高效液相色谱-紫外法检测酱油中的3-氯-1,2-丙二醇
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摘要
建立了一种新的高效液相色谱-紫外法(HPLC-UV)测定酱油中的有害物质3-氯-1,2-丙二醇(3-chloro-1,2-propanediol,3-MCPD)含量的方法。首先将3-MCPD与叠氮化钠反应,所得到的叠氮化产物进一步和苯乙炔发生CuAAC型点击反应,所得衍生物3-(4-苯基-1,2,3-三氮唑基)-1,2-丙二醇最后采用HPLC-UV进行分析检测。本检测方法对3-MCPD的检出限和定量限分别为0.1和0.3μg/mL,且线性关系良好(r~2=0.999)。对酱油样品进行加标回收实验,结果表明本方法的加标回收率为98.63%～100.17%,相对标准偏差(RSD值)为1.95%～4.74%。将本检测方法与国家标准检测方法GB 5009.191―2016进行对比检测,结果显示2种方法所得到的结果是一致的。
A novel high performance liquid chromatography-ultraviolet method(HPLC-UV) was developed for quantitatively determining the content of hazardous 3-chloro-1,2-propanediol(3-MCPD) in soy sauce.3-MCPD was first azidated with sodium azide,and the obtained azide product was further subjected to a CuAAC type click reaction with phenylacetylene,and the resulting derivative 3-(4-phenyl-1 H-1,2,3-triazol-1-yl) propane-1,2-diol(3-PTPD) was obtained and analyzed with HPLC-UV finally.The detection limits and quantitation limits of 3-MCPD were 0.1 and 0.3 μg/mL,respectively,and the linear relationship was good(r~2=0.999).The results of spiked recovery test of soy sauce samples showed that the recoveries of the method were from 98.63% to 100.17%,and the relative standard deviation(RSD value) was from 1.95% to 4.74%.This method is compared with the national standard test method GB 5009.191―2016 as well,and the results obtained by the two methods are consistent.
A novel high performance liquid chromatography-ultraviolet method(HPLC-UV) was developed for quantitatively determining the content of hazardous 3-chloro-1,2-propanediol(3-MCPD) in soy sauce.3-MCPD was first azidated with sodium azide,and the obtained azide product was further subjected to a CuAAC type click reaction with phenylacetylene,and the resulting derivative 3-(4-phenyl-1 H-1,2,3-triazol-1-yl) propane-1,2-diol(3-PTPD) was obtained and analyzed with HPLC-UV finally.The detection limits and quantitation limits of 3-MCPD were 0.1 and 0.3 μg/mL,respectively,and the linear relationship was good(r~2=0.999).The results of spiked recovery test of soy sauce samples showed that the recoveries of the method were from 98.63% to 100.17%,and the relative standard deviation(RSD value) was from 1.95% to 4.74%.This method is compared with the national standard test method GB 5009.191―2016 as well,and the results obtained by the two methods are consistent.
引文
[1] VELISEK J,DAVIDEK J,HAJSLOVA J,et al.Chlorohydrins in protein hydrolysates[J].Zeitschrift fur lebensmittel-untersuchung und-forschung,1978,167(4):241-244.
[2] 吴倩.黄酒中EC/Urea/3-MCPD的检测及EC/Urea的去除[D].武汉:华中农业大学,2018.
[3] 李祥,杨百勤,丁红梅.水解蛋白质调味液中氯丙醇的形成及其控制[J].中国酿造,2003,1(3):1-4.
[4] BUHRKE T,VOSS L,BRIESE A,et al.Oxidative inactivation of the endogenous antioxidant protein DJ-1 by the food contaminants 3-MCPD and 2-MCPD[J].Archives of toxicology,2017,92(4):1-11.
[5] BUHRKE T,SCHULTRICH K,BRAEUNING A,et al.Comparative analysis of transcriptomic responses to repeated-dose exposure to 2-MCPD and 3-MCPD in rat kidney,liver and testis[J].Food and chemical toxicology,2017,106(Part A):36-46.
