超高压脲包法提高模拟亚麻籽油中多不饱和脂肪酸分离效率
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摘要
采用超高压尿素包合法(脲包法)富集亚麻籽油中亚油酸和亚麻酸两种多不饱和脂肪酸(poly unsaturated fatty acids,PUFA),以非包合相PUFA含量及得率为考察指标。当尿素/混合脂肪酸质量比为3∶2且尿素-混合脂肪酸与95%乙醇溶液料液比为5∶14时,脲包混合液在20℃冷却30 min并采用300 MPa压力保压20 min后,亚麻籽油中PUFA质量分数可达96.05%,这与传统的冷冻脲包法(-18℃、18 h)对PUFA的分离效果(97.41%)类似,但非包合相中PUFA得率提高41.39%。采用差示扫描量热仪分析、扫描电子显微镜观察不同压力下尿素包合物(urea inclusion complexes,UIC)晶体热力学性质和晶体形貌,结果显示:当压力小于300 MPa时,增大压力可以促进UIC结晶形成六方晶系晶体,且晶体形态趋于规则,晶体分布密集。超高压脲包法能够提高亚麻籽油中PUFA的分离效率,且与压力促进包合物晶体趋于规则和稳定有关。
An ultra-high pressure-assisted urea adduction method was adopted to enrich thepoly unsaturated fatty acids(PUFA) linoleic acid and linolenic acid from linseed oil, and the content and yield of PUFA in the filtrate were investigated with respect to operating parameters. The content of PUFA in linseed oil was 96.05% when treated under the following conditions: mass ratio of urea to fatty acid mixed 3:2, ratio of urea-fatty acid mixed to 95%(V/V) ethanol 5:14, and cooling of urea inclusion mixture at 20 ℃ for 30 min followed by exposure to 300 MPa for 20 min, which was similar to that(97.41%) achieved by the traditional freezing method(-18 ℃, 18 h). Moreover, the yield of PUFA in the filtrate was increased by 41.39% when compared with that obtained by the traditional method. Subsequently, we investigated the thermodynamic properties and crystal morphology of urea inclusion complexes(UIC) under different stress conditions using a differential scanning calorimeter(DSC) and a scanning electron microscope(SEM). The results exhibited that UIC were more prone to form a hexagonal crystal structure with regular morphology and that the crystals formed were distributed more densely with increasing pressure up to 300 MPa. Accordingly, ultra-high pressure-assisted urea adduction could improve the separation efficiency of PUFA, because the crystal structure of UIC was more regular and stable under pressurized conditions.
An ultra-high pressure-assisted urea adduction method was adopted to enrich thepoly unsaturated fatty acids(PUFA) linoleic acid and linolenic acid from linseed oil, and the content and yield of PUFA in the filtrate were investigated with respect to operating parameters. The content of PUFA in linseed oil was 96.05% when treated under the following conditions: mass ratio of urea to fatty acid mixed 3:2, ratio of urea-fatty acid mixed to 95%(V/V) ethanol 5:14, and cooling of urea inclusion mixture at 20 ℃ for 30 min followed by exposure to 300 MPa for 20 min, which was similar to that(97.41%) achieved by the traditional freezing method(-18 ℃, 18 h). Moreover, the yield of PUFA in the filtrate was increased by 41.39% when compared with that obtained by the traditional method. Subsequently, we investigated the thermodynamic properties and crystal morphology of urea inclusion complexes(UIC) under different stress conditions using a differential scanning calorimeter(DSC) and a scanning electron microscope(SEM). The results exhibited that UIC were more prone to form a hexagonal crystal structure with regular morphology and that the crystals formed were distributed more densely with increasing pressure up to 300 MPa. Accordingly, ultra-high pressure-assisted urea adduction could improve the separation efficiency of PUFA, because the crystal structure of UIC was more regular and stable under pressurized conditions.
引文
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[26]BROWN M E,HOLLLNGSWORTH M D.Stress-induced domain reorientation in urea inclusion compounds[J].Nature,1995,376:323-327.DOI:10.1038/376323a0.
[27]ZULKURNAIN M,MALEKY F,BALASUBRAMANIAM V M.High pressure processing effects on lipids thermophysical properties and crystallization kinetics[J].Food Engineering Reviews,2016,8(4):393-413.DOI:10.1007/s12393-016-9144-4.
[28]袁野,潘见,孙艳辉,等.低温协同超高压脲包法分离大豆油脱臭馏出物中饱和脂肪酸工艺研究[J].安徽农业科学,2014,42(3):882-885.DOI:10.3969/j.issn.0517-6611.2014.03.087.
[29]胡小泓,张新才,周临桃,等.尿素包合物固相中回收脂肪酸的工艺研究[J].食品科学,2005,26(11):141-144.DOI:10.3321/j.issn:1002-6630.2005.11.030.
[30]郑玉梅,杨月欣,李建文.食用植物油脂中脂肪酸定量分析的气相色谱内标法研究[C]//第十六届全国卫生检验新技术学术研讨会论文集.杭州:中华预防医学会,2013:45.
