2-丙基-4，5-咪唑二甲酸金属配合物的合成、表征及生物活性研究
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摘要
本论文采用溶剂挥发法与水热合成法,以2-丙基-4,5-咪唑二甲酸作为有机配体与过渡金属反应,共合成得到了八个结构新颖的金属配合物。配合物[1] [Ca(C8H8N2O4)2(H2O)2]配合物[2] [Sr(C8H8N2O4)2(H2O)2]配合物[3] [Mn(C8H8N2O4)2(H2O)2]?4H2O配合物[4] [Cd(C8H8N2O4)2(H2O)2]?4H2O配合物[5] [Zn(C8H8N2O4)2(H2O)2]?4H2O配合物[6] [Mn (C8H8N2O4)2(H2O)2] ?2C3H7NO配合物[7] [Ni (C8H8N2O4)2(H2O)2] ?2C3H7NO配合物[8] [Cd(C8H8N2O4)2(H2O)2] ?2C3H7NO
通过单晶X-射线衍射仪对配合物的晶体结构进行了测定,并对配合物[1]、配合物[4]、配合物[6]进行了热稳定性分析,结果表明:
(1)配合物[1]与配合物[2]同构,属于八配位十二面体的空间构型。配体中一个羧基氧原子、咪唑环双键氮原子与中心离子形成双齿螯合环,另一个羧基氧原子则与配体单齿配位;配合物[3]、[4]、[5]同构,六配位空间八面体构型。配体中一个羧基氧原子、咪唑环双键氮原子与中心离子形成双齿螯合环,另一个羧基并未参与配位,有两个游离水分子;配合物[6]、[7]、[8]同构,六配位空间八面体构型。配体中一个羧基氧原子、咪唑环双键氮原子与中心离子形成双齿螯合环,两分子DMF游离。
(2)通过配合物[1]、[4]、[7]的热稳定性分析发现,配合物[4]在32.5℃即开始分解,骨架结构在148.9℃是稳定的;配合物[7]在72.88℃时开始分解,配合物三维骨架结构在146.95℃开始分解。配合物[1]在152.4℃之前是稳定的。对比三者热稳定性:配合物[1]>配合物[4]>配合物[7]。
运用评价化学品毒性藻类测试的标准实验方法,选择扁藻(Platymonas subcordiformis)作为藻种,配合物[5]与配合物[6]及其同金属离子的金属盐为研究对象开展了藻毒理实验,发现当金属离子达到一定浓度时能够抑制扁藻生长,随着浓度不断增大,该抑制作用不断增强。通过金属盐和配合物的对比,Zn2+、Ni2+的最低致毒浓度为1.5 mg/L,96h半数有效浓度分别为11.19 mg/L、9.73 mg/L,配合物[5]与配合物[7]的最低致毒浓度为20 mg/L,96h半数有效浓度分别为61.38 mg/L、79.07mg/L。金属盐对扁藻的最低致毒浓度更低,抑制作用更强。
本论文选择菌种为大肠杆菌(E.coli),通过酶标仪在600nm处扫描测定吸光值,研究了配合物对大肠杆菌生长的抑制作用。
(1)配体2-丙基-4,5-咪唑二甲酸在浓度达到1250μg/mL时能够完全抑制大肠杆菌的生长;
(2)在所测的六种金属盐中,CdCl2在浓度达到2500μg/mL时能够完全抑制大肠杆菌生长,CaCl2在浓度达到625μg/mL时对于大肠杆菌的生长表现出很明显的促进作用,随着浓度继续增加,大肠杆菌生长速度明显增大并迅速达到稳定期,Zn(CH3COO)2、Ni(NO3)2、SrCl2与Mn(CH3COO)2对于大肠杆菌的生长均均有一定的抑制作用;
(3)本论文合成得到的八种金属配合物中,配合物[1]、[2]、[3]、[6]、[8]在浓度达到1250μg/mL时完全抑制大肠杆菌的生长,配合物[5]在浓度达到625μg/mL时完全抑制大肠杆菌的生长,配合物[4]、[7]在浓度达到312μg/mL时完全抑制大肠杆菌的生长;
(4)对比配体、配合物与金属盐对大肠杆菌的抑制,配合物具有更好的抑制作用。配合物的抑制作用的加强跟配体与金属盐的配位结合有关,配位后二者均表现出对于大肠杆菌的抑制作用,比单个的配体及金属盐更强。
In our research, 2-propyl-4,5- imidazoledicarboxlic acid was used to react with metal salts and eight novel metal complexes were synthesized by the solution crystallization and hydrothermal method. Complexes [1] [Ca(C8H8N2O4)2(H2O)2] Complexes [2] [Sr(C8H8N2O4)2(H2O)2] Complexes [3] [Mn(C8H8N2O4)2(H2O)2]?4H2O Complexes [4] [Cd(C8H8N2O4)2(H2O)2]?4H2O Complexes [5] [Zn(C8H8N2O4)2(H2O)2]?4H2O Complexes [6] [Mn (C8H8N2O4)2(H2O)2] ?2C3H7NO Complexes [7] [Ni (C8H8N2O4)2(H2O)2] ?2C3H7NO Complexes [8] [Cd(C8H8N2O4)2(H2O)2] ?2C3H7NO
These complexes were characterized by single crystal X-ray diffraction, and the complex [1],complex [4] and complex [6] were analyzed by thermogravimetric analyses.
