乳脂肪干法分提组分化学组成及热力学特性
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摘要
在10～40℃范围内,通过逐级升温方式,将无水乳脂肪干法分提成低熔点L20、中熔点L30和L40、高熔点S40四组分,并通过气相色谱-质谱联用法对各组分中脂肪酸(fatty acid,FA)、甘油三酯(triglyceride,TAG)种类及含量进行测定。结果表明:随着分提温度升高,L20～S40,饱和脂肪酸(saturated fatty acid,SFA)含量呈递增而不饱和脂肪酸(unsaturated fatty acid,USFA)呈递减趋势,S40富含长链SFA,短链SFA及USFA较少,而L20与之正好相反,L30和L40FA组成则介于L20～S40之间;热图分析显示:高熔点TAG较多存在于S40中,低熔点TAG主要存在于L20中,L30和L40则富含中熔点TAG;通过差示扫描量热仪分析,发现乳脂肪及各分提组分结晶-熔化曲线存在显著差异,结晶温度和熔化温度由高到低依次为S40>L40>L30>L20(P<0.05),结晶/熔化温度高,液态油与固态脂发生相转变时所需要的相变潜热就大,这为搅打稀奶油原料选择,搅打温度、时间和贮存温度等工艺配方参数设计提供理论依据;通过X射线晶体衍射分析,在长间距衍射中,高熔点组分S40、L40显示结晶状态均为以β’晶型为主的α、β’、β多晶型混晶,而L20和L30中无晶型衍射峰,说明低熔点组分为无定型状态的油脂;在短间距衍射中显示乳脂肪、S40、L40晶体以二倍链长(2L)(40.76、13.49?)和三倍链长(3L)(29.44?)方式堆积,而L20和L30仅以2L方式堆积。综上所述,脂肪饱和程度高则晶体稳定性强,结晶-熔化所产生的热焓大,适合制备硬脂产品,反之,则适合制备软脂或对硬度要求不高的产品。通过对不同熔点乳脂肪理化性质的系统研究,为实际生产中乳脂肪类型的不同需求选择提供参考数据。
In this study, anhydrous milk fat was fractionated by stepwise melting into high-melting fraction(S40),middle-melting fraction(L40 and L30) and low-melting fraction(L20). Fatty acid(FA) and triacylglycerol(TAG)composition of each fraction were analyzed by gas chromatography-mass spectrometry(GC-MS). The crystal form and the thermodynamic profile were evaluated by X-ray diffraction(XRD) and differential scanning calorimetry(DSC),respectively. From the results, S40 was found to be rich in saturated long-chain fatty acids but lack short-chain fatty acids and unsaturated fatty acids, while the opposite was true for L20. L40 and L30 were between L20 and S40. The heat map showed that high-melting triacylglycerols(TAGs) were concentrated in S40, whereas low-melting TAGs predominated in L20. L40 and L30 were rich in middle-melting TAGs. There were striking differences in the thermodynamic profiles of the milk fat fractions, whose crystallization temperature(TC) and melting temperature(TM) followed the decreasing order of S40 > L40 > L30 > L20(P < 0.05).When the the TC or TM was higher, the phase transition enthalpy was higher. Moreover, the β' crystal was dominant in milk fat(MF), L40 and S40, but not in L20 or L30. Crystallization of MF, S40 and L40 showed the formation of 2 L(40.76 and 13.49 ?) and 3 L(29.44 ?) lamellar structures, whereas L30 and L20 showed the formation of only 2 L. In summary,higher degree of fat saturation leads to stronger crystal stability and larger enthalpy during the crystallization-melting process, which is suitable for the preparation of hard dairy products. In contrast, lower degree of fat saturation is suitable for preparing soft dairy products. This research provides a theoretical basis for the different requirements of milk fat production.
