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Syntheses and Characterizations of Cyanido-bridged Dinuclear Ru-complexes and Their MMCT Properties in the One-electron Oxidation State

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Chinese Journal of Structural Chemistry 2021年第10期40卷 1253-1264页

作者： LIU Yang ZHU Xiao-Quan WU Xin-Tao sheng tian-Lu College of Chemistry Fuzhou UniversityFuzhou 350002China State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002China University of Chinese Academy of Sciences Beijing 100049China

We have designed and synthesized a family of dinuclear cyanido-bridged complexes[PY5Me_(2)Ru(μ-CN)Ru(dppe)CpMe_(n)][PF_(6)]_(2) (PY5Me_(2)=2,6-bis (1,1-bis(2-pyridyl)ethyl) pyridine,Cp=cyclopentadienyl,n=0,2[PF6]_(2);n=1,3[PF6]_(2);n=5,4[PF6]_(2)) by using a mononuclear complex[PY5Me_(2)Ru(μ-CN)][PF_(6)](1) as the *** the three complexes have been fully characterized by including single-crystal X-ray diffraction *** one-electron oxidation complexes 2^(3+),3^(3+) and 4^(3+) obtained in situ all show a MMCT absorption band in the visible *** MMCT energy increases as the redox potential of the N-terminal fragments decreases,and the redox potential decreases as the number of methyl groups on the cyclopentadiene of the cyanido-nitrogen coordinated Ru metal increases,supported by the TDF/TDDFT calculations.

关键词： electron transfer mixed-valence metal to metal charge transfer(MMCT) cyanide bridge

Synthesis,Structure and Luminescence of a Novel 2D Cadmium Coordination Polymer with a Ligand Generated in situ

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Chinese Journal of Structural Chemistry 2007年第3期26卷 333-337页

作者： HUANG Xi-He sheng tian-Lu XIANG sheng-Chang FU Rui-Biao HU sheng-Min LI Ya-Min WU Xin-Tao State Key Laboratory of Structural Chemistry Fujian Institute of Research on theStructure of Matter The Chinese Academy of Sciences Fuzhou Fujian 350002 China

The hydrothermal reaction of 1,2-dicyanobenzene with NaN3 in the presence of Cd（NO3）2 affords a novel 2D cadmium tetrazolyl-benzoate, {Cd（tzbz）（H2O）}n （H2tzbz is 2-（5-tetrazolyl）-benzoate）. The tzbz ligand is generated in situ through the [2＋3] Sharpless cycloaddition reaction and hydrolyzation. Its crystal structure was determined by single-crystal X-ray diffraction method. The crystal crystallizes in the orthorhombic system, space group Pbca with a = 9.6659（19）, b = 7.6366（15）, c = 25.964（5）A, V= 1916.5（7）A^3, Z= 8, Mr = 318.57, Dc = 2.208 g/cm^3, F（000） = 1232 and p = 2.276 mm^-1. The Cd（Ⅱ） atom is coordinated by four tzbz ligands and one water molecule to form a severely distorted pentangle bipyramid. While each tzbz ligand connects to four Cd（Ⅱ） atoms in a μ4-η1, η, η1, η1, η1 coordination mode to construct a 2D architecture of the title complex. Additionally, the title complex exhibits strong fluorescence at room temperature in the solid state.

关键词： hydrothermal synthesis in situ crystal structure cadmium

酸性矿山废水对成熟期水稻根区理化因子及固氮微生物的影响

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生物技术通报 2024年第6期40卷 271-280页

作者：田胜尼张琴董玉飞丁洲叶爱华张明珠安徽农业大学生命科学学院合肥230036

【目的】酸性矿山废水(acid mine drainage,AMD)是一类低pH、高硫酸盐浓度和重金属富集的废水。探究成熟期水稻根区土壤固氮菌群落的丰度和组成及其对AMD的响应,并阐明土壤固氮菌群落结构变化的主要驱动因素。【方法】对取自安徽省铜陵... 详细信息

【目的】酸性矿山废水(acid mine drainage,AMD)是一类低pH、高硫酸盐浓度和重金属富集的废水。探究成熟期水稻根区土壤固氮菌群落的丰度和组成及其对AMD的响应,并阐明土壤固氮菌群落结构变化的主要驱动因素。【方法】对取自安徽省铜陵市矿区受AMD污染和未受污染的稻田土壤进行水稻盆栽试验,设置3组不同处理(A:AMD浇溉污染土、B:清洁水浇灌污染土、CK:清洁水浇灌未污染土),采用nifH基因高通量测序技术分析不同处理下的成熟期水稻根区土壤固氮菌群落特征。【结果】AMD污灌使得水稻根区土壤中SO42-、NO3-、重金属的含量显著上升,土壤酸化且固氮菌群落的多样性下降。水稻根区土壤的优势固氮菌包括Anaeromyxobacter、Geobacter等,CK处理中富集的固氮菌群数量显著高于A、B处理,且B处理中主要富集疣微菌门,CK处理中主要富集变形菌门。pH和重金属Cu、Pb、Zn是驱动水稻根区土壤固氮菌群落结构的主要因素。具有硫还原功能的Desulfovibrio和Desulfurivibrio对氮的变化贡献明显。【结论】AMD对水稻根区土壤化学性质和固氮菌产生显著影响,恢复清洁水灌溉可促进固氮菌的恢复。