(1) The result shows that Complex [1] is isostructural with complex [2], which is eight-coordinated in a distorted square antiprismatic environment, The ligand donor atoms are the tertiary N atoms of the imidazole rings and the carboxylate O atoms of two chelating 2-propyl-4,5- imidazoledicarboxlic acid ligands, the carboxy oxygen atoms of two additional imidazole ligands and two water molecules. complex [3], complex [4] and complex [5] are isostructural, six-coordinated in a slightly distorted octahedral geometry defined by the tertiary N atoms of the imidazole rings and the carboxylate O atoms of two chelating 2-propyl-4,5- imidazoledicarboxlic acid ligands and two coordinate water molecules. Two free water molecules are also present in the asymmetric system. complex [6], complex [7] and complex [8] are isostructural, six-coordinate by two N,O-bidentate 2-propyl-4,5- imidazoledicarboxlic acid ligands and two DMF mole cules in a distorted octahedral environment.
(2) The thermogravimetric analyses show that the complex [4] begins to decompose at 32.5℃and the structure is stable before 148.9℃, complex [7] begins to decompose at 72.88℃and the structure is stable before 146.95℃,however, complex [1] is stable until 152.4℃, therefore, the thermal stability of complex [1] is strongest, complex [4] is more stable than complex [7].
A standard method of algal bioassay for evaluating the toxicity of toxic chemical was applied in the experiments. when the concentration of the metal ion reached a certain value, Platymonas subcordiformis was inhibitted, with the increasement of the concentration, the inhibitory effect become much stronger, furthermore, the toxicities of the complex [5] and [6] with the corresbonding metal salts was compared, The lowest no observable effect concentrations (LNOEC) of Zn2+、Ni2+ on the growth of Platymonas subcordiformis were obversed to be 1.5 mg/L, and respectively, and 96h-EC50s were found to be 11.19 mg/L and 9.73 mg/L, respectively.However, The lowest no observable effect concentrations (LNOEC) of complex 5 and 6 were 20 mg/L and, and 96h-EC50s were 11.19 mg/L and 9.73 mg/L respectively. Therefore the toxicities of the metal salts on the growth of Platymonas subcordiformis is much stronger than that of the complexes.
The antibacterial activities against Escherichia coli bacteria under different concentrations of metallic complexes were measured by measuring the value of the absoption at the wavelength of 600nm by Microplate reader.
(1) 2-propyl-4,5-imidazoledicarboxlic acid inhibitted the Escherichia coli completely at the concentration of 1250μg/mL.
(2) In the selected six metal salts, CdCl2 inhibited the Escherichia coli completely at the concentration of 2500μg/mL, Cacl2 promoted the growth of Escherichia coli Apparently when the concentration reached at 625μg/mL, the speed of Escherichia coli increased significantly and quickly to achieve stable as the concentration of Cacl2 increased. Zn(CH3COO)2、Ni(NO3)2、SrCl2 and Mn(CH3COO)2.can inhibit the Escherichia coli also
(3) The eight synthesized metal complexes can inhibit the growth of Escherichia coli completely. complex [1],[2],[3],[6],[8] shows eqivalent inhibitory effect with 2-propyl-4,5- imidazoledicarboxlic acid with completed Inhibitory conc entration at the value of 1250μg/mL;however, the inhibitory effect of complex [5] is stronger than the 2-propyl-4,5-imidazoledicarboxlic acid with completed Inhibitory concentration at the value of 625μg/ml; Complex [4] and complex [7] shows the strongest inhibitory effect on Escherichia coli, with completed Inhibitory concentration at the value of 312μg/mL.
