建立简单、灵敏、快速的胶束增敏荧光法,对面膜中的荧光增白剂VBL进行定量检测.对检测条件进行选择,确定了最佳的检测条件:Ex=345 nm、Em=430 nm、Slit=5 nm,5 nm;根据荧光增白剂的光学性质、结合表面活性剂胶束增敏原理,对影响体系荧光强度的因素(增敏试剂种类、增敏剂浓度、温度等)进行了考察,确定的最佳增敏试剂为9.20×10-4 mol/L 的CTAB(即为临界胶束浓度),最佳实验条件为34 ℃;利用单因素分析结合正交设计对样品预处理条件(提取剂的种类、浓度、料液比,提取时间、温度等)进行了筛选,确定了荧光增白剂的最佳提取工艺:提取溶剂为体积分数90%乙醇,料液比1∶75(g∶mL),提取时间30 min,提取温度34 ℃.在最佳实验条件下,VBL+CTAB体系,在5.00×10-7~1.20×10-4 g/L内线性关系良好(r=0.995 8),检出限为1.91×10-7 g/L,平均回收率为101.64%~120.60%,相对标准偏差为1.41%~8.92%.本方法检测灵敏、重现性好、结果准确可靠,可用于面膜中荧光增白剂的定量检测,为中国相关监管机构对市场面膜的质量监测提供科学依据,对维护消费者身体健康有重要意义.
A simple, fast and sensitive analytical method was established for the determination of fluorescent whitening agent VBL in mask by micelle-sensitized fluorescence spectrometry. The detecting conditions were optimized. The wavelength of the excited and the emitted spectrum of VBL were 345 nm and 430 nm, respectively. The slit widths were 5nm, 5 nm. According to the spectroscopic properties of VBL and the sensitization principle of surfactant micelle, the factors that influence the fluorescence intensity of the system(such as the type of sensitizer, the concentration of sensitizer and the temperature)were investigated.- DOI:10.3969/j.issn.1000-1565.2018.04.006胶束增敏荧光法测定面膜中的荧光增白剂刘丽艳1,白洁1,2,韩文雅2,王亚文2,吴素焕1,韩艳梅1,梁翠霞2(1. 河北大学 医学综合实验中心,河北 保定 071000;2. 河北大学 公共卫生学院,河北 保定 071000)摘 要:建立简单、灵敏、快速的胶束增敏荧光法,对面膜中的荧光增白剂VBL进行定量检测.对检测条件进行选择,确定了最佳的检测条件:Ex=345 nm、Em=430 nm、Slit=5 nm,5 nm;根据荧光增白剂的光学性质、结合表面活性剂胶束增敏原理,对影响体系荧光强度的因素(增敏试剂种类、增敏剂浓度、温度等)进行了考察,确定的最佳增敏试剂为9.20×10-4 mol/L 的CTAB(即为临界胶束浓度),最佳实验条件为34 ℃;利用单因素分析结合正交设计对样品预处理条件(提取剂的种类、浓度、料液比,提取时间、温度等)进行了筛选,确定了荧光增白剂的最佳提取工艺:提取溶剂为体积分数90%乙醇,料液比1∶75(g∶mL),提取时间30 min,提取温度34 ℃.在最佳实验条件下,VBL+CTAB体系,在5.00×10-7~1.20×10-4 g/L内线性关系良好(r=0.995 8),检出限为1.91×10-7 g/L,平均回收率为101.64%~120.60%,相对标准偏差为1.41%~8.92%.本方法检测灵敏、重现性好、结果准确可靠,可用于面膜中荧光增白剂的定量检测,为中国相关监管机构对市场面膜的质量监测提供科学依据,对维护消费者身体健康有重要意义.关键词:荧光增白剂;胶束增敏;荧光分光光度法中图分类号:O657.39 文献标志码:A 文章编号:1000-1565(2018)04-0375-10Determination of fluorescent whitening agent in mask bymicellar enhanced fluorescence spectrometryLIU Liyan1, BAI Jie1,2,HAN Wenya2, WANG Yawen2, WU Suhuan1, HAN Yanmei1,LIANG Cuixia2(1.Medical Comprehensive Experimental Center, Hebei University, Baoding 071000, China;2. College of Public Health, Hebei University, Baoding 071000, China)Abstract: A simple, fast and sensitive analytical method was established for the determination of fluorescent whitening agent VBL in mask by micelle-sensitized fluorescence spectrometry. The detecting conditions were optimized. The wavelength of the excited and the emitted spectrum of VBL were 345 nm and 430 nm, respectively. The slit widths were 5nm, 5 nm. According to the spectroscopic properties of VBL and the sensitization principle of surfactant micelle, the factors that influence the fluorescence intensity of the system(such as the type of sensitizer, the concentration of sensitizer and the temperature)were investigated.