A method of capillary electrophoresis combined with dynamic pH junction online concentration for determination and profiling of seven phenolic acids in wines and beverages was developed. The sample containing 7 phenolic acids was dissolved in the specific background electrolyte, phosphate buffer at pH 3.5, which was different from the background electrolyte in electrophoretic separation medium,20 mmol/L borate buffer containing 25% methanol(V/V)at pH 9.2. The experimental factors influencing online concentration and analysis were systematically studied, induding detection wavelength, fraction of methanol in running background electrolyte, applied voltage and injection time. Under optimized conditions, the correlation coefficients for the calibration lines of the 7 phenolic acids were greater than 0.999 2, with limits of detection(S/N=3)in the range of 0.014~0.027 μg/mL. The recoveries for the selected phenolic- DOI:10.3969/j.issn.1000-1565.2019.06.006动态pH连接-毛细管电泳法测定和表征饮品中7种酚酸李美婷,陈跃,李亚茹,李怀栋, 周灿,褚晓雪,张红医(河北大学 化学与环境科学学院,河北 保定 071002)摘 要:建立了一种用于测定和表征葡萄酒和饮料中7种酚酸的毛细管电泳结合动态pH在线富集的方法.将含有7种酚酸的样品溶解于pH为3.5的磷酸盐背景电解质中,它与作为电泳分离介质的背景电解质不同(pH 9.2的20 mmol/L硼酸缓冲液中含有体积分数25%的甲醇).系统地研究了影响在线富集和分析的各种实验因素(检测波长、运行背景电解液中甲醇的含量、分离电压和进样时间等).在最优条件下, 7种酚酸的工作曲线的相关系数均大于0.999 2,检出限LOD(S/N=3)为0.014~0.027 μg/mL,加标回收率在 80%~130%.样品制备步骤非常简单,只需要用酸性背景电解质对样品进行稀释和过滤,一个样品的分析(包括样品处理和电泳分析)在大约16 min内完成.这种方法成功应用于葡萄酒和果汁中酚酸的测定和表征.关键词:毛细管电泳;动态pH连接;酚酸;葡萄酒;饮料中图分类号:O625.1 文献标志码:A 文章编号:1000-1565(2019)06-0594-11Determination and profiling of seven phenolic acids in wines and beverages by capillary electrophoresis with dynamic pH junctionLI Meiting,CHEN Yue,LI Yaru,LI Huaidong,ZHOU Can,CHU Xiaoxue, ZHANG Hongyi(College of Chemistry and Environmental Science, Hebei University, Baoding 071002,China)Abstract: A method of capillary electrophoresis combined with dynamic pH junction online concentration for determination and profiling of seven phenolic acids in wines and beverages was developed. The sample containing 7 phenolic acids was dissolved in the specific background electrolyte, phosphate buffer at pH 3.5, which was different from the background electrolyte in electrophoretic separation medium,20 mmol/L borate buffer containing 25% methanol(V/V)at pH 9.2. The experimental factors influencing online concentration and analysis were systematically studied, induding detection wavelength, fraction of methanol in running background electrolyte, applied voltage and injection time. Under optimized conditions, the correlation coefficients for the calibration lines of the 7 phenolic acids were greater than 0.999 2, with limits of detection(S/N=3)in the range of 0.014~0.027 μg/mL. The recoveries for the selected phenolic- 收稿日期:2019-02-15 基金项目:教育部留学回国人员科研启动基金(47批);河北省高等学校科学技术研究重点项目(ZD2019089);河北大学2018年实验室开放项目(sy201801);河北大学2019国家级和校级大学生创新创业计划项目(201910075018;2019191);2020年度河北大学研究生创新资助项目 第一作者:李美婷(1993—),女,河北廊坊人,河北大学在读硕士研究生.E-mail:1535582479@qq.com 通信作者:张红医(1967—),男,河北唐山人,河北大学教授,主要从事色谱、样品前处理和识别分析研究.E-mail:freetime20100401@163.comacids were in the range of 80%~130%. The sample preparation step was so simple that only dilution with acidic background electrolyte as well as filtration were required, leading to the analysis time for one sample 16 min, including sample treatment and electrophoretic analysis.The developedmethod was applied to determination and profiling of 7 phenolic acids in wines and beverages.
LI Meiting
,
CHEN Yue
,
LI Yaru
,
LI Huaidong
,
ZHOU Can
,
CHU Xiaoxue
,
ZHANG Hongyi
. Determination and profiling of seven phenolic acids in wines and beverages by capillary electrophoresis with dynamic pH junction[J]. Journal of Hebei University(Natural Science Edition), 2019
, 39(6)
: 594
-604
.
DOI: 10.3969/j.issn.1000-1565.2019.06.006
[1] ZGÓRKA G, GŁOWNIAK K. Variation of free phenolic acids in medicinal plants belonging to the Lamiaceae family[J]. Journal of Pharmaceutical and Biomedical Analysis, 2001, 26:79-87. DOI:10.1016/S0731-7085(01)00354-5.
[2] UYSAL U D, ATURKI Z, RAGGI M A, et al. Separation of catechins and methylxanthines in tea samples by capillary electrochromatography[J]. Journal of Separation Science, 2009, 32(7):1002-1010. DOI: 10.1002/jssc.200800634.
[3] BELMIRO T M C, PEREIRA C F, PAIM A P S. Red wines from south America: content of phenolic compounds and chemometric distinction by origin[J]. Microchemical Journal, 2017, 133:114-120. DOI: 10.1016/j.microc.2017.03.018.
