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将一系列苯并-10-氮杂-15-冠-5或吗啉基取代的不对称双Schiff碱配合物作为催化剂,在常压和120℃条件下用于催化氧化对二甲苯研究。探讨了Schiff配合物中心金属离子、Schiff碱配体中挂接的氮杂冠醚环、配体芳环上取代基等对催化氧化对二甲苯反应活性及其氧化产物选择性的影响。实验结果表明:配合物中氮杂冠醚的存在能显著缩短反应诱导期、提高催化活性和选择性;Schiff碱Mn(Ⅲ)配合物比Schiff碱Co(Ⅱ)和Schiff碱Cu(Ⅱ)具有更高的催化活性;氮杂冠醚Schiff碱Mn(Ⅲ)配合物催化氧化二甲苯的转化率和产物选择性分别达75%和90%。 相似文献
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本文将苯并-10-氮杂-15-冠-5或吗啉基取代的单Schiff碱过渡配合物作为催化剂,在常压和120℃条件下,以空气为氧源,研究了对二甲苯催化氧化反应。实验探讨了Schiff碱配合物中心金属离子、Schiff碱配体中挂接的氮杂冠醚环、配体芳环上取代基和反应时间等对对二甲苯催化氧化反应的影响。实验结果表明:Schiff碱配合物中氮杂冠醚的存在能显著缩短反应诱导期,提高催化反应活性和产物选择性;Schiff碱Mn(III)配合物比Schiff碱Co(II)具有更高的催化反应活性;氮杂冠醚Schiff碱Mn(III)配合物对于二甲苯的催化氧化反应转化率大于60%,对甲苯甲酸产物的选择性均高于70%。 相似文献
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邻香兰素对甲苯胺Schiff碱稀土配合物的制备和表征 总被引:4,自引:0,他引:4
前文曾报道了香兰素(3-甲氧基-4-羟基苯甲醛)与对甲基苯胺的Schiff碱稀土配合物。本文讨论邻香兰素(2-羟基-3-甲氧基苯甲醛)与对甲基苯胺的Schiff碱稀土配合物[LnL_2Cl·2H_2O]Cl_2(Ln:ce,Pr,Nd,Sm,Eu,Gd,Dy;L:Schiff碱)的制备和表征。 1 实验 1.1 配合物的制备 按文献方法,用等摩尔比的邻香兰素与对甲基苯胺在无水乙醇中先制成Schiff碱,然后按摩尔比1:2将稀土氯化物LnCl_3·nH_2O的无水乙醇溶液滴加到 相似文献
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将4种氮杂冠醚取代的双Schiff碱钴(H)、锰(m)配合物作为仿水解酶模型催化羧酸酯(PNPP)水解.考察了Schiff碱配合物中氮杂冠醚取代的位置、氮杂冠醚的数目对其仿水解酶性能的影响;探讨了Schiff配合物催化PNPP水解的动力学和机理;提出了配合物催化PNPP水解的动力学模型.结果表明,在25℃条件下随着缓冲溶液pH值的增大,配合物催化PNPP水解速率提高;四种氮杂冠醚取代的双Schiff碱配合物在催化PNPP水解反应中表现出良好的催化活性;氮杂冠醚3-取代的Schiff碱配合物CoL2的催化活性高于5-取代的Schiff碱配合物CoL1,含有2个氮杂冠醚的配合物CoL3的催化活性高于含有1个氮杂冠醚的配合物CoL2. 相似文献
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合成了三核锰(Ⅲ)Schiff碱配合物:Mn_3O(Salea)_2(C_2H_3O_2)_3·HC_2H_3O_2(其中Salea~(2-)为水杨醛缩乙醇胺Schiff碱阴离子),经元素分析、磁矩、化合价、电导率、热分析、红外、紫外光谱等进行表征,并利用氧电极进行了放氧活性测试,发现在对苯醌存在下配合物能促使水分解释放氧气,其反应受温度、对苯醌和配合物浓度等因素影响,并提出了可能的放氧反应方程. 相似文献
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将4种氮杂冠醚或吗啉取代的单Schiff碱锰(III)配合物作为仿水解酶模型催化α-吡啶甲酸对硝基苯酯(PNPP)水解。考察了单Schiff碱配体中取代基类型、氮杂冠醚取代的位置对其仿水解酶性能的影响;探讨了Schiff配合物催化PNPP水解的动力学和机理;提出了配合物催化PNPP水解的动力学模型。结果表明,在25℃条件下随着缓冲溶液pH值的增大,配合物催化PNPP水解速率提高,氮杂冠醚化单Schiff碱锰(III)配合物在催化PNPP水解反应中表现出良好的催化活性,Schiff碱配体结构显著影响配合物催化活性。 相似文献
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Seyed Ebrahim Hashemi Mahmood Payehghadr Zarrin Es'haghi Hadi Kargar 《International journal of environmental analytical chemistry》2013,93(12):1148-1163
ABSTRACTIn this approach, a new carbon paste electrode modified with N,N′-bis(5-bromo-2-hydroxybenzylidene)-2,2-dimethylpropane-1,3-diamine Schiff base ligand (L) was synthesised for selective and effective determination of Hg2+ ions in aqueous environmental samples using cyclic and square wave anodic stripping voltammetric methods. First, the selective detection of mercury ion was confirmed by evaluating the stability constants of metal complexes formed between the Schiff base ligand (L) and some desired cations by conductometric measurements. Afterwards, by preparing an effective carbon paste electrode modified with L, the experimental and instrumental parameters affecting the performance of modified electrode were investigated. Square wave anodic stripping voltammograms were obtained after applying an accumulation potential ?0.5 V and accumulation time 150 s in Britton–Robinson buffer solution at pH 2.0. The optimal square wave parameters found are pulse amplitude 75 mV, frequency 50 Hz and step potential 6 mV. The procedure exhibited linear range from 0.4 to 120 μg L?1 Hg2+ with a limit of detection of 0.042 μg L?1. The proposed electrode was proved to be highly selective in the presence of various cations and anions and was successfully used for determination of mercury in tobacco and several water samples. 相似文献
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An Electrochemical Sensor for Determination of Ultratrace Cd,Cu and Hg in Water Samples by Modified Carbon Paste Electrode Base on a New Schiff Base Ligand 下载免费PDF全文
Farzaneh Nourifard Mahmood Payehghadr Mehdi Kalhor Azizallah Nejadali 《Electroanalysis》2015,27(10):2479-2485
