavelength resonators consists of two dielectric layers with outer strip conductor... 相似文献
238.
239.
An Unprecedented Two‐Fold Nested Super‐Polyrotaxane: Sulfate‐Directed Hierarchical Polythreading Assembly of Uranyl Polyrotaxane Moieties
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Dr. Lei Mei Dr. Qun‐yan Wu Dr. Li‐yong Yuan Dr. Lin Wang Shu‐wen An Zhen‐ni Xie Dr. Kong‐qiu Hu Prof. Zhi‐fang Chai Prof. Peter C. Burns Prof. Wei‐qun Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(32):11329-11338
The hierarchical assembly of well‐organized submoieties could lead to more complicated superstructures with intriguing properties. We describe herein an unprecedented polyrotaxane polythreading framework containing a two‐fold nested super‐polyrotaxane substructure, which was synthesized through a uranyl‐directed hierarchical polythreading assembly of one‐dimensional polyrotaxane chains and two‐dimensional polyrotaxane networks. This special assembly mode actually affords a new way of supramolecular chemistry instead of covalently linked bulky stoppers to construct stable interlocked rotaxane moieties. An investigation of the synthesis condition shows that sulfate can assume a vital role in mediating the formation of different uranyl species, especially the unique trinuclear uranyl moiety [(UO2)3O(OH)2]2+, involving a notable bent [O=U=O] bond with a bond angle of 172.0(9)°. Detailed analysis of the coordination features, the thermal stability as well as a fluorescence, and electrochemical characterization demonstrate that the uniqueness of this super‐polyrotaxane structure is mainly closely related to the trinuclear uranyl moiety, which is confirmed by quantum chemical calculations. 相似文献
240.
Both residual Cesàro alpha-integrability (RCI( α)) and strongly residual Cesàro alpha-integrability (SRCI(α)) are two special kinds of extensions to uniform integrability, and both asymp-totically almost negative association (AANA) and asymptotically quadrant sub-independence (AQSI) are two special kinds of dependence structures. By relating the RCI(α) property as well as the SRCI(α) property with dependence condition AANA or AQSI, we formulate some tail-integrability conditions under which for appropriate α the RCI(α) property yields L1-convergence results and the SRCI(α) property yields strong laws of large numbers, which is the continuation of the corresponding literature. 相似文献