[31]杨明轩,周扬,陆俊,等.气相色谱内标法测定沙棘果肉油和种子油中的主要脂肪酸[J].湖北农业科学,2017,56(9):1734-1738.DOI:10.14088/j.cnki.issn0439-8114.2017.09.033.
[32]黄松,王杰,丁婕,等.三七中十八种游离氨基酸的柱前衍生化-HPLC法测定[J].中国医药工业杂志,2011,42(1):54-56.DOI:10.3969/j.issn.1001-8255.2011.01.017.
[33]鉏晓艳,耿胜荣,李新,等.酶溶性胶原蛋白肽及其β-环糊精包合物理化性质分析[J].中国食品学报,2017,17(1):209-216.DOI:10.16429/j.1009-7848.2017.01.027.
[34]陈迪钊,朱士龙,李勇,等.青藤碱-γ-环糊精包合物的性质及谱学分析[J].食品科学,2013,34(3):115-118.
[35]吴明一.尿素包合法纯化不饱和脂肪酸的研究[D].天津:天津大学,2007:1-9.
[36]DHALL M,MADAN A K.Studies on urea co-inclusion complexes of simvastatin for improvement of pharmaceutical characteristics[J].Journal of Inclusion Phenomena and Macrocyclic Chemistry,2015,81(1):105-120.DOI:10.1007/s10847-014-0439-x.
[37]凌满.尿素包合法和银化柱层析分离脂肪酸及尿素包合结晶物的研究[D].杨凌:西北农林科技大学,2014:1-9.
[2]RUIJTER M D H,BERECKI G,VERKERK A O,et al.Acute administration of fish oil inhibits triggered activity in isolated myocytes from rabbits and patients with heart failure[J].Circulation,2008,117(4):536-544.
[3]EL-BADRY A M,MORITZ W,CONTALDO C,et al.Prevention of reperfusion injury and microcirculatory failure in macrosteatotic mouse liver by omega-3 fatty acids[J].Hepatology,2007,45(4):855-863.DOI:10.1002/hep.21625.
[4]BAZINET R P,LAYéS.Polyunsaturated fatty acids and their metabolites in brain function and disease[J].Nature Reviews Neuroscience,2014,15(2):771-785.DOI:10.1038/nrn3820.
[5]田光晶,马丛丛,陈萌,等.亚麻籽油抗动脉粥样硬化作用的研究进展[J].中国油脂,2017,42(10):87-92.
[6]WU M Y,DING H,WANG S,et al.Optimizing conditions for the purification of linoleic acid from sunflower oil by urea complex fractionation[J].Journal of the American Oil Chemists Society,2008,85(7):677-684.DOI:10.1007/s11746-008-1245-7.
[7]WANASUNDARA U N,PETERSON R.Process for separating saturated and unsaturated fatty acids:US11624064[P].2007-12-27[2017-12-16].http://www.google.com/patents/US11624064.
[8]陶川东,鲁厚芳,梁斌.尿素包合法分离麻疯树籽油脂肪酸甲酯的研究[J].中国油脂,2013,38(5):64-68.DOI:10.3969/j.issn.1003-7969.2013.05.016.
[9]林非凡,谭竹钧.尿素包合法提高亚麻油中α-亚麻酸含量的工艺条件优化[J].广东工业大学学报,2011,28(4):79-82.DOI:10.3969/j.issn.1007-7162.2011.04.018.
[10]GU H B,MA X Y,WU J B,et al.Concentration ofα-linoleic acid of perilla oil by gradient cooling urea inclusion[J].Agricultural Sciences in China,2009,8(6):685-690.DOI:10.1016/S1671-2927(08)60265-5.
[11]PATIL D,NAG A.Production of PUFA concentrates from poultry and fish processing waste[J].Journal of the American Oil Chemists Society,2011,88(4):589-593.DOI:10.1007/s11746-010-1689-4.
[12]SALIMON J,ABDULLAH B M,SALISH N.Selectively increasing of polyunsaturated(18:2)and monounsaturated(18:1)fatty acids in Jatropha curcas seed oil by crystallization using D-optimal design[J].Chemistry Central Journal,2012,6(1):1-15.DOI:10.1186/1752-153X-6-65.
[13]PONGKET U,PIYATHEERAWONG W,THAPPHASARAPHONGS,et al.Enzymatic preparation of linoleic acid from sunflower oil:an experimental design approach[J].Biotechnology&Biotechnological Equipment,2015,29(5):926-934.DOI:10.1080/13102818.2015.1057523.
[14]王华,杨琦,薛刚.尿素包合法分离月见草油中γ-亚麻酸:包合工艺参数对结晶物的影响[J].食品科学,2010,31(8):125-131.
[15]刘凤霞,薛刚,高秋华,等.γ-亚麻酸包合工艺优化研究[J].中成药,2005,27(7):761-763.
[16]HAYES D G.Effect of temperature programming on the performance of urea inclusion compound-based free fatty acid fractionation[J].Journal of the American Oil Chemists Society,2006,83(3):253-259.DOI:10.1007/s11746-006-1201-3.