This paper describes the preparation and electrochemical application of a new chemically modified electrode for simple and highly sensitive simultaneous determination of copper, mercury and cadmium using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Firstly, a new bis‐Schiff base ligand, 2,2′‐((pyridine‐2,6‐diylbis (azanylylidene)) bis (methanylylidene))bis(4‐bromophenol) (ligand L ) has been synthesized by reaction of the 2,6‐diamino pyridine with 5‐bromo salicylaldehyde or salicylaldehyde at ethanol under refluxing. The structure of the synthesized compound resulted from the IR, 1HNMR, MS, UV spectroscopy and elemental analysis data. Afterwards, a novel, simple and effective chemically modified carbon paste electrode with ligand L was prepared. The electrochemical properties and applications of the modified electrode, including the pH, percentage of modifier, the electron transfer, optimized conditions, linear response and detection limit were investigated. High sensitivity and reproducibility, together with the ease of preparation and regeneration of the electrode surface by simple polishing, make the electrode very suitable for the voltammetric determination of copper, mercury and cadmium in several Merck samples and water samples. 相似文献
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Specific analytical problems often arise which can be easily solved if a mercury electrode of constant surface area is used as voltammetric sensor. In this work a membrane covered mercury electrode was prepared and used in solving various analytical tasks. One of them was the determination of water hardness. A sample injection method was developed applying EDTA reagent and a flow-through analytical system. Two different voltammetric enzyme electrodes (measuring glucose and L-amino acid) were prepared by using the membrane covered mercury electrode as base sensor. The application of the enzyme electrode in flow-through circumstances was proved to be very advantageous in determining selectively L-DOPA in the presence of the D-form. 相似文献
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Masato Ueda Takahiro Saito Keiichi Fujimori Takayo Moriuchi Yasuhiko Shibutani 《Analytical sciences》2004,20(12):1649-1653
To examine the directivity for improving the silver ion discrimination ability of a Schiff base, three kinds of tridentate ligands were synthesized and compared with the similar quadridentate ligand as the silver ionophore. Among the Schiff base derivatives tested, 3-(2-pyridylethylimino)-2-butanoneoxime, having one oxime and a pyridine substituent, was found to be the best ionophore for a silver-ion electrode. The electrode based on this derivative exhibited good silver-ion selectivity, -log Kpot(Ag+,K+) = 3.8, comparable to that of a quadridentate Schiff base, N,N'-bis(2'-hydroxyimino-1'-phenylpropyleden)-1,3-propanediamine, reported previously, except for a pseudo Nernstian response (35.6 mV decade(-1)) with a wide silver-ion activity change in the activity change from 5.0 x 10(-7) to 7.9 x 10(-2) mol dm(-3). 相似文献
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《Arabian Journal of Chemistry》2020,13(7):6072-6083
A Nickel Schiff base complex, insoluble in water, was synthesized and used as modifier. A Nickel Schiff base modified carbon paste electrode MCPE was build. The electrodes were characterized by scanning electron microscopy (SEM), energy dispersive X-Ray spectroscopy (EDXS), cyclic voltammetry and chronoamperometry. The modifier is elctroactive, a well defined redox couple of NiIII/NiII in alkaline medium was made in evidence. It presents a quasi-reversible system with electron transfer coefficient (0.38) and electron transfer rate of 4.5 s−1. The electrogenerated NiIII species on the surface of the electrode act as an excellent catalyst toward thiosulfate oxidation reaction with a chemical rate constant Kh equal to 23,6 M−1s−1. The different techniques involved in this study qualify our modified electrode as sensitive, reliable and very stable for thiosulfate analysis. 相似文献
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Construction of Modified Carbon Paste Electrode for Highly Sensitive Simultaneous Electrochemical Determination of Trace Amounts of Copper (II) and Cadmium (II) 下载免费PDF全文
Abbas Afkhami Morteza Soltani‐Shahrivar Hamed Ghaedi Tayyebeh Madrakian 《Electroanalysis》2016,28(2):296-303
A chemically modified electrode was constructed for rapid, simple, accurate, selective and highly sensitive simultaneous determination of Cu(II) and Cd(II) using square wave anodic stripping voltammetry. The electrode was prepared by incorporation of SiO2 nanoparticles, coated with a newly synthesized Schiff base, in carbon paste electrode. The limit of detection was found to be 0.28 ng mL?1 and 0.54 ng mL?1 for Cu(II) and Cd(II), respectively. The proposed chemically modified electrode was used for the determination of copper and cadmium in several foodstuffs and water samples. 相似文献