紫胶桐酸对映体的HPLC-ELSD法分离及其手性拆分热力学
|
摘要
建立紫胶桐酸对映体的色谱学拆分方法并探索其手性拆分的热力学规律。采用高效液相色谱-蒸发光散射检测器法,通过研究流动相组成、流动相比例、柱温等因素对拆分效果的影响,得到最佳分离条件:DAICEL CHIRAL PAK IF色谱柱(25 cm×0.46 cm i.d.,5μm),流速0.5 mL/min,流动相组成为0.1%甲酸-乙腈(40∶60,V/V),柱温30℃;蒸发光散射检测器条件:蒸发室温度70℃,漂移管温度60℃,载气流速1.6 L/min。拆分及表征结果表明,强碱皂化法提取所得紫胶桐酸为苏式结构的混旋体,其对映体相对含量分别为65.5%和34.5%,ee值为31%。拆分热力学研究结果显示,lnα与1/T以及lnk与1/T均呈良好的线性关系,R~2分别为0.997 2、0.995 1和0.998 0;2个对映体焓变与熵变之差ΔΔH为-3 453.0 J/mol和ΔΔS为-7.677 6 J/mol,均为负值,紫胶桐酸的对映体拆分过程受热焓控制。
The purposes of this study were to establish an enantiomeric separation method for aleuritic acid by high performance liquid chromatography with evaporative light-scattering detection(HPLC-ELSD) and to explore the thermodynamic pattern of the chiral resolution process. The optimum chromatographic conditions were determined by investigated the effect of mobile phase composition and column temperature. The best separation was achieved on a DAICEL CHIRAL PAK IF column (25 cm × 0.46 cm i.d., 5 μm) held at 30 ℃ using a mobile phase composed of a mixture of 0.1% formic acid solution and acetonitrile (40:60, V/V) at a flow rate of 0.5 mL/min. The optimum parameters of ELSD were determined as 70 ℃, 60 ℃ and 1.6 L/min for evaporator temperature, drift tube temperature and carrier gas(high purity nitrogen) flow rate, respectively. The results showed that aleuritic acid obtained by strong alkali saponification was a mixture of two threo-enantiomers (65.5:34.5) with an enantiomeric excess(ee) value of 31%. Thermodynamic analysis indicated that there was a good linear relationship between lnα, lnk1 and lnk2 and 1/T with correlation coefficients (R~2) of 0.997 2, 0.995 1 and 0.998 0, respectively. The difference of enthalpy change (ΔΔH) between two enantiomers was-3 453.0 J/mol and the difference of entropy change (ΔΔS) was-7.677 6 J/mol, suggesting that the resolution process was controlled by entropy change.
The purposes of this study were to establish an enantiomeric separation method for aleuritic acid by high performance liquid chromatography with evaporative light-scattering detection(HPLC-ELSD) and to explore the thermodynamic pattern of the chiral resolution process. The optimum chromatographic conditions were determined by investigated the effect of mobile phase composition and column temperature. The best separation was achieved on a DAICEL CHIRAL PAK IF column (25 cm × 0.46 cm i.d., 5 μm) held at 30 ℃ using a mobile phase composed of a mixture of 0.1% formic acid solution and acetonitrile (40:60, V/V) at a flow rate of 0.5 mL/min. The optimum parameters of ELSD were determined as 70 ℃, 60 ℃ and 1.6 L/min for evaporator temperature, drift tube temperature and carrier gas(high purity nitrogen) flow rate, respectively. The results showed that aleuritic acid obtained by strong alkali saponification was a mixture of two threo-enantiomers (65.5:34.5) with an enantiomeric excess(ee) value of 31%. Thermodynamic analysis indicated that there was a good linear relationship between lnα, lnk1 and lnk2 and 1/T with correlation coefficients (R~2) of 0.997 2, 0.995 1 and 0.998 0, respectively. The difference of enthalpy change (ΔΔH) between two enantiomers was-3 453.0 J/mol and the difference of entropy change (ΔΔS) was-7.677 6 J/mol, suggesting that the resolution process was controlled by entropy change.
