OXIDATION OF ALKYLBENZENES CATALYZED BY IRON( Ⅱ,Ⅲ)-1,10-PHENANTHROLINE AND 2, 2'-BIPYRIDINE COMPLEXES

Oxidation of alkybenzenes PhCH_2R(R=H, CH_3, C_2H_5 and n-C_3H_7) under 1 atm. of O_2 or air catalyzed by iron(Ⅱ, Ⅲ)-2,2'-bipyridine and 1,10-phenanthroline complexes, affords the aryl-substituted ketones and alcohols with the conversion of 15.00％～34.58％ containing of 97.60％～99.80％ ketones and alcohols. The turnover numbers of these catalysts are over 3500 mol-cat. ^(-1)for 3.5 h.

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.

An analytical method for Fe(Ⅱ) and Fe(Ⅲ) determination in pharmaceutical grade iron sucrose complex and sodium ferric gluconate complex

A robust voltammetric method has been developed and validated for the determination of Fe（Ⅱ） and Fe（Ⅲ） in pharmaceutical iron polysaccharidic complexes. Undesirable low molecular weight iron complexes, at concentration about 3% in the pharmaceutical formulation, can be easily determined with good accuracy and precision. This methodology can be proposed as a viable, environmentally sustainable substitute for the conventional Normal Pulse Polarographic method in US Pharmacopeia, with better analytical figures of merit, and reduced Hg consumption. A deeper insight in Fe（Ⅱ） and Fe（Ⅲ） composition can be gained by the combined use of a new potentiometric technique after chemical decomposition of the complex.

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。

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.

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.

CHARACTERIZATION OF IRON COMPLEXES SUPPORTED ON POLYMER AND THEIR CATALYTIC ACTIVITY IN BUTADIENE POLYMERIZATION

Styrene-acrylic acid copolymer (SAAC)-supported iron complex (SAAC·Fe)was characterized and the effect of the characteristic parameters on the catalytic activity of the complex was investigated. IR spectrum suggested that the complex SAAC·Fe possesses a structure of(C)and the Fe-O bond is higher in covalency.The complex SAAC·Fe with the structure of(C)shoved a higher catalytic activity in butadiene polymerization. When Fe/-COOH molar ratio in SAAC·Fe was about 0.2 the complex gave optimum catalytic activity. The catalytic activity of SAAC·Fe with the higher content of long sequence of acrylic acid units was low. When the content of the short sequence of acrylic acid units was predominant and at the same time the content of the short sequence was approximately equal to that of the long sequence for stryrene, the activity of the complex was high.

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.

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.

Synthesis, Crystal Structure and Magnetic Properties of a One-dimensional Loop-like Iron(Ⅱ) Complex:[Fe(Haip)_2(H_2O)_2]_n (Haip = 5-Ammoniumisophthalato)

An iron（Ⅱ） coordination polymer, [Fe（Haip）2（H2O）2]n （1, Haip = 5-ammoniumiso- phthalato）, has been hydro/solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectrum and magnetic measurement. Compound 1 crystalizes in monoclinic, space group P2/c with a = 6.9874（14）, b = 9.960（2）, c = 12.894（4） A, β = 117.47（2）°, Fe（C8H6NO4）2（H2O）2, Mr = 452.16, V= 796.2（3） A3, Z = 2, Dc = 1.886 g.cm-3, p = 1.017 mm-1, F（000） = 464.0, 2.71〈0〈28.42°, R = 0.0307, wR = 0.0840 and S = 1.005. Single-crystal X-ray diffraction analysis reveals that 1 features an infinite one-dimensional loop-like chain structure and Haip ligand in 1 is of zwitterionic form. Magnetic measurement results show the dominated ferromagnetic interactions among Fe11 atoms.

Synthesis, Fluorescence and Electrochemistry of Three New Ruthenium(Ⅱ) Complexes

ＩｎｔｒｏｄｕｃｔｉｏｎＥＬＣｉｓａｔｅｃｈｎｉｑｕｅｂｙｗｈｉｃｈａｃｈｅｍｉｌｕｍｉｎｅｓｃｅｎｔｒｅａｃｔｉｏｎｉｓｇｅｎｅｒａｔｅｄｆｒｏｍｔｈｅｒｅａｇｅｎｔｓｐｒｏｄｕｃｅｄｉｎｔｈｅｖｉｃｉｎｉｔｙｏｆａｎｅｌｅｃｔｒｏｄｅｓｕｒｆａｃ...

