疏水作用对离子交换色谱保留影响的研究
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摘要
论文考查了柱温、流动相和固定相的变化对离子交换色谱保留的影响,在此基础上建立了离子交换—疏水混合保留模型,并进行了离子交换色谱保留值的预测。
第一章首先在介绍了与离子交换保留机理探讨有关的基本知识的基础上,综述了气相色谱、液相色谱和离子色谱保留模型的发展状况;特别对文献报道的色谱机理的研究方法进行了介绍和讨论。为以后章节的离子交换色谱保留模型研究奠定基础并提供了方法指导。
第二章考察了柱温对离子交换色谱保留的影响,发现各种溶质离子在离子交换色谱固定相上的保留随柱温的升高呈现出不同的变化趋势。这一方面为离子交换色谱条件的选择和优化提出了新的思路,即可以通过改变柱温来改变选择性和分离度;另一方面,从变化趋势的一些差异上,可以看出离子交换色谱不仅仅是一个离子交换过程,还受到其它因素的影响。
第三章考察了固定相和流动相的变化对离子交换色谱保留的影响。考察的离子包括无机阴离子、有机脂肪酸及其取代物、苯甲酸及其取代物和肉桂酸及其取代物。考察的固定相具有相同的基本结构,但是交换容量和疏水作用位点数量不同。考察的流动相含有不同浓度的乙腈。各溶质离子的保留值随固定相和流动相的改变而呈现不同的变化规律,证明了离子交换色谱保留过程中疏水作用的存在。
在第二章和第三章的基础上,第四章综合考虑了离子交换作用和疏水作用对离子交换色谱保留的影响,经过一系列理论推导得到了离子交换—疏水混合保留模型,并通过泰勒公式将模型展开,得到了一个近似模型。然后根据实验所得的大量数据拟合得到了各溶质的保留模型,并采用留一法进行保留值预测,测试了模型的预测能力。结果表明,离子交换—疏水混合保留模型虽然存在一些不足,但是它能够较全面地反映离子交换色谱的保留机理,并能够比较准确地进行保留值的预测。
The thesis discussed the effect of column temperature,mobile phase and stationary phase on the retention value of ion-exchange chromatography. Based on this,an ion exchage-hydrophobic interaction retention model is built and retention value is predicted.
In chapter one,firstly,the basic knowledge about discussing ion-exchange chromatography retention mechanism is introduced.Secondly,the development of retention model of vapor phase chromatography, liquid chromatography and ion chromatography is summarized. The research methods of chromatography mechanism are introduced especially. All of these lay a foundation for the following research.
In chapter two,effect of column tempetature on ion-exchange chromatography retention value is discussed. It is found that the retention values of different kinds of analytes change in different direction with the change of column temperature. On the one hand,the phenomenon provides a new method for selecting and optimizing seperation condition of ion-exchange chromatography. That is,we can change selectivity and resolution by changing column temperature. On the other hand,some differences of the trends indicate that,except for ion-exchange process,there must be some other factors affecting ion-exchange chromatography retention.
In chapter three,effect of mobile phase and stationary phase on ion-exchange chromatography retention value is discussed. The analytes are inorganic anions,fatty acids, hydroxybenzoic acid, cinnamic acid and their substitutes. The stationary phases researched have similar structure,but their exchange capacity and amount of hydrophobic interaction point are different. The mobile phases researched contain acetonitrile of different concetration. The changes of retention value of different analytes show different trends with the change of mobile phase and stationary phase,which may indicate that hydrophobic interaction has effect on ion-exchange chromatography process.
On the basis of chapter two and three,a mixed retention model is derived in chapter four,which contains the effect of both ion exchange process and hydrophobic interaction. What's more, an approximate model is derived by Talor's Equiton.Then,the retention model of every analyte is available based on the datas we have got. At last,the models are used to predict retention value by leave-on-out method,and the prediction ability is tested. The results indicate that the retention models can reflect the retention mechanism more roundly and predict retention value relatively exactly,even though they have some limitations.
