以超音波輔助乳化微萃取法結合線上衍生GC-MS與UHPLC-QTOF-MS檢測尿液中防腐劑parabens成分

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周惠婷(Hui-Ting Zhou) 查詢紙本館藏

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化學學系

論文名稱

以超音波輔助乳化微萃取法結合線上衍生GC-MS與UHPLC-QTOF-MS檢測尿液中防腐劑parabens成分

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摘要(中)

對-羥基苯甲酸酯 (Alkyl p-hydroxybenzoates, 簡稱parabens) 因其無色無味、價格低廉、不易硬化或泥漿化，自20世紀以來被當作防腐劑之用途，常添加於化妝品、食品及藥物中，被人類廣泛使用。但近年來的相關研究顯示，parabens可能具有雌激素活性、干擾內分泌系統，並影響人類生殖系統功能，被列為潛在內分泌干擾物質，故檢測parabens在人體尿液中的含量是勢在必行的。
本研究開發出一套有效、溶劑使用量少、對環境友善且可快速檢測的方法來檢測人體尿液中的parabens。利用超音波輔助乳化微萃取法 (Ultrasound-assisted emulsification microextraction, USAEME) 進行樣品前處理，搭配線上衍生 (on-line derivatization) GC-MS和超高效液相層析高解析串聯質譜儀 (UHPLC-QTOF-MS) 進行定性與定量。
本方法利用實驗統計設計 (statistical experimental design) Box-Behnken design (BBD) 及變異數分析 (Analysis of variance, ANOVA) 來做萃取最佳化探討。最佳化後萃取條件為：將1 mL酵素水解後的尿液 (含有0.1 g的氯化鈉)，快速注入200 μL萃取劑乙酸乙酯，經由超音波震盪1分鐘後，以7000 rpm 離心10分鐘，取出上層液並吹氮回溶，使用GC-MS分析時取出10 μL並添加醋酸酐衍生試劑，再進入GC-MS中進行線上衍生並偵測；而使用UHPLC-QTOF-MS檢測時，只需直接進樣2 μL 就可以進行分析。
以GC-MS分析4種parabens的偵測極限為 0.01 - 0.02 ng/mL；在inter-days及intra-day的測試中，所得之相對標準偏差 (RSDs) 小於8 %；以UHPLC-QTOF-MS分析9種parabens時的偵測極限為0.12-0.25 ng/mL ，所得之相對標準偏差小於 10 %，顯示此萃取方法及以兩種儀器分析皆具有良好的再現性及穩定性。在收集的人體尿液中，利用GC-MS檢測時，大部分樣品皆被測得MeP、EtP、PrP、BuP，其在男性尿液的濃度介於 0.3 - 124.5 ng/mL 間；女性尿液的濃度介於 27.6 – 246.8 ng/mL 間，此結果顯示在女性尿液中，對-羥基苯甲酸酯濃度較高，這可能與其生活方式息息相關；而利用UHPLC-QTOF-MS檢測時，除了檢測到常見的四種parabens外，還發現其中一支樣品含有微量的PeP與HxP，由此結果可發現仍然有少許被禁用和毒性較高的parabens可能在台灣被使用中。

摘要(英)

