分子蒸馏对沙棘果油中8种塑化剂组分脱除及综合品质的影响
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摘要
沙棘果油因富含多种有益活性成分而成为价格高昂的食用植物油,但受生长环境、采摘方式、储存方法等因素的影响,其塑化剂含量存在超标风险。利用两级分子蒸馏工艺对沙棘果毛油中8种邻苯二甲酸酯类塑化剂(phthalic acid esters,PAEs)进行脱除,并对脱除前后沙棘果油的脂肪酸组成及活性成分含量进行检测分析,研究分子蒸馏对沙棘果毛油中PAEs脱除效果以及活性成分保留的影响。结果显示,本实验所取沙棘果毛油样品中邻苯二甲酸二正丁酯(di-butyl phthalate,DBP)和邻苯二甲酸二(2-乙基)己酯(bis(2-ethylhexyl) phthalate,DEHP)含量分别为1.626、10.933 mg/kg,明显超出GB 9685—2016《食品安全国家标准食品接触材料及制品用添加剂使用标准》限量(DBP含量不超过0.3 mg/kg、DEHP含量不超过1.5 mg/kg)。经一级分子蒸馏,DBP含量从1.626 mg/kg降至0.071 mg/kg,明显低于GB 9685—2016限量;经两级分子蒸馏,DEHP含量从10.933 mg/kg降低至0.668 mg/kg,明显低于GB 9685—2016限量,DBP、DEHP、邻苯二甲酸二异壬酯(diisononyl phthalate,DINP)及8种塑化剂含量总和的脱除率分别为98%、94%、85%和93%,VE、甾醇、黄酮类成分的保留率分别为14%、32%、46%,脂肪酸组成没有明显变化,基本无反式脂肪酸形成,游离脂肪酸质量分数明显降低。两级分子蒸馏工艺是脱除食用植物油中高含量PAEs的有效方法,但会造成油脂中VE、甾醇、黄酮类成分的较大损失。因此,为避免活性成分损失,在保证油脂中DBP和DEHP脱除达到GB 9685—2016限量时,可采用一级分子蒸馏,此时VE、甾醇、黄酮的保留率可分别提高至35%、55%、63%。
Sea buckthorn(Hippophae rhamnoides L.) pulp oil(SPO) is an expensive edible vegetable oil due to its beneficial bioactive ingredients,but this oil may pose a risk of phthalic acid esters(PAEs) exceeding the legal limits,depending on various factors such as growing environment,picking methods,and storage methods.In the present study,two-stage molecular distillation(MD) was used to remove 8 PAEs from SPO.Fatty acid composition and the contents of VE,phytosterol,and flavonoids in SPO were detected before and after MD to evaluate the effect of MD on the removal of PAEs and the retention of bioactive constituents.The results showed the contents of di-butyl phthalate(DBP)(1.626 mg/kg)and bis(2-ethylhexyl) phthalate(DEHP)(10.933 mg/kg) in raw sea buckthorn pulp oil(R-SPO) greatly exceeded the limits(0.3 and 1.5 mg/kg respectively) specified in China's national standard for the use of food contact materials and food additives.The content of DBP decreased from 1.626 to 0.071 mg/kg during the first stage of MD,which was far below the legal limit,and the content of DEHP reduced from 10.933 to 0.668 mg/kg during the whole MD process.The removal rates of DBP,DEHP,DINP and the sum of these PAEs and five others were 98%,94%,85% and 93%,respectively;after two-stage MD,the retention rates of VE,sterol and flavonoids were 14%,32%,and 46% respectively.Fatty acid composition of SPO did not change obviously,almost no trans-fatty acids were produced,whereas the proportion of free fatty acids decreased visibly.These results indicated that the two-stage molecular distillation process was an effective method to remove high concentrations of PAEs from edible vegetable oils,but it could result in large losses of nutrients such as VE,sterol and flavonoids.One-stage molecular distillation could reduce the contents of DBP and DEHP in edible vegetable oil to less than the legal limits while avoiding losses of nutrients,increasing the retention rates of VE,sterol and flavonoids up to 35%,55% and 63%,respectively.