第一章首先在介绍了与离子交换保留机理探讨有关的基本知识的基础上,综述了气相色谱、液相色谱和离子色谱保留模型的发展状况;特别对文献报道的色谱机理的研究方法进行了介绍和讨论。为以后章节的离子交换色谱保留模型研究奠定基础并提供了方法指导。
第二章考察了柱温对离子交换色谱保留的影响,发现各种溶质离子在离子交换色谱固定相上的保留随柱温的升高呈现出不同的变化趋势。这一方面为离子交换色谱条件的选择和优化提出了新的思路,即可以通过改变柱温来改变选择性和分离度;另一方面,从变化趋势的一些差异上,可以看出离子交换色谱不仅仅是一个离子交换过程,还受到其它因素的影响。
第三章考察了固定相和流动相的变化对离子交换色谱保留的影响。考察的离子包括无机阴离子、有机脂肪酸及其取代物、苯甲酸及其取代物和肉桂酸及其取代物。考察的固定相具有相同的基本结构,但是交换容量和疏水作用位点数量不同。考察的流动相含有不同浓度的乙腈。各溶质离子的保留值随固定相和流动相的改变而呈现不同的变化规律,证明了离子交换色谱保留过程中疏水作用的存在。
在第二章和第三章的基础上,第四章综合考虑了离子交换作用和疏水作用对离子交换色谱保留的影响,经过一系列理论推导得到了离子交换—疏水混合保留模型,并通过泰勒公式将模型展开,得到了一个近似模型。然后根据实验所得的大量数据拟合得到了各溶质的保留模型,并采用留一法进行保留值预测,测试了模型的预测能力。结果表明,离子交换—疏水混合保留模型虽然存在一些不足,但是它能够较全面地反映离子交换色谱的保留机理,并能够比较准确地进行保留值的预测。
The thesis discussed the effect of column temperature,mobile phase and stationary phase on the retention value of ion-exchange chromatography. Based on this,an ion exchage-hydrophobic interaction retention model is built and retention value is predicted.
In chapter one,firstly,the basic knowledge about discussing ion-exchange chromatography retention mechanism is introduced.Secondly,the development of retention model of vapor phase chromatography, liquid chromatography and ion chromatography is summarized. The research methods of chromatography mechanism are introduced especially. All of these lay a foundation for the following research.
In chapter two,effect of column tempetature on ion-exchange chromatography retention value is discussed. It is found that the retention values of different kinds of analytes change in different direction with the change of column temperature. On the one hand,the phenomenon provides a new method for selecting and optimizing seperation condition of ion-exchange chromatography. That is,we can change selectivity and resolution by changing column temperature. On the other hand,some differences of the trends indicate that,except for ion-exchange process,there must be some other factors affecting ion-exchange chromatography retention.
In chapter three,effect of mobile phase and stationary phase on ion-exchange chromatography retention value is discussed. The analytes are inorganic anions,fatty acids, hydroxybenzoic acid, cinnamic acid and their substitutes. The stationary phases researched have similar structure,but their exchange capacity and amount of hydrophobic interaction point are different. The mobile phases researched contain acetonitrile of different concetration. The changes of retention value of different analytes show different trends with the change of mobile phase and stationary phase,which may indicate that hydrophobic interaction has effect on ion-exchange chromatography process.
On the basis of chapter two and three,a mixed retention model is derived in chapter four,which contains the effect of both ion exchange process and hydrophobic interaction. What's more, an approximate model is derived by Talor's Equiton.Then,the retention model of every analyte is available based on the datas we have got. At last,the models are used to predict retention value by leave-on-out method,and the prediction ability is tested. The results indicate that the retention models can reflect the retention mechanism more roundly and predict retention value relatively exactly,even though they have some limitations.
引文
[1]牟世芬,刘克纳.离子色谱方法及应用.第一版.北京:化学工业出版社,2000.28-30.
[2]Fridzs J S.Journal of Chromatography A,2005,1085(1):8-17.
[3]Dill K A.Biochemistry.1990,29(31):7133-7155.
[4]Eriksson K O,Hydrophobic Interaction Chromatography In Protein puirfication.2nd Ed.Newyork:high resolution methods,1998:284-309.
[5]丁明玉,田松柏.离子色谱原理与应用.第一版.北京:清华大学出版社,2000.39-54.
[6]Nadkami R A,Brewer J M.Am Lab,1987,27(1):30-37.