Alkyl p-hydroxybenzoates, also known as parabens, was added in cosmetic, pharmaceutical and food as preservative since the 20th century. Because of its odorless, low prices and difficult hardening, they have widely been used by various applications. Recent studies have concluded that parabens might disrupt the endocrine system, affect funtions of human reproductive systems, and are classified as a potential endocrine disrupter. Therefore, it is important to develop a method to analyze paranbens in human urine.
This study demonstrates an efficient, less solvent used, eco-friendly and rapid analysis method for the determination of parabens in human urine. The method involved the use of ultrasound-assisted emulsification microextection (USAEME) coupled with on-line derivatization GC-MS or UHPLC-QTOF-MS.
The parameters of extaction method were optimized by Box-Behnken design and analysis of variance. The optimal conditions of USAEME were: after hydrolysis of 1 mL urine sample, 200 μL ethyl acetate (as an extractant) rapid injected into urine containing 0.1 g of sodium chloride in a conical bottom tube. After ultrasonication for 1 min and centrifugation at 7000 rpm for 10 min, the upper layer was taken and dried under nitrogen and reconsitituted with methanol. For using GC-MS analysis, a fraction of 10 μL was mixed with 1.0 μL acetic anhydride reagent and directly injected to GC-MS system to obtain on-line derivatization. For using UHPLC-QTOF-MS analysis, a fraction of 2 μL was directly injected into UHPLC system..
The detection limits with GC-MS was 0.01 - 0.02 ng/mL. Intra-day and inter-days precision (% RSD) for four analytes were less than 8 %; the detection limits with UHPLC-QTOF-MS was 0.12-0.25 ng/mL, the RSD for nine analytes were less than 10 %, indicated that these methods show a good stability and reproducibility. In real samples, MeP、EtP、PrP and BuP were detected in most urine samples by GC-MS, the total concentrations ranged from 0.3 to 124.5 ng/mL for male; and from 27.6 to 246.8 ng/mL for female. Female urine samples showed higher total concentrations for the four target parabens, which may indicate higher exposure due to lifestyle. Moreover, small amount of PeP and HxP was detected in one urine sample by UHPLC-QTOF-MS, this results indicate that some disabled and higher toxicity parabens were in use in Taiwan.

關鍵字(中)

★ parabens
★ 超音波輔助乳化微萃取法
★ GC-MS
★ UHPLC-QTOF-MS

關鍵字(英)

論文目次

摘要 i
Abstract iii
謝誌 v
目錄 vii
圖目錄 xiii
表目錄 xvii
第一章前言 1
1-1 研究源起 1
1-2 研究目標 3
第二章文獻回顧 5
2-1 防腐劑 (Preservative) 5
2-1-1 對-羥基苯甲酸酯簡介 6
2-1-2 環境流布與人體代謝 10
2-1-3 毒性研究 12
2-1-3-1 毒性探討與危害 12
2-1-3-2 人體暴露量 13
2-1-4 相關規範 14
2-1-5 用途 15
2-1-6 相關檢測文獻 16
2-2 氣相層析質譜儀 23
2-2-1 離子阱質譜儀 25
2-3 超高效液相層析高解析串聯質譜儀 26
2-3-1 電噴灑游離法 28
2-3-2 四極矩質譜儀 29
2-3-3 飛行時間質譜儀 30
2-3-4 四極矩飛行時間串聯式質譜儀 32
2-4 衍生化介紹 33
2-4-1 醯化反應 33
2-4-2 氣相層析質譜儀線上衍生化技術 35
2-5 β-D-glucosidase 及 Steroid sulfatase 酵素水解 37
2-6 分散式液液微萃取法 38
2-6-1 前言 38
2-6-2 原理 38
2-6-3 流程 39
2-6-4 影響因素 40
2-6-5 發展 41
2-7 超音波輔助乳化微萃取法 46
2-8 實驗設計 48
2-8-1 實驗設計簡介 48
2-8-2 反應曲面法 49
2-8-3 Box-Behnken Design 50
2-9 線性回歸 52
2-9-1 Mandel test 52
2-9-2 The Lack-of-Fit by ANOVA 54
2-10 基質效應 56
2-11 同位素內標定量法 58
第三章實驗步驟與樣品分析 59
3-1 實驗藥品與設備 59
3-1-1 實驗藥品 59
3-1-2 儀器設備 62
3-2 實驗步驟 63
3-2-1 標準品配製 63
3-2-2 氣相層析質譜儀參數設定 64
3-2-3 超高效液相層析串聯質譜儀參數設定 66
3-2-4 質量校正 67
3-2-5 氣相層析質譜儀之實驗流程 68
3-2-6 超高效液相層析串聯質譜儀之實驗流程 69
3-3 尿液採集 70
第四章結果與討論 71
4-1 氣相層析質譜儀對乙醯基化待測物的測定 71
4-1-1 衍生化效率之探討 71
4-1-2 乙醯基化待測物分析 72
4-1-3 乙醯基化待測物質譜圖 73
4-1-4 檢量線及偵測極限 75
4-2 UHPLC-QTOF-MS對待測物的測定 76
4-2-1 待測物分析 76
4-2-2 待測物之質譜圖 77
4-2-3 檢量線及偵測極限 81
4-3 超音波輔助乳化微萃取法最佳化條件探討 82
4-3-1 萃取溶劑種類選擇 82
4-3-2 震盪方式之比較 84
4-3-3 超音波輔助乳化萃取法實驗設計最佳化 85
4-3-4 因子間交互作用力之探討 88
4-4 GC-MS之Mandel test 與 The Lack-of-Fit test 92
4-4-1 Mandel test 92
4-4-2 The Lack-of-Fit test 93
4-5 尿液樣品酵素水解探討 94
4-6 真實尿液樣品之檢測 96
4-6-1 GC-MS之結果 96
4-6-2 UHPLC-QTOF-MS之結果 98
4-7 基質效應 102
4-7-1 GC-MS 102
4-7-2 UHPLC-QTOF-MS 103
4-8 方法確效 104
4-8-1 GC-MS 104
4-8-2 UHPLC-QTOF-MS 105
4-9 萃取方法比較 106
第五章結論 109
第六章參考文獻 111
附錄 121