Synthesis and Characterization of Aryl Acylguanidines and Their Copper(Ⅱ) Complexes

A series of eight N-mono-substituted aryl acylguanidines L1~8 were synthesized from the reactions of their parent acylthioureas and respective primary amines, including five R1C(O)N=C(NHR2)2 with balanced arms(denoted as R1–R2–R2: Ph–Ar’–Ar’, L1(1);Ph–Ar’’–Ar’’, L2(2);1-Naph–Ar’–Ar’, L3(3);1-Naph–Ar’’–Ar’’, L4(4);2-Naph–Ar’’–Ar’’, L[5(5);Ar’ = 2,6-Me2C6H3, Ar’’ = 2,6-iPr2C6H3) and three R1C(O)N=C(NHR2)NHR3 with unbalanced arms(denoted as R1–R2–R3: Ph–Ar’–Ph, L6(6);Ph–Ar’ –Ph, L7(7);Ph–Ar’ –Ar’, L8(8)). Treatment of L1~5(1~5) with copper acetate in a molar ratio of 2:1 in dichloromethane led to the formation of homoleptic Cu(Ⅱ) complexes trans-L2n’Cu(9~13), in which the Cu(Ⅱ) center was stabilized by deprotonated ligands Ln’(n = 1~5) in the O,N-bidentate mode. When similar reactions of L6(Ph–Ar’–Ph)(6) and L7(Ph–Ar’’–Ph)(7) that contain unbalanced arms were investigated, the Cu(Ⅱ) products trans-L26’Cu(14) and trans-L27’Cu(15) were formed by deprotonating the bulky amine groups in Ln(-NHAr’ for L6 and-NHAr’’ for L7) rather than the-NHPh group. In sharp contrast, trans-L28’Cu(16) was obtained from two-arm unbalanced L8(Ph–Ar’’–Ar’)(8) not by deprotonating the more bulky-NHAr’’ group but the relatively less bulky-NHAr’ group. In a further exploration, the reaction of 1:1 mixed ligands Ln and Lm with copper acetate was found to give only homoleptic Cu(Ⅱ) complex L2n’Cu instead of the heteroleptic one Ln’CuLm’. The in vitro antibacterial activity of Ln was evaluated against S. aureus, E. coli and C. albicans by determining the minimum inhibitory concentrations(MICs) using Kirby-Bauer test.

Synthesis, Crystal Structure, and Fluorescent and Thermal Stability Properties of Two New Cobalt(Ⅱ) Complexes with 2,2’-Bipy as Ligand

Two new cobalt(Ⅱ)complexes[Co2(2,2?-bipy)2(dpa)2(H2O)5]·4H2O(1)and Co(2,2?-bipy)3(SO4)]·7.5H2O(2)have been synthesized with diaphonic acid(H2dpa)and 2,2?-bipyridine(2,2?-bipy)as ligands.In 1,two neighboring cobalt(Ⅱ)ions are linked together by one bridging diaphonic acid group,forming an asymmetric dinuclear structure.1 crystallizes in triclinic,space group P1 with a=9.825(6),b=13.007(8),c=19.586(1)A,α=80.773(1)o,β=77.065(1)o,γ=85.902(1)o,Mr=431.4,V=2406.5(3)A^3,Dc=1.48 g/cm^3,Z=2,μ(Mo Kα)=0.767 mm-1,F(000)=1112,the final R=0.0379 and wR=0.0862.The central cobalt(Ⅱ)ions in 1 and 2 are coordinated with six atoms,forming distorted octahedral coordination geometry.The fluorescence and thermal stability properties of 1 and 2 are also reported.

Syntheses, Crystal Structures and Photoluminescence Properties of Cadmium(Ⅱ) and Nickel(Ⅱ) Complexes with 2-(2-Benzimidazolyl)quinoline

Two novel complexes, [Cd2（BMQU）2Cl4] （1） and [Ni（BMQU）2HPO4]·1.5H2O （2） （BMQU = 2-（2-benzimidazolyl）quinoline）, were synthesized by the hydrothermal method and characterized by elemental analysis, IR, and TG-DTG. The crystal structures were determined by single-crystal X-ray diffraction. Both 1 and 2 crystallize in the triclinic system, space group P . The data for 1： a = 0.8342（7）, b = 0.9226（9）, c = 1.0646（8） nm, α = 90.819（2）, β = 97.466（2）, γ = 98.280（2）°. The Cd（Ⅱ） is coordinated with three chlorine atoms and two nitrogen atoms of a BMQU molecule, generating a distorted square-pyramidal geometry. The dinuclear Cd（Ⅱ） complex is formed by two chlorine bridge bonds, and the one-dimensional chain structure is constructed with the hydrogen bond N-H…Cl and π-π stacking interaction. The data for 2： a = 1.2251（1）, b = 1.2451（1）, c = 1.2868（1） nm, α = 107.510（2）, β = 98.630（1）, γ = 109.921（2）°. The Ni（Ⅱ） is coordinated with four nitrogen atoms of two BMQU molecules and two oxygen atoms of a HPO42-, forming a distorted-octahedral geometry. The two-dimensional layer structure is formed by the hydrogen bonds and π-π stacking interaction between neighboring molecules. Complex 1 shows a strong blue fluorescence emission （λmax= 456 nm） at solid state.