[7]Nomonura M.Anal Chem,1987,59(1):50-59.
[8]Crowther J,Lo F B,Rawing M W,et al.Environ Sci Technol,1995,29(4):849-855.
[9]李国兴,施青红,朱岩.化学分析计量,2005,14(6):58-60.
[10]黄源,牟世芬.色谱,2000,18(5):412-419.
[11]Tapparo A,Giorgio B G,Analyst,1998,123(3):1771-1773.
[12]Tanaka K,Ohta K,Haddad P R,et al.J.Chromatogr A,1998,804(2):179-186.
[13]Motomizu S,Oshima M,Hironaka T.Analyst,1991,116(5):695-700.
[14]Dogan S,Haerdi W.Chimia,1981,35(2):339-342.
[15]Davies D M,Ibey J R.Anal Chim Acta,1987,194(1):275-279.
[16]Haddad P R,Nesterenko P N,Buchberger W.J.chromatograpy A,2008,1184(2):456-473.
[17]Glenn K M,Lucy C A,Haddad P R.J.Chromatography A,2007,1155(1):8-14.
[18]Hutchinson H P,Zakaria P,Bowie A R,Macka M,Avdalovic N,Haddad P R Anal.Chem,2005,77(2):407-416.
[19]Hosoya K,Hira N,Yarnamoto K,Nishimura M,Tanaka N.Anal.Chem2006,78(17):5729-5735.
[20]WuR A,Hu L H,Wang F J,Ye M L,Zou H F.J.Chromatography A,2008,1184(2):369
[21]Sato H.Anal.Chem.1990,62(15):1567-1573.
[22]Liapis A I,Grimies B A.J.Sep.Sci,2005,28(2):1909-1926.
[23]Penner N A,Nesterenko P N.J.Chromatography A,2000,884(1):41-51.
[24]周蓉,冯钰绮,达世禄.色谱,2002,20(3):193-196.
[25]王福安,杨长生,王文昌.色谱,1992,10(1):29-30.
[26]Kittivatanapiboon K,Jeyashoke N,Krisnangkura K.L.Chromatogr.Sci,1998,36(1):361.
[27]卢佩章,戴朝政,张祥民.色谱理论基础.第二版.北京:科学出版社,1997.99-102.
[28]Krisnangkura K,Tancharoom A,Konkao C,Jeyashoke N.J.Chromatogr.Sci,1997,35(1):329.
[29]王福安,马元凯.色谱1985,3(2):233-234.
[30]刘大壮,黄恩才,张量渠,王福安.化学学报,1963,29(2):227-229
[31]刘大壮,王福安.化学学报(增刊),1981:145-147.
[32]蔡显鄂,邓海滨,朱京.化学学报,1988,48(1):49-50.
[33]王福安,马元凯.色谱,1987,5(2):396-399.
[34]Wang F A,Tian Q L,Guo Y C,CaoT Z.Chin.Chem,Lett,1993,4(9):795-796.
[35]王福安.分子热力学与色谱保留.第一版.北京,气相出版社,2001:20-35.
[36]Hunter R J.Foundations of Colloid Science;Oxford University Press:Oxford,Springer-Verlag,1992.
[37]Kuhn R,Hoffstetter-Kuhn S.Capillary Electrophoresis:Principles and Practice;Berlin,1993.
[38]Stahlberg J.J.Anal.Chem.1994,66(4):440-449.
[39]Foti G,Hajos P,Kovats E.Talanta,1994,41(7):1073-1081.
[40]Foti G,Revesz G,Hajos P,Pellaton G,Kovats E.Anal.Chem,1996,68(16),2580-2589.
[41]Janos P.J.ChromatographyA,1997,789(1)3 - 19.
[42]邹汉法,张玉奎.卢佩章.离子对高效液相色谱法.河南,河南科学技术出版 社,1994.
[43]LePree J M,Cancino M E.Journal of Chromatography A,1998,829(1):41-63.
[44]Lochmuller H H,Reese C,Aschman A J.J.ChromatographyA,1993,656(1):3-18.
[45]Valko K,Snyder L R,Glajch J L.J.Chromatography A,1993,656(2):501-520.