參考文獻

1.台灣質譜學會，質譜分析技術原理與應用，2015。
2.黎正中、陳樹源，實驗設計與分析，2006。
3.衛生福利部食品藥物管理署，衛授食字號1051611716號, 2016 http://www.fda.gov.tw/TC/siteListContent.aspx?sid=1152&id=8568&chk=e8d90c513faf49b8a835d7b37d8ebcca¶m=pn%3D1%26sid%3D1152#.WL0VYfl95PZ
4.Assadi, Y.; Rezaee, M.; Mohammad-Reza, M. H.; Aghaee, E.; Ahmadi, F.; Berijani, S., Determination of organic compounds in water using dispersive liquid–liquid microextraction. Journal of Chromatography A, 2006, 1116, 1-9.
5.Aubert, N.; Ameller, T.; Legrand, J. J., Systemic exposure to parabens: pharmacokinetics, tissue distribution, excretion balance and plasma metabolites of [14C]-methyl-, propyl- and butylparaben in rats after oral, topical or subcutaneous administration. Food and Chemical Toxicology, 2012, 50, 445-454.
6.Bairati, C.; Goi, G.; Lombardo, A.; Tettamanti, G., The esters of p-hydroxy-benzoate (parabens) inhibit the release of lysosomal enzymes by mitogen-stimulated peripheral human lymphocytes in culture. Clinica Chimica Acta, 1994, 224, 147-157.
7.Ballesteros, O.; Vela-Soria, F.; Camino-Sánchez, F. J.; Zafra-Gómez, A.; Ballesteros, L.; Navalón, A., Matrix solid phase dispersion for the extraction of selected endocrine disrupting chemicals from human placental tissue prior to UHPLC-MS/MS analysis. Microchemical Journal, 2015, 118, 32- 39.
8.Błędzka, D.; Gromadzińska, J.; Wąsowicz, W., Parabens. From environmental studies to human health. Environment International, 2014, 67, 27-42.
9.Bruins, A. P., Mechanistic aspects of electrospray ionization. Journal of Chromatography A, 1998, 794, 345- 357.
10.Calafat, A. M.; Ye, X.; Kuklenyik, Z.; Bishop, A. M.; Needham, L. L., Quantification of the urinary concentrations of parabens in humans by on-line solid phase extraction-high performance liquid chromatography-isotope dilution tandem mass spectrometry. Journal of Chromatography B, 2006, 844, 53-59.
11.Calafat, A. M.; Ye, X.; Tao, L. J.; Needham, L. L., Automated on-line column-switching HPLC-MS/MS method for measuring environmental phenols and parabens in serum. Talanta, 2008, 76, 865-871.
12.Chen, H.; Chen, R.; Li, S., Low-density extraction solvent-based solvent terminated dispersive liquid–liquid microextraction combined with gas chromatography-tandem mass spectrometry for the determination of carbamate pesticides in water samples. Journal of Chromatography A, 2010a, 1217 (8), 1244-1248.
13.Chen, H.; Han, Y.; Jia, X.; Liu, X.; Duan, T., DLLME combined with GC–MS for the determination of methylparaben, ethylparaben, propylparaben and butylparaben in Beverage Samples. Chromatographia, 2010b, 72, 351-355.
14.Chen, P. H.; Chen, P. S.; Huang, S. D., Determination of pesticides in water and vegetable matter by manual shaking-enhanced, ultrasound assisted emulsification microextraction combined with gas chromatography-mass spectrometry. Agricultural and Biological Sciences, 2013, Chapter 15.
15.Chen, Q.; Pan, C. G.; Li, Y. J.; Zhang, M.; Gu, W., The combined effect of methyl- and ethyl-Paraben on lifespan and preadult development period of Drosophila melanogaster. Journal of Insect Science, 2016, 16, 1-8.
16.CIR, Final amended report on the safety assessment of methylparaben, ethylparaben, propylparaben, isopropylparaben, butylparaben, isobutylparaben, and benzylparaben as used in cosmetic products. International Journal of Toxicology, 2008, 27, 1–82.
