甜蜜素的电喷雾串联质谱行为及其在酒类分析检测中的应用研究
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摘要
采用国家标准规定的液相色谱-串联质谱法检测酒类甜蜜素过程中,常很难优化出正离子模式下所监测的202>122(ESI+)离子对。本论文比较正/负离子模式下甜蜜素在不同流动相体系中的电喷雾串联质谱行为。结果发现,负离子模式下,甜蜜素在不同流动相体系离子对较为稳定,为178>80(ESI-),但响应值有所差异;而正离子模式,甜蜜素所呈现的离子对会随流动相的变化出现加钠、脱钠加氨等现象。研究表明,在甲醇/5mmol乙酸铵(v/v=10/90)的条件下,正离子模式所呈现的离子对197>100(ESI+)信号强度较大,更适合质谱法分析检测中佐证使用。运用本文所优化的质谱条件,建立了酒类甜蜜素的检测方法,其线性范围在2.5~100μg/L内,标准曲线方程为Y=900.952X+391.716,所得线性相关系数为0.9990,经计算该方法检出限为0.66μg/L,定量限为2.2μg/L。不同浓度水平下样品加标回收率介于89.8%~98.6%,相对标准偏差均在5%以内。本研究为运用质谱法开展酒类中的甜蜜素的检测提供了更好的确证依据。
The national standards of sodium cyclamate detection in wine by HPLC-MS/MS often shows the difficulty in optimizing specific 202 > 122(ESI+)ion pair. Electrospray ionization tandem mass spectrometry was used in sodium cyclamate detection and compared under different mobile phase in this study. It is found that the under the negative ion mode,ion pair was 178 > 80(ESI-)and was stable with a difference response value;under the positive ion mode,ion pairs was changed with the mobile phrase such as adding sodium,removing sodium and adding ammonia actions. The results showed that the ion pair of 197 > 100(ESI+)with a stronger mass spectrum abundance in the mixture of 5 mmol ammonium acetate and methanol(v/v=10/90),was more suitable for mass spectrometry analysis. A new method of sodium cyclamate detection in wine was established by using the optimized mass spectrometry conditions. The linear range was 2.5 ～ 100 μg/L,standard curve was Y=900.952 X+391.716 and the linear correlation coeffi cient was 0.9990. The detection limit and the quantitative limit were 0.66 μg/L and 2.2 μg/L by calculation,respectively.The recovery rate of the sample was between 89.8 % and 98.6%,and the relative standard deviation was within 5%. This study provides a reference for using the mass spectrometry in the detection of sodium cyclamate in alcohol.
The national standards of sodium cyclamate detection in wine by HPLC-MS/MS often shows the difficulty in optimizing specific 202 > 122(ESI+)ion pair. Electrospray ionization tandem mass spectrometry was used in sodium cyclamate detection and compared under different mobile phase in this study. It is found that the under the negative ion mode,ion pair was 178 > 80(ESI-)and was stable with a difference response value;under the positive ion mode,ion pairs was changed with the mobile phrase such as adding sodium,removing sodium and adding ammonia actions. The results showed that the ion pair of 197 > 100(ESI+)with a stronger mass spectrum abundance in the mixture of 5 mmol ammonium acetate and methanol(v/v=10/90),was more suitable for mass spectrometry analysis. A new method of sodium cyclamate detection in wine was established by using the optimized mass spectrometry conditions. The linear range was 2.5 ～ 100 μg/L,standard curve was Y=900.952 X+391.716 and the linear correlation coeffi cient was 0.9990. The detection limit and the quantitative limit were 0.66 μg/L and 2.2 μg/L by calculation,respectively.The recovery rate of the sample was between 89.8 % and 98.6%,and the relative standard deviation was within 5%. This study provides a reference for using the mass spectrometry in the detection of sodium cyclamate in alcohol.
引文
[1]中华人民共和国国家卫生和计划生育委员会.GB 2760-2014食品安全国家标准食品添加剂使用标准[S].北京:中国标准出版社,2015.
