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Interactions Between Anticancer Pt(II) complexes and Human Erythrocyte Spectrin *
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作者 杨晓改 李荣昌 《Journal of Chinese Pharmaceutical Sciences》 CAS 1998年第3期9-14,共6页
The interactions between human erythrocyte spectrin(SP) and Pt(II) complexes with different composition and configuration were studied by fluorescence and circular dichroism spectra. The results showed that there are ... The interactions between human erythrocyte spectrin(SP) and Pt(II) complexes with different composition and configuration were studied by fluorescence and circular dichroism spectra. The results showed that there are 4.7×10 2 binding sites of cisplatin(CDDP) in a spectrin tetramer(SPT). Among them, about 70 sites with apparent binding constant K 1】3.47×10 6 were of highest affinity, 1.8×10 2 sites with K 2 = 3.47×10 6 were of high affinity, and other 2.2×10 2 sites with K 3 = 8.77×10 5 were of low affinity. The conformation change of spectrin, depending on the concentration of Pt(II) complex and molar ratio(R) of Pt(II) complex to spectrin, was induced by the binding of Pt(II) complexes. It indicated that the interaction of both CDDP and cis diaquodiamine platinum(DADP) with SP followed a two step first order kinetic process in the first stage (1 h), and the kinetic constants were determined. In the second stage, the induced conformation change, polymerization and depolymerization of SP were probably involved. It was noticed that in the reaction of SP and Pt(II) complexes with 1,2 cyclohexanediammine isomers as chiral carrier ligand, stereo matching played a more important role than the affinity of Pt(II) to thiol groups of SP. 展开更多
关键词 Pt (ii) complex SPECTRIN CONFORMATION Binding sites Kinetic CHIRAL
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Preparation of Platinum(II) Complexes with 1-β-D-Ribofuranosyl-1,2,4-triazole-3-carboxamide and its Deoxy-analogue 被引量:7
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作者 Wen PEI Kobe JOZE 《Chinese Chemical Letters》 SCIE CAS CSCD 2001年第6期559-562,共4页
The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-??-D-ribofuranosyl-1,2,4-t... The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-??-D-ribofuranosyl-1,2,4-triazole-3-carboxamide (Ribavirin) and its deoxy-analogue (deoxyribavirin). The preparation of 1-(2'-deoxy-?-D-ribofuranosyl) -1,2,4-triazole-3-carboxamide was also performed through a four-step procedure, protection of 3', 5'-dihydroxyl group of Ribavirin with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (TPDS-Cl), phenoxythio-carbonylation of the 2'-hydroxyl group of 3', 5'-O-TPDS-Ribavirin with phenoxythiocarbonyl-chloride (PTC-Cl), reduction of 2′-O-phenoxythiocarbonyl ester of 3', 5'-O-TPDS-Ribavirin with tri-n-butyltin hydride and AIBN, deprotection of 3', 5'-O-TPDS-Ribavirin with tetrabutylammon-ium fluoride in THF. 展开更多
关键词 Platinum(ii) complexes ribavirin and deoxyribavirin nucleobase platination complexation reaction antitumor agents
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Dioxygen Affinity and Catalytic Performance of Bis-(furaldehyde) Schiff Bases Co(II) Complexes in Cyclohexene Oxidation 被引量:4
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作者 Sun, B Chen, JR +1 位作者 Hu, JY Li, XJ 《Chinese Chemical Letters》 SCIE CAS CSCD 2001年第11期1043-1046,共4页
Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of th... Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of these complexes in pyridine at different temperature. These complexes could activate molecular oxygen and were used as catalysts in cyclohexene oxidation. The influence of ligand structure on the dioxygen affinity and catalytic activity of the complexes were discussed. 展开更多
关键词 Schiff base cobalt (ii) complex OXYGENATION catalytic oxidation CYCLOHEXENE
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Synthesis and Characterization of Chiral Mercury(II) and Cadmium(II) Complexes with 3,3'-Bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl 被引量:1
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作者 方煜 宣为民 +2 位作者 朱成峰 袁国赞 崔勇 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2011年第8期1147-1153,共7页