17.CTFA, A one-month oral toxicity evaluation of product CN 0031/9 containing butyl paraben and propyl paraben in the rat. Study R04579. CTFA Code No. 2-7-40, 1980.
18.CTFA, CIR safety data test summary: oral, dermal and ocular testing of product containing methyl paraben and propyl paraben. CTFA Code No. 2-7-15, 1979.
19.Darbre, P. D.; Aljarrah, A.; Miller, W. R.; Coldham, N. G.; Sauer, M. J.; Pope, G. S., Concentrations of parabens in human breast tumours. Journal of Applied Toxicology, 2004, 24, 5-13.
20.Elder, R. L., Final report on the safety assessment of methylparaben, ethylparaben, propylparaben and butylparaben. Journal of the American College of Toxicology, 1984, 3, 147–209.
21.Engel, L. S.; Buckley, J. P.; Yang, G.; Liao, L. M.; Satagopan, J.; Calafat, A. M.; Mattews, C. E.; Cai, Q., Ji, B. T.; Cai, H.; Engel, S. M.; Wolff, M. S.; Rothman, N.; Zheng, W.; Xiang, Y. B.; Shu, X. O.; Gao, Y. T.; Chow, W. H., Predictors and variability of repeat measurements of urinary phenols and parabens in a cohort of Shanghai women and men. Enviromental Health Perspectives, 2014, 122, 733-740.
22.Fan, Y. C.; Hu, Z. L.; Chen, M. L.; Tu, C. S.; Zhu, Y., Ionic liquid based dispersive liquid–liquid microextraction of aromatic amines in water samples. Chinese Chemical Letters, 2008, 19 (8), 985-987
23.Farajzadeh, M. A.; Djozan, D.; Bakhtiyari, R. F., Use of a capillary tube for collecting an extraction solvent lighter than water after dispersive liquid-liquid microextraction and its application in the determination of parabens in different samples by gas chromatography--flame ionization detection. Talanta, 2010, 81, 1360-1367.
24.Farajzadeh, M. A.; Mogaddam, M. R. A., Air-assisted liquid–liquid microextraction method as a novel microextraction technique; Application in extraction and preconcentration of phthalate esters in aqueous sample followed by gas chromatography–flame ionization detection. Analytica Chimica Acta, 2012, 728, 31-38.
25.Fatemi, M. H.; Hadjmohammadi, M. R.; Shakeri, P.; Biparva, P., Extraction optimization of polycyclic aromatic hydrocarbons by alcoholic‐assisted dispersive liquid–liquid microextraction and their determination by HPLC. Journal of Separation Science, 2012, 35 (1), 86-92.
26.FDRL, Teratologic evaluation of FDA 71–38 (methyl paraben) U.S. NTIS report (PB-221 785), 1972, 42.
27.Ferreira, S. L.; Bruns, R. E.; Ferreira, H. S.; Matos, G. D.; David, J. M.; Brandao, G. C.; Da Silva, E. G.; Portugal, L. A.; Dos Reis, P. S.; Souza, A. S.; Dos Santos, W. N., Box-Behnken design: an alternative for the optimization of analytical methods. Analytica Chimica Acta 2007, 597 (2), 179-86.
28.Ferreira-Casas, A. M.; Möder, M.; Fernández-Laespada, M. E., Stir bar sorptive extraction of parabens, triclosan and methyl triclosan from soil,sediment and sludge with in situ derivatization and determination by gas chromatography–mass spectrometry. Journal of Chromatography A, 2011, 1218, 3837–3844.
29.Handa, O.; Kokura, S.; Adachi, S.; Takagi, T.; Naito, Y.; Tanigawa, T.; Yoshida, N.; Yoshikawa, T., Methylparaben potentiates UV-induced damage of skin keratinocytes. Toxicology, 2006, 227 (1-2), 62-72.