[17]李新华,于济洋,李斌,等.离心对尿素包合法富集玉米油亚油酸效果的影响[J].食品工业科技,2008,5(9):110-112;115.
[18]安腾奇,成取林,余成山,等.溶剂结晶和尿素包合法提高油酸纯度的研究[J].中国油脂,2016,41(9):64-68.DOI:10.3969/j.issn.1003-7969.2016.09.014.
[19]范明明,王灿,张萍波,等.尿素包合和选择性加氢结合法制备高纯油酸[J].中国油脂,2017,42(4):53-57;63.DOI:10.3969/j.issn.1003-7969.2017.04.012.
[20]张海祥,方婷婷,潘文娟,等.响应曲面法优化尿素包合富集蚕蛹油α-亚麻酸的工艺[J].食品科学,2011,32(4):74-77.
[21]王车礼,王艳峰,程兴荣,等.梯度冷却尿素包合法分离脂肪酸甲酯[J].精细石油化工,2011,28(5):23-28.DOI:10.3969/j.issn.1003-9384.2011.05.007.
[22]HAYES D G,VAN ALSTINE J M,SETTERWALL F.Ureabased fractionation of seed oil samples containing fatty acids and acylglycerols of polyunsaturated and hydroxy fatty acids[J].Journal of the American Oil Chemists’Society,2000,77(2):207-213.DOI:10.1007/s11746-000-0033-5.
[23]HAYES D G,BENGTSSON Y C,VAN ALSTINE J M,et al.Urea complexation for the rapid,ecologically responsible fractionation of fatty acids from seed oil[J].Journal of the American Oil Chemists’Society,1998,75(10):1403-1409.DOI:10.1007/s11746-998-0190-9.
[24]ALSTINE J V.Triangular phase diagrams to predict the fractionation of free fatty acid mixtures via urea complex formation[J].Separation Science&Technology,2001,36(1):45-58.DOI:10.1081/SS-100000850.
[25]张正红,田松柏,刘泽龙,等.超声包合法分离测定重质油中链烷烃和环烷烃[J].西安石油大学学报(自然科学版),2006,21(5):68-71;94.DOI:10.3969/j.issn.1673-064X.2006.05.016.
[26]BROWN M E,HOLLLNGSWORTH M D.Stress-induced domain reorientation in urea inclusion compounds[J].Nature,1995,376:323-327.DOI:10.1038/376323a0.
[27]ZULKURNAIN M,MALEKY F,BALASUBRAMANIAM V M.High pressure processing effects on lipids thermophysical properties and crystallization kinetics[J].Food Engineering Reviews,2016,8(4):393-413.DOI:10.1007/s12393-016-9144-4.
[28]袁野,潘见,孙艳辉,等.低温协同超高压脲包法分离大豆油脱臭馏出物中饱和脂肪酸工艺研究[J].安徽农业科学,2014,42(3):882-885.DOI:10.3969/j.issn.0517-6611.2014.03.087.
[29]胡小泓,张新才,周临桃,等.尿素包合物固相中回收脂肪酸的工艺研究[J].食品科学,2005,26(11):141-144.DOI:10.3321/j.issn:1002-6630.2005.11.030.
[30]郑玉梅,杨月欣,李建文.食用植物油脂中脂肪酸定量分析的气相色谱内标法研究[C]//第十六届全国卫生检验新技术学术研讨会论文集.杭州:中华预防医学会,2013:45.
[31]杨明轩,周扬,陆俊,等.气相色谱内标法测定沙棘果肉油和种子油中的主要脂肪酸[J].湖北农业科学,2017,56(9):1734-1738.DOI:10.14088/j.cnki.issn0439-8114.2017.09.033.
[32]黄松,王杰,丁婕,等.三七中十八种游离氨基酸的柱前衍生化-HPLC法测定[J].中国医药工业杂志,2011,42(1):54-56.DOI:10.3969/j.issn.1001-8255.2011.01.017.
[33]鉏晓艳,耿胜荣,李新,等.酶溶性胶原蛋白肽及其β-环糊精包合物理化性质分析[J].中国食品学报,2017,17(1):209-216.DOI:10.16429/j.1009-7848.2017.01.027.
[34]陈迪钊,朱士龙,李勇,等.青藤碱-γ-环糊精包合物的性质及谱学分析[J].食品科学,2013,34(3):115-118.
[35]吴明一.尿素包合法纯化不饱和脂肪酸的研究[D].天津:天津大学,2007:1-9.
[36]DHALL M,MADAN A K.Studies on urea co-inclusion complexes of simvastatin for improvement of pharmaceutical characteristics[J].Journal of Inclusion Phenomena and Macrocyclic Chemistry,2015,81(1):105-120.DOI:10.1007/s10847-014-0439-x.
[37]凌满.尿素包合法和银化柱层析分离脂肪酸及尿素包合结晶物的研究[D].杨凌:西北农林科技大学,2014:1-9.