[6] RAJPAL S T,FENG C T,MARTHA S S.Evidence on the carcinogenicity of 3-monochloropropane-1,2-diol (3-MCPD; α-chlorohydrin)[G/OL].[S.l.:s.n.],California Environmental Protection Agency,2010.https://oehha.ca.gov/media/downloads/crnr/123mcpd.pdf.
[7] IARC (International Agency for Research on Cancer).Some chemicals present in industrial and consumer products,food and drinking-water,volumes 101[G/OL].[S.l.:s.n.],2013.https://monographs.iarc.fr/iarc-monographs-on-the-evaluation-of-carcinogenic-risks-to-humans-15/.Published online 11 December 2012.
[8] European-Commission (EC).Commission Regulation (EC) No.1881/2006 of 19 December 2006 setting maximum levels for certain contaminants in foodstuffs[G].Official Journal of the European Union,L364,2006:5-24.
[9] GENUALDI S,NYMAN P,DEJAGER L.Simultaneous analysis of 3-MCPD and 1,3-DCP in Asian style sauces using QuEChERS extraction and gas chromatography-triple quadrupole mass spectrometry[J].Journal of agricultural and food chemistry,2017,65(4):981-985.
[10] HAILE B,SATHEESH N.Review on 3-chloro-1,2-propanediol:a chloropropanol formed during food processing[J].Der pharma chemica,2017,9(7):84-90.
[11] LEE B Q,KHOR S M.3-Chloropropane-1,2-diol (3-MCPD) in soy sauce:a review on the formation,reduction,and detection of this potential carcinogen[J].Comprehensive reviews in food science and food safety,2015,14(1):48-66.
[12] LI Y,ZHENG C,SUN X,et al.Identification of 3-chloro-1,2-propandiol using molecularly imprinted composite solid-phase extraction materials[J].Analytical & bioanalytical chemistry,2014,406(25):6319-6327.
[13] XU X M,WU H W,HE H L,et al.Study of chloropropanols in soy sauce by gas chromatography-triple quadrupole mass spectrometry with coupled column separation without derivatisation[J].Food additives and contaminants-part A,2013,30(3):421-429.
[14] BAER I,CALLE B D L,TAYLOR P.3-MCPD in food other than soy sauce or hydrolysed vegetable protein (HVP)[J].Analytical and bioanalytical chemistry,2010,396(1):443-456.
[15] BERGER-PREISS E,GERLING S,APEL E,et al.Development and validation of an analytical method for determination of 3-chloropropane-1,2-diol in rat blood and urine by gas chromatography-mass spectrometry in negative chemical ionization mode[J].Analytical and bioanalytical chemistry,2010,398(1):313-318.
[16] HU Z,CHENG P,GUO M,et al.A novel approach of periodate oxidation coupled with HPLC-FLD for the quantitative determination of 3-chloro-1,2-propanediol in water and vegetable oil[J].Journal of agricultural and food chemistry,2013,61(27):6614-6621.
[17] 徐小民,何华丽,阮宇迪,等.气相色谱-三重四极杆串联质谱法同时测定调味品中的氨基甲酸乙酯和氯丙醇[J].色谱,2013,31(11):1129-1133.
[18] 易青,苗虹,吴永宁.在线凝胶渗透色谱-气相色谱-串联质谱非衍生化法测定食品中氯丙醇[J].分析化学,2016,44(5):678-684.
[19] CAO X J,SONG G X,GAO Y H,et al.A novel derivatization method coupled with GC-MS for the simultaneous determination of chloropropanols[J].Chromatographia,2009,70(3/4):661-664.
[20] PESSELMAN R L,FEIT M J.Determination of residual epichlorohydrin and 3-chloropropanediol in water by gas chromatography with electron-capture detection[J].Journal of chromatography A,1988,439(2):448-452.