In this study, anhydrous milk fat was fractionated by stepwise melting into high-melting fraction(S40),middle-melting fraction(L40 and L30) and low-melting fraction(L20). Fatty acid(FA) and triacylglycerol(TAG)composition of each fraction were analyzed by gas chromatography-mass spectrometry(GC-MS). The crystal form and the thermodynamic profile were evaluated by X-ray diffraction(XRD) and differential scanning calorimetry(DSC),respectively. From the results, S40 was found to be rich in saturated long-chain fatty acids but lack short-chain fatty acids and unsaturated fatty acids, while the opposite was true for L20. L40 and L30 were between L20 and S40. The heat map showed that high-melting triacylglycerols(TAGs) were concentrated in S40, whereas low-melting TAGs predominated in L20. L40 and L30 were rich in middle-melting TAGs. There were striking differences in the thermodynamic profiles of the milk fat fractions, whose crystallization temperature(TC) and melting temperature(TM) followed the decreasing order of S40 > L40 > L30 > L20(P < 0.05).When the the TC or TM was higher, the phase transition enthalpy was higher. Moreover, the β' crystal was dominant in milk fat(MF), L40 and S40, but not in L20 or L30. Crystallization of MF, S40 and L40 showed the formation of 2 L(40.76 and 13.49 ?) and 3 L(29.44 ?) lamellar structures, whereas L30 and L20 showed the formation of only 2 L. In summary,higher degree of fat saturation leads to stronger crystal stability and larger enthalpy during the crystallization-melting process, which is suitable for the preparation of hard dairy products. In contrast, lower degree of fat saturation is suitable for preparing soft dairy products. This research provides a theoretical basis for the different requirements of milk fat production.
引文
[1]罗洁,王紫薇,宋君红,等.不同品种牛乳脂质的共聚焦拉曼光谱指纹图谱[J].光谱学与光谱分析,2016,36(1):125-129.DOI:10.3964/j.issn.1000-0593(2016)01-0125-05.
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[5]MARANGONI A G,LENCKI R W.Ternary phase behavior of milk fat fractions[J].Journal of Agriculture and Food Chemistry,1998,46(10):3879-3884.DOI:10.1021/jf9801668.
[6]HARTEL R W.Applications of milk-fat fractions in confectionery products[J].Journal of the American Oil Chemists’Society 1996,73(8):945-953.DOI:10.1007/BF02523401.
[7]EL-RAHMAN A M A,MADKOR S A,IBRAHIM F S,et al.Physical characteristics of frozen desserts made with cream,anhydrous milk fat,or milk fat fractions[J].Journal of Dairy Science,1996,80(9):1926-1935.DOI:10.3168/jds.S0022-0302(97)76133-2.
[8]MARTINI M,ALTOMONTE I,SALARI F.The lipid component of Massese ewes’colostrum:morphometric characteristics of milk fat globules and fatty acid profile[J].International Dairy Journal,2012,24(2):93-96.DOI:10.1016/j.idairyj.2011.07.006.
[9]TZOMPA-SOSA D A,VAN VALENBERG H J,VAN AKEN G A,et al.Milk fat triacylglycerols and their relations with milk fatty acid composition,DGAT1 K232A polymorphism,and milk production traits[J].Journal of Dairy Science,2016,99(5):3624-3631.DOI:10.3168/jds.2015-10592.
[10]TZOMPA-SOSA D A,VAN AKEN G A,VAN HOOIJDONK A C,et al.Influence of C16:0 and long-chain saturated fatty acids on normal variation of bovine milk fat triacylglycerol structure[J].Journal of Dairy Science,2014,97(7):4542-4551.DOI:10.3168/jds.2014-7937.
[11]GRAIL D S,HARTEL R W.Kinetics of butterfat crystallization[J].Journal of the American Oil Chemists’Society,1992,69(8):741-747.DOI:10.1007/BF02635909.
[12]SILVA R C,SOARES F A S D M,MARUYAMA J M,et al.Effect of diacylglycerol addition on crystallization properties of pure triacylglycerols[J].Food Research International,2014,55:436-444.DOI:10.1016/j.foodres.2013.11.037.
[13]HIMAWAN C,STAROV V M,STAPLEY A G.Thermodynamic and kinetic aspects of fat crystallization[J].Advances in Colloid and Interface Science,2006,122(1/2/3):3-33.DOI:10.1016/j.cis.2006.06.016.
[14]PATEL A R,DEWETTINCK K.Current update on the influence of minor lipid components,shear and presence of interfaces on fat crystallization[J].Current Opinion in Food Science,2015,3:65-70.DOI:10.1016/j.cofs.2015.05.010.
[15]SMIDDY M A,HUPPERTZ T,VAN RUTH S M.Triacylglycerol and melting profiles of milk fat from several species[J].International Dairy Journal,2012,24(2):64-69.DOI:10.1016/j.idairyj.2011.07.001.