30.Hanson, S. R.; Best, M. D.; Wong, C. H., Sulfatases: structure, mechanism, biological activity, inhibition, and synthetic utility. Angewandte Chemie, 2004, 43, 5736-5763.
31.Jonkers, N.; Kohler, H. PE.; Dammshäuser, A.; Giger, W., Mass flows of endocrine disruptors in the Glatt River during varying weather conditions. Environmental Pollution, 2009, 157, 714-723.
32.Kannan, K.; Guo, Y.; Wang, L., Phthalates and parabens in personal care products from China:concentrations and human exposure. Archives of Environmental Contamination and Toxicology, 2014, 66, 113- 119.
33.Kannan, K.; Moreta, C.; Tena, M. T., Analytical method for the determination and a survey of parabens and their derivatives in pharmaceuticals. Environmental Research, 2015, 142, 452- 460.
34.Kannan, K.; Wang, L.; Wu, Y. H.; Zhang W., Characteristic profiles of urinary p-hydroxybenzoic acid and its esters (Parabens) in children and adults from the United States and China. Environmental Science & Technology, 2013, 47, 2069-2076.
35.Koeppe, E. S.; Ferguson, K. K.; Colacino, J. A.; Meeker, J. D., Relationship between urinary triclosan and paraben concentrations and serum thyroid measures in NHANES 2007-2008. Science of The Total Environment, 2013, 445-446, 299-305
36.Krebs-Smith, S.M.; Guenther, P.M.; Cook, A.; Thompson, F.E.; Cucinelli, J.; Udler, J., Foods commonly eaten in the United States: quantities consumed per eating occasion and in a day. NTIS PB 98-111719, 1997, 1–249.
37.Kubwabo, C.; Fan, X.; Rasmussena, P.; Jones-Otazob, H., Simultaneous quantitation of parabens, triclosan, and methyl triclosan in indoor house dust using solid phase extraction and gas chromatography-mass spectrometry. Journal of Environmental Monitoring, 2010, 12, 1891- 1897.
38.Lee, H. B.; Peart, T. E.; Svoboda, M. L., Determination of endocrine-disrupting phenols, acidic pharmaceuticals, and personal-care products in sewage by solid-phase extraction and gas chromatography-mass spectrometry. Journal of Chromatography A, 2005, 1094 (1-2), 122-129.
39.Lee, M. R.; Yang, T. J.; Tsai, F. J.; Chen, C. Y.; Yang, T. C., Determination of additives in cosmetics by supercritical fluid extraction on-line headspace solid-phase microextraction combined with gas chromatography–mass spectrometry. Analytica Chimica Acta, 2010, 668, 188- 194.
40.Leong, M. I.; Chang, C. C.; Fuh, M. R.; Huang, S. D., Low toxic dispersive liquid–liquid microextraction using halosolvents for extraction of polycyclic aromatic hydrocarbons in water samples. Journal of Chromatography A, 2010, 1217 (34), 5455-5461.
41.Leong, M. I.; Huang, S. D., Dispersive liquid–liquid microextraction method based on solidification of floating organic drop combined with gas chromatography with electron-capture or mass spectrometry detection. Journal of Chromatography A, 2008, 1211 (1), 8-12.
42.Liao, C.; Chen, L.; Kannan, K., Occurrence of parabens in foodstuffs from China and its implications for human dietary exposure. Environment International, 2013, 57, 68-74.
43.Marcé, R. M.; Ramírez, N.; Borrull, F., Determination of parabens in house dust by pressurised hot water extraction followed by stir bar sorptive extraction and thermal desorption–gas chromatography–mass spectrometry. Journal of Chromatography A, 2011, 1218, 6226- 6231.
