Synthesis, Structure, and DNA Binding of a Platinum(Ⅱ) Complex Based on the 3,4,5-Trimethoxy-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline

A new platinum（Ⅱ） complex of [Pt（chda）（3,4,5-triopip）]Cl·2H2O（1） based on 3,4,5-trimethoxy-phenyl-1 H-imidazo[4,5-f][1,10]phenanthroline（3,4,5-triopip） has been synthesized by hydrothermal methods and its consequences are characterized by elemental analysis, IR, single-crystal X-ray diffraction, UV-Vis absorption and fluorescent spectrum. The UV-Vis absorption studies reveal that the molecule undergoes considerable interaction with the nucleic acid. In this mononuclear structure, the platinum adopts a four-coordinated square planar geometry, which may favor the intercalation between the neighboring bases of the G-quadruplex（G4） DNA.

NETWORK CROWN ETHER POLYMERS WITH CENTRIC FUNCTIONAL GROUPS．Ⅱ．SYNTHESIS OF NETWORK CROWN ETHER POLYMER WITH PENDANT SULFIDE SIDE CHAIN AND ITS PLATINUM COMPLEX

Network crewn ether polymer with pendant sulfide side ohain in the networkstructure units has been synthesized via ring- opening copolymerization of β-ethylthioethyl glycidyl ether and diethylene glycol bisglycidyl ether. A kind of active catalyst suitable for this reaction was suggested. The title polymer was found tobe a good ligand for platinous chloride, and the platinous complex could catalyze thehydrosilylation of olefins with triethoxysilane efficiently.

Synthesis, Characterization and Cytotoxicity of Ammine/Methylamine Platinum(Ⅱ) Complexes with Carboxylates

Seven novel platinum （Ⅱ） complexes [ Pt（Ⅱ） （NH3） （CH3NH2）X2] （Ⅰ-Ⅶ ） （ X： CH3COO^-, CH2CICOO^- , CHCI2COO^- , C6H5-COO^- , p-CH3O--C6H4-COO^- , p-NH2-C6H4-COO^- , p-NO2--C6H4- COO^-） were prepared and characterized by means of elemental analysis, molar conductivity, thermal analysis, IR, UV, and ^1H NMR spectrometries. The cytotoxicity against HCT-8, BGC-823, MCF-7, EJ, and HL-60 cell lines increases in the following sequence： cisplatin 〉 Ⅳ 〉 Ⅴ 〉 Ⅵ 〉 Ⅶ 〉 Ⅰ 〉 Ⅱ 〉 Ⅲ. Moreover, the complexes （ Ⅰ --Ⅻ） display substantially greater activities agaist EJ and HL-60 cell lines than those against the cell lines from other carcinomas. They can induce a concentration-dependent accumulation of HL-60 cells in the G2/M phase of the cell cycle as cisplatin. There is no significant correlation between total DNA platination levels and cytotoxicity of the complexes.

Studies of the Intramolecular Aromatic-ring Stacking Interactions in the Ternary Platinum(Ⅱ) Complexes

The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA)+, where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mol/L, KNO 3; 25 ℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands(PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen)(PCA)- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.

Synthesis,Crystal Structure and DNA Interaction of a Chiral Platinum(Ⅱ)Complex with 2-(2,3-Dimethoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline

A new platinum（Ⅱ） complex of [Pt（chda）（2,3-dmopip）]Cl·H2O（1, chda = cyclohexan-ediamine, 2,3-dmopipH = 2-（2,3-dimethoxyphenyl）-1H-imidazo[4,5-f][1,10]phenanthroline） has been synthesized by hydrothermal methods and characterized by elemental analysis, IR, single-crystal X-ray diffraction, UV-vis and fluorescent spectrum. In complex 1, the platinum adopts a four-coordinated square planar geometry. The DNA-binding interaction has been investigated. The complex can bind to DNA by an intercalative mode, presenting high DNA-binding affinity.

Investigation of Absorption Spectra of Bis(alkylxanthato)-platinum(Ⅱ) Complexs

Being widely used as good ligands,xanthates and related compounds have been extensively investigated.However,reports on Pt（Ⅱ） xanthates have been sparse so far.Watt et al.reported the synthesis and characterization of Pt（S;COR）;（R=Me,Et）,but did not provide any absorption spectra of these complexes.We prepared twelve platinum （Ⅱ） xanthate complexes and examined their absorption spectra in detail.

