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甲烷氧化菌素-铜配合物催化过氧化氢氧化对苯二酚 总被引:1,自引:0,他引:1
为了探讨甲烷氧化菌素(Mb)-铜配合物(Mb-Cu)模拟过氧化物酶的可行性, 利用HP20大孔树脂、 Supelco LC-C18固相萃取和固定化金属亲和层析从甲基弯菌IMV3011中分离纯化得到Mb. 铬天青比色法显示Mb具有铜亲和性. 通过液相色谱-飞行时间质谱联用仪、 紫外光谱和荧光光谱对Mb结构进行了表征. 使用Mb-Cu配合物作为过氧化物酶模拟物, 利用紫外-可见分光光度法研究了Mb-Cu催化过氧化氢氧化对苯二酚的动力学. 考察了体系温度、 Mb-Cu添加量及过氧化氢浓度对催化反应的影响, 发现Mb-Cu符合生物催化剂条件影响的一般规律, 但比生物酶具有更高的热稳定性. 研究结果表明, Mb-Cu可作为催化氧化对苯二酚的过氧化物酶模拟酶. 相似文献
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甲烷氧化菌素催化纳米金合成 总被引:1,自引:1,他引:0
甲烷氧化菌素(methanobactin,mb)是具有过氧化氢还原酶活性的荧光肽.从甲基弯菌Methylosinus trichospo-rium IMV3011限铜培养介质中分离mb,采用紫外可见全波长扫描法观察mb催化对苯二酚还原氯金酸合成纳米金的作用和影响,当mb/氯金酸/对苯二酚反应液中mb的浓度分别是2.5×10-5mol/L、5.0×10-5mol/L和1.0×10-4mol/L时,形成的纳米金溶液的特征峰分别是561.5 nm(OD561=0.158)、548.0 nm(OD5 48=0.426)、536.5 nm(OD5 36=0.541),特征峰波长减小,对应的吸光值增大,表明mb能够催化对苯二酚还原氯金酸合成纳米金,并且可以通过调控mb的浓度控制纳米金的合成量及粒径大小. 相似文献
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醇-胺(氨)直接脱氢及氧化脱氢偶联生成酰胺具有原子经济性高和对环境友好等优点,因而受到广泛关注。研究发现,一些过渡金属钌及铑配合物、负载金及银纳米粒子、氧化锰分子筛(OMS-2)以及基于铜、铁化合物的催化体系在醇-胺(氨)直接脱氢或氧化脱氢偶联生成酰胺反应中显示出优良的催化性能。本文首先介绍了PNN-钌、NHC-钌配合物、铑配合物以及负载银原子簇催化的醇-胺(氨)直接脱氢偶联生成酰胺反应的研究进展,然后对负载纳米金粒子、氧化锰分子筛(OMS-2)以及基于铜、铁化合物的催化体系催化的不同氧化剂,包括分子氧、叔丁基过氧化氢以及分子碘氧化的氧化酰胺化反应进行了总结。对各催化剂或催化体系的适用范围和优缺点进行了分析,阐述了主要催化剂或催化体系的催化机理。此外,还对无过渡金属参与的醇-胺氧化酰胺化反应体系进行概述。最后,在总结现有成果的基础上指出了该领域的发展方向。 相似文献
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主要讨论了生物还原制备Au/γ-Al2O3催化剂用于催化葡萄糖氧化动力学的研究.利用甲烷氧化菌素(Methanobactin,Mb)作为还原剂及稳定剂制备了1%Au/γ-Al2O3催化剂.通过TEM分析,负载纳米金颗粒(Gold nanoparticles,AuNPs)粒径为3.48±0.881 nm.比较Mb及Au/γ-Al2O3催化剂的FTIR发现,在Au/γ-Al2O3催化剂表面整合有Mb基团.实验建立了幂指数速率模型,确定了D-葡萄糖、H2O2、催化剂、葡萄糖酸钠的反应级数,分别为:0.4696、0.3729、0.4088和-0.9794.同时通过阿伦尼乌斯曲线求得该催化剂活化能(Activation energy,Ea)为6.114 kJ/mol.最后通过验证该速率模型发现,预测值与实验值具有良好的拟合性. 相似文献
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以固载于微米级硅胶表面的聚4-乙烯吡啶-铜(Ⅱ)配合物(P4VP-Cu(Ⅱ)/SiO2)为催化剂,以分子氧为氧化剂,在常压下实施了将乙苯氧化为苯乙酮的催化氧化反应;用红外光谱、紫外光谱及液相色谱对产物的化学结构进行了表征;重点研究了催化剂的催化性能,以及各种条件(温度、催化剂性质、催化剂用量等)对催化氧化反应的影响;并分析了催化氧化反应的机理.研究结果表明,固载于硅胶表面的聚4-乙烯吡啶-Cu(Ⅱ)配合物能有效地活化分子氧,显著地催化氧化乙苯为苯乙酮的反应过程;该催化剂具有优良的催化活性与选择性,于130℃常压下通氧气反应10h,可使约60%的乙苯转化为苯乙酮,另一氧化产物α-甲基苄醇的含量则极少.另外,该催化剂具有较好的重复使用稳定性. 相似文献
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Nobukatsu Nemoto Hiroji Ishii Manabu Ihara Nobuo Takamiya Koji Ikeda 《Journal of polymer science. Part A, Polymer chemistry》1994,32(13):2457-2467
The oxidation of hydroquinone catalyzed by pyridine-Cu(II) complexes attached to polyorganosiloxane was investigated in the mixed solvent of methanol/water (vol. ratio 2/1). The catalytic oxidation followed Michaelis-Menten-like kinetics. The large k2 term related to a turnover number indicated that the present polymeric catalysts have a remarkable effect on the activation process. The methylene number between the side-chain acid amido and pyridyl groups of the polymeric ligand was shown to be closely related to the appearance of hydrophobic effects in both the substrate-binding and the activation processes as deduced from the Michaelis constant and the thermodynamic and activation parameters. The binding parameters for 4-methoxyphenol with pyridyl-functionalized polyorganosiloxanes supported that the flexible backbone is also effective in the oxidation of hydroquinone. The Cu(II) complexes with pyridyl-functionalized polyorganosiloxane would have the structures distorted from square planar formation, which would promote the reduction of Cu(II) to Cu(I), as concluded from ESR spectroscopy and electrochemical measurement. © 1994 John Wiley & Sons, Inc. 相似文献
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Enantioselective recognition of amino acids has been studied with C2-symmetric chiral pyridine bis(oxazoline)-copper(II) complexes at physiological pH condition. UV-visible titration revealed strong binding of submillimolar dissociation constant between pyridine bis(oxazoline)-copper(II) complex and amino acids in aqueous solution. Moderate selectivity of up to 2:1 between d- and l-amino acids was achieved. The enantiomers were baseline resolved by capillary electrophoresis, using the bis(l-lysine)-copper(II) complex as a chiral selector. 相似文献
