α-长链烷基甜菜碱的定量分析
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摘要
α-长链烷基甜菜碱(α-LAB)是一类以天然脂肪酸为原料开发得到的新型两性表面活性剂。本文建立了该表面活性剂及其合成过程中原料、主要副产物的定量分析方法,并考察了两种分析方法的适用条件以及影响因素。采用海明容量滴定法测定α-氯代十二酸(α-HDA)、十二酸(DA)和α-氯代十二酸(α-CDA)的的总含量;建立HPLC方法测定α-癸基甜菜碱(α-CB)、未反应原料DA和α-CDA、主要副产物α-HDA的含量。主要得到以下结论:
建立了海明容量法标定磷钨酸溶液浓度,该方法快速准确,RSD小于0.3%,测定结果与联苯胺重量法一致,因此可以取代联苯胺重量法标定磷钨酸。通过海明返滴定方法可以准确测定除去三甲胺后α-CB产品中活性物的含量,α-CB平均回收率为100.33%。α-癸基甜菜碱产品中残留脂肪酸(包括α-CDA、α-HDA和DA)总含量可用溴甲酚绿两相滴定法直接测定,实验发现:当样品溶液中氯化钠浓度小于5 g/L、α-CB的浓度小于20 g/L时,分析结果准确,DA的回收率为98-100%,体系中的三甲胺对滴定结果无明显影响,因此产品可以直接用于分析。
采用蒸发光散射检测器(ELSD),运用高效液相色谱,同时分析检测α-癸基甜菜碱产品组成。分析条件为:C18色谱柱(4.6 mm×250 mm,5μm),流动相为乙腈-甲醇-水的体积比为40.9:46.6:12.5(0.5%甲酸),流速为0.8 mL/min。该方法可以对α-癸基甜菜碱合成产品中的主产物α-癸基甜菜碱(α-CB)、副产物α-羟基十二酸(α-HDA)、未反应原料十二酸(DA)和α-氯代十二酸(α-CDA)进行良好分离和定量分析。该方法结果准确、灵敏度高,可作为其他方法的参照标准。
选择合适的流动相,实现了用HPLC-RID方法对α-CB准确定量分析,α-CB在1.6-32μg内呈现出良好的线性关系,检测限为1.2μg。
由混合脂肪酸合成得到的产品含有不同碳链的α-LAB,通过计算机辅助优化HPLC-ELSD方法,并经实验验证得到较满意的分离线性梯度洗脱的条件。这为分析混合α-LAB产品定量分析提供了色谱条件。
By the analysis of a novel type of amphoteric surfactants alpha-long chain alkyl betaine(α-LAB) prepared through ammonolysis of long chain fatty acid derivative alpha-chlorododecanoic acid with trimethylamine,the chemical methods to determine alpha-capric betaine and free fatty acids were developed.A method for the determination of alpha-capric betaine(α-CB),alpha-hydroxy dodecanoic acid(α-HDA),dodecanoic acid(DA) and alpha-chlorinated dodecanoic acid(α-CDA) by high performance liquid chromatography (HPLC) coupled with evaporative light-scattering detection(ELSD) and refractive index detector(RID) was developed,and the effect was investigated.The main points were as follows:
A novel rapid method for the standardization of phosphotungstic acid was developed by titration,the relative standard deviation is lower than 0.3%,and the result was consistent with the gravimetric analysis by Benzidine.A method to determine theα-LAB by back titration with Hamming was developed;the average recovery rate ofα-CB is 100.33%.
A method to determine the free fatty acids by in reaction products was developed by two-phase titration with bromocresol green indicator,and the scope of application was the concentration of NaCl andα-CB in sample solution must be lower than 5 g/L and 20 g/L, respectively.The average recovery rate of DA is 98-100%;the relative standard deviation is lower than 0.3%.There is no influence of trim ethyl amine in product for the result,so this method can determine free fatty acids directly.
A new method of HPLC-ELSD has been developed for the separation and quantitative analysis of the compose of alpha-capric betaine.This method employs an isocratic elution, mobile phase was composed of acetonitrile,methyl,water(V:V:V=40.9:46.6:12.5) and the flow of mobile phase was maintained at 0.8 mL/min.The separation and quantitative of alpha-capric betaine,alpha-hydroxy dodecanoic acid,alpha-chlorinated dodecanoic acid, dodecanoic acid were performed.This method has a high accuracy and sensitivity,so it can be the standards for other methods.
