Interactions Between Anticancer Pt(II) complexes and Human Erythrocyte Spectrin *

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.

电化学镀铂主盐在涡轮叶片Pt/Al涂层上的应用

电化学镀铂制备的Pt/Al涂层是延长涡轮叶片热端部件使用寿命的最重要技术,其中铂配合物是铂镀层中铂的来源,铂配合物的化学结构和理化性质直接影响电化学镀铂工艺,本文通过综述氯铂酸盐、磷酸氢四氨合铂、二亚硝基二氨合铂、羟铂酸钾、硫酸二亚硝基铂酸钾等5类常见铂配合物的化学结构、理化性质及其作为电化学镀铂主盐在铂镀层上的应用,以期对铂配合物的化学结构和理化性质与铂镀层的性能之间的影响关系有深入的理解,特别关注获得的铂镀层在热障涂层上的应用。

Elimination of GGTA1,CMAH,β4GalNT2 and CIITA genes in pigs compromises human versus pig xenogeneic immune reactions

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.

Synthesis and Crystal Structure of a Novel Tetranuclear Manganese(II) Complex with a Tripodal Peptide Ligand

The title complex, [Mn2(O-Py3A)(DPK-CH3O)(CH3OH)]2?2ClO4?4CH3OH (C64H70Cl2- Mn4N12O22, Py3AH = N-(bis(2?-pyridyl)methyl)-2-pyridinecarboxamide, DPK = di-2-pyridyl ketone) has been synthesized and its crystal structure was determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 12.667(9), b = 16.793(12), c = 17.070(13) ?, β = 100.997(13)o, V = 3565(5) ?3, Dc = 1.537 g/cm3, Mr = 1649.98, Z = 2, μ(MoKα) = 0.851 mm-1 and F(000) = 1696. The final R and wR are 0.0639 and 0.1320, respectively for 3979 observed reflec- tions with I > 2σ(I). In the tetranuclear complex, each Mn(II) atom is six-coordinated and the four Mn(II) atoms are coplanar, exhibiting a parallelogram arrangement; while the deprotonated ligands are oxidized to O-Py3A2- anions and cleaved to DPK-CH3O– anions (the monoanion of mono- methylated diol of DPK) furthermore.

Synthesis and Crystal Structure of Cu(II) Complex with 2,9-Bis(n-2',5'-diazaheptanyl)-1,10-phenanthroline

The Cu(II) complex with the ligand 2,9-bis(n-2?5?diazaheptanyl)-1,10-phenan- throline (L) has been synthesized and characterized by single-crystal X-ray diffraction. It crys- tallizes in the monoclinic system, space group P21/n with a = 12.549(4), b = 13.544(4), c = 16.767(5) ? = 107.179(5), C22H32Cl2N6CuO8, Mr = 642.98, V = 2722.5(13) 3, Z = 4, Dc = 1.569 g/cm3, ?= 1.056 mm-1, F(000) =1332, the final R = 0.0733 and wR = 0.1581. The X-ray analysis revealed that the Cu(II) ion is coordinated by six nitrogen atoms of the ligand, in which two nitrogen from phenanthroline and another two from the imine groups near phenanthroline are in the equatorial plane while the two from imine groups at the end of both arms in the axial positions. The coordination geometry can be described as a compressed octahedron.

Synthesis of Branched Polyethylene via Bulky α-Diimine Nickel(II)-Catalyzed Ethylene Chain-Walking Polymerization

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.

