金属酞菁催化儿茶酚胺的研究
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摘要
儿茶酚胺类物质包括肾上腺素(AD)、去甲肾上腺素(NA)和多巴胺(DA),它是人体内一类非常重要的神经递质,也是重要的激素物质。检测血浆、尿液及体液中的儿茶酚胺的浓度水平,对有关疾病的诊断和治疗具有重要意义。光纤生物传感技术是生物检测技术的最新发展方向之一。基于酶催化的光纤生物传感器在环境监测、食品工程、临床医学等很多领域具有广泛的应用前景。金属酞菁本身的化学性质非常稳定,又具有优良的催化性能,作为金属辅酶模型的研究一直受到人们的关注。本学位论文针对光纤生物传感器和临床医学检测存在的主要问题,制备并优化了生物敏感材料,构建了荧光猝灭型的光纤肾上腺素传感器,实现了对肾上腺素的检测。
本论文对两个方面的内容进行了研究:1、合成了5种金属酞菁(MPc)仿生酶作催化剂用于催化儿茶酚胺(CAs)氧化,研究了催化时间、仿生酶用量、溶液pH值和催化温度等对催化效率的影响;2、选用FePc为催化剂构建了基于金属酞菁仿生酶催化的光纤肾上腺素传感器,研究了传感器的性能。得到以下结论:
1、通过苯酐-尿素线路液相法制备了5种MPc(M=Mn~(2+),Fe~(2+),Co~(2+),Ni~(2+),Cu~(2+))仿生酶,用二甲苯替代高沸点溶剂缩短了反应时间,简化了反应后溶剂的去除和产物的提纯,制得了纯度高且结晶度好的片状或棒状的MPc晶体。
2、磷酸氢二钠-柠檬酸(PBS)缓冲体系中,5种仿生酶均能有效地催化CAs氧化,其相应的氧化产物分别为肾上腺素红、去甲肾上腺素红和黑色素。
5种仿生酶催化DA氧化的最佳催化反应条件为pH=8.0,仿生酶用量为1.00mg/mL,最佳温度因仿生酶种类不同而不同。MnPc的最适催化温度是50℃,FePc和CoPc是55℃,CuPc则是60℃最佳,而NiPc在50℃以上才有催化活性,并随着温度的升高催化活性任在增大。仿生酶催化AD和NA氧化的最佳条件为pH=8.0,T=55℃,仿生酶用量为1.00 mg/mL;其催化效率有如下顺序η_(MnP)C>η_(FePc)>η_(NiPc)>η_(CuPc)>η_(CoPc)。在最佳pH 8.0的条件下,MnPc具有最好的催化活性,但FePc具有更宽的pH使用范围。
3、构建的光纤肾上腺素传感器的性能:以pH 7.4 PBS缓冲体系为介质,在2.0×10~(-6)～9.0×10~(-5)mol/L范围,AD的浓度与光学敏感膜的相对滞后相移有较好的线性关系;检测下限为4.O×10~(-7)mol/L;响应时间为10 min,该传感器具有良好的重复性和稳定性。
Catecholamines,which contain adrenaline,nordrenaline and dopamine,are a kind of impotant neurotransmitters and incretions in hunman organism.It is of great significance to detect catecholamine levels in plasma,urine and body fluid for diagnosis and treatment of diseases.Fiber optic biosensor is the latest development of biological detection technology.Fiber optic biosensor based on enzyme catalysis has been prosperously applied in many fields,such as environment monitoring,food engineering,clinical medicine,etc.Metallophthalocyanine has been attracted attention as metal coenzyme due to its steady chemical properties and excellent catalytic ability.In this paper,in order to solve the existing problems in clinical medicine detection and the fiber optic biosensor,the optimized sensing materials are used for the fiber optic biosensor.Biosensor based on fluorescence quenching is designed and constructed,and has successfully been used to detect the concentrations of adrenalin.
In this paper,the systematic studies are conducted as following:First,five metallophthalocyanines(MPc) are synthesized and used to catalyze the oxidation of catecholamines(CAs).The influence factors of catalytic efficiency,such as catalytic time,the amount of MPc,the pH value of solution and temperature,have been investigated.Second,a novel fiber optic AD biosensor is designed and constructed using FePc as catalyzer,the performance of the novel biosensor is studied.The main conclusions are summarized as follows:
1.MPc(M=Mn~(2+),Fe~(2+),Co~(2+),Ni~(2+),Cu~(2+)) of high purity and good crystallinity are synthesized with phthalic anhydride and urea.The reaction time is shortened by using dimethylbenzene in place of high boiling point solvent,and it is easy to get the products.
2.In phosphate buffer solution(PBS),all MPc could effectively catalyze the oxidation of CAs.The corresponding oxidation products are adrenochrome, noradrenchrome and melanin,respectively.
The optimal conditions for the oxidation reaction of DA are pH 8.0 and the MPc amount of 1.00 mg/mL.The optimal temperatures are different for different MPc.The optimal temperature for MnPc and CuPc are 50℃and 60℃,respectively.FePc and CoPc have the same optimal temperature which is 55℃.Obvious catalysis of NiPc appears when temperature is above 50℃,and catalytic activity increase with the increase of temperature.For the oxidation reaction of AD and NA,the optimal catalytic conditions are namely:pH=8.0,T=55℃and the amout of MP is 1.00 mg/mL.MPc have the catalytic activity in order ofη_(MnPc)＞η_(FePc)＞η_(NiPc)＞η_(CuPc)＞η_(CoPc). Although MnPc shows the best catalytic activity under the optimal catalytic conditions,FePc could be used in larger pH range.
