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Syntheses,Structures And Properties Of Metal Complexes Based On Aminohydroxamic Acid

Posted on:2019-02-09Degree:MasterType:Thesis
Country:ChinaCandidate:J ZhangFull Text:PDF
GTID:2321330566962169Subject:Inorganic Chemistry
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Aminohydroxamic acid ligands contains ligands of N,O donor atoms,and the coordination atoms are easily when they reacted with transition metal ions or rare earth metal ions,most of which are metallacrowns.The investigation proved that metallacrown display unique ion recognition,biological activity and magnetic properties,and therefore have potential prospects and research in many fields such as magnetic materials,bioinorganic chemistry value.We have synthesise three hydroxamic acid ligands such as glycine hydroxamic acid,alanine hydroxamic acid and butyrat hydroxamic acid,they reacted with different metal salts obtained fifteen metal complexes,and they were characterized by X-ray single crystal diffraction,IR spectra and elemental analysis.UV,fluorescence and circular dichroism spectroscopy,further studied the interaction between the complexes and CT-DNA.The interaction between the complexes and bovine serum albumin?BSA?was studied by fluorescence spectroscopy and studied its cytotoxic activity.We study the magnetic properties of few complexes,the main work is as follows:1.Seven complexes were obtained by the reactions of glycine hydroxamic acid?H2glyha?theligandwithdifferentmetalsalts:{Nd?OAc?2[Cu5?glyha?5?H2O?4]}·NO3·3H2O?1?,{Pr?SCN?2?H2O?2[Cu5?glyha?5?H2O?2]}·?SCN?·6H2O?2?,{Dy?PhCOO?2?H2O?[Cu5?glyha?5]?H2O?2}·?ClO4?·5H2O?3?,{Pr?OH?[Cu5?glyha?5?H2O?]}2Cu?glyha?2·?N3?2·6H2O?4?,{Nd?OH?[Cu5?glyha?5?H2O?2]}2Cu?glyha?2·?N3?2·6H2O?5?,[Cu2?glyha??bpy?2?H2O?]·2?ClO4?·H2O?6?,[Cu2?glyha??phen?]2·2?ClO4??7?.Complexes 1-5 are 15-MC-5 metalcrown and have similar framework.The complex 6 and complex 7 are binuclear complexes.The DNA binding properties of complexes 1-7 with calf thymus DNA?CT-DNA?have also been investigated by UV-vis spectra,fluorescent spectra and CD spectra and the result indicate that strong intercalation interactions exist between complexes 1-7 and CT-DNA.Fluorescence spectroscopy revealed that the endogenous static quenching of the complexes with bovine serum albumin?BSA?.The complex 1-5 were texted on four kinds of human cancer cells?A549,Hela,HL-60,HCT-116?in vitro activity,different complexes showed different activity,most of the complexes showed moderate activity on tumor cells.The complexes 1,3,4 on HL-60 cell line showed moderate activity,and weak activity against other cell lines.Complexes 2,5 showed weak activity against four cancer cell lines.2.Five complexes were abtained by alanine hydroxamic acid?H2alaha?ligand was synthesizedandreactedwithCusaltandrareearthsalt:[Dy3Cu9?alaha?9?N3?6]·?N3?3·6H2O?8?,{[NdCu5?Alaha?5][Nd?C2O4?3?H2O?]}2·13H2O?9?,{[PrCu5?Alaha?5?OH?2]2?C2O4?·6H2O?10?,[Cu?alaha??bpy?2Cl]·Cl·4H2O?11?,[{Cu2?alaha??phen?2}{Cu2?alaha??phen?2?NO3?}]·3NO3?12?.The UV-visible spectra,fluorescence quenching spectra and circular dichroism showed that the interaction between the complexes and the CT-DNA was inserted.Fluorescence spectroscopy revealed that the endogenous static quenching of the complexes with bovine serum albumin?BSA?.The in vitro anti-tumor cell activity of complexes 8-10 was studied.Complex 8 and complex 10 exhibited moderate activity on HL-60 cell line and A549 cell line,respectively,and weak activity on other cell lines;complex 9 showed weak activity on four cell lines.The antitumor activity of 6,7,11,12 was compared,and the molecular docking analysis was conducted on the main binding sites of the complexes and BSA.Studies of the magnetic properties indicate the presence of dominant antiferromagnetic in complex 8-10.3.There are three metalcrown ethers were synthesized by butyrat hydroxamic acid?H2butyha?reacted with different metal salts:[Cu5?butyrat?4?H2O?2]·[Cu?N3?4]·5H2O?13?,{Dy[Cu4?butyrat?4]2}·Cl·2Br·8H2O?14?,[Cu5?butyrat?4?OH?]·[Pr??2-OAc?4·?H2O?2]·H2O?15?.The complexes are similar in structure to a 12-MC-4 metal crown ether,in which the complex 14 is a sandwich structure and exhibits single molecular magnet behaviors?SMMs?.Magnetic properties show that complexes are anti-ferromagnetic coupling between the metalcrown ether metal ions formed.
Keywords/Search Tags:Metallacrown, Aminohydroxamic acid, Coordination polymer, Magnetic properties, DNA binding
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