[2]阮伯龙.薄层色谱法快速同时测定饮料中甜蜜素、糖精钠和苯甲酸[J].中国卫生检验杂志,1991(2):109-110.
[3]陈少波,潘超华.食品中甜蜜素的紫外分光光度法测定[J].分析测试学报,2000(3):82-83.
[4]唐志国.近红外(NIR)光谱法测定果冻中甜蜜素的研究[D].江苏大学,2007.
[5]朱怀远,庄亚东,熊晓敏,万敏,沈晓晨,张映.离子色谱法直接测定食品添加剂中的甜蜜素[J].食品科学,2012,33(2):173-176.
[6]陈桐,丁晓静,李一正,赵旭东,赵珊.毛细管区带电泳-间接紫外法快速测定食品中的甜蜜素[J].色谱,2014,32(6):666-671.
[7]毛桂洁,于喆英,历荣.~1H-NMR法测定饮料中安赛蜜和甜蜜素的含量[J].黑龙江大学自然科学学报,2012,29(1):90-94,98.
[8]黄会秋.火焰原子吸收光谱法间接测定白酒中甜蜜素[J].理化检验(化学分册),2009,45(6):684-686.
[9]邵铁锋,李雪岷,陈勤伟,谢广发,沈国军.高效液相色谱法测定酒中甜蜜素[J].中国酿造,2004(12):31-32.
[10]陈冬纯,邓后勤.气相色谱法测定饮料中甜蜜素的条件优化[J].食品与机械,2014,30(2):84-87.
[11]胡强,王延云.气相色谱-质谱法对不同食品中甜蜜素的测定[J].食品科学,2009,30(14):235-237.
[12]吴世嘉,王洪新,陶冠军.超高效液相色谱-质谱同时测定白酒中6种微量甜味剂的研究方法[J].食品与生物学报,2010,29(5):670-675.
[13]胡强,王延云,李超豪,杨春林,吴卫,向乐曦.超高效液相色谱串联质谱法快速测定白酒中痕量甜味剂[J].食品科学,2013,34(20):232-236.
[14]中华人民共和国国家卫生和计划生育委员会.GB 5009.97-2016食品安全国家标准食品中环己基氨基磺酸钠的测定[S].北京:中国标准出版社,2016.
[15]李明春,张莹,尹礼国,冯学愚.白酒中甜蜜素测定方法的研究进展[J].酿酒科技,2010(7):93-95.
[16]封雷,蒲朝文,汪瑜,等.气相色谱法测定保健营养甜味剂中的甜蜜素[J].中国卫生检验杂志,2002,12(3):312.
[17]臧光楼,董明盛.白酒中甜蜜素检测方法的研究,食品科学,2009,10(30):261-264.
[18]邵明媛.液相色谱-串联质谱法同时测定调制乳制品中5种人工合成甜味剂[J].分析试验室,2017,36(1):96-99.
[19]柯润辉,王丽娟,安红梅,黄新望,尹建军,宋全厚.超高效液相色谱-串联质谱法同时测定白酒中氨基甲酸乙酯和8种甜味剂[J].食品与发酵工业,2016,42(4):174-178.
[20]梅婕,司冠儒,张温清,唐莹,周萍.高效液相色谱-串联质谱法测定白酒中6种甜味剂[J].酿酒科技,2016(3):122-124.
[21]李晶,杨叶昆,陈建华,缪恩铭,耿永勤,端凯,李雪梅,徐济仓.超高效液相色谱-串联质谱法测定香精香料中的甜味剂和色素[J].理化检验(化学分册),2015,51(12):1724-1728.
[22]卢巧梅,张兰.液相色谱-串联质谱法测定食品中甜味剂和抗氧化剂[J].分析测试技术与仪器,2015,21(3):140-145.
[23]刘国英,胡艳丽,万春环,汤有宏,王银辉,金先锋.超高效液相色谱-三重四级杆串联质谱仪(UPLC-MS/MS)同时测定白酒中4种微量甜味剂[J].酿酒科技,2015(6):92-94.