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Kramareva N. V. Finashina E. D. Kucherov A. V. Kustov L. M. 《Kinetics and Catalysis》2003,44(6):793-800
Peculiarities of the structure and physicochemical properties of copper–chitosan complexes prepared by different methods were studied by IR, UV-visible, ESR spectroscopy, and electron microscopy. The catalytic activity of redox copper centers stabilized by the chitosan matrix in the reactions of oxidation of o- and p-dihydroxybenzenes in an aqueous medium was determined. Quantitative ESR measurements provide evidence for the localization of virtually all copper ions introduced in the initial heterogeneous chitosan samples with copper contents below 1.5 wt % in the form of isolated Cu2+ ions in square planar coordination. The chitosan matrix was shown to strongly bind copper ions under conditions of redox transformations in the catalytic tests or upon prolonged heating in boiling water. Reoxidation of the samples with H2O2 results in quantitative restoration of the initial ESR signal of Cu(II). Heterogenized copper–chitosan samples exhibited high activity and stability in the catalytic oxidation of dihydroxybenzenes into quinones, whereas the homogeneous system was characterized by irreversible poisoning due to formation of copper–hydroquinone complexes. Preparation of the binary composite system with a thin heterogeneous copper–chitosan film supported on a macroporous silica allows one to dramatically enhance the specific catalytic activity and the efficiency of the active component. Such an approach may turn out to be useful in the synthesis of supported chitosan catalyst with a low noble metal content. 相似文献
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Wei Hu Jian-zhang Li Ying Wang Shen-xin Li Jia-qing Xie 《Journal of Dispersion Science and Technology》2013,34(1):88-95
Metallomicelles made from two Schiff base manganese(III) complexes (MnL1 and MnL2) and surfactants (CTAB and Brij35) were used as mimetic peroxidase in the catalytic oxidation of phenol by H2O2. The catalytic activity of the complexes (MnL1 and MnL2) were investigated. The mechanism and a kinetic mathematic model of the phenol catalytic oxidation were also studied. The results show the optimum acidity of the enzyme-like system in the paper is ca. pH 7.0, the optimum temperature which is ca. 35°C and the optimum molar ratio of H2O2 to the complex is ca. 30 in the complexes-H2O2-buffered solution; the Schiff base manganese(III) complexes and their metallomicelles as peroxidase mimics exhibit good catalytic activity and similar catalytic character to natural enzyme. 相似文献
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Ag. Stamatis P. Doutsi Ch. Vartzouma K.C. Christoforidis Y. Deligiannakis M. Louloudi 《Journal of molecular catalysis. A, Chemical》2009,297(1):44-53
Two new symmetrical acetylacetone-based Schiff bases, herein called LA and LB, have been synthesized. The complexes formed by their association with Mn(II) have been evaluated for catalytic alkene epoxidation with H2O2. The catalytic efficiency of Mn(II)/LA and Mn(II)/LB systems were shown to be switched on by ammonium acetate with remarkable effectiveness and selectivity towards epoxides. EPR spectroscopy for Mn(II)/LA shows that the catalytic centre is a mononuclear Mn complex. Additives that allow easier oxidation of Mn(II) to higher oxidation states, i.e. such as acetate and bicarbonate, can promote decisively the catalytic function. Additives that do not allow oxidation of Mn(II) to higher oxidation states, i.e. such as formate and oxalate, inhibit severely the catalytic function. Monocarboxylate ions, i.e. acetate, bicarbonate and formate do not disturb considerably the first coordination sphere of Mn(II). Dicarboxylate additives, i.e. such as oxalate, form strong complex with the Mn(II).Based on the catalytic and EPR data, a double role is suggested for ammonium acetate. This is to promote Mn(II) oxidation, and to function as a dual acid-base system, participating into the catalytic cycle. 相似文献