Sea buckthorn(Hippophae rhamnoides L.) pulp oil(SPO) is an expensive edible vegetable oil due to its beneficial bioactive ingredients,but this oil may pose a risk of phthalic acid esters(PAEs) exceeding the legal limits,depending on various factors such as growing environment,picking methods,and storage methods.In the present study,two-stage molecular distillation(MD) was used to remove 8 PAEs from SPO.Fatty acid composition and the contents of VE,phytosterol,and flavonoids in SPO were detected before and after MD to evaluate the effect of MD on the removal of PAEs and the retention of bioactive constituents.The results showed the contents of di-butyl phthalate(DBP)(1.626 mg/kg)and bis(2-ethylhexyl) phthalate(DEHP)(10.933 mg/kg) in raw sea buckthorn pulp oil(R-SPO) greatly exceeded the limits(0.3 and 1.5 mg/kg respectively) specified in China's national standard for the use of food contact materials and food additives.The content of DBP decreased from 1.626 to 0.071 mg/kg during the first stage of MD,which was far below the legal limit,and the content of DEHP reduced from 10.933 to 0.668 mg/kg during the whole MD process.The removal rates of DBP,DEHP,DINP and the sum of these PAEs and five others were 98%,94%,85% and 93%,respectively;after two-stage MD,the retention rates of VE,sterol and flavonoids were 14%,32%,and 46% respectively.Fatty acid composition of SPO did not change obviously,almost no trans-fatty acids were produced,whereas the proportion of free fatty acids decreased visibly.These results indicated that the two-stage molecular distillation process was an effective method to remove high concentrations of PAEs from edible vegetable oils,but it could result in large losses of nutrients such as VE,sterol and flavonoids.One-stage molecular distillation could reduce the contents of DBP and DEHP in edible vegetable oil to less than the legal limits while avoiding losses of nutrients,increasing the retention rates of VE,sterol and flavonoids up to 35%,55% and 63%,respectively.
引文
[1]刘洪章.沙棘生物学及化学成分研究[D].长春:吉林农业大学,2003:1-2.DOI:10.7666/d.y530549.
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[4]臧茜茜,邓乾春,从仁怀,等.沙棘油功效成分及药理功能研究进展[J].中国油脂,2015,40(5):76-81.DOI:10.3969/j.issn.1003-7969.2015.05.017.
[5]杨志刚,卢顺光,赵梅霞.沙棘属植物的生物化学和药理学研究综述[J].国际沙棘研究与开发,2005,3(4):1-8.DOI:10.3969/j.issn.1672-4836.2005.04.001.
[6]BAL L M,MEDA V,NAIK S N,et al.Sea buckthorn berries:a potential source of valuable nutrients for nutraceuticals and cosmoceuticals[J].Food Research International,2011,44(7):1718-1727.DOI:10.1016/j.foodres.2011.03.002.
[7]OLAS B.The beneficial health aspects of sea buckthorn(Elaeagnus rhamnoides(L.)A.Nelson)oil[J].Journal of Ethnopharmacology,2017,213:183-190.DOI:10.1016/j.jep.2017.11.022.
[8]刘超,徐婧,叶存奇,等.沙棘籽油和果油对小鼠实验性肝损伤的保护作用及对比研究[J].中国中药杂志,2006,31(13):1100-1102.DOI:10.3321/j.issn:1001-5302.2006.13.020.
[9]VASHISHTHA V,BARHWAL K,KUMAR A,et al.Effect of sea buckthorn seed oil in reducing cardiovascular risk factors:a longitudinal controlled trial on hypertensive subjects[J].Clinical Nutrition,2017,36(5):1231-1238.DOI:10.1016/j.clnu.2016.07.013.
[10]GUO X F,YANG B,CAI W W,et al.Effect of sea buckthorn(Hippophae rhamnoides L.)on blood lipid profiles:a systematic review and meta-analysis from 11 independent randomized controlled trials[J].Trends in Food Science&Technology,2017,61:1-10.DOI:10.1016/j.tifs.2016.11.007.
[11]PICHIAH P B T,MOON H J,PARK J E,et al.Ethanolic extract of sea buckthorn(Hippophae rhamnoides L.)prevents high-fat dietinduced obesity in mice through down-regulation of adipogenic and lipogenic gene expression[J].Nutrition Research,2012,32(11):856-864.DOI:10.1016/j.nutres.2012.09.015.
[12]SEZAI E,EMINE O,OZLEM O,et al.The genotypic effects on the chemical composition and antioxidant activity of sea buckthorn(Hippophae rhamnoides L.)berries grown in Turkey[J].Scientia Horticulturae,2007,115(1):27-33.DOI:10.1016/j.scienta.2007.07.004.
[13]YANG B R,KALIMO K O,TAHVONEN R L,et al.Effect of dietary supplementation with sea buckthorn(Hippopha?rhamnoides)seed and pulp oils on the fatty acid composition of skin glycerophospholipids of patients with atopic dermatitis[J].Journal of Nutritional Biochemistry,2000,11(6):338-340.DOI:10.1016/S0955-2863(00)00088-7.