- 收稿日期:2017-10-20 基金项目:国家自然科学基金资助项目(21605035);河北省自然科学基金资助项目(B2014201162);保定市科学技术与发展指导计划项目(12ZF054);河北大学中西部提升综合实力专项资金资助项目(20150505);河北大学实验室开放基金资助项目(sy201672);河北大学医学部第一批教育教学改革研究课题项目(YXB01-F-05) 第一作者:刘丽艳(1984—),女,河北唐山人,河北大学实验师,主要从事荧光分析、生化分析、生物传感器等研究. E-mail:liyanliu. ok@163.com 通信作者:白洁(1980—),女,河北保定人,回族,河北大学副教授,博士,主要从事荧光分析、生化分析、生物传感器等研究. E-mail:bj0427@126.com韩艳梅(1964—),女,河北保定人,河北大学教授,主要从事生理学方面研究.E-mail:hanyanmei6465@sina.com第4期刘丽艳等:胶束增敏荧光法测定面膜中的荧光增白剂According to the various factors, the optimal experimental conditions were that the sensitizer was CTAB,the concentration of CTAB was 9.20×10-4 mol/L(critical micelle concentrations, CMC)and the temperature was 34 ℃. Through single-factor and orthogonal experiments, the sample pretreatment methods for the VBL of the facial masks were optimized. The extraction solvent was 90% ethanol, the solid-liquid ratio was 1∶75(g∶mL), the extracting time was 30 min, and the extracting temperature was 34 ℃. The result showed that the fluorescence enhancement value of the CTAB was linearly proportional to the concentration of VBL in the range of 5.00×10-7~1.20×10-4 g/L.The limit of detection was found to be 1.91×10-7 g/L,the average recovery was 101.64%~120.60%, and the standard deviation was 1.41%~8.92%. This method is sensitive, reproducible and accurate, and suitable for quantitative detection of VBL in facial mask. The method can provide the scientific basis for the quality monitoring of the market mask in China’s relevant regulatory agencies, and is of great significance to the maintenance of consumer health.
[1] MISHRA H, ZHANG Y X, GEDDES C D.Metal enhanced fluorescence of the fluorescent brightening agent Tinopal-CBX near silver island film[J].Dyes and Pigments, 2011, 91(2): 225-230. DOI:10.1016/j.dyepig.2011.03.005.
[2] HU Z M, ZHOU Q, LEI T C, et al. Effects of hydroquinone and its glucoside derivatives on melanogenesis and antioxidation: Biosafety as skin whitening agents[J]. Journal of Dermatological Science, 2009, 55(3): 179-184. DOI:10.1016/j.jdermsci.2009.06.003.
[3] 余佩佩. 美白面膜中 7 种荧光增白剂的高效液相色谱测试方法研究[D]. 上海:东华大学, 2016: 1-46. YU P P.Determination of seven fluorescent whitening agents in whitening masks by high performance liquid chromatography[D]. Shang Hai: Dong Hua University, 2016: 1-46.
[4] 刘峻, 徐振华, 闫辉, 等. 纸张中荧光物质检测方法的对比[J].中国造纸, 2011, 30(4): 18-21. DOI: 10.11980/j.issn.0254-508X.2011.04.004. LIU J, XU Z H, YAN H, et al. Comparative analysis of fluorescence intensity and fluorescent migration in paper[J]. China Pulp & Paper, 2011, 30(4): 18-21. DOI: 10.11980/j.issn.0254-508X.2011.04.004.