[4] YANG P, LI H, WANG H, et al. Dispersive liquid-liquid microextraction method for HPLC determination of phenolic compounds in wine[J]. Food Analytical Methods, 2017, 10(7):2383-2397. DOI: 10.1007/s12161-016-0781-2.
[5] DE SOUZA DIAS F, LOVILLO M P, BARROSO C G, et al. Direct determination of phenolic acids and hydroxymethylfurfural in wines elaborated in Vale do São Francisco region-Brazil by HPLC DAD[J]. Analytical Methods, 2017, 9(4):643-648.DOI: 10.1039/c6ay02657e.
[6] REVILLA E, RYAN J M. Analysis of several phenolic compounds with potential antioxidant properties in grape extracts and wines by high-performance liquid chromatography–photodiode array detection without sample preparation[J]. Journal of Chromatography A, 2000, 881:461-469. DOI:10.1016/S0021-9673(00)00269-7.
[7] XIE H Y, HE Y Z. Green analytical methodologies combining liquid-phase microextraction with capillary electrophoresis[J]. Trends in Analytical Chemistry, 2010, 29(7): 629-63. DOI: 10.1016/j.trac.2010.02.017.
[8] LIN Y H, HUANG H C, HSU W L. Application of capillary electrophoresis with electrokinetic supercharging and sweeping for the on-line preconcentration of phenolic acids[J]. Analytical and Bioanalytical Chemistry, 2015, 407(23):7093-7100.DOI: 10.1007/s00216-015-8869-x.
[9] PETR J, VÍTKOVÁK, RANC V, et al. Determination of some phenolic acids in majorana hortensis by capillary electrophoresis with online electrokinetic preconcentration[J]. Journal of Agricultural and Food Chemistry, 2008, 56:3940-3944.DOI: 10.1021/jf8000179.
[10] HAMOUDOVÁ R F, URBÁNEK M, POSPÍŠIILOVÁ M, et al. Assay of phenolic compounds in red wine by on-line combination of capillary isotachophoresis with capillary zone electrophoresis[J]. Journal of Chromatography A, 2004, 1032(1-2):281-287.DOI: 10.1016/j.chroma.2004.01.014.
[11] SAFRA J, POSPISILOVA M, KAVALIROVA A. Development of a stacking-CZE method for the analysis of phenolic acids[J]. Journal of Pharmaceutical and Biomedical Analysis, 2006, 41(3):1022-1024. 10.1016/j.jpba.2006.01.025.
[12] PARVEEN S, MEMON S Q, SIYAL A N, et al. Large-volume sample staking of rice polyphenols prior to their determination by non-aqueous capillary electrophoresis[J]. Food Analytical Methods, 2016, 9(8):2152-2160. DOI: 10.1007/s12161-015-0394-1.
[13] ERDEMGIL F Z, SANLI S, SANLI N, et al. Determination of pK(a)values of some hydroxylated benzoic acids in methanol-water binary mixtures by LC methodology and potentiometry[J]. Talanta, 2007, 72(2):489-496. DOI: 10.1016/j.talanta.2006.11.007.
[14] BRITZ-MCKIBBIN P, CHEN D D Y. Selective focusing of catecholamines and weakly acidic compounds by capillary electrophoresis using a dynamic pH junction[J]. Analytical Chemistry, 2000, 72: 1242-1252. DOI:10.1021/ac990898e.
[15] DIAS F D S, KLASSEN A, TAVARES M F M, et al. Fast Determination of phenolic compounds in Brazilian wines from Vale do São Francisco region by CE[J]. Chromatographia, 2013, 76(9-10):559-563. DOI: 10.1007/s10337-013-2399-5.
[16] DA ROSA NENG N, SEQUEIROS R C, FLORENCIO NOGUEIRA J M. Combining bar adsorptive microextraction with capillary electrophoresis - application for pthe determination of phenolic acids in food matrices[J]. Electrophoresis, 2014, 35(17):2488-2494. DOI: 10.1002/elps.201400101.
[17] ��塁ANLI S, ��塁ANLI N, OZKAN S A, et al. Development and validation of a green capillary electrophoretic method for determination of polyphenolic compounds in Red Wine Samples[J]. Chromatographia, 2016, 79(19-20):1351-1358.DOI: 10.1007/s10337-016-3147-4.
[18] SHUI G, LEONG L P. Separation and determination of organic acids and phenoliccompounds in fruit juices and drinks by high-performance liquidchromatography[J]. Journal of Chromatography A, 2002, 977:89-96. DOI:10.1016/S0021-9673(02)01345-6.
[19] SAGRATINI G, MAGGI F, CAPRIOLI G, et al. Comparative study of aroma profile and phenolic content of Montepulciano monovarietal red wines from the Marches and Abruzzo regions of Italy using HS-SPME-GC-MS and HPLC-MS[J]. Food Chemistry, 2012, 132(3):1592-1599. DOI: 10.1016/j.foodchem.2011.11.108.
[20] PADILHA C V, MISKINIS G A, DE SOUZA M E, et al. Rapid determination of flavonoids and phenolic acids in grape juices and wines by RP-HPLC/DAD: Method validation and characterization of commercial products of the new Brazilian varieties of grape[J]. Food Chemistry, 2017, 228:106-115. DOI: 10.1016/j.foodchem.2017.01.137.