关键词： AMD 水稻根区土壤根区固氮微生物氮重金属

Synthesis and Structure of a Dinuclear Copper(Ⅱ)-ditetrazolate Involving in situ Ligand Synthesis

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Chinese Journal of Structural Chemistry 2007年第2期26卷 161-164页

作者： HUANG Xi-He sheng tian-Lu XIANG sheng-Chang FU Rui-Biao HU sheng-Min LI Ya-Min WU Xin-Tao State Key Laboratory of Structural Chemistry Fufian Institute of Research on theStructure of Matter The Chinese Academy of Sciences Fuzhou Fufian 350002 China

The hydrothermal reaction of 1,2-dicyanobenzene with NaN3 in the presence of CuC12, 2,2＇-bipyridine and H2O affords a novel dinuclear copper（Ⅱ）-ditetrazolate, [Cu（bpy）- （pdtz）]2 （Hpdtz = 5,5＂-1,2-phenylene-ditetrazole, bpy = 2,2＇-bipyridine）. The pdtz ligand is generated in situ through Sharpless 2＋3 cycloaddition reaction. Its crystal structure was determined by single-crystal X-ray diffraction method. The crystal crystallizes in the monoclinic system, space group P211n with a = 8.2096（16）, b = 18.580（4）, c = 11.838（2） A, β = 103.12（3）°, V = 1758.5（6） A^3, Z = 2, Mr = 863.83, Dc = 1.631 g/cm^3, F（000） = 876 and μ = 1.272 mm^-1. In this novel dinuclear structure, the pdtz ligand adopts a peculiar μ2-η1,η2 coordination mode.

关键词： hydrothermal synthesis in situ crystal structure copper ditetrazolate

Review on safe blasting technology in high-temperature coal seams in China

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Journal of Coal Science & Engineering(China) 2013年第3期19卷 337-344页

作者： Jian-sheng tian Kan YU State key Laboratory for Geomechanics & Deep Underground Engineering Xuzhou 221008 China School of Architecture & Civil Engineering China University of Mining & Technology Xuzhou 221116 China

In order to define the development direction of safe blasting technology in high-temperature coal seams in China, this paper presents a systematic, state-of-the-art review on safe blasting technology. Information such as high-temperature coal fire extinguishment and cooling, anti-high-temperature blasting supplies, heat insulation blasting setting, operation procedures for high-temperature blasting, and so on, are presented. Analysis shows that the development of effective technology for coal seam fire extinguishing and cooling, the manufacture of anti-high-temperature blasting supplies, especially priming materials, the development of heat insulation blasting setting, and the establishment of technical specifications suit large-scale blasting design and construction work at high-temperature coal seams, are the essential methods for safe blasting at high temperature coal seams.

关键词： high-temperature coal seams safety blasting anti-high-temperature blasting supplies heat insulation blasting setting

Synthesis and Crystal Structure of a Novel Heptanuclear Ruthenium- and Sodium-containing Polyoxomolybdate [{Na(H_2O)_3}_2{Ru(dmso)_3}_2(MoO_4)_3]·_3H_2O

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Chinese Journal of Structural Chemistry 2006年第7期25卷 783-788页

作者： HUANG Xi-He XIANG sheng-Chang FU Rui-Biao sheng tian-Lu ZHANG Jian-Jun LI Ya-Min WANG Long-sheng WU Xin-Tao State Key Laboratory of Structural Chemistry Fujian Institute of Research on theStructure of Matter The Chinese Academy of Sciences Fuzhou Fujian 350002 China

The title compound, [{Na（H2O）3}2lRu（dmso）3}2（MoO4）3]·3H2O, has been obtained by the reaction of Na2MoO4·2H2O with cis-Ru（dmso）4Cl2 in aqueous solution. Its crystal structure was determined by single-crystal X-ray diffraction method. The crystal crystallizes in the triclinic system, space group PI^- with a = 12.3333（3）, b = 12.6289（3）, c = 32.0284（14） A, α = 79.873（7）, β= 87.549（9）, γ = 64.500（4）°, V = 4429.5（2） A^3, Z = 4, Mr = 1358.85, Dc = 2.038 g/cm^3, F（000） = 2696 and μ = 1.874 mm^-1. The compound contains a novel pentanuclear triangle bipyramidal core, [{ Ru（dmso）3 } 2（MoO4）3]^2-, which consists of two { Ru（dmso）3 } ^2＋ fragments and three {μ2-MoO4}^2- units. Furthermore, the dmso ligands bridge the pentanuclear [Ru2Mo3] core and two [Na（H2O）3]^＋ fragments together, forming a neutral heptanuclear ruthenium- and sodiumcontaining polyoxomolybdate.