A high-performance liquid chromatography technique with refractive index detector has been developed for the determination ofα-CB by the change of mobile phase.The minimum limit of detection ofα-CB is about 1.2μg and ratio of mass to signal is essentially linear in the range of 1.6 to 32μg.
A method for the separation analysis of a mixture ofα-LAB prepared by fatty acid mixed was developed by computer-aided optimize and experimentation.The method provides an analytical condition for quantitative analysis of the mixture ofα-LAB.
建立了海明容量法标定磷钨酸溶液浓度,该方法快速准确,RSD小于0.3%,测定结果与联苯胺重量法一致,因此可以取代联苯胺重量法标定磷钨酸。通过海明返滴定方法可以准确测定除去三甲胺后α-CB产品中活性物的含量,α-CB平均回收率为100.33%。α-癸基甜菜碱产品中残留脂肪酸(包括α-CDA、α-HDA和DA)总含量可用溴甲酚绿两相滴定法直接测定,实验发现:当样品溶液中氯化钠浓度小于5 g/L、α-CB的浓度小于20 g/L时,分析结果准确,DA的回收率为98-100%,体系中的三甲胺对滴定结果无明显影响,因此产品可以直接用于分析。
采用蒸发光散射检测器(ELSD),运用高效液相色谱,同时分析检测α-癸基甜菜碱产品组成。分析条件为:C18色谱柱(4.6 mm×250 mm,5μm),流动相为乙腈-甲醇-水的体积比为40.9:46.6:12.5(0.5%甲酸),流速为0.8 mL/min。该方法可以对α-癸基甜菜碱合成产品中的主产物α-癸基甜菜碱(α-CB)、副产物α-羟基十二酸(α-HDA)、未反应原料十二酸(DA)和α-氯代十二酸(α-CDA)进行良好分离和定量分析。该方法结果准确、灵敏度高,可作为其他方法的参照标准。
选择合适的流动相,实现了用HPLC-RID方法对α-CB准确定量分析,α-CB在1.6-32μg内呈现出良好的线性关系,检测限为1.2μg。
由混合脂肪酸合成得到的产品含有不同碳链的α-LAB,通过计算机辅助优化HPLC-ELSD方法,并经实验验证得到较满意的分离线性梯度洗脱的条件。这为分析混合α-LAB产品定量分析提供了色谱条件。
By the analysis of a novel type of amphoteric surfactants alpha-long chain alkyl betaine(α-LAB) prepared through ammonolysis of long chain fatty acid derivative alpha-chlorododecanoic acid with trimethylamine,the chemical methods to determine alpha-capric betaine and free fatty acids were developed.A method for the determination of alpha-capric betaine(α-CB),alpha-hydroxy dodecanoic acid(α-HDA),dodecanoic acid(DA) and alpha-chlorinated dodecanoic acid(α-CDA) by high performance liquid chromatography (HPLC) coupled with evaporative light-scattering detection(ELSD) and refractive index detector(RID) was developed,and the effect was investigated.The main points were as follows:
A novel rapid method for the standardization of phosphotungstic acid was developed by titration,the relative standard deviation is lower than 0.3%,and the result was consistent with the gravimetric analysis by Benzidine.A method to determine theα-LAB by back titration with Hamming was developed;the average recovery rate ofα-CB is 100.33%.
A method to determine the free fatty acids by in reaction products was developed by two-phase titration with bromocresol green indicator,and the scope of application was the concentration of NaCl andα-CB in sample solution must be lower than 5 g/L and 20 g/L, respectively.The average recovery rate of DA is 98-100%;the relative standard deviation is lower than 0.3%.There is no influence of trim ethyl amine in product for the result,so this method can determine free fatty acids directly.
A new method of HPLC-ELSD has been developed for the separation and quantitative analysis of the compose of alpha-capric betaine.This method employs an isocratic elution, mobile phase was composed of acetonitrile,methyl,water(V:V:V=40.9:46.6:12.5) and the flow of mobile phase was maintained at 0.8 mL/min.The separation and quantitative of alpha-capric betaine,alpha-hydroxy dodecanoic acid,alpha-chlorinated dodecanoic acid, dodecanoic acid were performed.This method has a high accuracy and sensitivity,so it can be the standards for other methods.
A high-performance liquid chromatography technique with refractive index detector has been developed for the determination ofα-CB by the change of mobile phase.The minimum limit of detection ofα-CB is about 1.2μg and ratio of mass to signal is essentially linear in the range of 1.6 to 32μg.
