Synthesis,crystal structure,and biological activity of a nickel(II) complex constructed by 2-phenyl-4-selenazole carboxylic acid and 1,10-phenanthroline

A nickel(II) complex, [NiL(phen)₂]L·5H₂O (HL?=?2-phenyl-4-selenazole carboxylic acid, C₁₀H₇O₂NSe, phen?=?1,10-phenanthroline), was synthesized and characterized by elemental analysis and IR. The single crystal structure was determined by single-crystal X-ray diffraction. C₈₈H₇₈N₁₂Ni₂O₁₉Se₄ crystallized in the triclinic system, space group Pī. The interaction between the complex and the calf thymus DNA was studied by an ethidium bromide fluorescent probe. The antibacterial activities of the complex and ligand against five species of bacteria, Escherichia coli, Staphylococcus epidermidis, Streptococcus viridans, Staphylococcus aureus and Acinetobacter baumanii, were tested. The anticancer activities of the complex against human pancreatic cancer line PANC-28 and human hepatocarcinoma line HuH7 were also studied by employing an MTT assay.     

1′-苯基-3′-甲基-5′-氧代吡唑-4′-基-甲酰甲酸及1,10-二氮杂菲与稀土元素的三元配合物的合成及性质

用电导滴定法研究了乙醇-水溶液中稀土与1’-苯基-3’-甲基-5’-氧代吡唑-4’-基-甲酰甲酸及1,10-二氮杂菲的配合反应。合成了固态配合物。经化学分析与元素分析确定了配合物的化学组成为Ln_2L_3P_2·nH_2O,通过红外光谱、紫外光谱、~1H NMR谱、差热分析、溶解度等方法对配合物进行了表征,确定Ln_2L_3P_2·nH_2O为双核结构(L为四齿配体,P为二齿配体)。     

稀土氮杂环配合物的合成、 结构及抑菌活性

采用溶液合成法, 在室温下合成了一系列稀土配合[Ln(IAA)₂(phen)₂]·(NO₃)[Ln=Ce(1), Gd(2), Tb(3), Dy(4), Ho(5), HIAA=吲哚乙酸, phen=1,10-菲咯啉], 并通过元素分析、 红外光谱、 热重分析、 X射线单晶衍射、 X射线粉末衍射等方法对配合物进行了表征. 结果表明, 配合物15具有相同的结构, 对配合物2的单晶结构分析表明, 配合物2为超分子网络结构, 通过分子间氢键形成2D网络, 中心金属Gd(Ⅲ)为九配位, 具有单帽四方反棱柱几何构型. 此外, 对该系列配合物进行了抑菌活性的研究, 得到了抑菌活性与配合物组成的构效关系.     

Amino Acid Profile and Biological Properties of Silk Cocoon as Affected by Water and Enzyme Extraction

We compared the efficacy for protein extraction of water versus enzymatic extraction. The amino-acid composition, inhibitory activity against enzymes α-amylase and α-glucosidase, and anti-glycation activities of silk protein extract (SPE) were determined. We used water extraction (100 °C, six hours) and protease-enzymatic extraction. The microstructure of silk fibers was obviously different after extraction. The results showed that enzymatic extraction gave the greater values of protein content, amino acids, total phenolic content (TPC), and total flavonoid content (TFC), as well as all biological activities parameters tested, but it also provided a more bitter taste in the extract—contributing amino acids of 51% (arginine, phenylalanine, histidine, valine, tryptophan, isoleucine, and leucine) and less sweet and umami taste contributing amino acids than did water extraction, which could be more suitable to be used as concentrated nutraceuticals.     

基于吡啶二羧酸配体的稀土配合物的合成、结构及性质

以2,6-二甲基吡啶-3,5-二羧酸（H₂L₁）为主配体,1,10-菲咯啉（L₂）为辅配体,分别与五水合硝酸镝、六水合硝酸铽及六水合硝酸铕通过水热法合成[Dy₂（L₁）₃（L₂）₂]_n（1）、{[Tb₂（L₁）₃（L₂）₂]·5H₂O}_n（2）和{[Eu₂（L₁）₃（L₂）₂]·5H₂O}_n（3）三种配合物。通过单晶X射线衍射、红外光谱、荧光光谱和热重分析对其结构进行了表征与性质研究。结果表明,配合物1~3均以稀土离子为金属节点连接配体L₁^2-和L₂,形成无限延伸的一维链状结构。     

稀土N-苯基邻氨基苯甲酸-1,10-邻菲咯啉二元、三元配合物的合成、表征及其光物理性质

合成了几种新型的稀土(钆,铕,铽)的N-苯基邻氨基苯甲酸-1,10-邻菲咯啉的二元、三元配合物.以元素分析、红外光谱和紫外光谱进行了表征,确定了组成.同时以低温磷光光谱确定了配体的三重态能级为24330cm^-1,研究了配体与稀土离子的能级匹配.详细讨论了配合物的光物理性质如发光性能和配体与稀土离子之间以及有机配体之间的分子内能量传递机制,结果发现,铽的N-苯基邻氨基苯甲酸-1,10-邻菲咯啉配合物的发光性能良好.     