引文
[1]ANSARI M F,SARKHEL G.Improving coating properties of shellacepoxidised-novolac blends with melamine formaldehyde resin[J].Pigment&Resin Technology,2017,46(2):92-99.DOI:10.1108/PRT-02-2016-0022.
[2]KUMAR V,GUPTA S,MISHRA N K,et al.Laser-induced fabrication of gold nanoparticles on shellac-driven peptide nanostructures[J].Materials Research Express,2017,4(3):035036.DOI:10.1088/2053-1591/aa63e0.
[3]陈晓鸣,陈又清,张弘,等.紫胶虫培育与紫胶加工[M].北京:中国林业出版社,2008.
[4]李坤,郑华,张雯雯,等.响应面试验优化紫胶全无氯漂白工艺及其产物性能[J].食品科学,2016,37(22):41-51.DOI:10.7506/spkx1002-6630-201622007.
[5]LIMMATVAPORAT S,LIMMATVAPORAT C,PUTTIPIPATKHACHORN S,et al.Modulation of drug release kinetics of shellac-based matrix tables by in-situ polymerization throughannealing process[J].European Journal of Pharmaceutics and Biopharmaceutics,2008,69(3):1004-1013.DOI:10.1016/j.ejpb.2008.01.027.
[6]LI K,ZHENG H,ZHANG H,et al.A novel approach to the fabrication of bleachedshellac by a totally chlorine-free (TCF) bleachingmethod[J].RSC Advances,2016,6(60):55618-55625.DOI:10.1039/C6RA09132F.
[7]SINGH A N,UPADHYE A B,MHASKAR V V,et al.Chemistry of lac resin-VII:Pure lac resin-3:structure[J].Tetrahedron,1974,30(20):3689-3693.DOI:10.1016/S0040-4020(01)90652-0.
[8]KHAIRUDDI N,PRAMONO E,UTOMO S B,et al.FTIR studies on the effect of concentration of polyethylene glycol on polimerization of Shellac[J].Journal of Physics Conference Series,2016,776(1):012053.DOI:10.1088/1742-6596/776/1/012053.
[9]POOVARODOM N,PERMYANWATTANA W.Development of starch/shellac-based composites for food contact applications[J].Journal of Thermoplastic Composite Materials,2013,28(5):597-609.DOI:10.1177/0892705713486138
[10]SCHATTEMAN D,DE VOS W H,et al.Shellac as a natural material to structure a liquid oil-based thermo reversible soft matter system[J].RSC Advances,2013,3(16):5324-5327.DOI:10.1039/C3RA40934A.
[11]PATELA R,RAJARETHINEM P S,GREDOWSKA A,et al.Edible applications of shellac oleogels:spreads,chocolate paste and cakes[J].Food&Function,2014,5(4):645-652.DOI:10.1039/C4FO00034J.
[12]AL-GOUSOUSA J,PENNINGB M,LANGGUTHA P.Molecularinsights into shellac film coats from different aqueous shellac saltsolutions and effect on disintegration of enteric-coated soft gelatincapsules[J].International Journal of Pharmaceutics,2015,484(1/2):283-291.DOI:10.1016/j.ijpharm.2014.12.060.
[13]PHAECHAMUD T,MAHADLEKJ,CHUENBARN T.In situ forminggel comprising bleached shellac loaded with antimicrobialdrugs for periodontitis treatment[J].Materials and Design,2016,89:294-303.DOI:10.1016/j.matdes.2015.09.138.
[14]LI K,PAN Z D,GUAN C,et al.A tough self-assembled natural oligomer hydrogelbased on nano-size vesicle cohesion[J].RSCAdvances,2016,6(40):33547-33553.DOI:10.1039/C6RA03720H.
[15]WETHTHIMUNI M L,CAPSONI D,MALAGODI M,et al.Shellac/nanoparticles dispersions as protective materials for wood[J].Applied Physics A:Materials Science&Processing,2016,122:1058.DOI:10.1007/s00339-016-0577-7.