A method for the separation analysis of a mixture ofα-LAB prepared by fatty acid mixed was developed by computer-aided optimize and experimentation.The method provides an analytical condition for quantitative analysis of the mixture ofα-LAB.
引文
[1]Zajac J,Chorro C,Lindheimer M,etal.Thermodynamics of micellization and adsorption of zwitterionic surfactants in aqueous media.Langmuir 1997,13:1486-1495
[2]Kamenka N,Chevalier Y,Zana R.Aqueous-solutions of zwitterionic surfactants with varying carbon number of the intercharger group:1.micelle aggregation numbers.Langmuir,1995,11:3351-3355
[3]Szule R,Michael RF,Daniel H.Solution behavior of the zwitterionic surfactant octacapricdimethylbetaine[J].J Phys Chem B,1998,102:6487-6492
[4]Doussin S,Birlirakis N,Georgin D,etal.Novel zwitterionic reverse micelles for encapsulation of proteins in low-viscosity media[J].Chem Eur J.2006,12:4170-4175
[5]Yaseen M,Lu JR,Webster JRP,etal.The structure of zwitterionic phosphocholine surfactant monolayers[J].Langmuir,2006,22:5825-5832
[6]El-Aila HJY.Effect of urea and salt on micelle formation of zwitterionic surfactants[J].J Surfact Deterg,2005,8:165-168
[7]Edward Tunstall Messenger,Slmon Holland Nicholson.Surfactant Purification By An electrolytic Method[P].London,1,525,692,1978-09-20.
[8]李英,李干佐.十二烷基甜菜碱的界面活性及其体系的相态研究[J].化学物理学报,1998,11(3):6-8.
[9]J.Falbe.Surfactants in Consumer Products “Theory,Technology and Application”[M].Published by Springer-Verlag Heidelberg,1987,114-118.
[10]Maria del Mar Graciani Constante,Maria Amalia Rodriguez Rodriguez,Maria Munoz Perez,etal.Micellar Solutions of Sulfobetaine Surfactants in Water-Ethylene Glycol Mixtures:Surface Tension,Fluorescence,Spectroscopic,Conducto-metric,and Kinetic Studies[J].Langmuir,2005,21:7161-7169.
[11]Yves Chevalier,Flavien Melis,Jean Pierre Dalbiez.Structure of zwitterionic surfactant micelles:micellar size and intermicellar interactions[J].The journal of Phyical Chemistry,1992,96(21):8614-8619.
[12]Maria Munoz,Amalia Rodriguez,Maria del Mar Graciani,et al.Conductometric,Surface Tension,and Kinetic Studies in Mixed SDS-Tween 20 and SDS-SB3-12 Micellar Solutions[J].Langmuir,2004,20:10858-10867.
[13]曹玉华.日用化学品分析[M],无锡:江南大学,2003.45.
[14]甄录旭等.HPLC法测定枸杞子中甜菜碱的含量[J].安徽医药,2007,(8):703-704.
[15]张曲.电位滴定法测定脂肪烷基二甲基甜菜碱含量[J].石油与天然气化工,1999, 28(3):223-224.
[16]龚立冬,曹玉华,侯建霞.高效液相色谱-蒸发光散射检测法测定肉苁蓉中的甜菜碱[J].色谱,2007,3:280-281.
[17]Angela Tegeler,Wolfgang Ruess,Erich Gmahl.Determination of amphoretic surfactants in cosmetic cleansing products by high-performance liquid chromatography on a cation-exchange column[J].Talanta,1999,11.
[18]Laurence Zanna,Jean-Francois Haeuw.Separation and quantitative analysis of alkyl sulfobetaine-type detergents by high-performance liquid chromatography and light-scattering detection[J].Chromatography,2007,846:368-373.
[19]Hong Soon Park,Ho Ryul Ryu,Choong Kyun Rhee.Simultaneous separation of nine surfactants of various types by HPLC with evaporative light scattering detection[J].Talanta,2006,1:29-33.
[20]Ingalls ST,Minkler PE,Hoppel CL.Derivatization of carboxylic acids by reaction with 4'bromophenacyl trifluoromethane sulfonate prior to determination by high performance liquid chromatography[J].Chromatogr A,1984,299:365-376.
[21]申烨华等.扁桃油中脂肪酸组成的GC-MS法分析[J].分析试验室,2005,9:37-39.
[22]赵先恩等.藏药波棱瓜籽油脂中脂肪酸的HPLC与GC-MS分析[J].天然产物研究与开发,2009,21:76-83.
