Spectrophotometric determination of the formation constants of Calcium(Ⅱ) complexes with 1,2-ethylenediamine,1,3-propanediamine and 1,4-butanediamine in acetonitrile

In this work, with the purpose to explore the coordination chemistry of calcium complexes which could work as a partial model of manganese-calcium cluster, a spectrophotometric study to evaluate the stability of the complexes: Calcium(Ⅱ)-1,2-ethylendiamine, Calcium(Ⅱ)-1,3-propanediamine and Calcium(Ⅱ)-1,4-butanediamine in acetonitrile, were carried on. By processing the spectrophotometric data with the HypSpec program allows the determination of the formation constants. The logarithmic values of the formation constants obtained for Calcium(Ⅱ)-1,2-ethylendiamine, Calcium(Ⅱ)-1,3-propanediamine and Calcium(Ⅱ)-1,4-butanediamine were log β_(110) = 4.69, log β_(110)= 5.25 and log β_(110) = 4.072, respectively.

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.

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。

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.

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)。

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.

Two New Mn(Ⅱ)/Co(Ⅱ) Complexes Assembled by 2,5-Dihydroxy-1,4-benzenedicarboxylic Acid and Phenanthroline or Derivative

Two new complexes [Mn(DHTA)(PLQ)]n(1) and{[Co2(DHTA)(phen)2(H2 O)6]· DHTA}n(2)(H2 DHTA = 2,5-dihydroxy-1,4-benzenedicarboxylic acid, PLQ = 1,10-phenanthroline-5,6-quinone, phen = 1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, fluorescence spectrum, single-crystal and power X-ray diffraction. Complex 1 exhibits a two-dimensional(2 D) network, which was stabilized through O–H···O hydrogen bonding interactions. Complex 2 shows a zero-dimensional structure, which was further extended into a three-dimensional supramolecular structure through O–H···O hydrogen bonds and π-π interactions.

Syntheses, Structures and Photoluminescence of the Cadmium(Ⅱ) and Copper(Ⅱ) Complexes Based on 4'-(4''-Pyridyl)-2,2':6',2''-terpyridine and 1,4-Benzenedicarboxylic Acid Ligands

Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.

2-AMINOMETHYLPYRIDINE NICKEL(Ⅱ) COMPLEXES—SYNTHESIS,MOLECULAR STRUCTURE AND CATALYSIS OF ETHYLENE POLYMERIZATION

A series of new nickel(Ⅱ)complexes with 2-aminomethylpyridine ligands,(2-PyCH_2NHAr)_2NiBr_2(Ar=2,6- dimethylphenyl 2a;2,6-diisopropylphenyl 2b,2,6-difluorophenyl 2c),have been synthesized and used as catalyst precursors for ethylene polymerization in the presence of methylaluminoxane(MAO).The catalysts containing ortho-alkyl-substituents afford high molecular weight branched polyethylenes as well as a certain amount of oligomers.Enhancing the steric bulk of the alkyl substituent of the catalyst resulted in...

Syntheses and Magnetic Properties of Cu（Ⅱ）－RE（Ⅲ） Heterobinuclear Complexes with N，N′－Bis（3－carboxyisalicylidene）－trimethylenediamine

ine heterobinuclear complexes of Cu (Ⅱ)-RE (Ⅲ) with N, N′-bis-(3-car-boxylsalicylidene ) trimetliylenediamine (TS) were syntliesized and characterized bymeans of elemental analyses, molar conductivity, thermogravimetry,IR and elec-tronic spectra. The measurements of variable-temperature magnetic susceptibilitysliow that there exists only a very weak antiferromagnetic spin exchange interactionbetween the ions of Cut(Ⅱ) and RE(Ⅲ) in CuRETSCI . 3H_2O.

Syntheses,Crystal Structures,and Magnetic Properties of Cobalt(Ⅱ) Complexes with 1,1-Cyclohexanediacetic Acid

Two new Co（Ⅱ） coordination polymers,{[Co_3（Hchda）_2（chda）_2（bpp）_2（H_2O）_2]}_n 1 and {[Co（chda）（bpe）（H_2O）]·3H_2O}_n 2（H_2chda = 1,1-cyclohexanediacetic acid,bpp = 1,3-bis（4-pyridinyl）propane and bpe = 1,2-bis（4-pyridinyl）ethylene）,were hydrothermally synthesized and then characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis（TGA）,and single-crystal X-ray diffraction.Complex 1 possesses an infinite metal-organic layer based on triply bridged linear trinuclear subunits and complex 2 exhibits a square（4,4） grid layer with dangling lateral arms resulting from eight-membered rings above and below the layer.In addition,magnetic properties of complexes 1 and 2 are also given.

Hydrothermal Syntheses and Crystal Structures of Cobalt(Ⅱ) Complexes Constructed by Dipyrido[3,2-a:2',3'-c]phenazine and Different Carboxylate Ligands

Two new metal-organic complexes,{[Co2（bptc）（DPPZ）2（H2O）2]·H2O}n 1 and {[Co2（ccm）2（DPPZ）2]·2H2O}n 2,were obtained by the hydrothermal reactions of Co（NO3）2·6H2O with chelating ligand dipyrido[3,2-a：2＇,3＇-c]phenazine（DPPZ） and the corresponding carboxylic acid,namely,3,3＇,4,4＇-benzophenonetetracarboxylic acid（H4bptc） or 2-carboxycinnamic acid（H2ccm）,respectively.The complexes were structurally characterized by single-crystal X-ray diffraction,elemental analyses,IR spectra,and thermal gravimetry.1 presents unique chiral chain structures,which are further consolidated into three-dimensional supramolecular frameworks via noncovalent bonds,such as hydrogen bonding and π-π interactions.2 features infinite double-chain structures,which are connected by strong π-π interactions to result in three-dimensional supramolecular architectures.