Two homochiral mercury (1) and cadmium (2) complexes derived from chiral twisted biphenyl pyridine ligand (3,3'-bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl) have been synthesized and chara... Two homochiral mercury (1) and cadmium (2) complexes derived from chiral twisted biphenyl pyridine ligand (3,3'-bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl) have been synthesized and characterized by IR, microanalysis, TGA, UV-Vis, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 2. For 1, a = 14.2038(16), b = 14.3630(17), c = 7.0257(8), V = 1433.3(3)3, Mr = 878.91, Dc = 2.037 g/cm3, μ = 7.549 mm-1, F(000) = 824, the final GOF = 1.017, R = 0.0296 and wR = 0.0645 for 2925 observed reflections with I 2σ(I). For 2, a = 14.212(3), b = 14.392(3), c = 7.0498(14), V = 1442.0(5)3, Mr = 790.72, Dc = 1.821 g/cm3, μ = 2.924 mm–1, F(000) = 760, the final GOF = 1.075, R = 0.0340 and wR = 0.0834 for 3144 observed reflections with I 2σ(I). The crystal structures of 1 and 2 are isostructural and each adopts a two-dimensional supramolecular network which contains the C–H···π interactions. 展开更多
关键词 crystal structure chiral complex mercury(ii complex cadmium(ii complex
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Preparation, Characterization and Antimicrobial Studies of Mn(II) and Fe(II) Complexes with Schiff Base Ligand Derived from 2-aminophenol and 3-formyl-2-hydroxy-6-methoxyquinoline 被引量:1
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作者 Abubakar Muhammad Jabbi Habu Nuhu Aliyu +1 位作者 Sulaiman Isyaku Abdullahi Muhammad Kabir 《Open Journal of Inorganic Chemistry》 2020年第2期15-24,共10页
Schiff base derived from 2-aminophenol and 3-formyl-2-hydroxy-6-methoxyquinoline and its Mn(II) and Fe(II) complexes were synthesized and characterized by melting point and decomposition temperature, elemental analysi... Schiff base derived from 2-aminophenol and 3-formyl-2-hydroxy-6-methoxyquinoline and its Mn(II) and Fe(II) complexes were synthesized and characterized by melting point and decomposition temperature, elemental analysis, molar conductivity, infrared (IR) spectral analysis, atomic absorption spectroscopy (AAS) analysis, solubility test, and magnetic susceptibility. The Fourier-transform infrared spectroscopy (FTIR) spectral data of the Schiff base determined showed <span><span style="font-family:Verdana;">a band at 1622 cm</span><sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">&#8722;</span></span></span>1</span></sup><span style="font-family:Verdana;"> and this was assigned to the </span><i><span style="font-family:Verdana;">v </span></i><span style="font-family:Verdana;">(C=N), which is a feature of azomethine group. The same band was observed to shift to lower frequencies 1577 and 1599 cm</span><sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">&#8722;</span></span></span>1</span></sup><span style="font-family:Verdana;"> in the complexes suggesting coordination of the Schiff base with the respective metal(II) ions. Molar conductan</span></span><span><span style="font-family:Verdana;">ce values 14.58 and 12.65 Ω</span><sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">&#8722;</span></span></span>1</span></sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">&#8729;</span></span></span>cm</span><sup><span style="font-family:Verdana;">2</span></sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">&#8729;</span></span></span>mol</span><sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">&#8722;</span></span></span>1</span></sup><span style="font-family:Verdana;"> show that the metal complexes were non-electrolyte in nature. The magnetic susceptibility of the complexes was determined and the gram magnetic susceptibility of the complexes was found to be positive, revealing that they are paramagnetic. The elemental analysis of the complexes for C, N and H determined suggested 1:1 metal to ligand ratio. The result of the antimicrobial studies showed that, the metal(II) complexes exhibited better antibacterial and antifungal activity than the Schiff base.</span></span> 展开更多
关键词 Metal(ii) complexes Schiff Base Antibacterial and Antifungal Studies
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Comparative Studies of Some Novel Cu(II) Polymeric Complexes Derived from Cyanoacetylhydrazine (CAH;L). The Role of Solvents Used on the Structure and Geometry of the Isolated Cu<sup>2+</sup>Complexes 被引量:1
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作者 Mohsen M. Mostafa 《Open Journal of Inorganic Chemistry》 2021年第4期111-130,共20页