(4) Complexes has a much stronger inhibition on Escherichia coli than ligand and metal salts.The enhance of the inhibition related the coordination of ligand and meta salts,both oh them shown the inhibition on Escherichia coli, stronger than singal ligand or metal salt.
通过单晶X-射线衍射仪对配合物的晶体结构进行了测定,并对配合物[1]、配合物[4]、配合物[6]进行了热稳定性分析,结果表明:
(1)配合物[1]与配合物[2]同构,属于八配位十二面体的空间构型。配体中一个羧基氧原子、咪唑环双键氮原子与中心离子形成双齿螯合环,另一个羧基氧原子则与配体单齿配位;配合物[3]、[4]、[5]同构,六配位空间八面体构型。配体中一个羧基氧原子、咪唑环双键氮原子与中心离子形成双齿螯合环,另一个羧基并未参与配位,有两个游离水分子;配合物[6]、[7]、[8]同构,六配位空间八面体构型。配体中一个羧基氧原子、咪唑环双键氮原子与中心离子形成双齿螯合环,两分子DMF游离。
(2)通过配合物[1]、[4]、[7]的热稳定性分析发现,配合物[4]在32.5℃即开始分解,骨架结构在148.9℃是稳定的;配合物[7]在72.88℃时开始分解,配合物三维骨架结构在146.95℃开始分解。配合物[1]在152.4℃之前是稳定的。对比三者热稳定性:配合物[1]>配合物[4]>配合物[7]。
运用评价化学品毒性藻类测试的标准实验方法,选择扁藻(Platymonas subcordiformis)作为藻种,配合物[5]与配合物[6]及其同金属离子的金属盐为研究对象开展了藻毒理实验,发现当金属离子达到一定浓度时能够抑制扁藻生长,随着浓度不断增大,该抑制作用不断增强。通过金属盐和配合物的对比,Zn2+、Ni2+的最低致毒浓度为1.5 mg/L,96h半数有效浓度分别为11.19 mg/L、9.73 mg/L,配合物[5]与配合物[7]的最低致毒浓度为20 mg/L,96h半数有效浓度分别为61.38 mg/L、79.07mg/L。金属盐对扁藻的最低致毒浓度更低,抑制作用更强。
本论文选择菌种为大肠杆菌(E.coli),通过酶标仪在600nm处扫描测定吸光值,研究了配合物对大肠杆菌生长的抑制作用。
(1)配体2-丙基-4,5-咪唑二甲酸在浓度达到1250μg/mL时能够完全抑制大肠杆菌的生长;
(2)在所测的六种金属盐中,CdCl2在浓度达到2500μg/mL时能够完全抑制大肠杆菌生长,CaCl2在浓度达到625μg/mL时对于大肠杆菌的生长表现出很明显的促进作用,随着浓度继续增加,大肠杆菌生长速度明显增大并迅速达到稳定期,Zn(CH3COO)2、Ni(NO3)2、SrCl2与Mn(CH3COO)2对于大肠杆菌的生长均均有一定的抑制作用;
(3)本论文合成得到的八种金属配合物中,配合物[1]、[2]、[3]、[6]、[8]在浓度达到1250μg/mL时完全抑制大肠杆菌的生长,配合物[5]在浓度达到625μg/mL时完全抑制大肠杆菌的生长,配合物[4]、[7]在浓度达到312μg/mL时完全抑制大肠杆菌的生长;
(4)对比配体、配合物与金属盐对大肠杆菌的抑制,配合物具有更好的抑制作用。配合物的抑制作用的加强跟配体与金属盐的配位结合有关,配位后二者均表现出对于大肠杆菌的抑制作用,比单个的配体及金属盐更强。
In our research, 2-propyl-4,5- imidazoledicarboxlic acid was used to react with metal salts and eight novel metal complexes were synthesized by the solution crystallization and hydrothermal method. Complexes [1] [Ca(C8H8N2O4)2(H2O)2] Complexes [2] [Sr(C8H8N2O4)2(H2O)2] Complexes [3] [Mn(C8H8N2O4)2(H2O)2]?4H2O Complexes [4] [Cd(C8H8N2O4)2(H2O)2]?4H2O Complexes [5] [Zn(C8H8N2O4)2(H2O)2]?4H2O Complexes [6] [Mn (C8H8N2O4)2(H2O)2] ?2C3H7NO Complexes [7] [Ni (C8H8N2O4)2(H2O)2] ?2C3H7NO Complexes [8] [Cd(C8H8N2O4)2(H2O)2] ?2C3H7NO
These complexes were characterized by single crystal X-ray diffraction, and the complex [1],complex [4] and complex [6] were analyzed by thermogravimetric analyses.
