氧载体及其除氧应用的研究：Ⅰ.乙二胺—Co配合物的氧合作用

氧载体及其除氧应用的研究Ⅰ．乙二胺┐Ｃｏ配合物的氧合作用王吉德＊王瑶ａ张翼宋启军张含ｂ鹿毅ｃ李新寿（新疆大学化学系乌鲁木齐８３００４６）（ａ新疆进出口商品检验局，ｂ新疆钢铁研究所，ｃ新疆技术监督局）关键词氧载体，乙二胺，钴配合物，氧合作用１９９７－０...     

钴希夫碱配合物的合成及其氧合机制的研究——Ⅰ.配合物及其氧加合物的合成和表征

本文合成了一系列以水杨醛或萘酚醛同多胺缩合的四齿(N₂O₂)或五齿(N₃O₂)希夫碱为配体的钴希夫碱配合物及它们的氧加合物,用元素分析、红外光谱、磁化率以及ESR谱进行了表征,在续篇中将继续讨论配合物的吸氧行为和氧合机制。     

钴希夫碱配合物的合成及其氧合机制的研究——Ⅰ.配合物及其氧加合物的合成和表征

本文合成了一系列以水杨醛或萘酚醛同多胺缩合的四齿(N_2O_2)或五齿(N_3O_2)希夫碱为配体的钴希夫碱配合物及它们的氧加合物,用元素分析、红外光谱、磁化率以及ESR谱进行了表征,在续篇中将继续讨论配合物的吸氧行为和氧合机制。     

固相反应合成丙二胺合钴氧合性能的研究

0引言氧载体是一类能够可逆吸收分子氧的特殊金属配合物。由于它在贮氧、除氧上有潜在的应用价值及对探索生命科学的重要意义,使得氧载体的研究得以广泛的展开[1~3],目前对氧载体氧合性能的影响因素研究局限于溶剂、温度、配体等因素的研究[4~6],而不同金属盐对氧载体氧合性能影响的探讨很少见于报道。作者在实验中发现,当使用不同阴离子的钴盐进行固相合成氧载体时,所得氧载体吸收分子氧的性能有明显差异。为探讨固相反应中不同钴盐对钴配合物氧合性能的影响,本文以丙二胺为配体,与四种不同钴盐分别发生液鄄固反应和气鄄固反应,再通过氧合…     

组氨酸钴氧合配合物二聚体形态的电喷雾串联质谱验证研究

电喷雾质谱(ESI-MS)是一种软电离质谱技术,已在配合物的结构和机理的研究中显示了重要的作用。本文根据组氨酸钴(CoL2)(L=组氨酸)对分子氧活性很高,极易生成双核氧合配合物(CoL2-O2-CoL2)的特点,采用ESI-MS方法研究了组氨酸钴氧合物(CoL2-O2-CoL2)和组氨酸配合物ML2(M=Cu、Zn)。结果发现,质谱图中在相应于双核氧合配合物的高质荷比端(m/z>ML2),CoL2出现质谱峰,而组氨酸配合物ML2(M=Cu、Zn)在质谱图中高质荷比端没有出现质谱峰,只有配合物ML2的相关峰;这个结果证明了文献报道中的双核氧合配合物(CoL2-O2-CoL2)的存在,根据所得质谱结果,初步研究了组氨酸钴双核氧合配合物和ML2配合物的裂解规律。结果表明,可根据质谱数据中有无二聚体形态,做出Co配合物有无吸氧性能的初步判断,因此电喷雾质谱(ESI-MS)可做为研究Co配合物氧合反应和表征Co氧合配合物的有效分析手段。     