Quantum-Chemical Interpretation of the Spectroscopy of Highly Luminescent 1,3,5-Triazapentadiene Complexes of Platinum（Ⅱ）

The quantum-chemical calculations were performed to determine the nature of the equilibrium geometry of the ground and excited states of the 1,3,5-triazapentadiene complexes of platinum（Ⅱ） and theirs nature and structure of molecular orbitals.

STUDIES ON HETERO-MACROCYCLIC POLYETHER (Ⅱ). THE SYNTHESIS OF PLATINUM COMPLEX OF 10-SELENABENZO-15-CROWN-5 AND ITS CATALYTIC BEHAVIOR IN HYDROSILYLATION

The title complex (PtL_2Cl_2) was synthesized by reacting 10-selenabenzo-15-crown-5 (L) with potassium chloroplatinite. Its catalytic activity for the hydrosilylation of olefins by triethoxysilane, was investi gated.

Resonance Raman Spectra of Purified PS Ⅱ Core Antenna Complexes CP43 and CP47

PSⅡ core antenna complexes, CP43 and CP47, were purified from spinach (Spinacia oleracea L.) by DEAE Fractogel TSK 650S anion exchange chromatography. Their normal temperature (298 K) resonance Raman spectra were measured. The results suggest that all β carotenoids bound to CP43 and CP47 are in all trans configuration and likely in twisted conformations.

Effects of binuclear copper(Ⅱ)threonine complex on blood glucose, lipids and protection of the hearts and kidneys in diabetic mice

Aim To study the effects of binuclear copper （Ⅱ） threonine complex （Cu2 （Thr）4） as analogue of superoxide dismutase （SOD） on blood glucose, blood lipids and vessels of hearts and kidneys in diabetic mice. Methods Diabetic mouse model was established by intraperitioneal injection of alloxan. Low, middle, and high doses of Cu2（Thr）4 at 0.002%, 0.02% and 0.1% were given respectively to diabetic mice following lavage. The fasting blood glucose was determined after the diabetic mice were given Cu2 （Thr）4 for 0, 30, and 45 d. The diabetic mice were killed on the 45th day. Then glycosylated hemoglobin （HbAlc） and blood lipids were assayed, and pathologic changes in hearts and kidneys stained with HE were observed. Results Compared with the control group in which the diabetic mice were given distilled water, the value of blood glucose reduced significantly in middle dose group （P 〈 0.01 ）, followed by that in low dose group （P 〈 0.05）. TC level reduced markedly and HDL level increased significantly in all three treatment groups （P 〈 0.05）. Especially in middle dose group, cardiac muscle fibers were neatly arranged, nucleus and cytoplasm well distributed, glomeruli showing normal structure, cells well distributed and staining being normal. Conclusion Cu2 （Thr）4 reduces blood glucose, regulates blood lipids, and play protective action on the vessels of hearts and kidneys in diabetic mice. The effects of it in middle dose were better than those of other doses.

Spectral Properties and Characterization of the Modified PSⅡ Core Complexes

用组氨酸的特异性修饰剂 (DEPC)对PSⅡ核心复合物进行了化学修饰 ,并对其光谱性质进行了研究。研究结果表明 :修饰后的PSⅡ核心复合物的吸收光谱在红区发生了很大变化 ,随修饰时间的增加 ,6 80nm处的吸收逐渐下降。修饰后的PSⅡ核心复合物的荧光光谱在最初的 1min内出现荧光上升现象 ,然后逐渐下降 ,峰位蓝移。这些研究结果表明 ,组氨酸残基的修饰导致了原初电子供体P6 80结构的破坏 ,并对其功能产生了影响。

Purification and Spectral Characteristics of Cytochrome b-559 from Oxygen-evolving Photosystem Ⅱ Core Complexes of Spinach and Rice