Synthesis,Structures, Fluorescence Properties,and Natural Bond Orbital (NBO) Analysis of Two Metal [EuIII,CoII] Coordination Polymers Containing 1, 3‐Benzenedicarboxylate and 2‐(4‐methoxyphenyl)‐1H‐imidazo[4, 5‐f][1, 10]phenanthroline Ligands

Two new metal‐organic coordination polymers[Eu(m‐BDC)_1.5(MOPIP) · 1/2H₂O]_n ( 1 ) and [Co(m‐BDC)(MOPIP)₂ · 2H₂O]_n ( 2 ) [m‐H₂BDC = benzene‐1, 3‐dicarboxylic acid, MOPIP = 2‐(4‐methoxyphenyl)‐1H‐imidazo[4, 5‐f] 1 , 10 phenanthroline] were hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. The coordination polymers crystallize in monoclinic space group P2₁/m for 1 ( 2 : P2₁/n), with a = 9.779(2), b = 18.242(4), c = 17.146(3) Å, β = 106.41(3)° for 1 , and with a = 8.2153(16), b = 27.974(6), c = 17.974(4) Å, β = 100.40(3)° for 2 . The crystal structure of complex 1 is a zipper‐like chain of octacoordinate Eu³⁺ ions, in which Eu³⁺ ions are bridged in two coordination modes by m‐BDC²⁺ ligands and decorated by MOPIP ligands. The molecular structure of complex 2 consists of a hexacoordinte Co²⁺ atom, which generates a slightly distorted octahedral arrangement, and assembles into three‐dimensional supramolecular nets by π ··· π stacking interactions. Additionally, these two compounds show strong fluorescence in the solid state at room temperature. Natural bond orbital (NBO) analysis is performed by using the NBO method built in Gaussian 03 Program. The calculation results show a weak covalent interaction between the coordinated atoms and metal ions.     

An Experimental and Theoretical Study on Essential Oil of Aethionema sancakense: Characterization,Molecular Properties and RDG Analysis

This study aims to experimentally and theoretically examine the plant Aethionema sancakense, which was determined as a new species and whose essential oil and fatty acid compositions were characterized by GC/GC-MS technique. Linoleic acid (23.1%), α-humulene (19.8%), camphene (13.9%), and heptanal (9.7%) were found to be the major essential oil components of A. sancakense aerial part structures. The quantum chemical calculations of these four molecules that are very important to this plant were performed using the density functional method (DFT)/B3LYP with the 6-31 G (d, p) basis set in the ground state for the gas phase. The molecular structures, HOMO-LUMO energies, electronic properties, Fukui functions, and molecular electrostatic potential (MEP) surfaces of the major constituents of Aethionema sancakense essential oil were calculated and interpreted. Finally, the RDG-NCI analysis of these molecules was performed to determine the non-covalent interactions present within the molecules.     

Crystal Structures and Solution Studies of Two Novel Zinc(II) Complexes of a Proton Transfer Compound Obtained from 2, 6‐Pyridinedicarboxylic Acid and 1, 10‐Phenanthroline: Observation of Strong Intermolecular Hydrogen Bonds

The proton transfer compound LH₂ , (phenH⁺)₂(pydc^2—), has been prepared from 1, 10‐phenanthroline, phen, and 2, 6‐pyridinedicarboxylic acid, (dipicolinic acid), pydcH₂. Characterization was performed using solution and solid phase CP/MAS ¹³C NMR and IR spectroscopy. The reactions of this adduct with ZnSO₄·7H₂O and Zn(NO₃)₂·4H₂O give the complexes, [Zn(pydc)₂][Zn(phen)₂(H₂O)₂]·7H₂O (1) and [Zn(phen)₃]₄(H(Hpydc)₂)(NO₃)₇·26H₂O (2) , respectively. These complexes were characterized by ¹H and ¹³C NMR spectroscopy and single crystal X‐ray analysis. The complexes crystallize in the triclinic space group P1 with Z = 2. The unit cell dimensions for complex 1 and 2 are: a = 9.9838(9) Å, b = 14.7483(13) Å, c = 14.8365(13) Å and a = 12.640(4) Å, b = 15.855(5) Å, c = 21.830(7) Å, respectively. In complex 1 (pydc^2—) and phen, are tri‐ and bidentate ligands, respectively, and an anionic [Zn(pydc)₂]^2— and cationic [Zn(phen)₂(H₂O)₂]²⁺ complex are formed simultaneously. In complex 2 , three phen participate in complexation leaving hydrogen‐bis(pyridine‐2‐carboxylate), (H(Hpydc)₂)^— as a supramolecular anion. The fragments (H(Hpydc)₂)^—, 7 NO₃^—, and 26 H₂O in complex 2 are joined together by extensive and strong H‐bonding; therefore, the structure is composed of [Zn(phen)₃]₄⁸⁺, and an anionic hydrogen bond supramolecular assembly with the formula, {(H(Hpydc)₂(NO₃)₇)^8— · 26H₂O}_n. The anionic species (H(Hpydc)₂)^— has a special position at the inversion center, as well as one of the NO₃^— anions, which is disordered over the inversion center. Most of the hydrogen bonds in complex 2 represent strong H‐bonding. The protonation constants of the building blocks of the pydc‐phen adduct, the equilibrium constants for the reaction of (pydc^2—) with phenanthroline and the stoichiometry and stability of the Zn^II complex with LH₂ on aqueous solution were determined by potentiometric pH titration. The solution study results support self‐association between (pydc^2—) and (phenH⁺) with a stoichiometry for the Zn(II) complex similar to that observed for the isolated crystalline complex.     