[16]TZOMPA-SOSA D A.Milk fat triacylglycerols:their variability,relations with fatty acids,DGAT1,βpolymorphs and melting fractions[D].Wageningen:Wageningen University,2016:67-71.
[17]RAMADAN M F,AMER M M A,AWAD E S.Coriander(Coriandrum sativum L.)seed oil improves plasma lipid profile in rats fed a diet containing cholesterol[J].European Food Research&Technology,2008,227(4):1173-1182.
[18]TRAN T,ROUSSEAU D.Influence of shear on fat crystallization[J].Food Research International,2016,81:157-162.DOI:10.1016/j.foodres.2015.12.022.
[19]MéNDEZ-VELASCO C,GOFF H D.Fat structure in ice cream:a study on the types of fat interactions[J].Food Hydrocolloids,2012,29(1):152-159.DOI:10.1016/j.foodhyd.2012.02.002.
[20]TENGKU-ROZAINA T M,BIRCH E J.Effects of fractionation on melting and crystallisation profiles of hoki oil measured by DSC[J].Journal of Thermal Analysis and Calorimetry,2014,120(1):395-402.DOI:10.1007/s10973-014-3995-9.
[21]LOPEZ C,LESIEUR P,BOURGAUX C,et al.Thermal and structural behavior of milk fat[J].Journal of Colloid and Interface Science,2001,240(1):150-161.DOI:10.1006/jcis.2001.7664.
[22]MáRQUEZ A L,PéREZ M P,WAGNER J R.Solid fat content estimation by differential scanning calorimetry:prior treatment and proposed correction[J].Journal of the American Oil Chemists’Society,2012,90(4):467-473.DOI:10.1007/s11746-012-2190-z.
[23]KAYLEGIAN K E,LINDSAY R C.Performance of selected milk fat fractions in cold-spreadable butter[J].Journal of Dairy Science,1992,75(12):3307-3317.DOI:10.3168/jds.S0022-0302(92)78106-5.
[24]FATOUH A E,SINGH R K,KOEHLER P E,et al.Chemical and thermal characteristics of buffalo butter oil fractions obtained by multistep dry fractionation[J].LWT-Food Science and Technology,2003,36(5):483-496.DOI:10.1016/S0023-6438(03)00044-6.
[25]WANG F,LIU Y,SHAN L,et al.Blooming in cocoa butter substitutes based compound chocolate:investigations on composition,morphology and melting behavior[J].Journal of the American Oil Chemists’Society,2010,87(10):1137-1143.DOI:10.1007/s11746-010-1604-z.
[26]VAN AKEN G A,VISSER K A.Firmness and crystallization of milk fat in relation to processing conditions[J].Journal of Dairy Science,2000,83(9):1919-1932.DOI:10.3168/jds.S0022-0302(00)75067-3.
[27]GROTENHUIS E T,AKEN G A V,MALSSEN K F V,et al.Polymorphism of milk fat studied by differential scanning calorimetry and real-time X-ray powder diffraction[J].Journal of the American Oil Chemists’Society,1999,76(9):1031-1039.DOI:10.1007/s11746-999-0201-5.
[28]SATO K.Crystallization behaviour of fats and lipids:a review[J].Chemical Engineering Science,2001,56(7):2255-2265.DOI:10.1016/S0009-2509(00)00458-9.
[29]SABARIAH S,ALI A R M,CHONG C L.Chemical and physical characteristics of cocoa butter substitutes,milk fat and Malaysian cocoa butter blends[J].Journal of the American Oil Chemists’Society,1998,75(8):905-910.DOI:10.1007/s11746-998-0265-7.
[30]HERRERA M L,DE L G M,HARTEL R W.A kinetic analysis of crystallization of a milk fat model system[J].Food Research International,1999,32(4):189-198.DOI:10.1016/S0963-9969(99)00083-6.
[31]TIETZA R A,HARTELB R W.Effects of minor lipids on crystallization of milk fat-cocoa butter blends and bloom formation in chocolate[J].Journal of the American Oil Chemists’Society,2000,77(7):763-771.DOI:10.1007/s11746-000-0122-5.
