非水溶液中胶束性质及胶束酶催化的量热法研究
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摘要
非水溶液中表面活性剂性质的研究可以为进一步研究纤维素酶的胶束酶催化奠定理论基础。一些纤维素不溶于水而溶于某些有机溶剂,在非水环境中研究纤维素酶对纤维素的降解是酶催化反应新的研究方向。
具体研究内容如下:
1.CMC及热力学函数的确定及规律性
用微量量热仪测定了不同温度和不同浓度的不同醇条件下,非离子表面活性剂(TX-100和Brii35)在非水溶液中的热功率.时间曲线,从曲线上的转折点获得了临界胶束浓度(CMC)。根据曲线上的面积,求得胶束形成热(ΔH_m~θ),根据热力学理论,可获得ΔG_m~θ和ΔS_m~θ,这是一种获得CMC和热力学函数的新方法。结果表明:在含有相同浓度、相同碳原子数的醇的DMF体系中,ΔH_m~θ和ΔS_m~θ的值随着温度的升高而增加,ΔG_m~θ和CMC的值随着温度的升高而降低;在相同温度及相同浓度的醇的DMF体系中,CMC、ΔH_m~θ、ΔG_m~θ和ΔS_m~θ的值都随着醇中碳原子数目的增加而降低;TX-100和Brii35在相同温度及相同碳原子数的醇的DMF体系中,CMC、、ΔH_m~θ和ΔG_m~θ、ΔS_m~θ都随着醇的浓度的增加而下降。
2.胶束溶液中纤维素酶最佳酶解条件的研究
底物的浓度、酶的用量确定后,用八通道滴定微量量热仪分别测定不同含水量(W_o)、酸度(pH)和温度(T)下纤维素酶降解羧甲基纤维素钠的热功率—时间曲线。用对比进度法得出反应的表观米氏常数(K_m)和表观最大反应速率(V_(max)),建立了最大反应速率与W_o、酸度和温度之间的关系式,从而获得纤维素酶降解羧甲基纤维素钠的最佳反应条件。在非离子表面活性剂Brij35/异辛醇/环已烷反胶束体系中,最佳W_o为5.62、最佳酸度为4.92、最佳温度为318.88K。
3.常见离子对胶束溶液中纤维素酶催化反应的影响
测定了在相同浓度的不同离子存在时的热功率—时间曲线,比较得出离子对纤维素降解羧甲基纤维素钠反应的抑制与激活作用的规律。得出Na~+,K~+对纤维素酶催化反应有激活作用,并且激活作用由Na~+大于K~+;Mg~(2+),Ba~(2+)对纤维素酶催化反应有抑制的作用,其抑制作用由Ba~(2+)大于Mg~(2+)。Cl~-,NO_3~-对纤维素酶催化反应有激活的作用,其激活作用由Cl~-大于NO_3~-;SO_4~(2-)和SO_3~(2-)对纤维素酶催化反应有抑制作用,并且,抑制作用为SO_4~(2-)小于SO_3~(2-)。
本文的创新之处
1.利用微量量热法,根据热动力学理论获得热动力学参数并用来表征纤维素酶催化反应的特征及规律,确定胶束酶催化降解纤维素的最佳条件的研究是酶催化反应研究的新课题。
2.利用微量量热法研究非水溶液中非离子表面活性剂,助表面活性剂及溶剂的相互作用,用测得的CMC及胶束形成过程的热效应,得到胶束形成焓ΔH_m~θ,进而计算出ΔG_m~θ和ΔS_(m。)~θ这是获得CMC和热力学函数的新方法。
The property research of surfactant in non-aqueous solution can provide theoretical basis for the research of micelle enzyme catalysis of cellulase.Some cellulose is not water miscible, but it can be dissolved in certain organic solvent.The study of cellulose's degradation by cellulase in non-aqueous environment is a new research subject.
The main contents are as follows:
1.the determination and regularity of CMC and thermodynamic functions
The power-time curves of the micelle formation process were determined for non-ionic surfactant(TX-100 and Brij35) in non-aqueous solution under different temperatures and different alcohols of different concentrations by titration microcalorimetry.From the corresponding volume of the lowest point of the curves,the critical micelle concentration(CMC) was determined;from the area up the curves,the thermal effect and△H_m~θwere measured; according to the action principle of surfactant and thermodynamic theory,the△G_m~θand△S_m~θwere calculated.The conclusions were as follows:TX-100 and Brij35 in DMF system,the△H_m~θand△S_m~θincreased while the CMC and△G_m~θdecreased with the increment of temperature in the presence of same alcohol's concentration and carbon number;the CMC,△H_m~θ,△G_m~θand△S_m~θall decreased with the increment of alcohol's carbon number in the presence of same temperature and same alcohol's concentration;the CMC,△H_m~θ,△G_m~θand△S_m~θdecreased with the increment of alcohol's concentration.