Novel polymeric Cu<sup>2+</sup> complexes derived from the reaction of cyanoacetylhydrazine (<strong>CAH</strong>;<strong>L</strong>) with CuCl<sub>2</sub>•2H<sub>... Novel polymeric Cu<sup>2+</sup> complexes derived from the reaction of cyanoacetylhydrazine (<strong>CAH</strong>;<strong>L</strong>) with CuCl<sub>2</sub>•2H<sub>2</sub>O in different solvents were synthesized and characterized. The isolated solid polymeric complexes were investigated using modern conventional physicochemical and spectral (IR, <sup>1</sup>H-NMR, UV-Vis. ESR, Raman), magnetic and thermal studies. The results revealed that <strong>CAH</strong> behaves in different ways towards the coordination of the Cu<sup>2+</sup> ion. The promotion of solvents to the cyano group was discussed on the basis of the solvent and the Cu<sup>2+</sup> ion used. Magnetic and spectral studies suggest octahedral geometry is proposed for the Cu<sup>2+</sup> complexes. EPR studies indicate the existence of polymeric complexes depending on the results of <i>g</i>-values. The results suggest that the number of copper atoms ranges from three to twelve atoms. The molecular modeling is drawn and some chemical characteristics are calculated such as chemical reactivity and energy components are investigated between the different types of the ligands. 展开更多
关键词 Polymeric Cu(ii) complexes ESR Studies Cyanoacetylhydrazine DFT Studies
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Synthesis and Characterization of Nickel(II) and Copper(II) Complexes with Schiff Base (1R,2R)-(-)-Diaminocyclohexane-N,N'-bis(3-tert-butyl-5-(4'-benzoic acid)-salicylidene)
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作者 朱成峰 袁国赞 +1 位作者 盛恩宏 崔勇 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2009年第10期1304-1310,共7页
Two homochiral metallosalen complexes, Ni(salen) (salen = (1R,2R)-(-)-diamino- cyclohexane-N,N′-bis(3-tert-butyl-5-(4′-benzoic acid)-salicylidene) 1 and Cu(salen) 2, have been synthesized and characteri... Two homochiral metallosalen complexes, Ni(salen) (salen = (1R,2R)-(-)-diamino- cyclohexane-N,N′-bis(3-tert-butyl-5-(4′-benzoic acid)-salicylidene) 1 and Cu(salen) 2, have been synthesized and characterized by IR, microanalysis, TGA, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 4. For 1, a = 12.082(2), b = 15.447(3), c = 18.784(4)A^°, V= 3505.7(12)A^°3, Mr = 731.50, Dc = 1.386 g/cm^3, μ = 0.606 mm^-1, F(000) = 1544, the final GOOF = 1.043, R = 0.0496 and wR = 0.1248 for 4791 observed reflections with I 〉 2σ(I). For 2, a = 12.181(2), b = 15.501(3), c = 18.877(4) A^°, V = 3564.3(12)A^°3, Mr = 736.33, Dc = 1.372 g/cm^3, μ = 0.665 mm^-1, F(000) = 1548, the final GOOF = 1.062, R = 0.0575 and wR = 0.1508 for 4562 observed reflections with I 〉 2σ(I). The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. An infinite two-dimensional network is generated by hydrogen bonding interactions and intermolecular π…π interactions. 展开更多
关键词 crystal structure SALEN niekel(Ⅱ) complex copper(ii complex
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Electrochemical Tuning by Polarized UV Light Induced Molecular Orientation of Chiral Salen-type Mn(II) and Co(II) Complexes in an Albumin Matrix
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作者 Eirika Tsuda Yuya Mitsumoto +4 位作者 Kazuya Takakura Nobumitsu Sunaga Takashiro Akitsu Taro Konomi Masahiro Katoh 《Journal of Chemistry and Chemical Engineering》 2016年第2期53-59,共7页
The authors have prepared supramolecular systems as artificial metalloproteins composed of several chiral salen-type Mn(II) and Co(II) complexes in a HSA (human serum albumin) matrix. The docking was discussed b... The authors have prepared supramolecular systems as artificial metalloproteins composed of several chiral salen-type Mn(II) and Co(II) complexes in a HSA (human serum albumin) matrix. The docking was discussed by UV-vis spectral changes and a ligand-protein docking simulation program. After linearly polarized UV light irradiation, that anisotropy of molecular orientation of the complexes increased was confirmed by polarized IR spectra. The authors have observed that the electrochemical behavior of the aligned complexes incorporating diphenyl groups in HSA can be tuned without UV radiation damage of HSA higher structures. 展开更多
关键词 Redox potential Schiff base Mn(ii complex Co(ii complex albumin.