[14]CHEN L,ZHAO Y,LI L X,et al.Exposure assessment of phthalates in non-occupational populations in China[J].Science of the Total Environment,2012,427/428(12):60-69.DOI:10.1016/j.scitotenv.2012.03.090.
[15]TAN S W,WANG D L,CHI Z X,et al.Study on the interaction between typical phthalic acid esters(PAEs)and human haemoglobin(hHb)by molecular docking[J].Environmental Toxicology and Pharmacology,2017,53:206-211.DOI:10.1016/j.etap.2017.06.008.
[16]SVECHNIKOVA I,SVECHNIKOV K,S?DER O.The influence of di-(2-ethylhexyl)phthalate on steroidogenesis by the ovarian granulosa cells of immature female rats[J].Journal of Endocrinology,2007,194(3):603-609.DOI:10.1677/JOE-07-0238.
[17]WANG X,SHENG N,CUI R,et al.Gestational and lactational exposure to di-isobutyl phthalate via diet in maternal mice decreases testosterone levels in male offspring[J].Chemosphere,2017,172:260-267.DOI:10.1016/j.chemosphere.2017.01.011.
[18]EMA M,MIYAWAKI E.Adverse effects on development of the reproductive system in male offspring of rats given monobutyl phthalate,a metabolite of dibutyl phthalate,during late pregnancy[J].Reproductive Toxicology,2001,15(2):189-194.DOI:10.1016/S0890-6238(01)00111-3.
[19]SVECHNIKOV K,SVECHNIKOVA I,S?DER O.Inhibitory effects of mono-ethylhexyl phthalate on steroidogenesis in immature and adult rat Leydig cells in vitro[J].Reproductive Toxicology,2008,25(4):485-490.DOI:10.1016/j.reprotox.2008.05.057.
[20]张璇,汤桦,陈大舟,等.国内外增塑剂相关法规比较[J].标准科学,2010(12):47-51.DOI:10.3969/j.issn.1674-5698.2010.12.010.
[21]SHI L K,ZHANG M M,LIU Y L.Concentration and survey of phthalic acid esters in edible vegetable oils and oilseeds by gas chromatography-mass spectrometry in China[J].Food Control,2016,68:118-123.DOI:10.1016/j.foodcont.2016.03.027.
[22]张明明,刘玉兰,杨金强,等.油脂中邻苯二甲酸酯类塑化剂的吸附脱除研究[J].粮油食品科技,2015,23(5):32-36.DOI:10.3969/j.issn.1007-7561.2015.05.008.
[23]刘玉兰,张明明,杨金强.水蒸汽蒸馏法对油脂中DBP和DEHP脱除效果的研究[J].现代食品科技,2017,33(5):176-182.DOI:10.13982/j.mfst.1673-9078.2017.5.028.
[24]刘玉兰,杨金强,张明明,等.分子蒸馏法脱除油脂中塑化剂效果的研究[J].粮食与油脂,2016,29(2):19-22.DOI:10.3969/j.issn.1008-9578.2016.02.005.
[25]XIONG Y,ZHAO Z,ZHU L,et al.Removal of three kinds of phthalates from sweet orange oil by molecular distillation[J].LWT-Food Science and Technology,2013,53(2):487-491.DOI:10.1016/j.lwt.2013.04.012.
[26]曹九超,金青哲.食用油中塑化剂的污染途径及分析方法的研究进展[J].中国油脂,2013,38(5):1-5.DOI:10.3969/j.issn.1003-7969.2013.05.001.
[27]胡爱鹏,刘玉兰,张明明,等.气相色谱-质谱联用法直接测定植物油料中邻苯二甲酸酯类塑化剂[J].食品科学,2016,37(18):146-151.DOI:10.7506/spkx1002-6630-201618024.
[28]温运启,刘玉兰,王璐阳,等.不同食用植物油中维生素E组分及含量研究[J].中国油脂,2017,42(3):35-39.DOI:10.3969/j.issn.1003-7969.2017.03.007.
[29]周丛,吴海智,林源,等.脱臭工艺对玉米油中反式脂肪酸含量的影响[J].现代生物医学进展,2011,11(20):3864-3867.DOI:10.13241/j.cnki.pmb.2011.20.002.
[30]SURYAKUMAR G,GUPTA A.Medicinal and therapeutic potential of sea buckthorn(Hippophae rhamnoides L.)[J].Journal of Ethnopharmacology,2011,138(2):268-278.DOI:10.1016/j.jep.2011.09.024.