2.the study of optimum condition of cellulose's enzyme catalysis
After determining the concentration of substrate and the doseage of enzyme,the power-time curves of the Carboxymethyl Cellulose degradated by cellulose were separately measured by the TAM Air at different W_0,different acidity(pH) and different temperature(T) in different reverse micelles.Then Using reduced extent method,the apparent Michaelis constant(K_m) and the apparent maximum velocity(V_(max)) were calculated and the relationships between V_(max) and W_0, pH,T were established.So we obtained the optimum conditions of microcrystalline cellulose degradated by cellulase.In the reverse micelles of non-ionic surfactant Brij35/n-Hexanol/ cyclohexane,the optimum W_0 is 5.62,the optimum acidity is 4.92 and the optimum temperature is 318.88K.
3.the influence of common ions on enzyme catalysis of cellulose
The power - time curves of enzyme catalysis without ions and with the existence of ions of the same or different concentrations were determined and analyzed.By comparing,the regularities of activation or inhibition of different ions of the same concentration or of the same ion of different concentrations to enzyme catalysis were seen.It was found that Na~+ and K~+ were active to the enzyme catalysis and the effect of K~+ was weaker than that of Na~+;Mg~(2+) and Ba~(2+) were inhibitory to the reaction and the effect of Mg~(2+) was weaker than that of Ba~(2+)。Cl~- and NO_3~-were active to the enzyme catalysis and the effect of NO_3~- was weaker than that of Cl~-;SO_4~(2-) and SO_3~(2-) were inhibitory to the reaction and the effect of SO_4~(2-) was weaker than that of SO_3~(2-).
The innovation of this paper:
1.Thermodynamic parameters which obtained by microcalorirnetric method and thermodynamic theory are used to characterize cellulose's enzyme catalysis and to determine the optimum condition of the enzyme catalysis.This is a new subject for enzyme catalysis research.
2.microcalorimetric method is used to study the interactivity of non-ionic surfactant, cosurfactants and solvents in non-aqueous solution.The CMC and thermal effect are determined and the AH_m~θis obtained,then the△G_m~θand△S_m~θare calculated.This is a new method to gain CMC and thermodynamic function.
具体研究内容如下:
1.CMC及热力学函数的确定及规律性
用微量量热仪测定了不同温度和不同浓度的不同醇条件下,非离子表面活性剂(TX-100和Brii35)在非水溶液中的热功率.时间曲线,从曲线上的转折点获得了临界胶束浓度(CMC)。根据曲线上的面积,求得胶束形成热(ΔH_m~θ),根据热力学理论,可获得ΔG_m~θ和ΔS_m~θ,这是一种获得CMC和热力学函数的新方法。结果表明:在含有相同浓度、相同碳原子数的醇的DMF体系中,ΔH_m~θ和ΔS_m~θ的值随着温度的升高而增加,ΔG_m~θ和CMC的值随着温度的升高而降低;在相同温度及相同浓度的醇的DMF体系中,CMC、ΔH_m~θ、ΔG_m~θ和ΔS_m~θ的值都随着醇中碳原子数目的增加而降低;TX-100和Brii35在相同温度及相同碳原子数的醇的DMF体系中,CMC、、ΔH_m~θ和ΔG_m~θ、ΔS_m~θ都随着醇的浓度的增加而下降。
2.胶束溶液中纤维素酶最佳酶解条件的研究
底物的浓度、酶的用量确定后,用八通道滴定微量量热仪分别测定不同含水量(W_o)、酸度(pH)和温度(T)下纤维素酶降解羧甲基纤维素钠的热功率—时间曲线。用对比进度法得出反应的表观米氏常数(K_m)和表观最大反应速率(V_(max)),建立了最大反应速率与W_o、酸度和温度之间的关系式,从而获得纤维素酶降解羧甲基纤维素钠的最佳反应条件。在非离子表面活性剂Brij35/异辛醇/环已烷反胶束体系中,最佳W_o为5.62、最佳酸度为4.92、最佳温度为318.88K。
3.常见离子对胶束溶液中纤维素酶催化反应的影响
测定了在相同浓度的不同离子存在时的热功率—时间曲线,比较得出离子对纤维素降解羧甲基纤维素钠反应的抑制与激活作用的规律。得出Na~+,K~+对纤维素酶催化反应有激活作用,并且激活作用由Na~+大于K~+;Mg~(2+),Ba~(2+)对纤维素酶催化反应有抑制的作用,其抑制作用由Ba~(2+)大于Mg~(2+)。Cl~-,NO_3~-对纤维素酶催化反应有激活的作用,其激活作用由Cl~-大于NO_3~-;SO_4~(2-)和SO_3~(2-)对纤维素酶催化反应有抑制作用,并且,抑制作用为SO_4~(2-)小于SO_3~(2-)。
本文的创新之处
1.利用微量量热法,根据热动力学理论获得热动力学参数并用来表征纤维素酶催化反应的特征及规律,确定胶束酶催化降解纤维素的最佳条件的研究是酶催化反应研究的新课题。
2.利用微量量热法研究非水溶液中非离子表面活性剂,助表面活性剂及溶剂的相互作用,用测得的CMC及胶束形成过程的热效应,得到胶束形成焓ΔH_m~θ,进而计算出ΔG_m~θ和ΔS_(m。)~θ这是获得CMC和热力学函数的新方法。
The property research of surfactant in non-aqueous solution can provide theoretical basis for the research of micelle enzyme catalysis of cellulase.Some cellulose is not water miscible, but it can be dissolved in certain organic solvent.The study of cellulose's degradation by cellulase in non-aqueous environment is a new research subject.
