新型取代胡椒醛缩合不对称卟啉金属配合物的微波合成及其抗菌活性

doi:10.11944/j.issn.1000-0518.2015.05.140302

摘要/Abstract

摘要：

利用微波辐射加热方法合成了5-(3, 4-亚甲二氧基-6-硝基)苯基-10, 15, 20-三苯基卟啉和5-(3, 4-亚甲二氧基-6-硝基)苯基-10, 15, 20-三对氯苯基卟啉的Zn(Ⅱ)、Co(Ⅱ)、Mn(Ⅱ)金属配合物, 产物的结构用紫外-可见光谱、红外光谱、荧光光谱等技术手段进行了表征, 采用抑菌环方法研究了目标化合物对大肠杆菌和金黄色葡萄球菌的抗菌活性, 实验结果表明, 两个Co(Ⅱ)金属配合物在浓度为0.32 mmol/L时对Sa、Ec有较强的抑菌作用, 浓度为0.02 mmol/L时还有一定的抑菌作用;2个Zn(Ⅱ)和2个Mn(Ⅱ)配合物在浓度为0.16~0.32 mmol/L范围内对Sa、Ec有中等强度的抑菌作用。各金属配合物的抑菌活性大小顺序大体为:Por(Co)>Por(Mn)≈Por(Zn)。各配合物对金黄色葡萄球菌的抑制作用比大肠杆菌大约高10%~20%。

关键词: 不对称卟啉, 金属配合物, 微波合成, 结构表征, 抗菌活性

Abstract:

Zn(Ⅱ), Co(Ⅱ) and Mn(Ⅱ) complexes of 5-(2-nitro-4, 5-methylenedioxy)phenyl-10, 15, 20- triphenyl-porphyrin and 5-(2-nitro-4, 5-methylenedioxy) phenyl-10, 15, 20-tri(p-chlorophenyl)-porphyrin were synthesized by microwave irradiation. Their structures were characterized by UV-Vis, IR, fluoresence spectroscopies. The bactericidal activities of these metal compounds on Escherichia coli aureu(Ec) and Staphylococcusaureu(Sa) were studied with the inhibition ring test. These complexes show photosensitive antibacterial activities against these two bacteria. The Co(Ⅱ) complexes have obvious bacteriostatic activities against Ec and Sa at the concentration of 0.32 mmol/L and 0.02 mmol/L, respectively, and some bacteriostatic effects. The Zn(Ⅱ) and Co(Ⅱ) complexes have moderate antibacterial effects at 0.16~0.32 mmol/L. The order of the antibacterial activity of these complexes is Por(Co)>Por(Mn)≈Por(Zn). The bacteriostatic effects of the complexes on Ec are 10%~20% higher than those on Sa.

Key words: asymmetrical porphyrin, metal complex, microwave synthesis, characterization, antibacterial activity

中图分类号:

赵胜芳, 陈年友, 张寒梅, 张京, 李早英. 新型取代胡椒醛缩合不对称卟啉金属配合物的微波合成及其抗菌活性[J]. 应用化学, 2015, 32(5): 542-546.

ZHAO Shengfang, CHEN Nianyou, ZHANG Hanmei, ZHANG Jing, LI Zaoying. Microwave Synthesis and Antibacterial Activity of Novel Asymmetric Porphyrin Matal Complexes from Substituted Piperonal[J]. Chinese Journal of Applied Chemistry, 2015, 32(5): 542-546.