[23]Jing Sun,etal.Determination of 30 free fatty acids in two famous tibetan medicines by HPLC with fluorescence detection and mass spectrometric identification[J].Chromatographia,2007,65:469-476.
[24]毛培坤.表面活性剂产品工业分析[M].化学工业出版社,2003:20-22.
[25]D.C.C.Cullum.Introduction to surfactant analysis[M].Published by Blackie Academic and Professional,1994,177-180.
[26]J M Plantinga,J J Donkerbroek,R J Mulder.Determination of betaine and free amine in alkyldimethyl betaine by potentiometric titrations[J].JAOCS,1993,70(1):97-99.
[27]Valdes Martinez S E.Analyst,1983,108(1 290):1114.
[28]Hans Konig,Werner Strobel.Separation identification and determination of alkyl-and alkylphenol ether carboxylates by HPLC[J].J.of Analytical Chemistry.1990,(338):728-731.
[29]Ryo Koike,Fumihiko Kitagawa,Koji Otsuka.Simultaneous determination of amphoteric surfactants in detergents by capillary electrophoresis with indirect UV detection[J].J.Chromatogr.A,2007,(1139):136-142.
[30]R.Gerhards,I.jussofie,D.Kaseborn,S.Keune,R.Schulz.Modern methods for the analysis of cocoamidopropyl betaines[J].Tenside Surf.Det.1996,33(1):8-14.
[31]笠井,矢野,木村.日本化学会志(日),1971,2390.
[32]陆光崇.用改良的磷钨酸法侧定两性表面活性剂的活性物含量[J].日用化学工业,1982(4):36-37
[33]钟雷,丁悠丹.表面活性剂及其助剂分析[M].浙江科学技术出版社,1986,139-145
[34]K Tori,T Nakagawa.Colloid Chemical Properties of Ampholytic Surfactants I.Syntheses and Some Properties of Alkyl Betaines[J].Colloid & Polymer Science,1963,187(1):44-51.
[35]朱世永,陈世京.衍生物气相色谱法[M].北京:化学工业出版社,1993:119-121.
[36]Yoshiro Ogata,Toshiyuki Sugimoto,Morio Inaishi.α-Chlorimation of Long-chain Aliphatic Acids[J].Bulletin of the Chemical Society of Japan,1979,52(1):255-256.
[37]单亦初等.可调移动重叠分离图法用于高效液相色谱多台阶梯度分离条件优化的研究[J].色谱,2006,3:122-128.
[2]Kamenka N,Chevalier Y,Zana R.Aqueous-solutions of zwitterionic surfactants with varying carbon number of the intercharger group:1.micelle aggregation numbers.Langmuir,1995,11:3351-3355
[3]Szule R,Michael RF,Daniel H.Solution behavior of the zwitterionic surfactant octacapricdimethylbetaine[J].J Phys Chem B,1998,102:6487-6492
[4]Doussin S,Birlirakis N,Georgin D,etal.Novel zwitterionic reverse micelles for encapsulation of proteins in low-viscosity media[J].Chem Eur J.2006,12:4170-4175
[5]Yaseen M,Lu JR,Webster JRP,etal.The structure of zwitterionic phosphocholine surfactant monolayers[J].Langmuir,2006,22:5825-5832
[6]El-Aila HJY.Effect of urea and salt on micelle formation of zwitterionic surfactants[J].J Surfact Deterg,2005,8:165-168
[7]Edward Tunstall Messenger,Slmon Holland Nicholson.Surfactant Purification By An electrolytic Method[P].London,1,525,692,1978-09-20.
[8]李英,李干佐.十二烷基甜菜碱的界面活性及其体系的相态研究[J].化学物理学报,1998,11(3):6-8.
[9]J.Falbe.Surfactants in Consumer Products “Theory,Technology and Application”[M].Published by Springer-Verlag Heidelberg,1987,114-118.
[10]Maria del Mar Graciani Constante,Maria Amalia Rodriguez Rodriguez,Maria Munoz Perez,etal.Micellar Solutions of Sulfobetaine Surfactants in Water-Ethylene Glycol Mixtures:Surface Tension,Fluorescence,Spectroscopic,Conducto-metric,and Kinetic Studies[J].Langmuir,2005,21:7161-7169.
[11]Yves Chevalier,Flavien Melis,Jean Pierre Dalbiez.Structure of zwitterionic surfactant micelles:micellar size and intermicellar interactions[J].The journal of Phyical Chemistry,1992,96(21):8614-8619.