2-萘甲酸/1,10-菲啰啉共同构筑Mn(II)配合物的合成及固态发光

在溶剂热条件下,以2-萘甲酸(HL)与1,10-菲啰啉(phen)为配体、碳酸锰为金属源合成了一例双核锰配合物[Mn_(2)(L)_(4)(phen)_(2)(H_(2)O)_(2)](1)。通过单晶X射线衍射、元素分析、傅里叶变换红外光谱、粉末X射线衍射和热重分析等对配合物1进行结构表征。单晶衍射分析表明配合物1属于三斜晶系,P1空间群,晶胞参数为a=0.76989(5)nm,b=1.17586(5)nm,c=1.66830(9)nm,α=107.074(5)°,β=96.167(5)°,γ=106.901(5)°。不对称单元由一个锰离子、两个2-萘甲酸根、一个1,10-菲啰啉和一个水分子组成,Mn(II)呈扭曲的八面体构型。两个不对称单元之间通过羧基氧原子桥接形成双核分子,双核结构之间通过π…π堆积作用形成2D超分子结构。荧光光谱分析结果表明:配合物1具有良好的荧光性能,最大发射波长为416 nm(λ_(ex)=302 nm)。热重分析表明配合物1能够稳定到117℃,之后开始失水(失水量为3.18%),脱水之后的结构能稳定到223℃,之后有机骨架开始坍塌。Hirshfeld表面分析研究了分子间的相互作用。

Ti/IrO_2-Pt电极电化学降解酸性橙II染料废水研究

研究采用Ti/IrO2-Pt电极为阳极,对酸性橙II染料废水进行电化学降解研究。讨论了电解质、电流密度、溶液pH等工艺条件对酸性橙II降解的影响,对污染物的电化学降解过程进行了分析,并通过重复试验和电极表面形态比较等手段对电极耐用性进行了考察。结果表明,以氯化钠为电解质有助于酸性橙II的快速降解;加大氯化钠添加量和电流密度能缩短降解时间,但过高的电流密度会引起溶液中氯含量的流失;中性pH更有利于酸性橙II的降解。电化学降解过程中,Ti/IrO2-Pt电极可将各种中间产物无选择性的同步矿化。在氯化钠浓度为0.005 mol.L-1、电流密度10 mA.cm2、初始pH为6.8的条件下,质量浓度为50 mg.L-1的酸性橙II在30 min内被完全降解,电解2 h后TOC去除率达到45%左右。

几种(C^N)Pt^(II)Q 型配合物的电子结构和紫外-可见吸收光谱(英文)

在B3LYP/LANL2DZ水平上优化了三种(C^N)PtIIQ型配合物基态的几何结构,进行了频率计算,并采用含时密度泛函(TD-DFT)方法结合极化连续体模型(PCM)计算了目标配合物在CH2Cl2溶液中的电子结构和紫外-可见吸收光谱.计算值与文献报道值相似.计算结果表明这三种(C^N)PtIIQ型配合物在可见光区都有强度较大而且宽的吸收峰,它们的最低能量吸收峰的跃迁具有ILCT(配体内部电荷转移)和部分MLCT(金属向配体的电荷转移)的特征,不同于PtIIQ2型配合物在多数情况下表现出的ILCT的跃迁性质.

Preparation of Platinum(II) Complexes with 1-β-D-Ribofuranosyl-1,2,4-triazole-3-carboxamide and its Deoxy-analogue

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.

Synthesis, Structure and Physical Properties of a Barium(II) Complex with 5-Sulfoisophthalic Acid Sodium

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）.

Dioxygen Affinity and Catalytic Performance of Bis-(furaldehyde) Schiff Bases Co(II) Complexes in Cyclohexene Oxidation

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.

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)

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.

Synthesis and Crystal Structure of a Zinc(II) Complex with 2-(4′-Chlorine-benzoyl)-benzoic Acid and 1,10-Phenanthroline

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.

Synthesis, Crystal Structure and DNA Binding Studies of a Nickel(II) Complex with 2-Aminomethylbenzimidazole and Demethylcantharate

A new mixed-ligand nickel（Ⅱ） complex, [Ni（L）（DCA）（H2O）]·2H2O （L = C8H9N3, 2-aminomethyl-benzimidazole, DCA2- = 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, demethylcantharate, C8H8O5）, has been synthesized and characterized. The structure of the complex was determined by single-crystal X-ray diffraction. It is of monoclinic system, space group P21/c with a = 7.7211（7）, b = 12.0799（12）, c = 19.7867（19）, β = 100.390（6）°, V = 1815.2（3） nm3, Dc = 1.625 g·cm-3, Ζ = 4, F（000） = 928, R = 0.0314 and wR = 0.0822. In addition, the interaction between the complex and DNA was studied by means of fluorescence spectra and viscosity. The results indicate that the complex binds to DNA by the mode of partial intercalation with the Stern-Volmer constants Ksv of 3.81 × 104 mol·L-1.