3.The performance of the fiber optic AD biosensor is investigated.The dissolved oxygen and AD content are evaluated by relative phase delayΔψ.In PBS with pH 7.4, a linear relationship betweenΔψand AD concentration is observed in the range of 2.0×10~(-6)～9.0×10~(-5) mol/L,and the low limit of detection is 4.0×10~(-7) mol/L.The biosensor has good stability and repeatability,and its response time is 10 min.
本论文对两个方面的内容进行了研究:1、合成了5种金属酞菁(MPc)仿生酶作催化剂用于催化儿茶酚胺(CAs)氧化,研究了催化时间、仿生酶用量、溶液pH值和催化温度等对催化效率的影响;2、选用FePc为催化剂构建了基于金属酞菁仿生酶催化的光纤肾上腺素传感器,研究了传感器的性能。得到以下结论:
1、通过苯酐-尿素线路液相法制备了5种MPc(M=Mn~(2+),Fe~(2+),Co~(2+),Ni~(2+),Cu~(2+))仿生酶,用二甲苯替代高沸点溶剂缩短了反应时间,简化了反应后溶剂的去除和产物的提纯,制得了纯度高且结晶度好的片状或棒状的MPc晶体。
2、磷酸氢二钠-柠檬酸(PBS)缓冲体系中,5种仿生酶均能有效地催化CAs氧化,其相应的氧化产物分别为肾上腺素红、去甲肾上腺素红和黑色素。
5种仿生酶催化DA氧化的最佳催化反应条件为pH=8.0,仿生酶用量为1.00mg/mL,最佳温度因仿生酶种类不同而不同。MnPc的最适催化温度是50℃,FePc和CoPc是55℃,CuPc则是60℃最佳,而NiPc在50℃以上才有催化活性,并随着温度的升高催化活性任在增大。仿生酶催化AD和NA氧化的最佳条件为pH=8.0,T=55℃,仿生酶用量为1.00 mg/mL;其催化效率有如下顺序η_(MnP)C>η_(FePc)>η_(NiPc)>η_(CuPc)>η_(CoPc)。在最佳pH 8.0的条件下,MnPc具有最好的催化活性,但FePc具有更宽的pH使用范围。
3、构建的光纤肾上腺素传感器的性能:以pH 7.4 PBS缓冲体系为介质,在2.0×10~(-6)～9.0×10~(-5)mol/L范围,AD的浓度与光学敏感膜的相对滞后相移有较好的线性关系;检测下限为4.O×10~(-7)mol/L;响应时间为10 min,该传感器具有良好的重复性和稳定性。
Catecholamines,which contain adrenaline,nordrenaline and dopamine,are a kind of impotant neurotransmitters and incretions in hunman organism.It is of great significance to detect catecholamine levels in plasma,urine and body fluid for diagnosis and treatment of diseases.Fiber optic biosensor is the latest development of biological detection technology.Fiber optic biosensor based on enzyme catalysis has been prosperously applied in many fields,such as environment monitoring,food engineering,clinical medicine,etc.Metallophthalocyanine has been attracted attention as metal coenzyme due to its steady chemical properties and excellent catalytic ability.In this paper,in order to solve the existing problems in clinical medicine detection and the fiber optic biosensor,the optimized sensing materials are used for the fiber optic biosensor.Biosensor based on fluorescence quenching is designed and constructed,and has successfully been used to detect the concentrations of adrenalin.
In this paper,the systematic studies are conducted as following:First,five metallophthalocyanines(MPc) are synthesized and used to catalyze the oxidation of catecholamines(CAs).The influence factors of catalytic efficiency,such as catalytic time,the amount of MPc,the pH value of solution and temperature,have been investigated.Second,a novel fiber optic AD biosensor is designed and constructed using FePc as catalyzer,the performance of the novel biosensor is studied.The main conclusions are summarized as follows:
1.MPc(M=Mn~(2+),Fe~(2+),Co~(2+),Ni~(2+),Cu~(2+)) of high purity and good crystallinity are synthesized with phthalic anhydride and urea.The reaction time is shortened by using dimethylbenzene in place of high boiling point solvent,and it is easy to get the products.
2.In phosphate buffer solution(PBS),all MPc could effectively catalyze the oxidation of CAs.The corresponding oxidation products are adrenochrome, noradrenchrome and melanin,respectively.
The optimal conditions for the oxidation reaction of DA are pH 8.0 and the MPc amount of 1.00 mg/mL.The optimal temperatures are different for different MPc.The optimal temperature for MnPc and CuPc are 50℃and 60℃,respectively.FePc and CoPc have the same optimal temperature which is 55℃.Obvious catalysis of NiPc appears when temperature is above 50℃,and catalytic activity increase with the increase of temperature.For the oxidation reaction of AD and NA,the optimal catalytic conditions are namely:pH=8.0,T=55℃and the amout of MP is 1.00 mg/mL.MPc have the catalytic activity in order ofη_(MnPc)＞η_(FePc)＞η_(NiPc)＞η_(CuPc)＞η_(CoPc). Although MnPc shows the best catalytic activity under the optimal catalytic conditions,FePc could be used in larger pH range.
3.The performance of the fiber optic AD biosensor is investigated.The dissolved oxygen and AD content are evaluated by relative phase delayΔψ.In PBS with pH 7.4, a linear relationship betweenΔψand AD concentration is observed in the range of 2.0×10~(-6)～9.0×10~(-5) mol/L,and the low limit of detection is 4.0×10~(-7) mol/L.The biosensor has good stability and repeatability,and its response time is 10 min.
引文
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