[21] MEIERHANS D C,BRUEHLMANN S,MEILI J,et al.Sensitive method for the determination of 3-chloropropane-1,2-diol and 2-chloropropane-1,3-diol by capillary gas chromatography with mass spectrometric detection[J].Journal of chromatography A,1998,802(2):325-333.
[22] FABIAN M D,MILADY R N.Development of an analytical method for 3-monochloropropane-1,2-diol in soy sauce using 4-heptanone as derivatizing agent[J].Food additives and contaminants,2004,21(3):204-209.
[23] KUSTERS M,BIMBER U,OSSENBRUGGEN A,et al.Rapid and simple micromethod for the simultaneous determination of 3-MCPD and 3-MCPD esters in different foodstuffs[J].Journal of agricultural and food chemistry,2010,58(11):6570-6577.
[24] XU X,REN Y,WU P,et al.The simultaneous separation and determination of chloropropanols in soy sauce and other flavoring with gas chromatography-mass spectrometry in negative chemical and electron impact ionization modes[J].Food additives and contaminants,2006,23(2):110-119.
[25] KOLB H C,FINN M G,SHARPLESS K B.Click chemistry:diverse chemical function from a few good reactions[J].Angewandte chemie international edition,2001,40(11):2004-2021.
[26] TIWARI V K,MISHRA B B,MISHRA B,et al.Cu-catalyzed click reaction in carbohydrate chemistry[J].Chemical reviews,2016,116(5):3086-3240.
[27] 中华人民共和国国家卫生和计划生育委员会,国家食品药品监督管理总局.食品中氯丙醇及其脂肪酸酯含量的测定:GB 5009.191-2016[S].北京:中国标准出版社,2016.
[2] 吴倩.黄酒中EC/Urea/3-MCPD的检测及EC/Urea的去除[D].武汉:华中农业大学,2018.
[3] 李祥,杨百勤,丁红梅.水解蛋白质调味液中氯丙醇的形成及其控制[J].中国酿造,2003,1(3):1-4.
[4] BUHRKE T,VOSS L,BRIESE A,et al.Oxidative inactivation of the endogenous antioxidant protein DJ-1 by the food contaminants 3-MCPD and 2-MCPD[J].Archives of toxicology,2017,92(4):1-11.
[5] BUHRKE T,SCHULTRICH K,BRAEUNING A,et al.Comparative analysis of transcriptomic responses to repeated-dose exposure to 2-MCPD and 3-MCPD in rat kidney,liver and testis[J].Food and chemical toxicology,2017,106(Part A):36-46.
[6] RAJPAL S T,FENG C T,MARTHA S S.Evidence on the carcinogenicity of 3-monochloropropane-1,2-diol (3-MCPD; α-chlorohydrin)[G/OL].[S.l.:s.n.],California Environmental Protection Agency,2010.https://oehha.ca.gov/media/downloads/crnr/123mcpd.pdf.
[7] IARC (International Agency for Research on Cancer).Some chemicals present in industrial and consumer products,food and drinking-water,volumes 101[G/OL].[S.l.:s.n.],2013.https://monographs.iarc.fr/iarc-monographs-on-the-evaluation-of-carcinogenic-risks-to-humans-15/.Published online 11 December 2012.
[8] European-Commission (EC).Commission Regulation (EC) No.1881/2006 of 19 December 2006 setting maximum levels for certain contaminants in foodstuffs[G].Official Journal of the European Union,L364,2006:5-24.
[9] GENUALDI S,NYMAN P,DEJAGER L.Simultaneous analysis of 3-MCPD and 1,3-DCP in Asian style sauces using QuEChERS extraction and gas chromatography-triple quadrupole mass spectrometry[J].Journal of agricultural and food chemistry,2017,65(4):981-985.
[10] HAILE B,SATHEESH N.Review on 3-chloro-1,2-propanediol:a chloropropanol formed during food processing[J].Der pharma chemica,2017,9(7):84-90.
[11] LEE B Q,KHOR S M.3-Chloropropane-1,2-diol (3-MCPD) in soy sauce:a review on the formation,reduction,and detection of this potential carcinogen[J].Comprehensive reviews in food science and food safety,2015,14(1):48-66.