一种测定配合物稳定常数的新方法——高效液相色谱法

使用高效液相色谱(HPLC)测定金属离子配合物稳定常数的方法在近十几年中不断发展。本文为关于该法的综述,并作了一些评论。     

乙二胺钴氧合反应的电喷雾串联质谱研究

采用电喷雾多级串联质谱技术对氧载体模型化合物乙二胺钴氧合产物的的质谱裂解规律进行了探讨。以固相法合成的乙二胺钴吸氧初和吸氧6 d两个阶段为研究体系,在正离子电喷雾质谱条件下能够清楚地观测到乙二胺钴氧合配合物的特征碎片离子。对其中m/z 150.86的碎片峰进行子离子扫描,可得到失去中性氧分子(M=32)的子离子碎片峰(m/z 118.85),从而可进一步确认其为氧合配合物碎片峰。本文采用电喷雾多级串联质谱技术对吸氧初和吸氧饱和后的两个体系进行了合理的初步探讨,根据所得质谱数据对乙二胺钴氧合产物的结构、裂解规律及氧气的存在形态给出初步合理的推论,结果表明,吸氧过程是一个老化的过程,乙二胺钴配合物从吸氧初到吸氧饱和后,其形态经历了从双核过氧桥联配合物到双核过氧羟基双桥联配合物形态的转变。初步确立电喷雾质谱(ESI-MS)可做为研究氧合反应和表征氧合配合物的有效技术手段。     

Schiff碱钴配合物的固相合成及其氧合性能

以苯甲醛缩多胺Schiff碱为配体与不同阴离子钴盐通过固相反应合成了6个Schiff碱钴配合物.采用UV,IR,元素分析,摩尔电导率,热分析等方法研究了配合物在室温下与O2的作用,初步探讨了钴盐阴离子对配合物氧合性能的影响.     

组氨酸钴氧合反应的电喷雾串联质谱

组氨酸合钴配合物是重要的氧载体模型化合物,对揭示氧载体的可逆吸氧机理的研究有着重要的作用。本文以组氨酸合钴吸氧初和吸氧中期两个阶段为研究体系,采用电喷雾多级串联质谱技术对组氨酸合钴氧载体的质谱裂解规律进行了研究。在其质谱裂解图谱中发现了氧合配合物碎片峰,将该氧合配合物碎片峰进一步裂解,可得到失去中性氧分子的子离子碎片峰,从而对其氧合形式进行了确认,根据所得质谱数据对组氨酸合钴氧合产物的结构、裂解规律及氧气的存在形态给出合理的推论。结果表明,吸氧过程是一个动态的变化过程,组氨酸合钴配合物吸氧初和吸氧24h后,分子氧均以超氧型形式存在,但其型态经历了从双核超氧桥联配合物到双核双桥联超氧羟基配合物的转变。对此过程的研究一直缺乏直接测定方法未被完全确定。本文采用电喷雾多级串联质谱技术对此氧合反应的机理进行了探讨,并初步确立电喷雾质谱（ESI-MS）可做为研究氧合反应和表征氧合配合物的有效技术手段。     

极谱配位吸附波测定配合物表观稳定常数的方法研究

对目前利用配位吸附波测定配合物表观稳定常数的常用方法进行了修正,提出了更具有普遍适用性的测定配合物表观稳定常数的理论公式,并对计算方法进行了探讨,获得了预期的满意的结果。     

Ion pairing between dissolved poly(o-phenylenediamine) and halogenide ions

An electrically conductive polymer, poly(o-phenylenediamine) (PoPD), is soluble in dimethylsulfoxide (DMSO) without any pretreatment. Cyclic voltammograms of dissolved PoPD were measured in DMSO solutions containing halogenide ions and two reversible redox peak currents were evident. The redox potential shifted with the concentration of the dissolved halogenide ion. The relationship between the potential shift and the concentration determined the relative association constant of PoPD for four halogenide ions: 104 mol⁻¹ dm⁻³ for F⁻; 32 mol⁻¹ dm⁻³ for Cl⁻; 29 mol⁻¹ dm⁻³ for Br⁻ and 9 mol⁻¹ dm⁻³ for I⁻.     

