含氮杂环金属模型化合物的合成、表征及其催化活性的研究与应用
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摘要
多酚氧化酶(如酪氨酸酶和儿茶酚氧化酶等)和过氧化氢酶是两类能有效催化氧化酚类化合物的含金属酶,在工业废水的降解中有广泛的应用。由于天然酶的局限性,合成小分子金属配合物来模拟酶的活性,成为开发新型催化剂的一种有效途径。此外,通过对小分子模型化合物的研究,还可以获得许多关于酶催化机理的信息。
本课题通过化学手段合成了一系列含有类似于多酚氧化酶和过氧化氢酶活性中心结构的模型化合物。主要包括两类金属模型配合物,一类是含苯并咪唑环的系列化合物：[MnⅡ2(bbaa)2(H20)2](ClO4)2(1),[MnⅡ(bba)2](cba)(ClO4)(2),[Mnn(bba)(H20)Cl2](3)及相应的铜化合物[CuⅡ(bbaa)(H20)(N03)](4)和[CuⅡ(bba)Cl2](5)；以及氨基酸席夫碱类化合物：[CuⅡ(hppg)Cl](6),[CuⅡ2(hppg)2Cl2](7)及相应的铁化合物[FeⅢ(hppg)Cl2](H20)2(8)和锰化合物[MnⅢ(hppg)]Im4(H20)4(N03)2(9),其中bbaa=N,N-(二(2-苯并咪唑基-甲基)胺基)乙酸,bba=(二(2-苯并咪唑基-甲基))胺,cba=2-氯苯甲酸,hppg=N-(2-羟基苯基)-N-(2-甲基吡啶)甘氨酸。合成的化合物通过元素分析、紫外、单晶衍射等方法表征测定。
通过对化合物1,3,4和5的结构及催化氧化三种酚类底物的作用的比较,以及反应底物、温度、氧化剂等对于模型化合物的催化活性的影响,我们发现,化合物4的活性最好,能很好的催化氧化苯酚、邻苯二酚和2,6-二甲氧基酚。此外,相比金属铜化合物,金属锰化合物催化氧化酚类的活性低,更容易随反应条件的变化而改变。通过对化合物6,7,8和9的催化氧化条件的研究及相应的催化动力学参数的比较发现,对于不同金属的氨基酸-席夫碱类化合物而言,铁化合物催化氧化2,6-二甲氧基酚的活性最好,与底物的亲和性也最好。另一方面,通过对中间氧化产物的研究,我们对金属酶的催化机理也有了更深入的认识。
Polyphenol oxidase (such as tyrosinase, catechol oxidase, and so on) and catalase are two important metal containing enzymes, which can catalytic oxidize phenolic compounds and are extensively used in the phenolic compounds removal in industry. Synthesizing new enzyme model complexes that mimic the structures of active sites of the enzymes is one of effective method to obtain new catalysts. In addition, we can also gain some insight on the mechanism of enzyme catalytic reaction from the study of model compounds.
Two groups of model complexes were synthesized, one is benzimidazolyl containing metal compounds:[MnⅡ2(bbaa)2(H2O)2](ClO4)2 (1), [MnⅡ(bba)2](cba)(ClO4) (2) [MnⅡ(bba)(H2O)Cl2] (3), and copper complexes [CuⅡ(bbaa)(H2O)(NO3)] (4) and [CuⅡ(bba)Cl2] (5); the other group is Schiff base containing compounds:[CuⅡ(hppg)Cl](6), [CuⅡ2(hppg)2Cl2] (7), [FeⅢ(hppg)Cl2](H2O)2 (8) and [MnⅢ(hppg)](Im)4(H2O)4(NO3)2 (9). In which, bbaa= N,N-bis(2-benzimidazolyl methyl)amino acetic acid, bba= bis(2-benzimidazolylmethyl) amine, cba= 2-chloro benzoic acid, hppg= N-(2-hydroxybenzyl)-N-(2-picolyl) glycine.
Through comparing the structures of 1,3,4, and 5, and their relative catalytic activities with three phenolic compounds as substrates, and the effects of substrates, temperature, and oxidants on their oxidation activities, we found that complex 4 was most active in group one, it can oxidize phenol, catechol, and 2,6-dimethoxyphenol as well. Comparing to the copper complexes, manganese complexes are less active. The acitivity of manganese complexes were easy affected by the reaction conditions. In the second group, ferric complex 8 is most active and had higher affinity to 2,6-dimethoxyphenol. Based on the intermediates of the catalytic reactions with these compounds, the oxidation reaction mechanisms of these catalysts were discussed.