44.Mason, M. M.; Cate, C. C.; Baker, J., Toxicology and carcinogenesis of various chemicals used in the preparation of vaccines. Clinical Toxicology, 1971, 4 (2), 185-204.
45.Matthews, C.; Davidson, J.; Bauer, E.; Morrison, J.L.; Richardson, A.P., p-Hydroxybenzoic acid esters as preservatives. II. Acute and chronic toxicity in dogs, rats, and mice. Journal of American Pharmaceutical Association, 1956, 45, 260–267.
46.McCann, J.; Choi, E.; Yamasaki, E.; Ames, B. N., Detection of carcinogens as mutagens in the Salmonella / microsome test : assay of 300 chemicals. Proceedings of the National Academy of Sciences of the United States of America, 1975, 72, 5135-5139.
47.Meeker, J. D.; Yang, T.; Ye, X.; Calafat, A. M.; Hauser, R., Urinary concentrations of parabens and serum hormone levels, semen quality parameters, and sperm DNA damage. Environmental Health Perspectives, 2011, 119, 252-257.
48.Mudiam-Reddy, M. K.; Jain, R.; Chauhan, A.; Ratnasekhar, C.; Murthy, R. C.; Khan, H. A., Simultaneous derivatisation and preconcentration of parabens in food and other matrices by isobutyl chloroformate and dispersive liquid–liquid microextraction followed by gas chromatographic analysis. Food Chemistry, 2013, 141, 436–443.
49.Myridakis, A.; Balaska, E.; Gkaitatzi, C.; Kouvarakis, A.; Stephanou, E. G., Determination and separation of bisphenol A, phthalate metabolites and structural isomers of parabens in human urine with conventional high-pressure liquid chromatography combined with electrospray ionisation tandem mass spectrometry. Analytical and Bioanalytical Chemistry, 2015, 407, 2509-2518.
50.Nakagawa, Y.; Moldeus, P., Mechanism of p-hydroxybenzoate ester-induced mitochondrial dysfunction and cytotoxicity in isolated rat hepatocytes. Biochemical Pharmacology, 1998, 55, 1907–1914.
51.Navalón, A.; Vela-Soria, F.; Ballesteros, O.; Zafra-Gómez, A.; Ballesteros, L., A multiclass method for the analysis of endocrine disrupting chemicals in human urine samples. Sample treatment by dispersive liquid–liquid microextraction. Talanta, 2014, 129, 09- 218.
52.Pavón- Pérez, J. L.; Ferreira-Casas, A. M.; Laespada- Fernández, M. E.; Cordero, B. M., In situ aqueous derivatization as sample preparation technique for gas chromatographic determinations. Journal of Chromatography A, 2013, 1296, 70- 83.
53.Pompy, L.; Karlin, A.; Capuano, C.M.; Cottrell, J.E.; Hartung, J., Paraben preservatives do not increase intracranial pressure incats. Anesthesiology, 1991, 75, 669–672.
54.Püttmann, W.; Potouridis, T.; Berger, E., Analysis of alkyl esters of p-hydroxybenzoic acid (parabens) in baby teethers via gas chromatography-quadrupole mass spectrometry (GC-qMS) using a stable isotope dilution assay (SIDA). Analytical Methods, 2016, 8, 3466- 3474.
55.Ramaswamy, B. R.; Shanmugam, G.; Radhakrishnan, V.; Tao, H., GC–MS method for the determination of paraben preservatives in the human breast cancerous tissue. Microchemical Journal, 2010, 96, 391- 396.
56.Ramaswamy, B. R.; Shanmugam, G.; Velu, G.; Rengarajan, B.; Joakim-Larsson, D. G., GC–MS analysis and ecotoxicological risk assessment of triclosan, carbamazepine and parabens in Indian rivers. Journal of Hazardous Materials, 2011, 186, 1586–1593.