参考文献

[1]	LI Ya, SHEN Lihong, WANG Jiansen, et al.Synthesis and Antitumor Activity in Vitro of 5-Fluorouracil-1-alkylaxg-phenyl-tetra m-Chlorophenyl Porphyrin Compounds[J]. Chinese J Appl Chem, 2013, 30(1):38-42(in Chinese). 李雅, 申利红, 王建森, 等. 5-氟尿嘧啶-1-烷氧苯基三间氯苯基卟啉的合成及其体外抗癌活性[J]. 应用化学, 2013, 30(1):38-42.
[2]	CHEN Nianyou, ZHAO Shengfang, DONG Jiaqing, et al.Microwave Synthesis and Electron Transfer Properties of a Series of New Porphyrin-anthraquinone Hybrids with Dipeptide Link and Their Metal Complexes[J]. Chem J Chinese Univ, 2011, 32(7):1466-1471(in Chinese). 陈年友, 赵胜芳, 董甲庆, 等. 系列二肽链键联的卟啉-蒽醌及其金属配合物的微波合成及电子转移性质[J]. 高等学校化学学报, 2011, 32(7):1466-1471.
[3]	ZHAO Shengfang, CHEN Nianyou, GUO Xin, et al.Synthesis of meso-Tetra(4-carboxylphenyl)porphyrin and Metal Complex and the Selective Recognition with Carbohydrates[J]. Chinese J Org Chem, 2010, 30(12):1898-1903(in Chinese). 赵胜芳, 陈年友, 郭鑫, 等. meso-四(4-羧基苯基)卟啉及金属配合物的合成和对糖类的选择识别[J]. 有机化学, 2010, 30(12):1898-1903.
[4]	HUANG Qimao, LI Qing, WANG Siwei, et al.Synthesis and Photosensitivity of β-Arylcrwn Porphyrins[J]. Chem Bioeng, 2012, 29(7):22-25(in Chinese). 黄齐茂, 李清, 王司卫, 等. β-萘并冠醚卟啉的合成及光敏活性[J]. 化学与生物工程, 2012, 29(7):22-25.
[5]	YU Kegui, LI Donghong, ZHOU Chenghe, et al.Synthesis and Antimicrobial Activity of a Novel Cationic Porphyrins[J]. Acta Acad Midicinae Militaris Tertiae, 2010, 32(1):41-45(in Chinese). 于克贵, 李东红, 周成合, 等. 新型阳离子卟啉的设计合成与抗微生物活性[J]. 第三军医大学学报, 2010, 32(1):41-45.
[6]	Shakir M, Azim Y, Chishti H T N, et al. Synthesis, Characterization of Complexes of Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ) and Zn(Ⅱ) with 12-Membered Schiff Base Tetraazamacrocyclic Ligand and the Study of Their Antimicrobial and Reducing Power[J]. Spectrochim Acta Part A, 2006, 65(2):490-496.
[7]	ZHOU Chenghe, ZHANG Feifei, GAN Linling, et al. Research in Supramolecular Chemical Drugs[J]. Sci China Ser B:Chem, 2009, 39(3):208-252(in Chinese). 周成合, 张飞飞, 甘淋玲, 等. 超分子化学药物研究[J]. 中国科学B辑:化学, 2009, 39(3):208-252.
[8]	CHEN Baiquan, HUANGFU ChaoShen. Effect of Piperonal am ino-s-Triazole Schiff Base on Apoptosis of Hepatocarcinoma BEL-7402 Cells[J]. Chinese J New Drugs, 2010, 19(19):1803-1806(in Chinese). 陈百泉, 皇甫超申. 胡椒醛缩氨基均三唑席夫碱对BEL-7402人肝癌细胞具有抑制增殖和诱导凋亡的作用[J]. 中国新药杂志, 2010, 19(19):1803-1806.
[9]	MA Jing, TAO Minli, ZHOU Xueqin, et al.Synthesis and Spectral Property of Novel Porphyrins Condensed[J]. Fine Chem, 2006, 23(8):771-775(in Chinese). 马静, 陶敏莉, 周雪琴, 等. 胡椒醛缩合卟啉化合物的合成及其光谱性能[J]. 精细化工, 2006, 23(8):771-775.
[10]	ZHAO Shengfang, CHEN Nianyou, CHENG Xing'an, et al. Synthesis and Characterization of Novel Unsymmetrical Porphyrins Condensed from Substituted Piperonal[J]. Chinese J Org Chem, 2005, 25(7):805-809(in Chinese). 赵胜芳, 陈年友, 程兴安, 等. 几种取代胡椒醛缩合不对称卟啉化合物的合成及结构表征[J]. 有机化学, 2005, 25(7):805-809.
[11]	XU Jingou, WANG Zunben. Fluorimetry[M]. 3th Ed. Beijing:Science Press, 2006, 10:43-44, 45-48, 62(in Chinese). 许金钩, 王尊本. 荧光分析法[M]. 第3版. 北京:科学出版社, 2006, 10:43-44, 45-48, 62.
[12]	Singh K, Barwa M S, Tyagi P, et al.Synthesis and Characterization of Cobalt(Ⅱ), Nickel(Ⅱ), Copper(Ⅱ) and Zinc(Ⅱ) Complexes with Schiff Base Derived from 4-Amino-3-mercapto-6-methyl-5-oxo-1, 2, 4-triazine[J]. Eur J Med Chem, 2007, 42(3):394-402.
[13]	Nitzan Y, Gutterman M, Malik Z, et al.Inactivation of Gram-Negative Bacteria by Photosensitized Porohyrins[J]. Photochem Photobiol, 1992, 55:89-96.

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