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In vitro antitumor activity and targeted sites of two novel platinum-based(II) complexes on SW620 colon cancer cell line
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作者 Rui Li Baolin Liu Hongzhuan Yin Feng Xu Qi Su 《The Chinese-German Journal of Clinical Oncology》 CAS 2011年第9期510-516,共7页
Objective:The aim of our study was to evaluate the in vitro antitumor activity of two novel platinum-based(II) complexes(2.3-pyridinedicarboxylic acid dehydrate platinum and 2.3-pyrazinedicarboxylic acid dehydrate pla... Objective:The aim of our study was to evaluate the in vitro antitumor activity of two novel platinum-based(II) complexes(2.3-pyridinedicarboxylic acid dehydrate platinum and 2.3-pyrazinedicarboxylic acid dehydrate platinum),which were concurrently provided with hydrophilic carboxyl group and lipophilic pyrazinyl or pyridyl group,on SW620 colorectal cancer cell line and the impact of the two compounds on the cell cycle and apoptosis of the cells when compared with the oxaliplatin,desiring the new ligand combined with hydrophilic and lipophilic properties would facilitate the transportation and transmembrane of the drugs,showing a better antitumor activity.Methods:After SW620 cells were treated with different doses of the three platinum-based agents for 24,48 and 72 h,the cell proliferation inhibition rate was determined using methyl thiazolyl tetrazolium(MTT) assay;the morphology of cells were evaluated under inverted microscope;the changes in cell cycle were determined using flow cytometry;the percent apoptosis was measured using Annexin V/PI double staining and the micromorphology of the cells after drug exposure was evaluated using scanning electron microscopy.Results:The evaluation on the proliferation inhibition rate revealed that the three platinum-based agents inhibited the SW620 cells in a time-and dose-dependent manner and showed different strengths as pyridine > pyrazine > Oxa.Under optical microscope,the morphological changes such as cell shrinkage,round cells and dead cells were frequently observed after drug exposure.Cell cycle determination showed that all of the three agents could function to block the cells converting from phase S to phase G2M.Apoptosis evaluation revealed that the three agents promoted the apoptosis of SW620 cells in a time-and dose-dependent manner and showed different strengths as pyridine > pyrazine > Oxa.Typical early and late apoptotic morphological changes could be detected during electron microscopy.Conclusion:The two novel platinum-based(II) complexes showed a stronger antitumor effect on SW620 cells than oxaliplatin,with the targeted site at a certain phase of cell cycle and apoptosis. 展开更多
关键词 platinum-based(ii complex SW620 cell line antitumor activity targeted site
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Two Cu(II)-Nitronyl Nitroxide Complexes Including Cyclic Dimer: Synthesis, Structures and Magnetic Interactions
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作者 Jing Chen Chenzhuo Liu +1 位作者 Youjuan Zhang Qinglun Wang 《Open Journal of Inorganic Chemistry》 CAS 2022年第4期57-69,共13页
Using two new flexible and functional nitronyl nitroxide radicals as ligands, two copper (II) complexes {[Cu(hfac)<sub>2</sub>]<sub>3</sub>(NITmPhO3Py)<sub>2</sub>}<sub>n... Using two new flexible and functional nitronyl nitroxide radicals as ligands, two copper (II) complexes {[Cu(hfac)<sub>2</sub>]<sub>3</sub>(NITmPhO3Py)<sub>2</sub>}<sub>n</sub> (1) and [Cu(hfac)<sub>2</sub><sub> </sub>(NIToPhO3Py)]<sub>2</sub> (2) (NITmPhO3Py = 2-[(3-methoxy-pyridinyl)phen-3-yl]- 4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, NIToPhO3Py = 2-[(3-methoxy-pyridinyl)phen-2-ly]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, hfac = hexafluoroacetylacetone), have been characterized structurally and magnetically. The X-ray crystal analyses showed that complex 1 displayed a chain polymer structure which formed with {[Cu(hfac)<sub>2</sub>]<sub>3</sub>(NITmPhO3Py)<sub>2</sub>}<sub>n</sub> due to the cross-linking of two cyclic binuclear fragments {[Cu(hfac)<sub>2</sub>]<sub>2</sub>(NITmPhO3- Py)<sub>2</sub>} via the bridging unit [Cu(hfac)<sub>2</sub>];complex 2 presented a binuclear cyclic structure [Cu(hfac)<sub>2</sub>]<sub>2</sub>(NIToPhO3Py)<sub>2</sub>. The magnetic behaviors of the two complexes 1 and 2 have been investigated. Magnetic studies showed that antiferromagnetic interactions dominated in complex 1, while there existed ferromagnetic interactions between Cu(II) and coordinated NO group in complex 2. 展开更多