[32]王风艳.月桂酸类代可可脂巧克力起霜机理及品质改善[D].无锡:江南大学,2012:27-30.
[33]DIMICK P S,REDDY S Y,ZIEGLER G R.Chemical and thermal characteristics of milk-fat fractions isolated by a melt crystallization[J].Journal of the American Oil Chemists’Society,1996,73(12):1647-1652.DOI:10.1007/BF02517966.
[2]高希西.乳脂肪甘油三酯分析及黄油分馏物组成与物化特性研究[D].沈阳:沈阳农业大学,2016:5-7.
[3]CAMPOS R J,LITWINENKO J W,MARANGONI A G.Fractionation of milk fat by short-path distillation[J].Journal of Dairy Science.,2003,86(3):735-745.DOI:10.3168/jds.S0022-0302(03)73654-6.
[4]LOPEZ C,BOURGAUX C,LESIEUR P,et al.Milk fat and primary fractions obtained by dry fractionation 1.Chemical composition and crystallisation properties[J].Chemistry and Physics of Lipids,2006,144(1):17-33.DOI:10.1016/j.chemphyslip.2006.06.002.
[5]MARANGONI A G,LENCKI R W.Ternary phase behavior of milk fat fractions[J].Journal of Agriculture and Food Chemistry,1998,46(10):3879-3884.DOI:10.1021/jf9801668.
[6]HARTEL R W.Applications of milk-fat fractions in confectionery products[J].Journal of the American Oil Chemists’Society 1996,73(8):945-953.DOI:10.1007/BF02523401.
[7]EL-RAHMAN A M A,MADKOR S A,IBRAHIM F S,et al.Physical characteristics of frozen desserts made with cream,anhydrous milk fat,or milk fat fractions[J].Journal of Dairy Science,1996,80(9):1926-1935.DOI:10.3168/jds.S0022-0302(97)76133-2.
[8]MARTINI M,ALTOMONTE I,SALARI F.The lipid component of Massese ewes’colostrum:morphometric characteristics of milk fat globules and fatty acid profile[J].International Dairy Journal,2012,24(2):93-96.DOI:10.1016/j.idairyj.2011.07.006.
[9]TZOMPA-SOSA D A,VAN VALENBERG H J,VAN AKEN G A,et al.Milk fat triacylglycerols and their relations with milk fatty acid composition,DGAT1 K232A polymorphism,and milk production traits[J].Journal of Dairy Science,2016,99(5):3624-3631.DOI:10.3168/jds.2015-10592.
[10]TZOMPA-SOSA D A,VAN AKEN G A,VAN HOOIJDONK A C,et al.Influence of C16:0 and long-chain saturated fatty acids on normal variation of bovine milk fat triacylglycerol structure[J].Journal of Dairy Science,2014,97(7):4542-4551.DOI:10.3168/jds.2014-7937.
[11]GRAIL D S,HARTEL R W.Kinetics of butterfat crystallization[J].Journal of the American Oil Chemists’Society,1992,69(8):741-747.DOI:10.1007/BF02635909.
[12]SILVA R C,SOARES F A S D M,MARUYAMA J M,et al.Effect of diacylglycerol addition on crystallization properties of pure triacylglycerols[J].Food Research International,2014,55:436-444.DOI:10.1016/j.foodres.2013.11.037.
[13]HIMAWAN C,STAROV V M,STAPLEY A G.Thermodynamic and kinetic aspects of fat crystallization[J].Advances in Colloid and Interface Science,2006,122(1/2/3):3-33.DOI:10.1016/j.cis.2006.06.016.
[14]PATEL A R,DEWETTINCK K.Current update on the influence of minor lipid components,shear and presence of interfaces on fat crystallization[J].Current Opinion in Food Science,2015,3:65-70.DOI:10.1016/j.cofs.2015.05.010.
[15]SMIDDY M A,HUPPERTZ T,VAN RUTH S M.Triacylglycerol and melting profiles of milk fat from several species[J].International Dairy Journal,2012,24(2):64-69.DOI:10.1016/j.idairyj.2011.07.001.
[16]TZOMPA-SOSA D A.Milk fat triacylglycerols:their variability,relations with fatty acids,DGAT1,βpolymorphs and melting fractions[D].Wageningen:Wageningen University,2016:67-71.