[24]周彬,吕任一,肖丽恒,李萍,何学梅,杨芩,杨丽娜.超高效液相色谱串联质谱同时测定酒类产品中多种人工合成甜味剂[J].食品科学,2014,35(12):218-222.
[25]徐春祥,秦金平.液相色谱-质谱联用直接测定白酒中的甜蜜素[J].食品与发酵工业,2006(2):106-107.
[26]刘晓霞,丁利,刘锦霞,张莹,黄志强,王利兵,陈波.高效液相色谱-串联质谱法测定食品中6种人工合成甜味剂[J].色谱,2010,28(11):1020-1025.
[27]欧盟非强制执行法案2002-657-EC(质谱分析方法鉴定点数).
[28]肖晶,方从容,杨大进,王紫菲,刘玉洁.高效液相色谱-质谱法测定酒中甜蜜素含量的研究[J].中国食品卫生杂志,2013,25(3):254-256.
[29]陈晓红,赵永纲,姚珊珊,李小平,金米聪.超快速液相色谱-串联质谱法测定黄酒和葡萄酒中的9种防腐剂和甜味剂[J].色谱,2011,29(12):1147-1154.
[30]嵇超,冯峰,陈正行,孙利,储晓刚.高效液相色谱-串联质谱法测定葡萄酒中的5种人工合成甜味剂[J].色谱,2010,28(8):749-753.
[31]阮丽萍,蔡梅,吉文亮,马永建.高效液相色谱-串联质谱法同时测定调味品中8种人工合成甜味剂[J].中国食品卫生杂志,2013,25(4):331-335.
[32]刘佟,杨悠悠,王浩,苗雨田,杨永坛.超高效液相色谱-串联质谱法测定饮品中7种人工合成甜味剂[J].分析测试技术与仪器,2015,21(4):218-224.
[33]刘印平,路杨,杨立新,常凤启,王丽英.超高效液相色谱-串联质谱法快速测定饮料中22种添加剂[J].食品安全质量检测学报,2015,6(3):980-986.
[2]阮伯龙.薄层色谱法快速同时测定饮料中甜蜜素、糖精钠和苯甲酸[J].中国卫生检验杂志,1991(2):109-110.
[3]陈少波,潘超华.食品中甜蜜素的紫外分光光度法测定[J].分析测试学报,2000(3):82-83.
[4]唐志国.近红外(NIR)光谱法测定果冻中甜蜜素的研究[D].江苏大学,2007.
[5]朱怀远,庄亚东,熊晓敏,万敏,沈晓晨,张映.离子色谱法直接测定食品添加剂中的甜蜜素[J].食品科学,2012,33(2):173-176.
[6]陈桐,丁晓静,李一正,赵旭东,赵珊.毛细管区带电泳-间接紫外法快速测定食品中的甜蜜素[J].色谱,2014,32(6):666-671.
[7]毛桂洁,于喆英,历荣.~1H-NMR法测定饮料中安赛蜜和甜蜜素的含量[J].黑龙江大学自然科学学报,2012,29(1):90-94,98.
[8]黄会秋.火焰原子吸收光谱法间接测定白酒中甜蜜素[J].理化检验(化学分册),2009,45(6):684-686.
[9]邵铁锋,李雪岷,陈勤伟,谢广发,沈国军.高效液相色谱法测定酒中甜蜜素[J].中国酿造,2004(12):31-32.
[10]陈冬纯,邓后勤.气相色谱法测定饮料中甜蜜素的条件优化[J].食品与机械,2014,30(2):84-87.
[11]胡强,王延云.气相色谱-质谱法对不同食品中甜蜜素的测定[J].食品科学,2009,30(14):235-237.
[12]吴世嘉,王洪新,陶冠军.超高效液相色谱-质谱同时测定白酒中6种微量甜味剂的研究方法[J].食品与生物学报,2010,29(5):670-675.
[13]胡强,王延云,李超豪,杨春林,吴卫,向乐曦.超高效液相色谱串联质谱法快速测定白酒中痕量甜味剂[J].食品科学,2013,34(20):232-236.
