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高价银配合物的合成、表征及抗菌性能研究

发布时间:2019-06-12 15:08
【摘要】:银系抗菌材料由于高效、无毒、耐药性低等特点被广泛应用在日用品、纺织和医药等领域。其中,高价银抗菌材料比单价银或纳米银具有更强的抗菌能力、抗氯离子干扰能力、良好的光稳定性等优点,是一种非常具有潜力的抗菌材料,正被人们所关注。高价银氧化物是目前应用较多的高价银抗菌材料,但由于其高的氧化能力,易与别的基底材料发生反应,尤其是Ag2O3,很不稳定,难以保存。已报道的高价银配合物抗菌材料也存在稳定性较差等问题。基于上述的分析,本文合成了几种高价银配合物,并对大肠杆菌(E.coli)和金黄色葡萄球菌(S.aureus)的抗菌性能进行了研究,目前还未见相关文献报道。具体的内容如下:(1)采用吡啶、2-氨基吡啶为配体,合成了较稳定的吡啶双氮二价银配合物([Ag(py)2(N2)2](OH)2)及2-氨基吡啶二价银配合物([Ag(2-Apy)3(OH)](HSO4)·H2O),采用元素分析、红外光谱(FT-IR)及X-射线光电子能谱(XPS)对配合物进行了表征。通过生长抑制曲线和最小抑菌浓度(MIC)对配合物的抗菌性能进行研究,两种配合物在0.5μg/mL的低浓度下可对E.coli和S.aureus产生明显的抑制作用,对E.coli的MIC值均为5μg/mL,对S.aureus的MIC值均为20μg/mL。光稳定测试表明两种配合物均具有优越的光稳定性。(2)采用模板合成法合成了硫酸亚乙基二双胍,进一步合成了其三价银配合物,采用氢核磁共振(1HNMR)、元素分析、FT-IR及XPS对配体及配合物进行了表征。亚乙基二双胍三价银配合物在0.5μg/mL的浓度下对E.coli和S.aureus可产生抑制作用,而硫酸亚乙基二双胍即使在800μg/mL对两种细菌生长也没有表现出抑制作用,三价银配合物对两种细菌的MIC分别为10μg/mL和40μg/mL,同样具有很好的光稳定性。对上述两种二价银配合物及三价银配合物的抗菌机理进行初步了探究,根据实验结果,我们推测:高价银配合物在抗菌的过程中,发生氧化还原反应,并产生自由基。(3)合成了水溶性阴离子卟啉四-(4-磺酸钠苯基)卟啉(Na4TPPS)及水溶性阳离子卟啉四-(4-N,N,N-三甲氨基苯基)卟啉(TAPP),并进一步合成了其二价、三价银配合物。采用1HNMR、紫外光谱、元素分析、FT-IR及XPS对卟啉及配合物进行了表征。采用抑菌圈实验、MIC、最小杀菌浓度(MBC)检测以上物质对E.coli和S.aureus的光毒性及暗毒性。结果表明:阳离子卟啉及其高价银配合物比阴离子卟啉及其配合物对两种细菌具有更明显的抗菌效果,这与细菌的表面结构相关。三价银卟啉比二价银卟啉及自由卟啉具有更强的暗毒性,自由卟啉和三价银卟啉具有更强的光毒性。紫外光谱表明三价银卟啉在黑暗的条件下就能产生自由基等活性物质,且在光照下产量更大。
[Abstract]:Silver antibacterial materials are widely used in daily necessities, textiles, medicine and other fields because of their high efficiency, non-toxicity and low drug resistance. Among them, high-priced silver antibacterial materials have stronger antibacterial ability, chloride ion interference resistance, good photostability and other advantages than monovalent silver or nano-silver. It is a very potential antibacterial material, which is being paid more and more attention. High price silver oxide is a kind of high price silver antibacterial material which is widely used at present, but because of its high oxidation ability, it is easy to react with other substrate materials, especially Ag2O3, is very unstable and difficult to preserve. It has been reported that the antibacterial materials of high valence silver complexes also have some problems, such as poor stability. Based on the above analysis, several high valence silver complexes were synthesized and the antibacterial properties of Escherichia coli (E.coli) and Staphylococcus aureus (S.aureus) were studied. The main contents are as follows: (1) stable pyridine bivalent silver complexes ([Ag (py) 2 (N 2) 2] (OH) 2) and 2 aminopyridinium bivalent silver complexes ([Ag (2-Apy) 3 (OH)] (HSO4) H 2O) were synthesized by using pyridine and 2 aminopyridines as ligands. The complexes were characterized by elemental analysis, infrared spectroscopy (FT-IR) and X ray photoelectron spectroscopy (XPS). The antibacterial properties of the complexes were studied by growth inhibition curve and minimum inhibitory concentration (MIC). The two complexes had obvious inhibitory effects on E.coli and S.aureus at low concentration of 0.5 渭 g / mL, and the MIC values of 5 渭 g / mL, for E.coli were 20 渭 g / mL. for S.aureus. The photostability test showed that the two complexes had superior photostability. (2) Ethylene dibiguanidine sulfate was synthesized by template synthesis, and its trivalent silver complex was further synthesized. The ligands and complexes were characterized by hydrogen nuclear magnetic resonance (1HNMR), elemental analysis, FT-IR and XPS. Ethyl dibiguanidine trivalent silver complexes can inhibit E.coli and S.aureus at the concentration of 0.5 渭 g / mL, while ethyldibiguanidine sulfate has no inhibitory effect on the growth of the two bacteria even at 800 渭 g / mL. The MIC of trivalent silver complexes is 10 渭 g / mL and 40 渭 g / mL, respectively. The antibacterial mechanism of the above two silver complexes and trivalent silver complexes was preliminarily studied. according to the experimental results, we speculate that the high valence silver complexes redox and produce free radicals in the antibacterial process. (3) Water-soluble anion porphyrin tetra-(4-sulfophenyl) porphyrin (Na4TPPS) and water-soluble cationic porphyrin tetra-(4 鈮,

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