[5] 屈鹏峰, 傅武胜, 刘文菁, 等. 纱布吸附-紫外灯照射法测定食品接触纸及其制品中荧光增白剂[J].中国食品卫生杂志, 2016, 28(3): 352-355.DOI: 10. 13590 /j.cjfh.2016. 03. 016. QU P F, FU W S, LIU W J, et al. Determination of fluorescent whitening agents in food contact paper by UV irradiation method combined with gauze absorption[J]. Chinese Journal of Food Hygiene, 2016, 28(3): 352-355. DOI: 10. 13590 /j.cjfh.2016. 03. 016.
[6] 李伟, 刘学民, 陈凤生, 等. 荧光增白剂VBL与阳离子Gemini表面活性剂溶液的光谱研究[J].光谱实验室, 2008,25(4):519-522. DOI: 10.3969/j.issn.1004-8138.2008.04.001. LI W, LIU X M, CHEN F S, et al. Spectroscopic studies of fluorescent whitening agent VBL interaction with cationic gemini surfactant solution[J]. Chinese Journal of Spectroscopy Laboratory, 2008, 25(4): 519-522. DOI: 10.3969/j.issn.1004-8138.2008.04.001.
[7] EDUARDO T I, TERESA D Z. Whitening regenerated cellulose fibers using fluorescent agent, surfactants, and salt-color indices measurements[J]. Journal of Applied Polymer Science, 2012, 124(5): 4371-4380. DOI:10.1002/app.35549.
[8] 张舒心, 柴欣生, 田迎新,等. 一种测定纸制品中可迁移性荧光增白剂含量的双波长紫外光谱方法[J].光谱学与光谱分析, 2015, 35(7): 1921-1925. DOI:10.3964/j.issn.1000-0593(2015)07-1921-05. ZHANG S X, CHAI X S, TIAN Y X, et al. A method for determination of migratable fluorescent whitening agents in paper products by dual-wavelength UV spectroscopy[J].Spectroscopy and Spectral Analysis, 2015, 35(7): 1921-1925. DOI:10.3964/j.issn.1000-0593(2015)07-1921-05.
[9] SHU W C, DING W H.Determination of fluorescent whitening agents in infant clothes and paper materials by ion-pair chromatography and fluorescence detection[J].Journal of the Chinese Chemical Society, 2009, 56(4): 797-803. DOI: 10.1002/jccs.200900118.
[10] 冼燕萍, 郭新东, 罗海英, 等. 固相萃取-超高效液相色谱分离测定洗涤用品中 4 种荧光增白剂[J].色谱, 2013,31(2):162-169. DOI: 10.3724/SP.J.1123.2012.09041. XIAN Y P, GUO X D, LUO H Y, et al. Determination of four fluorescent whitening agents in laundry detergents by solid phase extraction combined with ultra-high performance liquid chromatography [J]. Chinese Journal of Chromatography, 2013, 31(2): 162-169. DOI: 10.3724/SP.J.1123.2012.09041.
[11] CHANG M L, CHANG C M. Simultaneous HPLC determination of hydrophilic whitening agents in cosmetic products [J]. Journal of Pharmaceutical and Biomedical Analysis, 2003, 33(4):617-626. DOI: 10.1016/S0731-7085(03)00343-1.
[12] WANG Q, CHEN X B, QIU B, et al. Ionic liquid as a mobile phase additive in high-performance liquid chromatography for the simultaneous determination of eleven fluorescent whitening agents in paper materials [J].Journal of separation science, 2016, 39(7): 1242-1248. DOI:10.1002/jssc.201501050.
[13] QIU B, CHEN X B, WANG B, et al. Long-chain ionic liquid based mixed hemimicelles and magnetic dispersed solid-phase extraction for the extraction of fluorescent whitening agents in paper materials [J]. Journal of Separation Science, 2017, 40(11): 2459-2466. DOI: 10.1002/jssc.201601399.
[14] LIAO H Y. Simultaneous determination of four fluorescent whitening agents(including trans and cis isomers)in facial mask by dispersive solid-phase extraction combined with ultra high performance liquid chromatography and diode array detection [J]. Journal of Separation Science, 2016, 39(19): 3683-3689. DOI:10.1002/jssc.201600757.
[15] YAMAJI N, HAYAKAWA K, TAKADA H. Role of photodegradation in the fate of fluorescent whitening agents(FWAs)in lacustrine environments [J].Environmental Science Technology, 2010, 44(20): 7796-7801. DOI: 10.1021/es100465v.
