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作 者:张新村[1] 岳凡[1] 黄艳[1] 程翔[1] 文红梅[1] 胡地 王吉德[1]
机构地区:[1]石油天然气精细化工教育部&自治区重点实验室,新疆大学化学化工学院,乌鲁木齐830046
出 处:《无机化学学报》2013年第11期2387-2393,共7页Chinese Journal of Inorganic Chemistry
基 金:国家自然科学基金(No.20961010;21162027;21261022)资助项目
摘 要:本文用UV-Vis光谱和氧电极法对结构相似的His-Co、Hio-Co、Hit-Co 3组配合物氧合性能进行了对比研究。由配合物光谱随pH变化的A-pH曲线,可知3组配合物均在pH 6.0以后开始发生氧合反应,在pH 6.0~10.0的范围内His-Co有2种氧合物种生成,其他2组配合物均只有1种氧合配合物生成。用等摩尔比法对氧合配合物的组成比进行了测定,得知Co∶His与Co∶Hio的配位比为1∶2,而Co∶Hit为1∶3;在室温水溶液中和pH 7的条件下,用UV-Vis在波长384 nm下分别考察了3组配合物的氧合性能和它们的抗老化能力,结果表明3组配合物在室温水溶液中均可发生氧合反应,但氧合性能有很大差异,His-Co经过110 h累计560次可逆循环,仍然具有5%氧合性能,而Hio、Hit分别经过59次/54 h、5次/10.2 h循环后氧合性能衰减至5%。3组配合物的抗老化能力的大小顺序为:His-Co>>Hio-Co>Hit-Co。研究结果初步说明:三配位原子配体配合物的可逆吸氧性能好于二配位原子配体的配合物,氨基酸配合物优于氨基醇配合物。Oxygenation of three complexes His-Co, Hio-Co and Hit-Co were determined by UV-Vis spectrophotometry and oxygen electrode, respectively. The curve of absorption change with pH showed that the oxygenation reactions took place after pH 6.0 for all three complexes. His-Co has two oxygenated species in pH 6.0-10.0, whereas, Hio-Co and Hit-Co only formed one oxygenated species. The results obtained from the equimolar ratio method showed the molar ration for Co:His and Co:Hio is 1:2,whereas Co:Hit is 1:3. Oxygenation properties and anti-aging processes of three complexes were determined by UV-Vis spectrophotometry at A =384 nm in room temperature in pH 7.0, respectively. The results revealed that all three complexes can uptake dioxygen reversibly whereas there are obvious differences in their oxygenations, especially in the deoxygenation rate. His-Co kept 5% oxygenation capacity after 560 cycles/110 h continuous oxygenation, while Hio-Co and Hit- Co sustained 59 cycles/54 h and 5 cycles/10.2 h, respectively. The order of anti-aging rate of the complexes is His-Co 〉〉Hio-Co 〉Hit-Co. The results suggested that the uptaking dioxygen reversibility of the complex with a ligand of three coordinating atoms is better than the complex with a ligand of two coordinating atoms, and the uptaking dioxygen reversibility of the aminoacid complex is better than that of alkamine complex.
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