三邻氯苄基和三邻氟苄基锡吡咯烷氨荒酸酯的合成及晶体结构

Tri(o-chlorbenzyl)tin dithiotetrahydropyrrolocarbamate 1 and tri(o-fluorbenzyl)tin dithiotetrahydropyrrolocar-bamate 2 were synthesized. Their structures were characterized by elementary analysis， IR and ¹H NMR and the crystal structures were determined by X-ray single crystal diffraction. The crystal 1 belongs to triclinic with space group ， a=0.9076(4)nm， b=1.0663(5)nm， c=1.5193(7)nm， α=75.811(6)°，β=89.344(6)°， γ=72.665(6)°， Z=2， V=1.3577(11)nm³， D_c=1.569g·cm^-3， μ=1.406mm^-1， F(000)=644， R=0.0282， wR=0.0617. The crystal 2 belongs to monoclinic with space group P2₁/c， a=1.355(2)nm， b=1.0143(16)nm， c=1.986(3)nm， β=109.94(2)°， Z=4， V=2.565(7)nm³， D_c=1.539g·cm^-3， μ=1.195mm^-1，F(000)=1200， R=0.0467， wR=0.0788. In the crystals of 1 and 2， the structures consist of discrete molecules containing five-coordinate tin atom in a distorted trigonal bipyramidal configuration. CCDC: 1， 213679; 2， 213680.     

Effect of the protonation level of poly(o-phenylenediamine) (PoPD) on the ac impedance of humidity-sensitive PoPD/poly(vinyl alcohol) composite film

A composite film consisting of poly(o-phenylenediamine) (PoPD) and poly(vinyl alcohol) (PVA) has been prepared, and the effect of the protonation level of PoPD on the response of the composite to humidity been investigated by ac impedance measurements. The electrochemical system of the PoPD/PVA composite in a humid atmosphere is represented by an electrochemical equivalent circuit containing film (R_film, C_film), Warburg (W) and interfacial (R_ct, C_dl) impedance. R_film was increased with decreasing protonation level of the PoPD in relative humidity regions higher than 40%, but it was almost independent of the protonation level in humidity regions lower than this percentage.     

Poly(o-phenylenediamine)/MWNTs composite film as a hole conductor in solid-state dye-sensitized solar cells

All solid-state dye-sensitized solar cells were fabricated using in situ electrochemically polymerized poly(o-phenylenediamine)/MWNTs (PoPD/MWNTs) as a hole transport materiel. The electrochemical behaviors of PoPD/MWNTs indicated that the electron exchange efficiency improves obviously of PoPD after the addition of carbon nanotubes. The PoPD/MWNTs composite film was deposited on the dye anchored porous TiO₂ electrode and I–V characterization was performed under simulated AM 1.5 illumination. Fabricated devices for the PoPD/MWNT composites prepared in 0.1 g/L MWNTs showed a photoresponse with an open-circuit voltage V_OC of 479 mV and a short-circuit current density (I_SC) of 0.572 mA/cm² with the overall conversion efficiency of 0.13%, higher than those of the cell with only PoPD (i.e., I_SC = 0.275 mA/cm², V_OC = 462 mV, FF = 0.35, η = 0.04%). It is obvious that the introduction of MWNTs to PoPD composites could improve the cell performance.     

金刚烷胺邻香兰素Schiff碱稀土配合物的合成、表征及抗菌活性研究

The new solid complexes [LnL₂(NO₃)₂]NO₃ (L=C₁₈H₂₃NO₂, N-2-hydroxy-3-methoxy-benzaldehyde-1-aminoadamanantane, Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y) of rare earth nitrates with Schiff base derived from o-vanillin and adamantaneamine have been synthesized in non-aqueous system and characterized by elemental analysis, molar conductance, infrared spectra, ¹H NMR spectra, thermal analysis. The coordination modes of the bonding in these complexes were discussed and the possible structure were proposed. Every central Ln(Ⅲ) ion in the complexes coordinates with both two Schiff base ligands via four oxygen atoms of the phenol hydroxy groups and methoxy groups and two nitrates via their four oxygen atoms. Their coordination numbers are eight. In addition, the antibacterial activity of the Schiff base ligand and the complexes were studied.     

香草醛缩多胺Schiff碱Co(II)配合物固相合成及氧合性能研究

采用固相反应合成了三个新的席夫碱钴(II)配合物, 在室温下, 将其与O₂作用, 1 mol配合物吸收2 mol O₂, 得到三种固态氧合配合物[Co•(L₁)₂•(O₂)₂](NO₃)₂•2H₂O [L₁＝N,N-二(4-羟基-3-甲氧基苯亚甲基)二乙烯三胺], [Co•(L₂)₂•(O₂)₂](NO₃)₂•2H₂O [L₂＝N,N-二(4-羟基-3-甲氧基苯亚甲基)三乙烯四胺]和[Co•(L₃)₂•(O₂)₂](NO₃)₂•2H₂O (L₃＝N,N-二(4-羟基-3-甲氧基苯亚甲基)四乙烯五胺]. 通过元素分析、红外光谱、核磁共振氢谱(¹H NMR), TG/DTA、摩尔电导率、紫外等测试手段确定了氧合配合物的组成. 采用失重法测定了氧合配合物中的配位氧, 确定1 mol钴配合物吸收2 mol O₂, 其中1 mol O₂用来和钴离子配位形成超氧配合物.     