关键词 Flexible Nitronyl Nitroxide Cu(ii) Complex SYNTHESIS Characterization Magnetic Property
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α-Glucosidase Inhibition by New Schiff Base Complexes of Zn(II)
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作者 Rie Miyazaki Hiroyuki Yasui Yutaka Yoshikawa 《Open Journal of Inorganic Chemistry》 2016年第2期114-124,共11页
There are many reports that divalent alkaline earth, first-row transition metals, and Zn(II) ions have α-glucosidase inhibitory effects. Cu(II) and Zn(II) ions, in particular, have strong α-glucosidase inhibitory ef... There are many reports that divalent alkaline earth, first-row transition metals, and Zn(II) ions have α-glucosidase inhibitory effects. Cu(II) and Zn(II) ions, in particular, have strong α-glucosidase inhibitory effects. Several Schiff bases also display α-glucosidase inhibitory effects. In this study, we focused on safe and highly effective complexes including Zn(II) ion. We prepared and characterized the Zn(II) complexes with four different Schiff bases (N-salicylidene-β-alanine (N-sβ), N-N’-bis (salicylidene) ethylenediamine (N-bsE), N, N’-bis (salicylidene)-phenylenediamine (N-bsP), and 1-[(2-dimethylaminoethylimino) methyl]naphtholate (DMN)) and investigated their α-glucosidase inhibitory effects in vitro, using α-glycosidases from Saccharomyces sp. and rat small intestine, and in vivo, using a sucrose tolerance test. The Zn(II) complexes with DMN showed the highest in vitro and in vivo α-glucosidase inhibitory effects in this study. 展开更多
关键词 α-Glucosidase Inhibitory Effect Zn(ii) complexes Schiff Bases Diabetes Mellitus
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Elimination of GGTA1,CMAH,β4GalNT2 and CIITA genes in pigs compromises human versus pig xenogeneic immune reactions
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作者 Jing Xu Jilong Ren +11 位作者 Kai Xu Minghui Fang Meina Ka Fei Xu Xin Wang Jing Wang Zhiqiang Han Guihai Feng Ying Zhang Tang Hai Wei Li Zheng Hu 《Animal Models and Experimental Medicine》 CAS CSCD 2024年第4期584-590,共7页
Background:Pig organ xenotransplantation is a potential solution for the severe organ shortage in clinic,while immunogenic genes need to be eliminated to improve the immune compatibility between humans and pigs.Curren... Background:Pig organ xenotransplantation is a potential solution for the severe organ shortage in clinic,while immunogenic genes need to be eliminated to improve the immune compatibility between humans and pigs.Current knockout strategies are mainly aimed at the genes causing hyperacute immune rejection(HAR)that occurs in the first few hours while adaptive immune reactions orchestrated by CD4 T cell thereafter also cause graft failure,in which process the MHCⅡmolecule plays critical roles.Methods:Thus,we generate a 4-gene(GGTA1,CMAH,β4GalNT2,and CIITA)knockout pig by CRISPR/Cas9 and somatic cell nuclear transfer to compromise HAR and CD4 T cell reactions simultaneously.Results:We successfully obtained 4KO piglets with deficiency in all alleles of genes,and at cellular and tissue levels.Additionally,the safety of our animals after gene editing was verified by using whole-genome sequencing and karyotyping.Piglets have survived for more than one year in the barrier,and also survived for more than 3 months in the conventional environment,suggesting that the piglets without MHCⅡcan be raised in the barrier and then gradually mated in the conventional environment.Conclusions:4KO piglets have lower immunogenicity,are safe in genomic level,and are easier to breed than the model with both MHCⅠandⅡdeletion. 展开更多
关键词 CD4 T cell genetically edited pig immune rejection major histocompatibility complex ii XENOTRANSPLANTATION
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Samarium(II) Diiodide Induced Polarity Inversion of π-Allyl Palladium Complexes: The Formation of Allylic Selenides
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作者 XinJianZHAO HuaRongZHAO 《Chinese Chemical Letters》 SCIE CAS CSCD 2002年第5期396-397,共2页
Allylic acetates were reduced with Pd(0)-SmI2 in the presence of ArSeBr to form corresponding allylic selenides in good yields.