[16] JIANG D G, CHEN L S, FU W S, et al. Simultaneous determination of 11 fluorescent whitening agents in food-contact paper and board by ion-pairing high-performance liquid chromatography with fluorescence detection[J].Journal of separation science, 2015, 38(4): 605-611. DOI 10.1002/jssc.201401110.
[17] 杜志峰,冼燕萍, 刘付建, 等. 液相色谱-高分辨飞行时间质谱法测定食品接触纸包装材料中的 7 种荧光增白剂[J].分析化学,2014, 42(5): 636-642. DOI: 10.3724 /SP.J.1096.2014.30829. DU Z F, XIAN Y P, LIU F J, et al. Simultaneous determination of seven fluorescent whitening agents in food contact paper package materials by high performance liquid chromatography tandem triple TOF-high resolution mass spectrometry[J]. Chinese Journal of Analytical Chemistry, 2014, 42(5): 636-642. DOI: 10.3724 /SP.J.1096.2014.30829.
[18] CHEN H C, WANG S P, DING W H. Determination of fluorescent whitening agents in environmental waters by solid-phase extraction and ion pair liquid chromatography-tandem mass spectrometry [J]. Journal of Chromatography A, 2006, 1102(1-2):135-142. DOI:10.1016/j.chroma.2005.10.025.
[19] CHEN H C, DING W H. Hot-water and solid-phase extraction of fluorescent whitening agents in paper materials and infant clothes followed by unequivocal determination with ion-pair chromatography-tandem mass spectrometry [J]. Journal of Chromatography A, 2006, 1108(2):202-207. DOI:10.1016/j.chroma.2006.01.011.
[20] JOLON M D, CHARISA D C, SCOTT D B, et al. The photoyellowing of stilbene-derived fluorescent whitening agents-mass spectrometric characterization of yellow photoproducts [J].Photochemistry and Photobiology, 2008,84(1): 145-153. DOI: 10.1111/j.1751-1097.2007.00210.x.
[21] JOLIN M D, STEFAN C, CHARISA D C, et al. Photoproducts formed in the photoyellowing of collagen in the presence of a fluorescent whitening agent[J]. Photochemistry and Photobiology, 2009, 85(6): 1314-1321. DOI: 10.1111 j.1751-1097.2009.00614.x.
[22] JIN W, WANG W Y, ZHANG Y L, et al. Determination of phenolic whitening agents in cosmetics by micellar electrokinetic capillary chromatography with amperometric detection[J]. Chinese Chemical Letters, 2013, 24(7): 636-638. DOI: 10.1016/j.cclet.2013.04.023
[23] KUO T Y, WANG S P, LIN C H. Online identification of the fluorescent whitening agent 4,4-bis(2-sulfostyrol)biphenyl using a sweeping technique combined with capillary electrophoresis/77 K fluorescence spectroscopy[J]. Electrophoresis, 2005, 26(22): 4355-4359. DOI: 10. 1002/elps. 200500325.
[24] 郭雅先, 俞世荣, 魏庆询, 等.表面活性剂对Ag+-H2QS-K2S2O8荧光体系的增敏作用及其分析应用[J].高等学校化学学报, 1988, 9(8): 786-789. DOI:10.3321/j.issn:0251-0790.1988.08.006. GUO Y G, YU S R, WEI Q X, et al. The enhanced effect of surfactant on the Ag+-H2QS-K2S2O8 fluorescence system and its analytical application [J].Chemical Journal of Chinese Universities, 1988, 9(8): 786-789. DOI:10.3321/j.issn:0251-0790.1988.08.006.
[25] 赵燕燕,耿成光,白洁,等.胶束增敏同步荧光-双波长法同时测定血浆中儿茶酚胺类神经递质[J].河北大学学报(自然科学版),2010,30(3):264-270.DOI:10.3969/j.issn.1000-1565.2010.03.010. ZHAO Y Y,GENG C G,BAI J,et al. Simultaneous determination of catecholamines neurotransmitters in blood plasma by micellar enhanced synchronous scanning-dual wavelength fluorimetry[J].Journal of Hebei University(Natural Science Edition),2010,30(3):264-270.DOI:10.3969/j.issn.1000-1565.2010.03.010.