关键词： synthesis crystal structure ruthenium sodium polyoxomolybdate

Divergent synthesis of aryl amines and dihydroquinazolinones via electrochemistry-enabled rhodium-catalyzed C–H functionalization

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中国科学:化学英文版 2023年第10期66卷 2863-2870页

作者： Yi-Kang Xing Zhen-Hua Wang Ping Fang Cong Ma tian-sheng Mei State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic ChemistryUniversity of Chinese Academy of SciencesShanghai 200032China

Electrochemistry-enabled rhodium-catalyzed C–H amination and amination cyclization of arene assisted by a weakly coordinating amide have been reported. Additionally, aryl amines and dihydroquinazolinones could be obtained selectively by controlling the electric current. Mechanistic studies suggested that the amination reaction likely involves an electrochemical oxidation-induced reductive elimination of a high valent rhodium intermediate, which led to the amination reaction even proceeding smoothly at room temperature.

关键词： organic electrochemistry rhodium catalysis C-H functionalization divergent synthesis

Effect of deep brain stimulation on substantia nigra neurons in a rat model of Parkinson＇s disease

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Chinese Medical Journal 2012年第22期125卷 4072-4075页

作者： WU sheng-tian MA Yu ZHANG Kai ZHANG Jian-guo Capital Med Univ Dept Neurosurg Beijing Tiantan Hosp Beijing 100050 Peoples R China Beijing Neurosurg Inst Beijing 100050 Peoples R China

Background Parkinson＇s disease （PD） is a common neurodegenerative disease, which occurs mainly in the elderly. Recent studies have demonstrated that apoptosis plays an important role in the occurrence and development of PD. Subthalamic nucleus deep brain stimulation （STN-DBS） has been recognized as an effective treatment for PD. Recent clinical observations have shown that STN-DBS was able to delay early PD progression, and experiments in animal models have also demonstrated a protective effect of STN-DBS on neurons. However, the correlation between the neuron-protective effect of STN-DBS and the progression of substantia nigra pars compacta （SNc） neuronal apoptosis is still unknown. The aim of this study was to investigate the protective effect and potential mechanism of STN-DBS on SNc neurons in PD rats. Methods After the establishment of a PD rat model by unilateral/2-point injection of 6-hydroxydopamine in the medial forebrain bundle of the brain, DBS by implanting electrodes in the STN was administered. Behavioral changes were observed, and morphological changes of SNc neurons were analyzed by Nissl staining and DNA in situ end-labeling. Through extracellular recording of single neuron discharges and microelectrophoresis, the causes of and changes in SNc excitability during STN-DBS were analyzed, and the protective effect and potential mechanism of action of STN-DBS on SNc neurons in PD rats was investigated. Results SNc neuron apoptosis was significantly decreased （P 〈0.05） in the stimulation group, compared with the sham stimulation PD group. Spontaneous discharges of SNc neurons were observed in normal rats and PD model rats, and the mean frequency of spontaneous discharges of SNc neurons in normal rats （（40.65＋11.08） Hz） was higher than that of residual SNc neurons in PD rats （（36.71＋9.23） Hz）. Electrical stimulation of the STN in rats was associated with elevated excitation in unilateral SNc neurons. However, administering the gamma-aminobutyric acid recep

关键词： Parkinson's disease apoptosis deep brain stimulation excitatory neurotransmitter

Evolution model for scientific collaboration network with local-world information

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The Journal of China Universities of Posts and Telecommunications 2014年第2期21卷 15-20,31页

作者： tian sheng-wen LIAO Jian-xin WANG Jing-yu QI Qi State Key Laboratory of Networking and Switching Technology Beijing University of Posts and Telecommunications School of Information and Electrical Engineering Ludong University

In order to reveal the intrinsic properties of scientific collaboration networks, a new local-world evolution model on a scientific collaboration network is proposed by analysing the network growth mechanism. The act degree as the measurement of preferential attachment is taken, and the local-world information of nodes is taken into account. Analysis and simulation show that the node degree and the node strength obey the power-law distribution. Low average path length and high clustering coefficient are approved. Experiment indicates that the model can depict efficiently the topological structure and statistical characteristics of real-life scientific collaboration networks.

关键词： scientific collaboration network evolution model local-world information scale-flee act degree