关键词 Allyl acetates allylic selenides arylselenenyl bromides palladium complexes polarity inversion. Samarium(ii) Diiodide Induced Polarity Inversion of p-Allyl Palladium complexes: The Formation of Allylic Selenides Xin Jian ZHAO1 Hua Rong ZH
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Synthesis of Branched Polyethylene via Bulky α-Diimine Nickel(II)-Catalyzed Ethylene Chain-Walking Polymerization
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作者 Zhengquan Dong Pei Li +1 位作者 Guoyong Xu Fuzhou Wang 《Open Journal of Organic Polymer Materials》 2024年第1期1-12,共12页
The catalysis of olefin polymerization through the chain-walking process is a subject of great interest. In this contribution, the successful synthesis of a Brookhart-type unsymmetrical α-diimine nickel catalyst Ni, ... The catalysis of olefin polymerization through the chain-walking process is a subject of great interest. In this contribution, the successful synthesis of a Brookhart-type unsymmetrical α-diimine nickel catalyst Ni, which contains both dibenzhydryl and phenyl groups, was determined by X-ray crystallography. The compound has a pseudo-tetrahedral geometry at the Ni center, showing pseudo-C2-symmetry. Upon activation with modified methylaluminoxane (MMAO), Ni1 exhibits high catalytic activity up to 1.02 × 107 g PE (mol Ni h)−1 toward ethylene polymerization, enabling the synthesis of high molecular weight branched polyethylene. The molecular weights and branching densities could be tuned over a very wide range. The polymerization results indicated the possibility of precise microstructure control, depending on the polymerization temperature. The branching densities were decreased with increasing the polymerization temperature. 展开更多
关键词 Ethylene Polymerization α-Diimine Ni(ii) Complex Chain-Walking Polymerization Branched Polyethylene
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Theoretical Studies on Structures and Spectroscopic Properties of Highly Efficient Phosphorescent [Ru(terpy)(phen)X]+ Complexes
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作者 金丽 张建坡 +1 位作者 张红星 白福全 《Chinese Journal of Chemical Physics》 SCIE CAS CSCD 2011年第4期391-398,I0003,共9页
The ground and the lowest-lying triplet excited state geometries, electronic structures, and spectroscopic properties of three mixed-ligand Ru(II) complexes [Ru(terpy)(phen)X]+ (terpy=2,2',6',2″-terpyridine... The ground and the lowest-lying triplet excited state geometries, electronic structures, and spectroscopic properties of three mixed-ligand Ru(II) complexes [Ru(terpy)(phen)X]+ (terpy=2,2',6',2″-terpyridine, phen=l,10-phenanthroline, and X=-C-=CH (1), X=Cl (2), X-CN (3)) were investigated theoretically using the density functional theory method. The ground and excited state geometries have been fully optimized at the B3LYP/LanL2DZ and UB3LYP/LanL2DZ levels, respectively. The absorption and emission spectra of the com- plexes in CHaCN solutions were calculated by time-dependent density functional theory with the PCM solvent model. The calculated bond lengths of Ru-C, Ru-N, and Ru-Cl in the ground state agree well with the corresponding experimental results. The highest occupied molecular orbital were dominantly localized on the Ru atom and monodentate X ligand for 1 and 2, Ru atom and terpy ligand for a, while the lowest unoccupied molecular orbital were π*(terpy) type orbital. Therefore, the lowest-energy absorptions of 1 and 2 at 688 and 631 nln are attributed to a dyz (Ru)+Tr/p(X)--π* (terpy) transition with MLCT/XLCT (metal-to-ligand charge transfer/X ligand to terpy ligand charge transfer) character, whereas that of 3 at 529 nm is related to a dyz (Ru)+π(terpy)-π* (terpy) transition with MLCT and ILCT transition character. The calculated phosphorescence of three complexes at 1011 nm (1), 913 nm (2), and 838 nm (3) have similar transition properties to that of the lowest-lying absorption. It is shown that the lowest lying absorptions and emissions transition character of these Ru(II) complexes can be tuned by changing the electron-withdrawing ability of the monodentate ligand. 展开更多