[46]Schoenmakers P J,Yijssen R.J.Chromatography A,1993,656(2):577-590.
[47]戴朝政,卢佩章,李浩春.色谱.1988.6(2):81-85.
[48]刘冰.不同分析方法在气相色谱定量结构一保留研究中的应用.[硕士学位论文].济南:山东大学,2007.
[49]张雪萍.气相色谱定量结构-保留关系研究.[硕士学位论文].北京:北京化工大学.2004.
[50]Hatsis P,Lucy C A.J.Chromatography A,2001,920(1):3 - 11.
[51]Baba Y,Yoza N,Ohashi S.J.Chromatography A,1985,348(1):27-37.
[52]Baba Y,Yoza N,Ohashi S.J.Chromatography A,1985,350(1):119-125.
[53]Fortier N E,Fritz J S.Talanta,1987,34(4):415-418.
[54]Rey M A,Pohl C A.J.Chromatogr.A,1996,739(1):87-97.
[55]Pirogov A V,Obrezkov O N,Shpigun O A.J.Anal.Chem.(Transl.Zh.Anal.Khim.)52:152.
[56]黄维,张宁.甘肃环境研究与检测.1995.8(3):17-18.
[57]Barron L,Nesterenko P N,Paull B.J.Chromatography A,2005,1072(2):207 -215.
[58]张祥民.现代色谱分析.第一版,上海:复旦大学出版社,2004,1-39
[59]Horvath K.Haios R J.ChromatograDhy A,2006,1104(1):78-81.
[60]刘勇建,牟世芬等.色谱,2003,21(2):181-183.
[61]刘肖,汪琼.化学试剂,2006,28(8):471-474.
[62]朱岩.离子色谱原理及应用.第一版.杭州:浙江大学出,2002.44.
[63]杨世钺,杨正刚.色谱,1994,12(1):25-27.
[2]Fridzs J S.Journal of Chromatography A,2005,1085(1):8-17.
[3]Dill K A.Biochemistry.1990,29(31):7133-7155.
[4]Eriksson K O,Hydrophobic Interaction Chromatography In Protein puirfication.2nd Ed.Newyork:high resolution methods,1998:284-309.
[5]丁明玉,田松柏.离子色谱原理与应用.第一版.北京:清华大学出版社,2000.39-54.
[6]Nadkami R A,Brewer J M.Am Lab,1987,27(1):30-37.
[7]Nomonura M.Anal Chem,1987,59(1):50-59.
[8]Crowther J,Lo F B,Rawing M W,et al.Environ Sci Technol,1995,29(4):849-855.
[9]李国兴,施青红,朱岩.化学分析计量,2005,14(6):58-60.
[10]黄源,牟世芬.色谱,2000,18(5):412-419.
[11]Tapparo A,Giorgio B G,Analyst,1998,123(3):1771-1773.
[12]Tanaka K,Ohta K,Haddad P R,et al.J.Chromatogr A,1998,804(2):179-186.
[13]Motomizu S,Oshima M,Hironaka T.Analyst,1991,116(5):695-700.
[14]Dogan S,Haerdi W.Chimia,1981,35(2):339-342.
[15]Davies D M,Ibey J R.Anal Chim Acta,1987,194(1):275-279.
[16]Haddad P R,Nesterenko P N,Buchberger W.J.chromatograpy A,2008,1184(2):456-473.
[17]Glenn K M,Lucy C A,Haddad P R.J.Chromatography A,2007,1155(1):8-14.
[18]Hutchinson H P,Zakaria P,Bowie A R,Macka M,Avdalovic N,Haddad P R Anal.Chem,2005,77(2):407-416.
[19]Hosoya K,Hira N,Yarnamoto K,Nishimura M,Tanaka N.Anal.Chem2006,78(17):5729-5735.
[20]WuR A,Hu L H,Wang F J,Ye M L,Zou H F.J.Chromatography A,2008,1184(2):369
[21]Sato H.Anal.Chem.1990,62(15):1567-1573.
[22]Liapis A I,Grimies B A.J.Sep.Sci,2005,28(2):1909-1926.
[23]Penner N A,Nesterenko P N.J.Chromatography A,2000,884(1):41-51.
