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Synthese,Cr-ystal Stucture And Intraction With DNA Of Complexes With4-Methyl-1,2,3-Thiadiazol-5-carboxylic Acid

Posted on:2013-06-24Degree:MasterType:Thesis
Country:ChinaCandidate:J B ShenFull Text:PDF
GTID:2231330374993411Subject:Organic Chemistry
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Elictor, which is friendly to environment,refers to any chemical that can trigger plant immunosystem and induces the systemic acquired resistance of the host plant. It has characters of broad-spectrum, persistence and hystereticnature. Thiadiazol derivatives are widely used in the area of pesticides and pHarmaceutics due to their extensive biological activity. Among thiadiazol compound, biological activity of1,3,4-thiadiazol compound and1,2,3-thiadiazol compound have reported for many times, while research on1,2,3-thiadiazol complex is comparatively inadequate and the related report on its biological activity is even less. Acibenzolar-S-methyl (BTH) and3’-chlor-4,4’-dimethyl-1,2,3-thiadiazole-5-carbox-anilide (TDL) which both contain the structure of1,2,3-thiadiazol are the typical representative of commercial plant activator, they have capacity of degradation by releasing N2in an irreversible way.To design and synthesize some complexes, we use4-methyl-1,2,3-thiadiazol-5-carboxylic acid as first ligand,4,4’-bipyridine (Bipy) or1,10-phenanthroline (phen) as auxiliary ligand. We also carried out a pilot study on the interaction between calf thymus DNA (ct-DNA) and antiproliferative activity of the compounds. The main work is as following:1、Introduction Part:A brief summary about the synthesis, pesticide biological activity, research process of1,2,3-thiadiazol derivatives and the study of the plant activator were described.2、Using4-methyl-1,2,3-thiadiazol-5-carboxylic acid as first ligand,4,4’-bipyridine (Bipy) or1,10-phenanthroline (phen) as auxiliary ligand, ten transition metal complexes were synthesized by traditional solution methods, the single crystal of all of which were all obtained. The composition of these complexes was analysed by elemental analysis, IR spectra and TGA. The general formula of complexes can be presented as:[AgL]n(1),[CuL2(H2O)2]n(2),[Mn3L6(H2O)4]n(3),[CoL2(H2O)4]-2H2O(4),[CuNaL3]n(5),[Mn2(OH)2(phen)4(H2O)2]2L-7H2O(6),[Mn2Cl2(phen)4(H2O)2]2L-3H2O(7),[ML(phen)(H2O)2]L [M=Cu(8), Zn(9)],[ZnL2(Bipy)(H2O)]n(10).3、Twelve lanthanide complexes,[LnL3(H2O)2]n-nH2O[Ln=Tb(11), Dy(12), Ho(13), Yb(14)],[LnL3(H2O)2]n[Ln=Ce(15), Sm(16)],[Ln2L4(NO3)2(H2O)6][Ln=Ce(17), Gd(18), Tb(19), Dy(20), Ho(21)],[NdL2(CH3COO)(H2O)2](22), were synthesized with4-methyl-1,2,3-thiadiazol-5-carboxylic acid. It is proved that they all belong to allomerisms by means of IR, elemental analysis, TG-DTG, X-ray single crystal diffraction and Powder diffraction. The results show that the crystal structure of12complexes belong to three categories by X-ray diffraction analysis.4、The interaction between HL,11compounds and DNA are studied by EB fluorescent probe. Compared the constants Ksp,the result show all complexes can insert into DNA in different degree, the binding ability of the complex1is the weakest, while complex7is the strongest. Except complex1, the binding ability of the complexes is stronger than HL, the result is probably attributed to the generation of two-demensional network between ligand and Ag atom, which leads to the ability of inserting into DNA weakest because of steric factor. On the other hand, because of the thiazole ring and small volume, other complexes can insert to the DNA base pair easily. As auxiliary ligand, phen and Bipy has aromatic ring and large conjugate plane, which leads to the binding ability relatively strong.
Keywords/Search Tags:4-methy1-1, 2, 3-thiadiazol-5-carboxylic acid, complex, crystalstructure, DNA
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