[12] LI Y,ZHENG C,SUN X,et al.Identification of 3-chloro-1,2-propandiol using molecularly imprinted composite solid-phase extraction materials[J].Analytical & bioanalytical chemistry,2014,406(25):6319-6327.
[13] XU X M,WU H W,HE H L,et al.Study of chloropropanols in soy sauce by gas chromatography-triple quadrupole mass spectrometry with coupled column separation without derivatisation[J].Food additives and contaminants-part A,2013,30(3):421-429.
[14] BAER I,CALLE B D L,TAYLOR P.3-MCPD in food other than soy sauce or hydrolysed vegetable protein (HVP)[J].Analytical and bioanalytical chemistry,2010,396(1):443-456.
[15] BERGER-PREISS E,GERLING S,APEL E,et al.Development and validation of an analytical method for determination of 3-chloropropane-1,2-diol in rat blood and urine by gas chromatography-mass spectrometry in negative chemical ionization mode[J].Analytical and bioanalytical chemistry,2010,398(1):313-318.
[16] HU Z,CHENG P,GUO M,et al.A novel approach of periodate oxidation coupled with HPLC-FLD for the quantitative determination of 3-chloro-1,2-propanediol in water and vegetable oil[J].Journal of agricultural and food chemistry,2013,61(27):6614-6621.
[17] 徐小民,何华丽,阮宇迪,等.气相色谱-三重四极杆串联质谱法同时测定调味品中的氨基甲酸乙酯和氯丙醇[J].色谱,2013,31(11):1129-1133.
[18] 易青,苗虹,吴永宁.在线凝胶渗透色谱-气相色谱-串联质谱非衍生化法测定食品中氯丙醇[J].分析化学,2016,44(5):678-684.
[19] CAO X J,SONG G X,GAO Y H,et al.A novel derivatization method coupled with GC-MS for the simultaneous determination of chloropropanols[J].Chromatographia,2009,70(3/4):661-664.
[20] PESSELMAN R L,FEIT M J.Determination of residual epichlorohydrin and 3-chloropropanediol in water by gas chromatography with electron-capture detection[J].Journal of chromatography A,1988,439(2):448-452.
[21] MEIERHANS D C,BRUEHLMANN S,MEILI J,et al.Sensitive method for the determination of 3-chloropropane-1,2-diol and 2-chloropropane-1,3-diol by capillary gas chromatography with mass spectrometric detection[J].Journal of chromatography A,1998,802(2):325-333.
[22] FABIAN M D,MILADY R N.Development of an analytical method for 3-monochloropropane-1,2-diol in soy sauce using 4-heptanone as derivatizing agent[J].Food additives and contaminants,2004,21(3):204-209.
[23] KUSTERS M,BIMBER U,OSSENBRUGGEN A,et al.Rapid and simple micromethod for the simultaneous determination of 3-MCPD and 3-MCPD esters in different foodstuffs[J].Journal of agricultural and food chemistry,2010,58(11):6570-6577.
[24] XU X,REN Y,WU P,et al.The simultaneous separation and determination of chloropropanols in soy sauce and other flavoring with gas chromatography-mass spectrometry in negative chemical and electron impact ionization modes[J].Food additives and contaminants,2006,23(2):110-119.
[25] KOLB H C,FINN M G,SHARPLESS K B.Click chemistry:diverse chemical function from a few good reactions[J].Angewandte chemie international edition,2001,40(11):2004-2021.
[26] TIWARI V K,MISHRA B B,MISHRA B,et al.Cu-catalyzed click reaction in carbohydrate chemistry[J].Chemical reviews,2016,116(5):3086-3240.
[27] 中华人民共和国国家卫生和计划生育委员会,国家食品药品监督管理总局.食品中氯丙醇及其脂肪酸酯含量的测定:GB 5009.191-2016[S].北京:中国标准出版社,2016.