[16]刘世平,张弘,周梅村,等.微波皂化法制备紫胶桐酸[J].食品科学,2011,32(14):79-84.
[17]廖亚龙,柴希娟.超声皂化法提取紫胶桐酸[J].化学工程,2007,35(2):72-74.DOI:10.3969/j.issn.1005-9954.2007.02.018.
[18]NAGAPPAYYA S K,GAIKAR V G.Extraction of aleuritic acid fromseedlac and purification by reactive adsorption on functionalized polymers[J].Industrial&Engineering Chemistry Research,2010,49(14):6547-6553.DOI:10.1021/ie902061e.
[19]哈成勇,邹耀洪.国产紫胶桐酸的分离与鉴定[J].林产化工通讯,1991(3):18-21.
[20]刘世平,张弘,周梅村,等.高效液相色谱-示差折光法检测紫胶桐酸[J].食品科学,2011,32(22):260-263.
[21]HEREDIA-GUERRERO J A,SAN-MIGUEL M A,SANSOM M S,et al.Aleuritic (9,10,16-trihydroxypalmitic) acid self-assembly on mica[J].Physical Chemistry Chemical Physics Pccp,2010,12(35):10423-10428.DOI:10.1039/c0cp00163e.
[22]SUBRAMANIAN G B V,SHARMA R.Synthesis of(Z)-7-tetradecenylacetate&sec.butyl(Z)-7-tetradecenoate from aleuritic acid[J].Synthetic Communications,1989,19(7/8):1197-1202.DOI:10.1080/00397918908054523.
[23]高山,刘兰香,张弘,等.9,10-二羟基环十六内酯的合成[J].化学世界,2016,57(4):213-216.
[24]廖亚龙,刘中华.天然紫胶桐酸提取及表征[J].南京林业大学学报(自然科学版),2007,31(2):88-92.
[25]BENTEZ J J,HEREDIA-GUERRERO J A,GUZMAN-PUYOL S,et al.polyester films obtained by noncatalyzed melt-condensation polymerization of aleuritic(9,10,16-trihydroxyhexadecanoic)acid in air[J].Journal of Applied Polymer Science,2015,132(4):41328.DOI:10.1002/APP.41328.
[26]BENTEZ J J,HEREDIA-GUERRERO J A,GUZMAN-PUYOL S,et al.Long-chain polyhydroxyesters from natural occurringaleuritic acid as potential material for food packaging[J].Soft Materials,2015,13(1):5-11.DOI:10.1080/1539445X.2014.993476.
[27]BENTEZ J J,HEREDIA-GUERRERO J A,VARGAS-PARODY MI D,et al.Biodegradable polyester films from renewable aleuritic acid:surface modifications induced by melt-polycondensation in air[J].Journal of Physics D Applied Physics,2016,49(17):175601.DOI:10.1088/0022-3727/49/17/175601.
[28]AMES D E,GOODBURN T G,JEVANS A W,et al.Synthesis and some reactions of (±)-aleuritic acid[J].Journal of the Chemical Society C:Organic,1968:268-270.DOI:10.1039/J39680000268.
[29]WENG W,ZENG Q L,YAO B X,et al.Influence of mobile phase compositionon the apparent thermodynamic characteristics in liquid chromatographic enantioseparation on a tartardiamide-based stationary phase[J].Chromatographia,2005,61(11/12):561-566.DOI:10.1365/s10337-005-0560-50009-5893/05/06.
[30]óBRIEN T,CROCKER L,THOMPSON R,et al.Mechanistic aspectsof chiral discrimination on modified cellulose[J].Analytical Chemistry,1997,69:1999-2007.DOI:10.1021/ac961241l.
[31]QI P P,WANG X Y,ZHANG H,et al.Rapid Enantioseparation and determination of isocarbophos enantiomers in orange pulp,peel,and kumquat by chiral HPLC-MS/MS[J].Food Analytical Methods,2015,8(2):531-538.DOI:10.1007/s12161-014-9922-7.