关键词 Mixed-ligand Ru(ii complexes Electronic structure Spectroscopic property DFT calculation UB3LYP method
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Differential response of injured and healthy retinas to syngeneic and allogeneic transplantation of a clonal cell line of immortalized olfactory ensheathing glia:a double-edged sword
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作者 María Norte-Muñoz María Portela-Lomba +9 位作者 Paloma Sobrado-Calvo Diana Simón Johnny Di Pierdomenico Alejandro Gallego-Ortega Mar Pérez JoséMCabrera-Maqueda Javier Sierra Manuel Vidal-Sanz María Teresa Moreno-Flores Marta Agudo-Barriuso 《Neural Regeneration Research》 SCIE CAS 2025年第8期2395-2407,共13页
Olfactory ensheathing glia promote axonal regeneration in the mammalian central nervous system,including retinal ganglion cell axonal growth through the injured optic nerve.Still,it is unknown whether olfactory enshea... Olfactory ensheathing glia promote axonal regeneration in the mammalian central nervous system,including retinal ganglion cell axonal growth through the injured optic nerve.Still,it is unknown whether olfactory ensheathing glia also have neuroprotective properties.Olfactory ensheathing glia express brain-derived neurotrophic factor,one of the best neuroprotectants for axotomized retinal ganglion cells.Therefore,we aimed to investigate the neuroprotective capacity of olfactory ensheating glia after optic nerve crush.Olfactory ensheathing glia cells from an established rat immortalized clonal cell line,TEG3,were intravitreally injected in intact and axotomized retinas in syngeneic and allogeneic mode with or without microglial inhibition or immunosuppressive treatments.Anatomical and gene expression analyses were performed.Olfactory bulb-derived primary olfactory ensheathing glia and TEG3 express major histocompatibility complex classⅡmolecules.Allogeneically and syngenically transplanted TEG3 cells survived in the vitreous for up to 21 days,forming an epimembrane.In axotomized retinas,only the allogeneic TEG3 transplant rescued retinal ganglion cells at 7 days but not at 21 days.In these retinas,microglial anatomical activation was higher than after optic nerve crush alone.In intact retinas,both transplants activated microglial cells and caused retinal ganglion cell death at 21 days,a loss that was higher after allotransplantation,triggered by pyroptosis and partially rescued by microglial inhibition or immunosuppression.However,neuroprotection of axotomized retinal ganglion cells did not improve with these treatments.The different neuroprotective properties,different toxic effects,and different responses to microglial inhibitory treatments of olfactory ensheathing glia in the retina depending on the type of transplant highlight the importance of thorough preclinical studies to explore these variables. 展开更多
关键词 cell therapy immune recognition major histocompatibility complex class ii(MHCii) neuroprotection olfactory ensheathing glia retinal ganglion cells
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Synthesis, Structure and Physical Properties of a Barium(II) Complex with 5-Sulfoisophthalic Acid Sodium 被引量:9
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作者 吴刚 王小锋 +1 位作者 韦昊 刘振锋 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2011年第8期1095-1100,共6页
An alkaline earth metal-organic framework [Ba(Hsip)(H2O)4]n (1, NaH2sip = 5-sulfoisophthalic acid sodium) has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba(II) ... An alkaline earth metal-organic framework [Ba(Hsip)(H2O)4]n (1, NaH2sip = 5-sulfoisophthalic acid sodium) has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba(II) atom coordinates to one ligand Hsip3- and four water molecules with a distorted nine-coordinated monocapped tetragonal antiprism geometry. Each Hsip2- anion acts as a μ3-bridging ligand, in which two carboxylate groups adopt the same bidentate chelating coordinating model and the sulfonate group takes a monodentate coordinating model, resulting in a wave-like two-dimensional network with a (6, 3) topological structure. The two-dimensional networks are further linked by O–H···O to form a three-dimensional structure. Luminescent property and thermal stability of complex 1 are investigated. 1 belongs to the orthorhombic system, space group Pna21 with a = 7.3333(2), b = 16.7044(3), c = 10.4817(2), Z = 4, V = 1283.99(5)3, Mr = 453.58, Dc = 2.346 g/cm3, F(000) = 880, μ = 3.314 mm–1, the final R = 0.0261 and wR = 0.0592 for 2425 observed reflections with I 2σ(I). 展开更多