Cytochrome b_559 in photosystem Ⅱ reaction center was purified from spinach ( Spinacia oleracea L.) and rice ( Oryza sativa L.) by a rapid and simple procedure. Their low temperature fluorescence emission and excitation spectra, ultraviolet fluorescence spectra and absolute absorption spectra were presented. The author's purification methods, which enhanced the yield of pure protein and shorted the time for isolation, have several advantages: 1. use of oxygen_evolving PSⅡ core complexes as the starting material in order to avoid disturbing from other cytochromes; 2. isocratic elution of cytochrome b_559 from a DEAE_Sephacel column for eliminating the impurity and yielding the protein in pure state; 3. a simple column procedure for removal of excess Triton X_100. Purified cytochromes b_559 from these species have similar optical spectra and mobility during gel electrophoresis under native conditions. From the results of novel electrophoresis (Tricine_SDS_PAGE), cytochrome b_559 from both spinach and rice reveal two polypeptide bands (apparent molecular weight 9 kD and 4 kD, respectively). By measuring of 77 K fluorescence spectra, it was shown that for the purified cytochrome b_559 there were two excitation peaks at 439 nm and 413 nm, and two emission peaks at 563 nm and 668 nm. This is the first indication that Cyt b_559 is able to emit fluorescence and also transfer excited electrons to chlorophyll. By the use of ultraviolet fluorescence spectra, it was demonstrated for the first time that the location of Trp residue could be in the hydrophobic transmembrane region of cytochrome b_559.

MHC-Ⅱ联合MHC-Ⅰ免疫组化染色在特发性炎性肌病诊断中的应用价值探讨

目的探讨主要组织相容性复合体(MHC)-Ⅱ联合MHC-Ⅰ免疫组化染色在特发性炎性肌病(IIM)诊断中的应用价值。方法收集2010年3月至2018年4月在首都医科大学宣武医院神经内科行肌肉活检患者的标本29份,并通过医院电子病历系统收集患者的临床资料,包括4种IIM[皮肌炎(DM)5例,多发性肌炎(PM)5例,散发性包涵体肌炎(IBM)4例及坏死性自身免疫性肌病(NAM)5例]和2种非炎性肌病(NIM)[肌营养不良(MD)5例,dysferlinopathy肌病5例]。将标本进行苏木精-伊红(HE)染色及MHC-Ⅰ、MHC-Ⅱ免疫组化染色。结果免疫组化染色结果显示,PM、DM及IBM患者肌肉标本MHC-Ⅰ阳性率达100.0%,NAM和MD患者肌肉标本MHC-Ⅰ阳性率为80.0%,dysferlinopathy肌病患者肌肉标本MHC-Ⅰ阳性率为20.0%。PM和IBM患者肌肉标本MHC-Ⅱ阳性率分别为40.0%、50.0%,其余类型疾病患者肌肉标本的MHC-Ⅱ免疫组化染色均呈阴性。结论相较于MHC-Ⅰ免疫组化染色,MHC-Ⅱ免疫组化染色在鉴别IIM与NIM中有较高的特异性。MHC-Ⅱ联合MHC-Ⅰ免疫组化染色对不同肌病类型的诊断有较好的临床应用价值。

五角双锥构型的场诱导Co^(Ⅱ)单离子磁体

利用CoCl_(2)·6H_(2)O和2,6-二乙酰吡啶双(氨基脲)(H_(2)dapsc)在水和乙醇的混合溶剂中回流反应得到一例具有五角双锥构型的单核Co~Ⅱ配合物[Co(H_(2)dapsc)(H_(2)O)Cl]Cl·2H_(2)O(1),其中中性的H_(2)dapsc配体分子提供5个配位原子构成其赤道平面,1个水分子和1个Cl^(-)离子则占据其轴向位置,同时在其固态结构中包含1个价态平衡Cl^(-)离子和晶格水分子。直流磁化率研究表明,该配合物具有强的磁各向异性;交流磁性质表明其存在慢磁弛豫行为,直接和拉曼过程同时主导其弛豫,自旋翻转能垒为55.55 K。结合理论计算可以得出,导致该配合物慢磁弛豫行为的主要原因是五角双锥结构的面内各向异性,计算得到的D、E值为45.68、-0.32 cm^(-1)。

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.

Pd(Ⅱ)与氯苯基苯并咪唑配合物的合成及特性研究

合成了Pd(Ⅱ)与2-(邻-氯苯基)苯并咪唑(OCBM)的配合物,采用元素分析、UV、IR、摩尔电导率等进行表征。圆二色性研究发现,配合物在187 nm和245 nm处呈正科顿效应,而在193 nm处呈负科顿效应。荧光性质研究表明,配合物的特征荧光发射峰出现在578 nm和592 nm处,荧光寿命τ578和τ592分别为0.25 ns和0.30 ns。Pd(Ⅱ)配合物可发射黄色和黄绿色荧光。

Novel cobalt(Ⅱ) complexes of amino acids-Schiff bases catalyzed aerobic oxidation of various alcohols to ketones and aldehyde

Two cobalt（Ⅱ） complexes 1 and 2 of Schiff bases derived from amino acids were synthesized and used for oxidation of benzyl alcohol with molecular oxygen at different conditions of pH,solvent,temperature and complex/alcohol molar ratio to optimize reaction conditions and to evaluate the catalytic efficiency of new cobalt Schiff base complexes.Under obtained optimum conditions,various alcohols were oxidized to corresponding aldehydes and ketones.

