液相色谱-同位素比值质谱法测定食醋中乳酸和乙酸的δ~(13)C值
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摘要
建立液相色谱-同位素比值质谱联用技术(LC-IRMS)测定食醋中乳酸和乙酸碳同位素比值δ~(13)C的方法。样品经沉淀剂沉淀蛋白质和C18固相萃取(SPE)净化后,采用Zorbax SB-Aq(250 mm×4. 6 mm,5μm)耐水反相色谱柱分离,用0. 3 mL/min 0. 05%H3PO4水溶液洗脱,柱温30℃。样本范围内,山西老陈醋和镇江香醋的乳酸和乙酸δ~(13)C值范围分别为-23. 40‰～-22. 39‰,-19. 52‰～-15. 16‰和-28. 06‰～-20. 81‰,-28. 28‰～-26. 90‰,白醋和米醋的乙酸δ~(13)C值范围分别为-29. 53‰～-18. 98‰和-29. 49‰～-13. 87‰。对4类食醋的乳酸和乙酸δ~(13)C值进行单因素方差分析,结果表明可以有效区分山西老陈醋、镇江香醋、白醋和米醋。该方法可应用于食醋产品标识的真实性鉴别研究中。
A method was developed for the determination of δ~(13)C value of lactic acid and acetic acid in vinegar by liquid chromatography isotope ratio mass spectrometry( LC-IRMS). The samples were purified by precipitated protein,and then were operated by C18 solid phase extraction column( SPE).The compounds were separated by a Zorbax SB-Aq column( 250 mm × 4. 6 mm,5 μm) with water resistant reversed phase,which were eluted with 0. 05% H_3PO_4 water solution at 0. 3 m L/min. The column temperature was 30℃. The range of δ~(13)C value of lactic acid and acetic acid in Shanxi mature vinegar and Zhenjiang fragrant vinegar was-23. 40‰ ～-22. 39‰,-19. 52‰ ～-15. 16‰ and-28. 06‰ ～-20. 81‰,-28. 28‰ ～-26. 90‰,respectively. The range of δ~(13)C value of acetic acid in white vinegar and rice vinegar was-29. 53‰ ～-18. 98‰ and-29. 49‰ ～-13. 87‰,respectively. The analysis of variance result showed that the determination of δ~(13)C value of lactic acid and acetic acid in vinegar by LC-IRMS can effectively distinguish Shanxi mature vinegar,Zhenjiang fragrant vinegar,white vinegar and rice vinegar. The method is accurate and stable,and can be applied to the authenticity identification of vinegar products.
A method was developed for the determination of δ~(13)C value of lactic acid and acetic acid in vinegar by liquid chromatography isotope ratio mass spectrometry( LC-IRMS). The samples were purified by precipitated protein,and then were operated by C18 solid phase extraction column( SPE).The compounds were separated by a Zorbax SB-Aq column( 250 mm × 4. 6 mm,5 μm) with water resistant reversed phase,which were eluted with 0. 05% H_3PO_4 water solution at 0. 3 m L/min. The column temperature was 30℃. The range of δ~(13)C value of lactic acid and acetic acid in Shanxi mature vinegar and Zhenjiang fragrant vinegar was-23. 40‰ ～-22. 39‰,-19. 52‰ ～-15. 16‰ and-28. 06‰ ～-20. 81‰,-28. 28‰ ～-26. 90‰,respectively. The range of δ~(13)C value of acetic acid in white vinegar and rice vinegar was-29. 53‰ ～-18. 98‰ and-29. 49‰ ～-13. 87‰,respectively. The analysis of variance result showed that the determination of δ~(13)C value of lactic acid and acetic acid in vinegar by LC-IRMS can effectively distinguish Shanxi mature vinegar,Zhenjiang fragrant vinegar,white vinegar and rice vinegar. The method is accurate and stable,and can be applied to the authenticity identification of vinegar products.
引文
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[3] Li G Q,Lu Z M,Yu Y J,et al. Chin. Condiment,2013,38(11):63李国权,陆震鸣,余永建,等.中国调味品,2013,38(11):63
[4] Fei X Q,Wu B,Shen C Y,et al. Chinese J. Chromatogr.,2011,29(1):15费晓庆,吴斌,沈崇钰,等.色谱,2011,29(1):15
[5] Simsek A,Bilsel M,Goren A C. Food Chem.,2012,130(4):1115
[6] Zhu W X,Yang J Z,Yang N,et al. Chin. J. Anal. Chem.,2014,33(12):1402祝伟霞,杨冀州,杨娜,等.分析试验室,2014,33(12):1402
[7] Guyon F,Auberger P,Gaillard L,et al. Food Chem.,2014,146(3):36
[8] Guyon F,Gaillard L,Salago6ty M H,et al. Anal. Bioanal. Chem.,2011,401(5):1551
[9] LiX M,Jia G Q,Cao Y Z,et al. Chinese J. Chromatogr.,2013,31(12):1201李学民,贾光群,曹彦忠,等.色谱,2013,31(12):1201
[10] Ehtesham E,Baisden W T,Keller E D,et al. Geochim. Cosmochim. Ac.,2013,111:105
[11] Erasmus S W,Muller M,Van d R M,et al. Food Chem.,2016,192:997
[12] Federica C,Anita P,Luana B,et al. Food Chem.,2016,196:98
[13] Wang G S,Tang K T,Lu F,et al. Chin Brew.,2010,29(7):166王贵双,唐坤甜,鲁绯,等.中国酿造,2010,29(7):166
[14] Yu Y J,Deng X Y,Lu Z M,et al. Food Sci.,2014,35(4):55余永建,邓晓阳,陆震鸣,等.食品科学,2014,35(4):55
[15] Zhang L. Chin. Condiment,2016,41(8):118张林.中国调味品,2016,41(8):118
[16] Shu J,Chen X,Pan C D,et al. Chin. Condiment,2013,38(8):95舒静,陈轩,潘从道,等.中国调味品,2013,38(8):95
[17] Du H F,Dong A J,Nie Z Q,et al. Food Fermen. Ind.,2015,41(1):196杜宏福,董爱静,聂志强,等.食品与发酵工业,2015,41(1):196
[18] Fei X Q,Shen C Y,Wu B,et al. J. Chin. Mass Spectr. Soc.,2014,35(2):144费晓庆,沈崇钰,吴斌,等.质谱学报,2014,35(2):144
[19] Zhang J J,Dou S. Chin. J. Soil Sci.,1999,30(5):235张晋京,窦森.土壤通报,1999,30(5):235