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锌配合物的合成、表征、晶体结构&蛋白质的超分子显色反应研究与应用

Synthesis, Characterization and Crystal Structure of Zinc (Ⅱ) Complexes & Study on Supermolecule Color Reaction of Protein and Its Applications

【作者】 马卫兴

【导师】 陆路德; 杨绪杰; 汪信;

【作者基本信息】 南京理工大学 , 应用化学, 2004, 博士

【摘要】 以氧化锌、5-磺基水杨酸及三(2-氨基乙基)胺为原料在甲醇-水混合溶剂介质中反应,合成了具有4N+0型配位环境的混配物[Zn(tren)(5-HSSA)]。以乙酸锌、三(2-氨基乙基)胺及四氟硼酸钠为原料在甲醇介质中反应,合成了具有4N+0型配位环境的乙酸根桥连的双核锌混配物[(tren)Zn(CH3COO)Zn(tren)](BF43。以三氟乙酸锌和3-羟基吡啶为原料在甲醇介质中反应,合成了一种新的具有60型配位环境的含锌混配聚合物{[Zn(CF3COO)2(C5H4ONH)](H2O)}n。以乙酸锌、3-羟基吡啶和苯甲酰三氟丙酮或乙酰丙酮为原料在甲醇介质中反应,分别合成了二种新的具有40+N型配位环境的含β-二酮的锌混配物[Zn(C6H5COCHCOCF32(C5H4ONH)]和[Zn(acac)2(C5H4ONH)]。以乙酸锌或三氟乙酸锌和2-氨基苯并噻唑为原料在甲醇介质中反应,分别合成了二种新的具有20+2N型配位环境的含2-氨基苯并噻唑的羧酸锌混配物[Zn(CH3COO)2(C7H6NS)2]和[Zn(CF3COO)2(C7H6NS)2]。以高氯酸锌、2-乙酰吡啶及不等臂多胺2-氨基乙基-二(3-氨基丙基)胺为原料在甲醇介质中反应,合成了新的具有5N型配位环境的异构体复晶-席夫碱锌配合物{[2-C5H4NC(CH3)NCH2CH2N(CH2CH2CH2NH22Zn] [2-C5H4NC(CH3)NCH2CH2CH2N(CH2CH2NH2)CH2CH2CH2NH2Zn](ClO44}。以乙酸锌、水杨醛和苄胺为原料在甲醇介质中反应,合成了具有20+2N型配位环境的锌席夫碱配合物{[O-C6H4O(CH=NCH2C6H5)]2Zn}。培养了这9种配合物的单晶,用元素分析、红外光谱、核磁共振氢谱、热重分析进行了谱学表征,并通过单晶X-射线衍射首次获得了这9种配合物的晶体结构。 首次提出了超分子显色反应的概念。在弱酸性条件下,用可见吸收光谱技术研究了一种绿色染料固绿FCF、三种单偶氮变色酸(苦胺酸偶氮变色酸、铬偶氮KS及对磺基苯偶氮变色酸)和虎红与蛋白质的超分子显色反应,详细研究了这些超分子显色反应的最佳条件,拟订了分析方法,并成功地应用于实际人血清中总蛋白的测定,探讨了蛋白质与这些小分子有机试剂的超分子显色反应机理。

【Abstract】 A new mixed coordination compound [Zn(tren) (5-HSSA)] with 4N + O coordinated environment was synthesized based on the reaction of ZnO,5-sulfosalicylic acid and tren in water-methanol mixed solvents where tren was tris(2-aminoethyl)amine. A new mixed acetate bridged coordination compound [(tren)Zn(CH3COO) Zn (tren)](BF4)3} containing two zinc(II) with 4N + O coordinated environment was synthesized based on the reaction of zinc acetate, sodium tetrafluoroborate and tren in methanol medium. A new mixed coordinated polymer{{[Zn(CF3COO)2(C5H4ONH)](H2O)}n} containing zinc(II) with 60 coordinated environment was synthesized based on the reaction of zinc trifluoroacetate and 3-hydroxypyridine in methanol medium. Two new (J-diketone mixed coordination compounds [Zn(acac)2(CsH4ONH)] and[Zn(C6H5COCHCOCF3)2(C5H4ONH)]}containing zinc(II) with 4N + O coordinated environment, were synthesized based on the reaction of zinc acetate, 3-hydroxypyridine and acetylaceton or benzoyl trifluoroacetone in methanol medium. Two new mixed coordination compounds {[Zn(CH3COO)2(C7H6NS)2] and [Zn(CF3COO)2(C7H6NS)2] containing zinc(II) carboxylate with2-aminobenzothiazole with 2N + 20 coordinated environment were synthesized based on the reaction of zinc acetate or zinc trifluoroacetate and 2-aminobenzothiazole in methanol medium. A new schiff base complexes {[2-C5H4NC(CH3)NCH2CH2N(CH2CH2CH2NH2)2Zn] [ 2-C5H4NC(CH3)NCH2CH2 CH2N(CH2CH2NH2) CH2CH2CH2NH2Zn](C104)4} with 5N coordinated environment was synthesized based on the reaction of zinc perchlorate, 2-acetylpyridine and inequilateral organic polyamine 2-aminoethyl-bi(3-aminopropyl)amine in methanol medium. The schiff base complex {[O-C6H4O(CH=NCH2C6H5)]2Zn}containing zinc(II) with 2N + 2O coordinated environment were synthesized based on the reaction of zinc acetate, salicylal and benzylamine in methanol medium. The single crystals of these nine kinds of complexes mentioned above were cultured, and characterized by elemental analysis, IR, NMR and TG. A total of nine crystal structures of these complexes were determined by X-ray single crystal diffraction and first reported.The new concept of supermolecule color reaction was proposed in this paper for the first time. The supermolecule color reaction of proteins with the green dye fastgreen FCF, three single azo chromotrope dyes such as picramazo chrom, chromazol KS and 2-(4-sulfophenylazo)-chromotropic acid, and Rose Bengal were studied with spectrophotometric technique in weak acidic medium, respectively. The analytical methods were proposed based on the investigations of reaction conditions for these supermolecule color reactions, successful applied to determination of total proteins in human serum samples, and the supermolecule color reaction mechanisms of protein with mentioned acidic dye were studied.

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