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Binuclear Copper(Ⅱ) Complex with 3-(Pyridin-2-yl)-1,2,4-triazole

One novel binuclear copper（Ⅱ） complex [Cu 2 （Hpt） 2 （CO 3） 2 （H 2 O） 2 ]·H 2 O with copper carbonate and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） was hydrothermally synthesized and characterized by IR and X-ray diffraction analysis.The complex crystallizes in triclinic,space group P2 1 /n with a=0.6862（1）,b=0.7805（1）,c=1.1983（2） nm,α=72.03（2）,β=107.72（3）,γ=75.28（2）o,V=0.5884 nm 3,D c=2.105 g/cm 3,Z=1,F（000）=357,GOOF=1.041,the final R=0.01859 and wR=0.04348.The whole molecule is composed of two cooper ions,two Hpt molecules,two carbonate and three water molecules,forming a binuclear structure.The crystal structure shows that the cooper ion is coordinated with three nitrogen atoms from two Hpt molecules,two oxygen atoms from one carbonic acid and one water molecule,forming a distorted square pyramidal geometry.The TG analysis result shows that the title complex is stable under 131.0 ℃.

Synthesis, Structure and Properties of a Strontium(Ⅱ) Complex with 2, 3-Pyrazinedicarboxylic Acid

Complex [Sr2（pdc）2（H2O）7]·H2O （1, H2pdc = 2,3-pyrazinedicarboxylic acid） has been synthesized and characterized by single-crystal X-ray diffraction studies and FT-IR. Structural determination reveals that there are two crystallographically independent strontium ions in 1. The coordination geometry of Sr（1） is a nine-coordinated distorted monocapped tetragonal antiprism, while Sr（2） is a nine-coordinated distorted monocapped tetragonal prism. The ligand pdc2- takes two different connecting modes and links St（If） centers to generate a 2D layer structure. The 2D layers are linked through O-H...O and O-H...N hydrogen bonds to form a 3D framework structure. Thermal stability and luminescent properties of complex 1 are investigated. 1 belongs to the monoclinic system, space group P21/n with a = 10.7182（10）, b = 7.0377（6）, c = 29.225（3） A, β = 95.7170（10）°, Z = 4, V = 2193.5（3） A3, Mr = 651.56, Dc = 1.973 g/cm3, F（000） = 1296,μ = 4.951 mm-1, the final R = 0.0318 and wR = 0.0726 for 3938 observed reflections with I 〉 2σ（/）.

Synthesis, Crystal Structure and Antitumor Activity in Vitro of a New Benzoate Binuclear Cupper(Ⅱ ) Complex

The title compound, [Cu2（C7H5O2）4（C2H6O）2], was synthesized by the reaction of benzoic acid, copper acetate and ethanol in an aqueous solution. Trypan blue dye exclusion method was used in experiment. X-ray single-crystal analysis has revealed that compound 1 （C32H32Cu2O10） crystallizes in the monoclinic system, space group C2/c, Mr = 703.66, a = 47.340（5）, b = 6.6613（4）, c = 22.028（2）A,β = 113.284（4）°, V = 6380.6（10） A^3, Z = 8, Dc= 1.465 g/cm^3, F（000） = 2896,μ = 1.388 mm^-11, the final R = 0.0515 and wR = 0.1172 for 5712 observed reflections with I 〉 2σ（I）. X-ray crystal structure analysis suggests that compound [CH2（C7H5O2）4（C2H6O）2] has a binuclear structure with two Cu（II） atoms coordinated by four benzoate groups and two ethanol molecules. The crystal packing is stabilized by intermolecular O-H...O hydrogen bonds. The compound inhibits the proliferation of K562 cells （chronic myeloid leukemic cells） significantly and dose-dependently in 48 h, and IC50 of K562 is 17.3μg/mL by trypan blue dye exclusion method.