(1) The result shows that Complex [1] is isostructural with complex [2], which is eight-coordinated in a distorted square antiprismatic environment, The ligand donor atoms are the tertiary N atoms of the imidazole rings and the carboxylate O atoms of two chelating 2-propyl-4,5- imidazoledicarboxlic acid ligands, the carboxy oxygen atoms of two additional imidazole ligands and two water molecules. complex [3], complex [4] and complex [5] are isostructural, six-coordinated in a slightly distorted octahedral geometry defined by the tertiary N atoms of the imidazole rings and the carboxylate O atoms of two chelating 2-propyl-4,5- imidazoledicarboxlic acid ligands and two coordinate water molecules. Two free water molecules are also present in the asymmetric system. complex [6], complex [7] and complex [8] are isostructural, six-coordinate by two N,O-bidentate 2-propyl-4,5- imidazoledicarboxlic acid ligands and two DMF mole cules in a distorted octahedral environment.
(2) The thermogravimetric analyses show that the complex [4] begins to decompose at 32.5℃and the structure is stable before 148.9℃, complex [7] begins to decompose at 72.88℃and the structure is stable before 146.95℃,however, complex [1] is stable until 152.4℃, therefore, the thermal stability of complex [1] is strongest, complex [4] is more stable than complex [7].
A standard method of algal bioassay for evaluating the toxicity of toxic chemical was applied in the experiments. when the concentration of the metal ion reached a certain value, Platymonas subcordiformis was inhibitted, with the increasement of the concentration, the inhibitory effect become much stronger, furthermore, the toxicities of the complex [5] and [6] with the corresbonding metal salts was compared, The lowest no observable effect concentrations (LNOEC) of Zn2+、Ni2+ on the growth of Platymonas subcordiformis were obversed to be 1.5 mg/L, and respectively, and 96h-EC50s were found to be 11.19 mg/L and 9.73 mg/L, respectively.However, The lowest no observable effect concentrations (LNOEC) of complex 5 and 6 were 20 mg/L and, and 96h-EC50s were 11.19 mg/L and 9.73 mg/L respectively. Therefore the toxicities of the metal salts on the growth of Platymonas subcordiformis is much stronger than that of the complexes.
The antibacterial activities against Escherichia coli bacteria under different concentrations of metallic complexes were measured by measuring the value of the absoption at the wavelength of 600nm by Microplate reader.
(1) 2-propyl-4,5-imidazoledicarboxlic acid inhibitted the Escherichia coli completely at the concentration of 1250μg/mL.
(2) In the selected six metal salts, CdCl2 inhibited the Escherichia coli completely at the concentration of 2500μg/mL, Cacl2 promoted the growth of Escherichia coli Apparently when the concentration reached at 625μg/mL, the speed of Escherichia coli increased significantly and quickly to achieve stable as the concentration of Cacl2 increased. Zn(CH3COO)2、Ni(NO3)2、SrCl2 and Mn(CH3COO)2.can inhibit the Escherichia coli also
(3) The eight synthesized metal complexes can inhibit the growth of Escherichia coli completely. complex [1],[2],[3],[6],[8] shows eqivalent inhibitory effect with 2-propyl-4,5- imidazoledicarboxlic acid with completed Inhibitory conc entration at the value of 1250μg/mL;however, the inhibitory effect of complex [5] is stronger than the 2-propyl-4,5-imidazoledicarboxlic acid with completed Inhibitory concentration at the value of 625μg/ml; Complex [4] and complex [7] shows the strongest inhibitory effect on Escherichia coli, with completed Inhibitory concentration at the value of 312μg/mL.
(4) Complexes has a much stronger inhibition on Escherichia coli than ligand and metal salts.The enhance of the inhibition related the coordination of ligand and meta salts,both oh them shown the inhibition on Escherichia coli, stronger than singal ligand or metal salt.
引文
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