[24]周蓉,冯钰绮,达世禄.色谱,2002,20(3):193-196.
[25]王福安,杨长生,王文昌.色谱,1992,10(1):29-30.
[26]Kittivatanapiboon K,Jeyashoke N,Krisnangkura K.L.Chromatogr.Sci,1998,36(1):361.
[27]卢佩章,戴朝政,张祥民.色谱理论基础.第二版.北京:科学出版社,1997.99-102.
[28]Krisnangkura K,Tancharoom A,Konkao C,Jeyashoke N.J.Chromatogr.Sci,1997,35(1):329.
[29]王福安,马元凯.色谱1985,3(2):233-234.
[30]刘大壮,黄恩才,张量渠,王福安.化学学报,1963,29(2):227-229
[31]刘大壮,王福安.化学学报(增刊),1981:145-147.
[32]蔡显鄂,邓海滨,朱京.化学学报,1988,48(1):49-50.
[33]王福安,马元凯.色谱,1987,5(2):396-399.
[34]Wang F A,Tian Q L,Guo Y C,CaoT Z.Chin.Chem,Lett,1993,4(9):795-796.
[35]王福安.分子热力学与色谱保留.第一版.北京,气相出版社,2001:20-35.
[36]Hunter R J.Foundations of Colloid Science;Oxford University Press:Oxford,Springer-Verlag,1992.
[37]Kuhn R,Hoffstetter-Kuhn S.Capillary Electrophoresis:Principles and Practice;Berlin,1993.
[38]Stahlberg J.J.Anal.Chem.1994,66(4):440-449.
[39]Foti G,Hajos P,Kovats E.Talanta,1994,41(7):1073-1081.
[40]Foti G,Revesz G,Hajos P,Pellaton G,Kovats E.Anal.Chem,1996,68(16),2580-2589.
[41]Janos P.J.ChromatographyA,1997,789(1)3 - 19.
[42]邹汉法,张玉奎.卢佩章.离子对高效液相色谱法.河南,河南科学技术出版 社,1994.
[43]LePree J M,Cancino M E.Journal of Chromatography A,1998,829(1):41-63.
[44]Lochmuller H H,Reese C,Aschman A J.J.ChromatographyA,1993,656(1):3-18.
[45]Valko K,Snyder L R,Glajch J L.J.Chromatography A,1993,656(2):501-520.
[46]Schoenmakers P J,Yijssen R.J.Chromatography A,1993,656(2):577-590.
[47]戴朝政,卢佩章,李浩春.色谱.1988.6(2):81-85.
[48]刘冰.不同分析方法在气相色谱定量结构一保留研究中的应用.[硕士学位论文].济南:山东大学,2007.
[49]张雪萍.气相色谱定量结构-保留关系研究.[硕士学位论文].北京:北京化工大学.2004.
[50]Hatsis P,Lucy C A.J.Chromatography A,2001,920(1):3 - 11.
[51]Baba Y,Yoza N,Ohashi S.J.Chromatography A,1985,348(1):27-37.
[52]Baba Y,Yoza N,Ohashi S.J.Chromatography A,1985,350(1):119-125.
[53]Fortier N E,Fritz J S.Talanta,1987,34(4):415-418.
[54]Rey M A,Pohl C A.J.Chromatogr.A,1996,739(1):87-97.
[55]Pirogov A V,Obrezkov O N,Shpigun O A.J.Anal.Chem.(Transl.Zh.Anal.Khim.)52:152.
[56]黄维,张宁.甘肃环境研究与检测.1995.8(3):17-18.
[57]Barron L,Nesterenko P N,Paull B.J.Chromatography A,2005,1072(2):207 -215.
[58]张祥民.现代色谱分析.第一版,上海:复旦大学出版社,2004,1-39
[59]Horvath K.Haios R J.ChromatograDhy A,2006,1104(1):78-81.
[60]刘勇建,牟世芬等.色谱,2003,21(2):181-183.
[61]刘肖,汪琼.化学试剂,2006,28(8):471-474.
[62]朱岩.离子色谱原理及应用.第一版.杭州:浙江大学出,2002.44.
[63]杨世钺,杨正刚.色谱,1994,12(1):25-27.