57.Regueiro, J.; Becerril, E.; Garcia-Jares, C.; Llompart, M., Trace analysis of parabens, triclosan and related chlorophenols in water by headspace solid-phase microextraction with in situ derivatization and gas chromatography-tandem mass spectrometry. Journal of Chromatography A, 2009, 1216 (23), 4693-702.
58.Regueiro, J.; Llompart, M.; Garcia-Jares, C.; Garcia-Monteagudo, J. C.; Cela, R., Ultrasound-assisted emulsification-microextraction of emergent contaminants and pesticides in environmental waters. Journal of Chromatography A, 2008, 1190 (1-2), 27-38.
59.Rodriguez, I.; Canosa, P.; Rubi, E.; Cela, R., Determination of parabens and triclosan in indoor dust using matrix solid-phase dispersion and gas chromatography with tandem mass spectrometry. Analytical Chemistry, 2007, 79, 1675- 1681.
60.Rodríguez-Mozaz, S.; Jakimska, A.; Huerta, B.; Barganska, Z.; Kot-Wasika, A.; Barceló, D., Development of a liquid chromatography–tandem mass spectrometry procedure for determination of endocrine disrupting compounds in fish from Mediterranean rivers. Journal of Chromatography A, 2013, 1306, 44- 58.
61.Routledge, J; Parker, J; Odum, J; Ashby, J; Sumpter, J.P., Some alkyl hydroxy benzoate preservatives (parabens) are estrogenic. Toxicology and Applied Pharmacology, 1998, 153, 12–9.
62.Rowlingson, J. C., Toxicity of local anasthetic additives. Regulatory Anesthesiology, 1993, 18, 453–460.
63.Rudel, R. A.; Camann, D. E.; Spengler, J. D.; Korn, L. R.; Brody, J. G., Phthalates, alkylphenols, pesticides, polybrominated diphenyl ethers and other endocrine-disrupting compounds in indoor air and dust. Environmental Science & Technology, 2003, 37, 4543-4553.
64.SCCS, No 358/20142, 2014
http://data.europa.eu/eli/reg/2014/358/oj
65.Schlittenbauer, L.; Seiwert, B.; Reemtsma, T., Ultrasound-assisted hydrolysis of conjugated parabens in human urine and their determination by UPLC–MS/MS and UPLC–HRMS. Analytical and Bioanalytical Chemistry, 2016, 408, 1573- 1583.
66.Skoog, D. A.; Holler, F. J.; Nieman, T. A., Principles of Instrumental Analysis. 5th ed., Thomson Brooks/ Cole, 2002.
67.Soni, M. G.; Carabin, I. G.; Burdock, G. A., Safety assessment of esters of p-hydroxybenzoic acid (parabens). Food and Chemical Toxicology , 2005, 43, 985-1015.
68.Tadeo, J. L.; Núnez, L.; García-Valcárcel, A. I.; Turiel, E., Determination of parabens in environmental solid samples by ultrasonic-assisted extraction and liquid chromatography with triple quadrupole mass spectrometry. Journal of Chromatography A, 2008, 1214, 178-182.
69.Tena, M. T.; Canosa, P.; Perez-Palacios, D.; Garrido-Lopez, A.; Rodriguez, I.; Rubi, E.; Cela, R., Pressurized liquid extraction with in-cell clean-up followed by gas chromatography–tandem mass spectrometry for the selective determination of parabens and triclosan in indoor dust. Journal of Chromatography A, 2007, 1161, 105–112.
70.Terasaki, M.; Makino, M., Determination of chlorinated by-products of parabens in swimming pool water. Journal of Environmental Analytical Chemistry, 2008, 88, 911–922.
71.Tsai, T. F.; Lee, M. R., Determination of Antioxidants and Preservatives in Cosmetics by SPME Combined with GC–MS. Chromatographia 2008, 67, 425-431.
72.Vela-Soria, F.; Ballesteros, O.; Zafra-Gómez, A.; Ballesteros, L.; Navalón, A., UHPLC-MS/MS method for the determination of bisphenol A and its chlorinated derivatives, bisphenol S, parabens, and benzophenones in human urine samples. Analytical and Bioanalytical Chemistry, 2014, 406, 3773-3785.