本课题通过化学手段合成了一系列含有类似于多酚氧化酶和过氧化氢酶活性中心结构的模型化合物。主要包括两类金属模型配合物,一类是含苯并咪唑环的系列化合物：[MnⅡ2(bbaa)2(H20)2](ClO4)2(1),[MnⅡ(bba)2](cba)(ClO4)(2),[Mnn(bba)(H20)Cl2](3)及相应的铜化合物[CuⅡ(bbaa)(H20)(N03)](4)和[CuⅡ(bba)Cl2](5)；以及氨基酸席夫碱类化合物：[CuⅡ(hppg)Cl](6),[CuⅡ2(hppg)2Cl2](7)及相应的铁化合物[FeⅢ(hppg)Cl2](H20)2(8)和锰化合物[MnⅢ(hppg)]Im4(H20)4(N03)2(9),其中bbaa=N,N-(二(2-苯并咪唑基-甲基)胺基)乙酸,bba=(二(2-苯并咪唑基-甲基))胺,cba=2-氯苯甲酸,hppg=N-(2-羟基苯基)-N-(2-甲基吡啶)甘氨酸。合成的化合物通过元素分析、紫外、单晶衍射等方法表征测定。
通过对化合物1,3,4和5的结构及催化氧化三种酚类底物的作用的比较,以及反应底物、温度、氧化剂等对于模型化合物的催化活性的影响,我们发现,化合物4的活性最好,能很好的催化氧化苯酚、邻苯二酚和2,6-二甲氧基酚。此外,相比金属铜化合物,金属锰化合物催化氧化酚类的活性低,更容易随反应条件的变化而改变。通过对化合物6,7,8和9的催化氧化条件的研究及相应的催化动力学参数的比较发现,对于不同金属的氨基酸-席夫碱类化合物而言,铁化合物催化氧化2,6-二甲氧基酚的活性最好,与底物的亲和性也最好。另一方面,通过对中间氧化产物的研究,我们对金属酶的催化机理也有了更深入的认识。
Polyphenol oxidase (such as tyrosinase, catechol oxidase, and so on) and catalase are two important metal containing enzymes, which can catalytic oxidize phenolic compounds and are extensively used in the phenolic compounds removal in industry. Synthesizing new enzyme model complexes that mimic the structures of active sites of the enzymes is one of effective method to obtain new catalysts. In addition, we can also gain some insight on the mechanism of enzyme catalytic reaction from the study of model compounds.
Two groups of model complexes were synthesized, one is benzimidazolyl containing metal compounds:[MnⅡ2(bbaa)2(H2O)2](ClO4)2 (1), [MnⅡ(bba)2](cba)(ClO4) (2) [MnⅡ(bba)(H2O)Cl2] (3), and copper complexes [CuⅡ(bbaa)(H2O)(NO3)] (4) and [CuⅡ(bba)Cl2] (5); the other group is Schiff base containing compounds:[CuⅡ(hppg)Cl](6), [CuⅡ2(hppg)2Cl2] (7), [FeⅢ(hppg)Cl2](H2O)2 (8) and [MnⅢ(hppg)](Im)4(H2O)4(NO3)2 (9). In which, bbaa= N,N-bis(2-benzimidazolyl methyl)amino acetic acid, bba= bis(2-benzimidazolylmethyl) amine, cba= 2-chloro benzoic acid, hppg= N-(2-hydroxybenzyl)-N-(2-picolyl) glycine.
Through comparing the structures of 1,3,4, and 5, and their relative catalytic activities with three phenolic compounds as substrates, and the effects of substrates, temperature, and oxidants on their oxidation activities, we found that complex 4 was most active in group one, it can oxidize phenol, catechol, and 2,6-dimethoxyphenol as well. Comparing to the copper complexes, manganese complexes are less active. The acitivity of manganese complexes were easy affected by the reaction conditions. In the second group, ferric complex 8 is most active and had higher affinity to 2,6-dimethoxyphenol. Based on the intermediates of the catalytic reactions with these compounds, the oxidation reaction mechanisms of these catalysts were discussed.
引文
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