Synthesis, Crystal Structure and Calculated β Value of a Tetrahedral Zinc (II) Complex——Zn(2-NH_2py)_2Br_2

A new zinc(II) complex, Zn(2-NH2py)2Br2 (py=pyridine), has been synthesized, and its molecular structure has been confirmed by IR, elemental analysis and -ray crystal structure analysis. Its space group is P21/n with Mr=413.43 (C10H12Br2N4Zn), a=7.435(2), b=12.865(3), c=14.186(4)? b=94.08(2)? V=1353.5(5) 3, Z=4, Dc=2.029 g/cm3, F(000)=328, ?2.378mm－1, R=0.0283, wR=0.0501. The total observed reflections with I≥2?I) were 5314, of which the independent reflections were 3106. The complex structure contains a distorted tetrahedron formed by four atoms coordinated to zinc atom, namely two bromide atoms and two nitrogen atoms. The two ZnBr bond lengths within one molecule, 2.3763(6) and 2.4002(5)? respectively, are not equal; and so are the two ZnN bond lengths, which are 2.031(2) and 2.044(2)?respectively. The calculation results using PM3 method through MOPAC software package in Chem 3D show that its first molecular hyperpolarizability b value is 5.210－30esu, which is comparable with that of p-nitroaniline. No bulk SHG effect has been detected due to the centrosymmetric space group.

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc(II) Complex with 2,2′-Diphenic Acid and 2,2′-Bipyridine Ligands

A new dinuclear complex [Zn（dpa）（bipy）（H2O）]2 （dpa = 2,2＇-diphenic acid, bipy = 2,2＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 10.960（2）, b = 9.4841（18）, c = 20.599（4）, β = 104.452（3）o, V = 2073.4（7）3, C48H36N4O10Zn2, Mr = 959.55, Dc = 1.537 g/cm3, μ（MoKα） = 1.225 mm-1, F（000） = 984, Z = 2, the final R = 0.0364 and wR = 0.0843 for 2788 observed reflections （I 〉 2σ（I））. In the crystal structure, the zinc atom is five-coordinated with two carboxylate oxygen atoms from different dpas, one coordinated water molecule and two nitrogen atoms from bipy ligands, showing a slightly distorted triangular bipyramidal geometry. Furthermore, it exhibits a zero-dimensional network structure with a sixteen-membered ring and shows yellow photoluminescent property at room temperature.

Synthesis, Crystal Structure and Properties of a Copper Complex with the Bicycle[2.2.1]-2-heptene-5,6-dicarboxylic Acid

A new copper complex 2{Cu（C10H8N2）[C8H11O2（COO）]（H2O）3}·（H2O）5 with bicycle[2.2.1]hept-2-en-5,6-dicarboxylic acid（H2L） [C7H8（COOH）2], basic copper carbonate and 2,2＇-bipyridine has been synthesized in the mixed solvents of methanol and water. It crystallizes in the triclinic system, space group P1, with a = 7.4626（5）, b = 11.9779（8）, c = 12.9841（8）A, α = 109.7040（10）, β = 98.7550（10）, γ = 90.6240（10）°, V = 1077.50（12）A3, Dc = 1.538 g/cm^3, Z = 1, F（000） = 520, GOOF = 1.065, R = 0.0360 and wR = 0.0950. The copper ion is coordinated with four oxygen atoms from one H2 L molecule and three water molecules together with two nitrogen atoms from the 2,2＇-bipyridine molecule, forming a distorted octahedral coordination geometry. The thermal stability and electrochemical properties were also studied.

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

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.

Mild Hydrothermal Synthesis and Optical Properties of the Complex Fluoride KMgF_3 Doped with Eu

KMgF3 doped with Eu was synthesized by mild hydrothermal method at 240C for the first time. The excitation and emission spectra of the KMgF3 : Eu2+ phosphor were measured. Comparing with the sample synthesized through solid state reaction, the variation in the excitation spectra at 360 nm resulted from the existences of VK color centers; the low emission intensity was due to Eu2+ having transferred part energy to VK color centers.