The main contents are as follows:
1.the determination and regularity of CMC and thermodynamic functions
The power-time curves of the micelle formation process were determined for non-ionic surfactant(TX-100 and Brij35) in non-aqueous solution under different temperatures and different alcohols of different concentrations by titration microcalorimetry.From the corresponding volume of the lowest point of the curves,the critical micelle concentration(CMC) was determined;from the area up the curves,the thermal effect and△H_m~θwere measured; according to the action principle of surfactant and thermodynamic theory,the△G_m~θand△S_m~θwere calculated.The conclusions were as follows:TX-100 and Brij35 in DMF system,the△H_m~θand△S_m~θincreased while the CMC and△G_m~θdecreased with the increment of temperature in the presence of same alcohol's concentration and carbon number;the CMC,△H_m~θ,△G_m~θand△S_m~θall decreased with the increment of alcohol's carbon number in the presence of same temperature and same alcohol's concentration;the CMC,△H_m~θ,△G_m~θand△S_m~θdecreased with the increment of alcohol's concentration.
2.the study of optimum condition of cellulose's enzyme catalysis
After determining the concentration of substrate and the doseage of enzyme,the power-time curves of the Carboxymethyl Cellulose degradated by cellulose were separately measured by the TAM Air at different W_0,different acidity(pH) and different temperature(T) in different reverse micelles.Then Using reduced extent method,the apparent Michaelis constant(K_m) and the apparent maximum velocity(V_(max)) were calculated and the relationships between V_(max) and W_0, pH,T were established.So we obtained the optimum conditions of microcrystalline cellulose degradated by cellulase.In the reverse micelles of non-ionic surfactant Brij35/n-Hexanol/ cyclohexane,the optimum W_0 is 5.62,the optimum acidity is 4.92 and the optimum temperature is 318.88K.
3.the influence of common ions on enzyme catalysis of cellulose
The power - time curves of enzyme catalysis without ions and with the existence of ions of the same or different concentrations were determined and analyzed.By comparing,the regularities of activation or inhibition of different ions of the same concentration or of the same ion of different concentrations to enzyme catalysis were seen.It was found that Na~+ and K~+ were active to the enzyme catalysis and the effect of K~+ was weaker than that of Na~+;Mg~(2+) and Ba~(2+) were inhibitory to the reaction and the effect of Mg~(2+) was weaker than that of Ba~(2+)。Cl~- and NO_3~-were active to the enzyme catalysis and the effect of NO_3~- was weaker than that of Cl~-;SO_4~(2-) and SO_3~(2-) were inhibitory to the reaction and the effect of SO_4~(2-) was weaker than that of SO_3~(2-).
The innovation of this paper:
1.Thermodynamic parameters which obtained by microcalorirnetric method and thermodynamic theory are used to characterize cellulose's enzyme catalysis and to determine the optimum condition of the enzyme catalysis.This is a new subject for enzyme catalysis research.
2.microcalorimetric method is used to study the interactivity of non-ionic surfactant, cosurfactants and solvents in non-aqueous solution.The CMC and thermal effect are determined and the AH_m~θis obtained,then the△G_m~θand△S_m~θare calculated.This is a new method to gain CMC and thermodynamic function.
引文
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