[32]周英,张世浩,刘维屏,等.敌草胺对映体的高效液相色谱分离及手性拆分热力学研究[J].农药学学报,2006,8(3):260-264.DOI:10.3321/j.issn:1008-7303.2006.03.013.
[2]KUMAR V,GUPTA S,MISHRA N K,et al.Laser-induced fabrication of gold nanoparticles on shellac-driven peptide nanostructures[J].Materials Research Express,2017,4(3):035036.DOI:10.1088/2053-1591/aa63e0.
[3]陈晓鸣,陈又清,张弘,等.紫胶虫培育与紫胶加工[M].北京:中国林业出版社,2008.
[4]李坤,郑华,张雯雯,等.响应面试验优化紫胶全无氯漂白工艺及其产物性能[J].食品科学,2016,37(22):41-51.DOI:10.7506/spkx1002-6630-201622007.
[5]LIMMATVAPORAT S,LIMMATVAPORAT C,PUTTIPIPATKHACHORN S,et al.Modulation of drug release kinetics of shellac-based matrix tables by in-situ polymerization throughannealing process[J].European Journal of Pharmaceutics and Biopharmaceutics,2008,69(3):1004-1013.DOI:10.1016/j.ejpb.2008.01.027.
[6]LI K,ZHENG H,ZHANG H,et al.A novel approach to the fabrication of bleachedshellac by a totally chlorine-free (TCF) bleachingmethod[J].RSC Advances,2016,6(60):55618-55625.DOI:10.1039/C6RA09132F.
[7]SINGH A N,UPADHYE A B,MHASKAR V V,et al.Chemistry of lac resin-VII:Pure lac resin-3:structure[J].Tetrahedron,1974,30(20):3689-3693.DOI:10.1016/S0040-4020(01)90652-0.
[8]KHAIRUDDI N,PRAMONO E,UTOMO S B,et al.FTIR studies on the effect of concentration of polyethylene glycol on polimerization of Shellac[J].Journal of Physics Conference Series,2016,776(1):012053.DOI:10.1088/1742-6596/776/1/012053.
[9]POOVARODOM N,PERMYANWATTANA W.Development of starch/shellac-based composites for food contact applications[J].Journal of Thermoplastic Composite Materials,2013,28(5):597-609.DOI:10.1177/0892705713486138
[10]SCHATTEMAN D,DE VOS W H,et al.Shellac as a natural material to structure a liquid oil-based thermo reversible soft matter system[J].RSC Advances,2013,3(16):5324-5327.DOI:10.1039/C3RA40934A.
[11]PATELA R,RAJARETHINEM P S,GREDOWSKA A,et al.Edible applications of shellac oleogels:spreads,chocolate paste and cakes[J].Food&Function,2014,5(4):645-652.DOI:10.1039/C4FO00034J.
[12]AL-GOUSOUSA J,PENNINGB M,LANGGUTHA P.Molecularinsights into shellac film coats from different aqueous shellac saltsolutions and effect on disintegration of enteric-coated soft gelatincapsules[J].International Journal of Pharmaceutics,2015,484(1/2):283-291.DOI:10.1016/j.ijpharm.2014.12.060.
[13]PHAECHAMUD T,MAHADLEKJ,CHUENBARN T.In situ forminggel comprising bleached shellac loaded with antimicrobialdrugs for periodontitis treatment[J].Materials and Design,2016,89:294-303.DOI:10.1016/j.matdes.2015.09.138.
[14]LI K,PAN Z D,GUAN C,et al.A tough self-assembled natural oligomer hydrogelbased on nano-size vesicle cohesion[J].RSCAdvances,2016,6(40):33547-33553.DOI:10.1039/C6RA03720H.
[15]WETHTHIMUNI M L,CAPSONI D,MALAGODI M,et al.Shellac/nanoparticles dispersions as protective materials for wood[J].Applied Physics A:Materials Science&Processing,2016,122:1058.DOI:10.1007/s00339-016-0577-7.
[16]刘世平,张弘,周梅村,等.微波皂化法制备紫胶桐酸[J].食品科学,2011,32(14):79-84.