关键词 Ba(ii complex sulfonate group carboxylate group luminescent property thermal stability
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Synthesis and Structure of Nickel(II) Compound with Tetradentate Schiff-base Ligand and Diazido Monohydrate 被引量:5
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作者 牛德仲 路再生 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 北大核心 2001年第5期387-390,共4页
The complex [Ni(L)(N3)2](H_2O (L=N,N(-Bis(2-pyridylaldehyde) condensation 1,3-diaminopropane) was synthesized by the reaction of NiCl2(6H_2O with 2-pyridylaldehyde and 1,3-diaminopropane and sodium azide in the ethan... The complex [Ni(L)(N3)2](H_2O (L=N,N(-Bis(2-pyridylaldehyde) condensation 1,3-diaminopropane) was synthesized by the reaction of NiCl2(6H_2O with 2-pyridylaldehyde and 1,3-diaminopropane and sodium azide in the ethanol. A single-crystal X-ray study shows that the complex is a six-coordinated nickel (II) with an octahedral environment compound (C15H18N10NiO). The crystal is orthogonal, space group Pbca, with unit cell parameters: a = 13.577(3), b = 15.261(3), c = 17.554(4) ?, V= 3637(1) ?3, Z=8, Mr=413.10, Dc=1.509 g/cm3, ( = 1.096 mm-1, F(000) = 1712, T = 293(2)K, R = 0.0411, wR = 0.1048 for 2888 reflections with I >2( (I). The distances between Ni and N atoms (N(1), N(2), N(3), N(4)) range from 2.050(2) to 2.140(2)?. The distances of Ni-N(5) and Ni-N(8) are 2.115(3) and 2.133(3)?, respectively. The solvent molecule H_2O(O(1)) is linked by hydrogen bonds with O(1) and N(5) and N(8) atoms. Their distances are 2.881(+x, +y, +z) and 2.893(0.5+x, y, 0.5+z)?, respectively. 展开更多
关键词 crystal structure nickel (ii) complex 2-pyridylaldehyde 1 3-diaminopropane azido complex
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Synthesis, Structure and Fluorescence of a Copper(II) Complex [Cu_2(bipy)_2(Hpht)_2Cl](Hpht)(bipy=2,2'-Bipyridine,H_2pht=o-Phthalic Acid) 被引量:4
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作者 李强 郑发鲲 +3 位作者 蔡丽珍 陈文通 郭国聪 黄锦顺 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 北大核心 2005年第3期354-358,共5页
The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was det... The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature. 展开更多
关键词 copper(ii) complex crystal structure SYNTHESIS LUMINESCENCE
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Synthesis and Crystal Structure of a Zinc(II) Complex with 2-(4′-Chlorine-benzoyl)-benzoic Acid and 1,10-Phenanthroline 被引量:5
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作者 李秀梅 王庆伟 刘博 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2011年第11期1646-1649,共4页
A new metal-organic complex Zn2(cbba)4(phen)2 (Hcbba = 2-(4'chlorine-ben- zoyl)benzoic acid, phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by elemental analy... A new metal-organic complex Zn2(cbba)4(phen)2 (Hcbba = 2-(4'chlorine-ben- zoyl)benzoic acid, phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The compound crystallizes in orthorhombic, space group Pbcn with a = 12.0821(II), b = 18.3140(17), c = 30.961(3) A, V= 6850.7(11) A^3, C80H48C14N4O12Zn2, Mr= 1529.76, Dc = 1.483 g/cm^3,μ(MoKa) = 0.925 mm^-1, F(000) = 3120, Z = 4, the final R = 0.0559 and wR = 0.1146 for 3963 observed reflections (I〉 2σ(I)). In the crystal structure, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from the phen ligand, showing a distorted square-pyramidal geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions and shows yellow photoluminescent property at room temperature. 展开更多
关键词 hydrothermal synthesis crystal structure zinc(ii complex
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