Preparation,Properties, and Reactions of Metal‐Containing Heterocycles. CX [1] Crystal Structure of 1, 1'‐Bis{[4‐(1, 10‐phenanthroline‐3‐yl‐ethynyl)‐2, 5‐dipropoxy‐phenyl]ethynyl}ferrocene

The crystal structure of 1, 1'‐bis{[4‐(1, 10‐phenanthroline‐3‐yl‐ethynyl)‐2, 5‐dipropoxy‐phenyl]ethynyl}ferrocene ( 1 ) is reported. This compound crystallizes with two chloroform solvent molecules in the monoclinic space group P2₁/c (No. 14), a = 15.4253(11), b = 23.2003(10), c = 17.2630(13) Å, β = 90.866(9)° and Z = 4. Both arms of the ferrocene moiety are parallel displaced with the four nitrogen atoms pointing to the same direction.     

Synthesis,Crystal Structure and Magnetic Properties of a 1‐D Polymer, [Cu(NITpPy)2(H2TCB)(H20)]·2H2O

A novel complex [Cu(NnpPy)₂(H_lTCB)(H₁O)]·2H₂O (NITpPy = 2‐(pyrid‐4′‐yl)‐4,4,5,5‐tetramethyl‐1, 3‐dioxoimidazoline; H₂TCB = 1, 5‐dicarboxybenzene carboxylic‐2, 4‐diacid) has been synthesized and characterized by X‐ray crystallography analysis. The crystal structure consists of infinite chains of Cu‐(NITpPy)₂(H₂O) units linked by H₂TCB ligands. The complex crystallizes in triclinic system with space group PI. Crystal data: a = 1.0594(2) nm, b = 1.3830(3) nm, c = 1.5551(3) nm, a = 67.75(3)°, β = 89.83(3)°, γ = 70.54(3)°. The variable magnetic susceptibility studies lead to magnetic coupling constant values of J₁= ?11.18 cm‐¹ (Cu—Rad) and J₂ = ?4.06 cm^?1 (Cu—Cu).     

含联苯三羧酸及二咪唑基吡啶配体的两个锌配位聚合物的合成、结构及荧光性质

以3,3’,5-联苯三羧酸(biphenyl-3,3’,5-tricarboxylicacid,H₃bpta)、2,6-二(1-咪唑基)吡啶(2,6-bis(imidazole-1-yl)pyridine,bip)、Zn(NO₃)₂·6H₂O和ZnCl₂为原料,在水热条件下合成了配位聚合物{[Zn₃(H₂O)₇(bpta)₂]·5H₂O}_n(1)和{[Zn₂Cl(bpta)(bip)₂]·2H₂O}_n(2)。并利用红外、元素分析和X-射线单晶衍射等对其结构进行表征。X-射线单晶衍射分析表明：化合物1属于单斜晶系,C2/c空间群,a=3.3171(11)nm,b=1.4957(5)nm,c=0.6951(2)nm,β=91.50°,Z=4;化合物2属于单斜晶系,P2/c 空间群,a=1.9604(4)nm,b=1.0357(2)nm,c=1.9987(4)nm,β=101.97(3)°,Z=4。化合物1通过bpta桥联Zn(Ⅱ)形成1D链,通过配位水与羧基氧之间的氢键作用构筑成3D结构。化合物2中bip桥联Zn(Ⅱ)构成1D螺旋链状结构,进一步通过bpta桥连形成2D网状结构。此外,对化合物1和2进行了热稳定性分析和荧光性质研究。     

2-丙基-1H-4, 5-咪唑二酸构筑的混核锌-钕配位聚合物的合成、晶体结构及磁性质

通过水热方法,合成了一个杂金属的配位聚合物{[NdZn(H2pimda)3(Hpimda)(H2O)2]·H2O}n(1),(H3pimda=2-丙基-1H-4,5-咪唑二酸),并对其结构和磁性质进行了研究。结构分析结果表明配合物1的晶体属于单斜晶系,P21/c空间群。配合物1是由配体2-丙基-1H-4,5-咪唑二酸连接而成的二维层状结构,该二维层通过氢键延伸为三维超分子结构。磁性研究表明,配合物1中相邻钕离子间存在着反铁磁相互作用。