Synthesis and Characterization of Two Binuclear Macrocyclic Zinc(Ⅱ) Complexes by Anion Exchange

Two macrocyclic zinc（Ⅱ） complexes {[ZnL（VO3）2]·0.33H2O}n（1） and [ZnL（H2O）2][Ni（CN）4]（2）（L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane） have been obtained from the reactions of [ZnL]（ClO4）2 with NH4VO3 and K2[Ni（CN）4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn（Ⅱ） atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2＋, forming one-dimensional channels occupied by guest water molecules. The monomers of [ZnL（H2O）2]2＋ and [Ni（CN）4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.

Hydrothermal Syntheses,Crystal Structures,and Characterization of Two Zinc(Ⅱ)Complexes Containing Flexible Bis(benzimidazole)Ligands

Two zinc（II） complexes, namely, [Zn（L1）Cl2]2 （1） and {[Zn（L2）（tbta）]·3H2O}n （2） （L1 = 1,3-bis（2-methylbenzimidazol-1-ylmethyl）benzene, H2tbta = tetrabromoterephthalic acid, L2 = 1,3-bis（2-methylbenzimidazol-1-yl）-2-propanol） have been successfully obtained under hydrothermal conditions. Complex 1 displays binuclear structure which is further extended into a 1D supramolecular chain through π–π stacking. Complex 2 features 2D （4,4） network based on L2/tbta2– double linker. The thermal stability, fluorescence properties and catalytic activities of two complexes for degradation of Methyl orange in a Fenton-like process were discussed.

Studies on Lead(Ⅱ) Complexes of Ferrocenylaldehyde Aroylhydrazones

The complexes of four ferrocenylaldehyde aroylhydrazones with lead(Ⅱ) were synthesized and characterized. Their compositions, bonding forms and properties were researched by means of elemental analysis, IR, UV Vis, 1H NMR spectra, thermal analysis and molar conductance. The free ligands which existed in the keto form coordinated to lead(Ⅱ) in the enol form to form neutral complexes. The molar ratio of the ligand to lead(Ⅱ) is 2∶1 and the thermal stability of the complex is higher than that of the corresponding ligand because of the formation of the stable chelate ring. The ligands and the complexes are all non electrolytes.

Chiral Resolution of β-dl-Phenylalanine Using Chiral Macrocyclic Nickel(Ⅱ) Complexes

The reactions of chiral four-coordinated nickel（Ⅱ） complex [Ni（RR-L）]（ClO4）2/[Ni（SS- L）]（ClO4）2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni（RR-L）（β-d-HPhe）]（ClO4）2（1） and [Ni（SS-L）（β-l-HPhe）]（ClO4）2（2）, respectively（L = 5,5,7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, HPhe = phenylalanine）. Single-crystal X-ray diffraction analyses revealed that the nickel（Ⅱ） atom displays a distorted octahedral coordination geometry by coordinating with four nitrogen atoms of L in a folded configuration, and two carboxylate oxygen atoms of β-d/l-HPhe in cis-position in both complexes. The monomers of [Ni（RR-L）（β-d-HPhe）]2＋ and [Ni（SS-L）（β-l-HPhe）]2＋ are connected through intermolecular hydrogen bonds to generate one-dimensional zigzag chains, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy.

Hydrothermal Syntheses, Crystal Structures and Luminescence Properties of Cu(Ⅱ) and Cd(Ⅱ) Complexes Assembled by 6-Hydroxypicolinic Acid and 1,10-Phenanthroline

Two new complexes based on 6-hydroxypicolinic acid(H_2picO) and 1,10-phenanthroline(phen), such as [Cu_4(picO)_4(phen)_4]·12 H_2O(1) and {[Cd_4(picO)_4(phen)_4(H_2O)_2]·5H_2O}_n(2), have been synthesized and characterized by IR, elemental analyses, thermogravimetric analyses and X-ray diffraction technique. Single-crystal X-ray diffraction analyses revealed that the two complexes both crystallize in the triclinic system, space group P(16)-. For complex 1, the picO ligands adopt a tridentate coordination mode to link copper(Ⅱ) ions into dimmers. PicO ligands also adopt a tridentate mode in complex 2, which connects the cadmium(Ⅱ) to form a one-dimensional chain. Moreover, luminescent properties of 1 and 2 were also investigated.

Syntheses and Crystal Structures of Two New Hg(Ⅱ) and Cd(Ⅱ) Complexes with 2,3,5,6-Tetrakis-(2-pyridyl)Pyrazine

Under thermal gradient in solution phase, the reaction of Hg（Ⅱ） and Cd（Ⅱ） salts with 2,3,5,6-tetrakis-（2-pyddyl）pyrazine （tppz） in 1：1 molar ratio afforded dinuclear [{HgI2}2}- tppz）] （1） and mononuclear [CdI2（tppz）] （2） complexes. Single-crystal X-ray diffraction structural analysis reveals that the tppz acts as bis-tridentate and tridentate chelating ligands in 1 and 2, respectively. Metal（Ⅱ） ions adopt a distorted square pyramidal geometry and have the same coor- dination environment in both complexes. Based on the 1H NMR spectroscopy measurements, both complexes decompose in solution and release free tppz.