[31]侯霄.沙棘果油的检测分析[J].中国现代中药,2016,18(12):1602-1605.DOI:10.13313/j.issn.1673-4890.2016.12.015.
[32]LI Zheng,SHI Longkai,ZHAO Chenwei,et al.Fatty acid,phytochemical,oxidative stability and in vitro,antioxidant property of sea buckthorn(Hippopha?rhamnoides L.)oils extracted by supercritical and subcritical technologies[J].LWT-Food Science and Technology,2017,86:507-513.DOI:10.1016/j.lwt.2017.08.042.
[33]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.
[2]BEVERIDGETH J.沙棘化学组分和一些物理特性[J].国际沙棘研究与开发,2005,3(2):1-6;20.DOI:10.3969/j.issn.1672-4836.2005.02.001.
[3]VINCZE I,BANYAISTEFANOVITS E,VATAI G.Concentration of sea buckthorn(Hippophae rhamnoides L.)juice with membrane separation[J].Separation and Purification Technology,2007,57(3):455-460.DOI:10.1016/j.seppur.2006.06.020.
[4]臧茜茜,邓乾春,从仁怀,等.沙棘油功效成分及药理功能研究进展[J].中国油脂,2015,40(5):76-81.DOI:10.3969/j.issn.1003-7969.2015.05.017.
[5]杨志刚,卢顺光,赵梅霞.沙棘属植物的生物化学和药理学研究综述[J].国际沙棘研究与开发,2005,3(4):1-8.DOI:10.3969/j.issn.1672-4836.2005.04.001.
[6]BAL L M,MEDA V,NAIK S N,et al.Sea buckthorn berries:a potential source of valuable nutrients for nutraceuticals and cosmoceuticals[J].Food Research International,2011,44(7):1718-1727.DOI:10.1016/j.foodres.2011.03.002.
[7]OLAS B.The beneficial health aspects of sea buckthorn(Elaeagnus rhamnoides(L.)A.Nelson)oil[J].Journal of Ethnopharmacology,2017,213:183-190.DOI:10.1016/j.jep.2017.11.022.
[8]刘超,徐婧,叶存奇,等.沙棘籽油和果油对小鼠实验性肝损伤的保护作用及对比研究[J].中国中药杂志,2006,31(13):1100-1102.DOI:10.3321/j.issn:1001-5302.2006.13.020.
[9]VASHISHTHA V,BARHWAL K,KUMAR A,et al.Effect of sea buckthorn seed oil in reducing cardiovascular risk factors:a longitudinal controlled trial on hypertensive subjects[J].Clinical Nutrition,2017,36(5):1231-1238.DOI:10.1016/j.clnu.2016.07.013.
[10]GUO X F,YANG B,CAI W W,et al.Effect of sea buckthorn(Hippophae rhamnoides L.)on blood lipid profiles:a systematic review and meta-analysis from 11 independent randomized controlled trials[J].Trends in Food Science&Technology,2017,61:1-10.DOI:10.1016/j.tifs.2016.11.007.
[11]PICHIAH P B T,MOON H J,PARK J E,et al.Ethanolic extract of sea buckthorn(Hippophae rhamnoides L.)prevents high-fat dietinduced obesity in mice through down-regulation of adipogenic and lipogenic gene expression[J].Nutrition Research,2012,32(11):856-864.DOI:10.1016/j.nutres.2012.09.015.
[12]SEZAI E,EMINE O,OZLEM O,et al.The genotypic effects on the chemical composition and antioxidant activity of sea buckthorn(Hippophae rhamnoides L.)berries grown in Turkey[J].Scientia Horticulturae,2007,115(1):27-33.DOI:10.1016/j.scienta.2007.07.004.
[13]YANG B R,KALIMO K O,TAHVONEN R L,et al.Effect of dietary supplementation with sea buckthorn(Hippopha?rhamnoides)seed and pulp oils on the fatty acid composition of skin glycerophospholipids of patients with atopic dermatitis[J].Journal of Nutritional Biochemistry,2000,11(6):338-340.DOI:10.1016/S0955-2863(00)00088-7.
[14]CHEN L,ZHAO Y,LI L X,et al.Exposure assessment of phthalates in non-occupational populations in China[J].Science of the Total Environment,2012,427/428(12):60-69.DOI:10.1016/j.scitotenv.2012.03.090.
[15]TAN S W,WANG D L,CHI Z X,et al.Study on the interaction between typical phthalic acid esters(PAEs)and human haemoglobin(hHb)by molecular docking[J].Environmental Toxicology and Pharmacology,2017,53:206-211.DOI:10.1016/j.etap.2017.06.008.