[14]中华人民共和国国家卫生和计划生育委员会.GB 5009.97-2016食品安全国家标准食品中环己基氨基磺酸钠的测定[S].北京:中国标准出版社,2016.
[15]李明春,张莹,尹礼国,冯学愚.白酒中甜蜜素测定方法的研究进展[J].酿酒科技,2010(7):93-95.
[16]封雷,蒲朝文,汪瑜,等.气相色谱法测定保健营养甜味剂中的甜蜜素[J].中国卫生检验杂志,2002,12(3):312.
[17]臧光楼,董明盛.白酒中甜蜜素检测方法的研究,食品科学,2009,10(30):261-264.
[18]邵明媛.液相色谱-串联质谱法同时测定调制乳制品中5种人工合成甜味剂[J].分析试验室,2017,36(1):96-99.
[19]柯润辉,王丽娟,安红梅,黄新望,尹建军,宋全厚.超高效液相色谱-串联质谱法同时测定白酒中氨基甲酸乙酯和8种甜味剂[J].食品与发酵工业,2016,42(4):174-178.
[20]梅婕,司冠儒,张温清,唐莹,周萍.高效液相色谱-串联质谱法测定白酒中6种甜味剂[J].酿酒科技,2016(3):122-124.
[21]李晶,杨叶昆,陈建华,缪恩铭,耿永勤,端凯,李雪梅,徐济仓.超高效液相色谱-串联质谱法测定香精香料中的甜味剂和色素[J].理化检验(化学分册),2015,51(12):1724-1728.
[22]卢巧梅,张兰.液相色谱-串联质谱法测定食品中甜味剂和抗氧化剂[J].分析测试技术与仪器,2015,21(3):140-145.
[23]刘国英,胡艳丽,万春环,汤有宏,王银辉,金先锋.超高效液相色谱-三重四级杆串联质谱仪(UPLC-MS/MS)同时测定白酒中4种微量甜味剂[J].酿酒科技,2015(6):92-94.
[24]周彬,吕任一,肖丽恒,李萍,何学梅,杨芩,杨丽娜.超高效液相色谱串联质谱同时测定酒类产品中多种人工合成甜味剂[J].食品科学,2014,35(12):218-222.
[25]徐春祥,秦金平.液相色谱-质谱联用直接测定白酒中的甜蜜素[J].食品与发酵工业,2006(2):106-107.
[26]刘晓霞,丁利,刘锦霞,张莹,黄志强,王利兵,陈波.高效液相色谱-串联质谱法测定食品中6种人工合成甜味剂[J].色谱,2010,28(11):1020-1025.
[27]欧盟非强制执行法案2002-657-EC(质谱分析方法鉴定点数).
[28]肖晶,方从容,杨大进,王紫菲,刘玉洁.高效液相色谱-质谱法测定酒中甜蜜素含量的研究[J].中国食品卫生杂志,2013,25(3):254-256.
[29]陈晓红,赵永纲,姚珊珊,李小平,金米聪.超快速液相色谱-串联质谱法测定黄酒和葡萄酒中的9种防腐剂和甜味剂[J].色谱,2011,29(12):1147-1154.
[30]嵇超,冯峰,陈正行,孙利,储晓刚.高效液相色谱-串联质谱法测定葡萄酒中的5种人工合成甜味剂[J].色谱,2010,28(8):749-753.
[31]阮丽萍,蔡梅,吉文亮,马永建.高效液相色谱-串联质谱法同时测定调味品中8种人工合成甜味剂[J].中国食品卫生杂志,2013,25(4):331-335.
[32]刘佟,杨悠悠,王浩,苗雨田,杨永坛.超高效液相色谱-串联质谱法测定饮品中7种人工合成甜味剂[J].分析测试技术与仪器,2015,21(4):218-224.
[33]刘印平,路杨,杨立新,常凤启,王丽英.超高效液相色谱-串联质谱法快速测定饮料中22种添加剂[J].食品安全质量检测学报,2015,6(3):980-986.