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Palladium(II) complexes of 2‐(2′‐pyridyl)quinoline (PQ), namely [PdX2(PQ)] (X = Br?, I?, N3?, NO2?, SCN?, acac) and [PdCl(NO3)(PQ)] have been synthesized via substitution reactions of [PdCl2(PQ)] with an excess of sodium salts and acetylacetone. The complexes have been characterized by elemental analysis, conductivity measurements, IR, 1H and 13C NMR spectroscopy. Selected complexes have been further characterized using electrospray ionization (ESI) and ion trap mass spectroscopy (ITMS). Some complexes are found to catalyze the rapid air oxidation of α‐olefins under Wacker oxidation. The chlorohydrin products are produced in good to excellent yields while oxidation products are obtained in low yields. The [PdCl2(PQ)] complex is found to have the highest catalytic activity. 相似文献
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制备了以铜、钴、锰为中心离子的三种单核金属配合物L1Cu、L1Co、L1Mn (L1=N,N'-(2-羟乙基)丙二酰胺)和三种双核金属配合物L2Cu、L2Co、L2Mn (L2=N,N'-{2-(2-羟乙基氨基)乙基}丙二酰胺). 研究发现在缓冲溶液中六种金属配合物能将对甲氧基苦杏仁酸(4-MMA)高选择性地氧化成对甲氧基苯甲醛(AAD)以及少量对甲氧基苯甲酸(4-MBA), AAD的选择性(S)大于96%. 然而不同的催化体系在反应速率上表现了很大的不同: 铜金属配合物的催化活性最好; 双核配合物表现出更高的催化效率. 研究了酒石酸(TA)、磷酸(H3O4)、醋酸(HAc)三种缓冲溶液体系对L1Cu催化H2O2氧化4-MMA反应的影响, 结果表明缓冲溶液种类对反应速率和选择性影响很大.研究了35℃时弱酸性条件(pH值从2.5到4.5的范围内)在酒石酸缓冲溶液中六种金属配合物催化H2O2氧化4-MMA的动力学, 计算出不同pH值条件下催化反应的表观反应速率常数kobs, 并且讨论了pH值对催化反应的影响. 相似文献
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Seema Yadav Sriparna Ray Ajeet Singh Shaikh M. Mobin Tapta Kanchan Roy Chandrakanta Dash 《应用有机金属化学》2020,34(11):e5942
Dinuclear gold(I)-N-heterocyclic carbene complexes were developed for the hydrohydrazidation of terminal alkynes. The gold(I)-N-heterocyclic carbene complexes 2a-2b were synthesized in good yields from silver complexes synthesized in situ, which in turn were obtained from the corresponding imidazolium salts with Ag2O in dichloromethane as a solvent. The new air-stable gold(I)-NHC complexes, 2a - 2b, were characterized using NMR spectroscopy, elemental analysis, infrared, and mass spectroscopy studies. The gold(I) complex 2a was characterized using X-ray crystallography. Bis-N-heterocyclic carbene–based gold(I) complexes 2a - 2b exhibited excellent catalytic activities for hydrohydrazidation of terminal alkynes yielding acylhydrazone derivatives. The working catalytic system can be used in gram-scale synthesis. In addition, the catalytic reaction mechanism of the hydrohydrazidation of terminal alkynes by gold(I)-NHC complex was studied in detail using density functional theory. 相似文献
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Wei Hu Jian-zhang Li Ying Wang Ju Du Chang-wei Hu 《Journal of Dispersion Science and Technology》2013,34(10):1476-1483
The two Schiff base cobalt(II) complexes, CoL1 and CoL2, were synthesized and characterized. The metallomicelle made up of the cobalt(II) complexes and surfactants (CTAB, LSS and Brij35), as mimic peroxidase metalloenzyme, were used in the catalytic oxidation of phenol by H2O2. The mechanism and a kinetic mathematic model of the phenol catalytic oxidation were studied. The acid effect of reaction system, structural effect of the complexes, and effect of temperature on the rate of the phenol oxidation catalyzed by the mimetic peroxidases have been discussed. The results showed that the schiff base cobalt(II) complexes and their metallomicelles as peroxidase mimics exhibit good catalytic activity and similar catalytic character to natural enzyme. 相似文献