[12]Maria Munoz,Amalia Rodriguez,Maria del Mar Graciani,et al.Conductometric,Surface Tension,and Kinetic Studies in Mixed SDS-Tween 20 and SDS-SB3-12 Micellar Solutions[J].Langmuir,2004,20:10858-10867.
[13]曹玉华.日用化学品分析[M],无锡:江南大学,2003.45.
[14]甄录旭等.HPLC法测定枸杞子中甜菜碱的含量[J].安徽医药,2007,(8):703-704.
[15]张曲.电位滴定法测定脂肪烷基二甲基甜菜碱含量[J].石油与天然气化工,1999, 28(3):223-224.
[16]龚立冬,曹玉华,侯建霞.高效液相色谱-蒸发光散射检测法测定肉苁蓉中的甜菜碱[J].色谱,2007,3:280-281.
[17]Angela Tegeler,Wolfgang Ruess,Erich Gmahl.Determination of amphoretic surfactants in cosmetic cleansing products by high-performance liquid chromatography on a cation-exchange column[J].Talanta,1999,11.
[18]Laurence Zanna,Jean-Francois Haeuw.Separation and quantitative analysis of alkyl sulfobetaine-type detergents by high-performance liquid chromatography and light-scattering detection[J].Chromatography,2007,846:368-373.
[19]Hong Soon Park,Ho Ryul Ryu,Choong Kyun Rhee.Simultaneous separation of nine surfactants of various types by HPLC with evaporative light scattering detection[J].Talanta,2006,1:29-33.
[20]Ingalls ST,Minkler PE,Hoppel CL.Derivatization of carboxylic acids by reaction with 4'bromophenacyl trifluoromethane sulfonate prior to determination by high performance liquid chromatography[J].Chromatogr A,1984,299:365-376.
[21]申烨华等.扁桃油中脂肪酸组成的GC-MS法分析[J].分析试验室,2005,9:37-39.
[22]赵先恩等.藏药波棱瓜籽油脂中脂肪酸的HPLC与GC-MS分析[J].天然产物研究与开发,2009,21:76-83.
[23]Jing Sun,etal.Determination of 30 free fatty acids in two famous tibetan medicines by HPLC with fluorescence detection and mass spectrometric identification[J].Chromatographia,2007,65:469-476.
[24]毛培坤.表面活性剂产品工业分析[M].化学工业出版社,2003:20-22.
[25]D.C.C.Cullum.Introduction to surfactant analysis[M].Published by Blackie Academic and Professional,1994,177-180.
[26]J M Plantinga,J J Donkerbroek,R J Mulder.Determination of betaine and free amine in alkyldimethyl betaine by potentiometric titrations[J].JAOCS,1993,70(1):97-99.
[27]Valdes Martinez S E.Analyst,1983,108(1 290):1114.
[28]Hans Konig,Werner Strobel.Separation identification and determination of alkyl-and alkylphenol ether carboxylates by HPLC[J].J.of Analytical Chemistry.1990,(338):728-731.
[29]Ryo Koike,Fumihiko Kitagawa,Koji Otsuka.Simultaneous determination of amphoteric surfactants in detergents by capillary electrophoresis with indirect UV detection[J].J.Chromatogr.A,2007,(1139):136-142.
[30]R.Gerhards,I.jussofie,D.Kaseborn,S.Keune,R.Schulz.Modern methods for the analysis of cocoamidopropyl betaines[J].Tenside Surf.Det.1996,33(1):8-14.
[31]笠井,矢野,木村.日本化学会志(日),1971,2390.
[32]陆光崇.用改良的磷钨酸法侧定两性表面活性剂的活性物含量[J].日用化学工业,1982(4):36-37
[33]钟雷,丁悠丹.表面活性剂及其助剂分析[M].浙江科学技术出版社,1986,139-145
[34]K Tori,T Nakagawa.Colloid Chemical Properties of Ampholytic Surfactants I.Syntheses and Some Properties of Alkyl Betaines[J].Colloid & Polymer Science,1963,187(1):44-51.
[35]朱世永,陈世京.衍生物气相色谱法[M].北京:化学工业出版社,1993:119-121.
[36]Yoshiro Ogata,Toshiyuki Sugimoto,Morio Inaishi.α-Chlorimation of Long-chain Aliphatic Acids[J].Bulletin of the Chemical Society of Japan,1979,52(1):255-256.
[37]单亦初等.可调移动重叠分离图法用于高效液相色谱多台阶梯度分离条件优化的研究[J].色谱,2006,3:122-128.