[16]SVECHNIKOVA I,SVECHNIKOV K,S?DER O.The influence of di-(2-ethylhexyl)phthalate on steroidogenesis by the ovarian granulosa cells of immature female rats[J].Journal of Endocrinology,2007,194(3):603-609.DOI:10.1677/JOE-07-0238.
[17]WANG X,SHENG N,CUI R,et al.Gestational and lactational exposure to di-isobutyl phthalate via diet in maternal mice decreases testosterone levels in male offspring[J].Chemosphere,2017,172:260-267.DOI:10.1016/j.chemosphere.2017.01.011.
[18]EMA M,MIYAWAKI E.Adverse effects on development of the reproductive system in male offspring of rats given monobutyl phthalate,a metabolite of dibutyl phthalate,during late pregnancy[J].Reproductive Toxicology,2001,15(2):189-194.DOI:10.1016/S0890-6238(01)00111-3.
[19]SVECHNIKOV K,SVECHNIKOVA I,S?DER O.Inhibitory effects of mono-ethylhexyl phthalate on steroidogenesis in immature and adult rat Leydig cells in vitro[J].Reproductive Toxicology,2008,25(4):485-490.DOI:10.1016/j.reprotox.2008.05.057.
[20]张璇,汤桦,陈大舟,等.国内外增塑剂相关法规比较[J].标准科学,2010(12):47-51.DOI:10.3969/j.issn.1674-5698.2010.12.010.
[21]SHI L K,ZHANG M M,LIU Y L.Concentration and survey of phthalic acid esters in edible vegetable oils and oilseeds by gas chromatography-mass spectrometry in China[J].Food Control,2016,68:118-123.DOI:10.1016/j.foodcont.2016.03.027.
[22]张明明,刘玉兰,杨金强,等.油脂中邻苯二甲酸酯类塑化剂的吸附脱除研究[J].粮油食品科技,2015,23(5):32-36.DOI:10.3969/j.issn.1007-7561.2015.05.008.
[23]刘玉兰,张明明,杨金强.水蒸汽蒸馏法对油脂中DBP和DEHP脱除效果的研究[J].现代食品科技,2017,33(5):176-182.DOI:10.13982/j.mfst.1673-9078.2017.5.028.
[24]刘玉兰,杨金强,张明明,等.分子蒸馏法脱除油脂中塑化剂效果的研究[J].粮食与油脂,2016,29(2):19-22.DOI:10.3969/j.issn.1008-9578.2016.02.005.
[25]XIONG Y,ZHAO Z,ZHU L,et al.Removal of three kinds of phthalates from sweet orange oil by molecular distillation[J].LWT-Food Science and Technology,2013,53(2):487-491.DOI:10.1016/j.lwt.2013.04.012.
[26]曹九超,金青哲.食用油中塑化剂的污染途径及分析方法的研究进展[J].中国油脂,2013,38(5):1-5.DOI:10.3969/j.issn.1003-7969.2013.05.001.
[27]胡爱鹏,刘玉兰,张明明,等.气相色谱-质谱联用法直接测定植物油料中邻苯二甲酸酯类塑化剂[J].食品科学,2016,37(18):146-151.DOI:10.7506/spkx1002-6630-201618024.
[28]温运启,刘玉兰,王璐阳,等.不同食用植物油中维生素E组分及含量研究[J].中国油脂,2017,42(3):35-39.DOI:10.3969/j.issn.1003-7969.2017.03.007.
[29]周丛,吴海智,林源,等.脱臭工艺对玉米油中反式脂肪酸含量的影响[J].现代生物医学进展,2011,11(20):3864-3867.DOI:10.13241/j.cnki.pmb.2011.20.002.
[30]SURYAKUMAR G,GUPTA A.Medicinal and therapeutic potential of sea buckthorn(Hippophae rhamnoides L.)[J].Journal of Ethnopharmacology,2011,138(2):268-278.DOI:10.1016/j.jep.2011.09.024.
[31]侯霄.沙棘果油的检测分析[J].中国现代中药,2016,18(12):1602-1605.DOI:10.13313/j.issn.1673-4890.2016.12.015.
[32]LI Zheng,SHI Longkai,ZHAO Chenwei,et al.Fatty acid,phytochemical,oxidative stability and in vitro,antioxidant property of sea buckthorn(Hippopha?rhamnoides L.)oils extracted by supercritical and subcritical technologies[J].LWT-Food Science and Technology,2017,86:507-513.DOI:10.1016/j.lwt.2017.08.042.
[33]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.
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