[17]RAMADAN M F,AMER M M A,AWAD E S.Coriander(Coriandrum sativum L.)seed oil improves plasma lipid profile in rats fed a diet containing cholesterol[J].European Food Research&Technology,2008,227(4):1173-1182.
[18]TRAN T,ROUSSEAU D.Influence of shear on fat crystallization[J].Food Research International,2016,81:157-162.DOI:10.1016/j.foodres.2015.12.022.
[19]MéNDEZ-VELASCO C,GOFF H D.Fat structure in ice cream:a study on the types of fat interactions[J].Food Hydrocolloids,2012,29(1):152-159.DOI:10.1016/j.foodhyd.2012.02.002.
[20]TENGKU-ROZAINA T M,BIRCH E J.Effects of fractionation on melting and crystallisation profiles of hoki oil measured by DSC[J].Journal of Thermal Analysis and Calorimetry,2014,120(1):395-402.DOI:10.1007/s10973-014-3995-9.
[21]LOPEZ C,LESIEUR P,BOURGAUX C,et al.Thermal and structural behavior of milk fat[J].Journal of Colloid and Interface Science,2001,240(1):150-161.DOI:10.1006/jcis.2001.7664.
[22]MáRQUEZ A L,PéREZ M P,WAGNER J R.Solid fat content estimation by differential scanning calorimetry:prior treatment and proposed correction[J].Journal of the American Oil Chemists’Society,2012,90(4):467-473.DOI:10.1007/s11746-012-2190-z.
[23]KAYLEGIAN K E,LINDSAY R C.Performance of selected milk fat fractions in cold-spreadable butter[J].Journal of Dairy Science,1992,75(12):3307-3317.DOI:10.3168/jds.S0022-0302(92)78106-5.
[24]FATOUH A E,SINGH R K,KOEHLER P E,et al.Chemical and thermal characteristics of buffalo butter oil fractions obtained by multistep dry fractionation[J].LWT-Food Science and Technology,2003,36(5):483-496.DOI:10.1016/S0023-6438(03)00044-6.
[25]WANG F,LIU Y,SHAN L,et al.Blooming in cocoa butter substitutes based compound chocolate:investigations on composition,morphology and melting behavior[J].Journal of the American Oil Chemists’Society,2010,87(10):1137-1143.DOI:10.1007/s11746-010-1604-z.
[26]VAN AKEN G A,VISSER K A.Firmness and crystallization of milk fat in relation to processing conditions[J].Journal of Dairy Science,2000,83(9):1919-1932.DOI:10.3168/jds.S0022-0302(00)75067-3.
[27]GROTENHUIS E T,AKEN G A V,MALSSEN K F V,et al.Polymorphism of milk fat studied by differential scanning calorimetry and real-time X-ray powder diffraction[J].Journal of the American Oil Chemists’Society,1999,76(9):1031-1039.DOI:10.1007/s11746-999-0201-5.
[28]SATO K.Crystallization behaviour of fats and lipids:a review[J].Chemical Engineering Science,2001,56(7):2255-2265.DOI:10.1016/S0009-2509(00)00458-9.
[29]SABARIAH S,ALI A R M,CHONG C L.Chemical and physical characteristics of cocoa butter substitutes,milk fat and Malaysian cocoa butter blends[J].Journal of the American Oil Chemists’Society,1998,75(8):905-910.DOI:10.1007/s11746-998-0265-7.
[30]HERRERA M L,DE L G M,HARTEL R W.A kinetic analysis of crystallization of a milk fat model system[J].Food Research International,1999,32(4):189-198.DOI:10.1016/S0963-9969(99)00083-6.
[31]TIETZA R A,HARTELB R W.Effects of minor lipids on crystallization of milk fat-cocoa butter blends and bloom formation in chocolate[J].Journal of the American Oil Chemists’Society,2000,77(7):763-771.DOI:10.1007/s11746-000-0122-5.
[32]王风艳.月桂酸类代可可脂巧克力起霜机理及品质改善[D].无锡:江南大学,2012:27-30.
[33]DIMICK P S,REDDY S Y,ZIEGLER G R.Chemical and thermal characteristics of milk-fat fractions isolated by a melt crystallization[J].Journal of the American Oil Chemists’Society,1996,73(12):1647-1652.DOI:10.1007/BF02517966.
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