[17]廖亚龙,柴希娟.超声皂化法提取紫胶桐酸[J].化学工程,2007,35(2):72-74.DOI:10.3969/j.issn.1005-9954.2007.02.018.
[18]NAGAPPAYYA S K,GAIKAR V G.Extraction of aleuritic acid fromseedlac and purification by reactive adsorption on functionalized polymers[J].Industrial&Engineering Chemistry Research,2010,49(14):6547-6553.DOI:10.1021/ie902061e.
[19]哈成勇,邹耀洪.国产紫胶桐酸的分离与鉴定[J].林产化工通讯,1991(3):18-21.
[20]刘世平,张弘,周梅村,等.高效液相色谱-示差折光法检测紫胶桐酸[J].食品科学,2011,32(22):260-263.
[21]HEREDIA-GUERRERO J A,SAN-MIGUEL M A,SANSOM M S,et al.Aleuritic (9,10,16-trihydroxypalmitic) acid self-assembly on mica[J].Physical Chemistry Chemical Physics Pccp,2010,12(35):10423-10428.DOI:10.1039/c0cp00163e.
[22]SUBRAMANIAN G B V,SHARMA R.Synthesis of(Z)-7-tetradecenylacetate&sec.butyl(Z)-7-tetradecenoate from aleuritic acid[J].Synthetic Communications,1989,19(7/8):1197-1202.DOI:10.1080/00397918908054523.
[23]高山,刘兰香,张弘,等.9,10-二羟基环十六内酯的合成[J].化学世界,2016,57(4):213-216.
[24]廖亚龙,刘中华.天然紫胶桐酸提取及表征[J].南京林业大学学报(自然科学版),2007,31(2):88-92.
[25]BENTEZ J J,HEREDIA-GUERRERO J A,GUZMAN-PUYOL S,et al.polyester films obtained by noncatalyzed melt-condensation polymerization of aleuritic(9,10,16-trihydroxyhexadecanoic)acid in air[J].Journal of Applied Polymer Science,2015,132(4):41328.DOI:10.1002/APP.41328.
[26]BENTEZ J J,HEREDIA-GUERRERO J A,GUZMAN-PUYOL S,et al.Long-chain polyhydroxyesters from natural occurringaleuritic acid as potential material for food packaging[J].Soft Materials,2015,13(1):5-11.DOI:10.1080/1539445X.2014.993476.
[27]BENTEZ J J,HEREDIA-GUERRERO J A,VARGAS-PARODY MI D,et al.Biodegradable polyester films from renewable aleuritic acid:surface modifications induced by melt-polycondensation in air[J].Journal of Physics D Applied Physics,2016,49(17):175601.DOI:10.1088/0022-3727/49/17/175601.
[28]AMES D E,GOODBURN T G,JEVANS A W,et al.Synthesis and some reactions of (±)-aleuritic acid[J].Journal of the Chemical Society C:Organic,1968:268-270.DOI:10.1039/J39680000268.
[29]WENG W,ZENG Q L,YAO B X,et al.Influence of mobile phase compositionon the apparent thermodynamic characteristics in liquid chromatographic enantioseparation on a tartardiamide-based stationary phase[J].Chromatographia,2005,61(11/12):561-566.DOI:10.1365/s10337-005-0560-50009-5893/05/06.
[30]óBRIEN T,CROCKER L,THOMPSON R,et al.Mechanistic aspectsof chiral discrimination on modified cellulose[J].Analytical Chemistry,1997,69:1999-2007.DOI:10.1021/ac961241l.
[31]QI P P,WANG X Y,ZHANG H,et al.Rapid Enantioseparation and determination of isocarbophos enantiomers in orange pulp,peel,and kumquat by chiral HPLC-MS/MS[J].Food Analytical Methods,2015,8(2):531-538.DOI:10.1007/s12161-014-9922-7.
[32]周英,张世浩,刘维屏,等.敌草胺对映体的高效液相色谱分离及手性拆分热力学研究[J].农药学学报,2006,8(3):260-264.DOI:10.3321/j.issn:1008-7303.2006.03.013.