二茂铁甲酸(三邻氯苄基)锡配合物的合成、结构和量子化学研究

The novel complex tri(o-chlorobenzyl)tin ferrocenecarboxylate have been synthesized.The crystal structure of the complex has been determined by X-ray diffraction.The crystal belong to orthorhombic with space group Pbca with a=0.1242(5), b=1.7242(7), c=3.0583(13)nm, V=5.928(4)nm³,Z=8, D_c=1.623g·cm^-3,μ(MoKα)= 0.1631cm^-1,F(000)=2896,R₁=0.0461,wR₂=0.0931. The bond lengths of Sn-C is 0.2148(4), 0.2152(6) and 0.2176(5)nm, respectively. The Sn-O is 0.2073(4)nm. The tin atom has a distorted tetrahedral geometry. The study on title complex has been performed,with quantum chemistry calculation by means of G98W package and taking Lanl2dz basis set. The stability of the complex, some frontier molecular orbital energies, the populations of the atomic net charges in complex and composition characteristics of some frontier molecular orbitals have been investigated. CCDC: 184267.     

三乙四胺钴配合物氧合结构和老化机理

以固相法合成的三乙四胺钴配合物为研究体系,采用正离子电喷雾串联质谱、紫外-可见吸收光谱、拉曼共振光谱和红外光谱等表征手段,研究了配合物与氧分子的相互作用过程及配合物在吸氧过程中的结构变化。结果表明,三乙四胺钴配合物的吸氧过程是一个动态的变化过程,氧合产物由双氧双桥联的氧合配合物CoⅢL-(O2)2-CoⅢL形式向双羟基桥联的老化配合物CoⅢL-(OH)2-CoⅢL形式转变;18O2同位素标记实验验证了Co-O-O-Co的存在。酸解实验说明OH桥联配合物的形成是造成可逆性差的根本原因。这些结果为探知多胺钴配合物的氧合结构和老化机理提供了新的研究方法和实验依据。     

三乙四胺钴配合物氧合结构和老化机理

以固相法合成的三乙四胺钴配合物为研究体系,采用正离子电喷雾串联质谱、紫外-可见吸收光谱、拉曼共振光谱和红外光谱等表征手段,研究了配合物与氧分子的相互作用过程及配合物在吸氧过程中的结构变化.结果表明,三乙四胺钴配合物的吸氧过程是一个动态的变化过程,氧合产物由双氧双桥联的氧合配合物Co^ⅢL-(O₂)₂-Co^ⅢL形式向双羟基桥联的老化配合物Co^Ⅲ-L-(OH)₂-Co^ⅢL形式转变;¹⁸O₂同位素标记实验验证了Co-O-O-Co的存在.酸解实验说明OH桥联配合物的形成是造成可逆性差的根本原因.这些结果为探知多胺钴配合物的氧合结构和老化机理提供了新的研究方法和实验依据.     

Vapor phase hydrogenation of o -chloronitrobenzene ( o -CNB) over alumina supported palladium catalyst — a kinetic study

Kinetics of the vapor phase hydrogenation of o-chloronitrobenzene (o-CNB) over Pd/Al₂O₃ catalyst has been studied in a downflow microreactor under atmospheric pressure. Reaction rates have been measured at three different temperatures with respect to the partial pressures of o-CNB and hydrogen. The order of the reaction with respect to o-CNB was 0.53 at 280°C and increased with increasing temperature. However, with respect to hydrogen, a negative order was observed at 280°C, which decreased further with increasing in temperature. The apparent activation energy (Ea), from the Arrhenius plot was found to be 41 kJ/mol. On the basis of kinetic results a surface mechanism is suggested.