73.Viglino, L.; Prévost, M.; Sauvé, S., High throughput analysis of solid-bound endocrine disruptors by LDTD-APCI-MS/MS. Journal of Enviromental Monitoring, 2011, 13, 583-590.
74.Vocadlo, D. J.; Davies, G. J.; Laine, R.; Withers, S. G., Catalysis by hen egg-white lysozyme proceeds via a covalent intermediate. Nature, 2001, 412, 835-838.
75.Wang, L.; Liu, T.; Liu, F.; Zhang, J.; Wu, Y.; Sun, H., Occurrence and profile characteristics of the pesticide imidacloprid, preservative parabens, and their metabolites in human urine from rural and urban China. Enviromental Science Technology, 2015, 49, 14633- 14640.
76.Wu, Q.; Chang, Q.; Wu, C.; Rao, H.; Zeng, X.; Wang, C.; Wang, Z., Ultrasound-assisted surfactant-enhanced emulsification microextraction for the determination of carbamate pesticides in water samples by high performance liquid chromatography. Journal of Chromatography A, 2010, 1217 (11), 1773-1778.
77.Xu, L.; Wang, Q.; Ma, L.; Yin, C., Developments in injection port derivatization. Journal of Chromatography A, 2013, 1296, 25- 35.
78.Ye, X.; Bishop, A. M.; Needham, L. L.; Calafat, A. M., Automated on-line column-switching HPLC-MS/MS method with peak focusing for measuring parabens, triclosan, and other environmental phenols in human milk. Analytica Chimica Acta, 2008a, 622, 150- 156.
79.Ye, X.; Tao, L. J.; Needham, L. L.; Calafat, A. M., Automated on-line column-switching HPLC–MS/MS method for measuring environmental phenols and parabens in serum. Talanta, 2008b, 76, 865–871.
80.Yiantzi, E.; Psillakis, E.; Tyrovola, K.; Kalogerakis, N., Vortex-assisted liquid–liquid microextraction of octylphenol, nonylphenol and bisphenol-A. Talanta, 2010, 80 (5), 2057-2062.
81.Yoshinaga, J.; Shiraia, S.; Yoshinaga, J.; Shiraishib, H.; Mizumoto, Y., Urinary excretion of parabens in pregnant Japanese women. Reproductive Toxicology, 2013, 35, 96- 101.
82.Zgoła-Grześkowiak, A.; Grześkowiak, T., Dispersive liquid-liquid microextraction. TrAC Trends in Analytical Chemistry, 2011, 30, 1382-1399.
83.Zhang, G.; Annan, R. S.; Carr, S. A.; Neubert, T. A., Overview of peptide and protein analysis by mass spectrometry. Current Protocols in Protein Science, 2010, 16.1.1-16.1.30.
84.Zhang, Y.; Lee, H. K., Determination of ultraviolet filters in water samples by vortex-assisted dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry. Journal of Chromatography A, 2012, 1249, 25-31.
85.Zhou, F.; Zhang, L.; Liu, A.; Shen, Y.; Yuan, J.; Yu, X.; Feng, X.; Xu, Q.; Cheng, C., Measurement of phenolic environmental estrogens in human urine samples by HPLC-MS/MS and primary discussion the possible linkage with uterine leiomyoma. Journal of Chromatography. B, 2013, 938, 80-85.
86.Zhou, Z.; Lu, D.; Feng, C.; Wang, D.; Lin, Y.; Simon, H. S.; She, J.; Xu, Q.; Wu, C.; Wang, G., Analysis of twenty phenolic compounds in human urine:hydrochloric acid hydrolysis, solid-phase extraction based on K2CO3-treated silica, and gas chromatography tandem mass spectrometry. Analytical and Bioanalytical Chemistry, 2015, 407, 4131–4141.

指導教授

丁望賢

審核日期

2017-6-21

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