| 研究生: |
邱意騰 I-Teng Chiu |
|---|---|
| 論文名稱: |
以新開發雙重震盪輔助基質固相分散萃取法檢測蔬菜樣品中防曬乳成分之殘留 |
| 指導教授: | 丁望賢 |
| 口試委員: | |
| 學位類別: |
碩士 Master |
| 系所名稱: |
理學院 - 化學學系 Department of Chemistry |
| 論文出版年: | 2022 |
| 畢業學年度: | 110 |
| 語文別: | 中文 |
| 論文頁數: | 104 |
| 中文關鍵詞: | 雙重震盪輔助基質固相分散萃取法 、二苯基甲酮 、防曬乳成分 、超高效液相層析儀串聯電灑游離-四極桿飛行時間質譜儀 、實驗設計 、綠色化學分析方法 |
| 相關次數: | 點閱:9 下載:0 |
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本研究開發了一套快速方便、直接萃取且符合綠色分析化學的樣品前處理方法來檢測市售蔬菜樣品中五種防曬乳成分-二 苯基甲酮 (benzophenones, 簡稱 BPs) 的殘留。由於在護膚保養品、汽車部件、食品外包裝塗料當中都有使用 BPs,然而近期研究指出,BPs 在生物系統中不僅含有潛在的危害性,且藉由生物積累的方式,易對環境生物及人類造成負面影響。
而本研究新開發了雙重震盪輔助基質固相分散萃取法(double-vortex-assisted matrix solid-phase dipersion, 簡稱 DVA-MSPD),省去了使用研缽研磨及固相萃取過程中管柱沖提的過程,接著再利用超高效液相層析串聯電灑游離 (+) −四極桿飛行時間質譜儀 (UHPLC−ESI(+)−QTOF−MS) 進行後續檢測。並利用 Multilevel Categoric Design 選擇實驗過程中非數值因子的種類,以及使用 Box−Behnken Design (BBD)中的變異數分析(Analysis of Variance, ANOVA)優化各項數值因子以找出實驗的最佳條件。本實驗方法最佳條件為:取0.2 g 蔬菜粉末與0.2 g C18吸附劑,震盪1分鐘使其均勻分散,省去了傳統研缽的使用。加入7 mL 萃取劑甲醇並震盪3分鐘進行萃取,代替了以往 SPE 管柱沖提的部分。以5500 rpm 離心15分鐘,取出上層液,吹氮濃縮到乾,再以200 μL 甲醇回溶,然後以3 μL 進樣到UHPLC-ESI-QTOF-MS 進行檢測。
使用 DVA-MSPD 方法,成功測量5種 BPs,定量極限(LOQ) 介於1-9.5 ng/g, Inter−day 和 Inter−day 的相對標準偏差(RSD) 介於2 %−14 % 之間,而萃取回收率則介在67 %−120 % 之間,表示本方法呈現良好的準確性及穩定度。而在市售的蔬菜樣品中都有檢測到不同濃度的 BPs 殘留。
In this study, A novel double-vortex-assisted matrix solid-phase(DVA-MSPD)technique, without the use of motor/pestle and SPE-column elution procedure, was developed to determine the presence of five benzophenone-type (BPs) UV-filters in marketed vegetables. This procedure is a straightforward, simple and efficient method. The target analyte were rapidly extracted from the vegetable and then detected by an ultrahigh-performance liquid chromatography and electrospray ionization(+)-quadrupole time-of-flight mass spectrometry (UHPLC-ESI(+)-QTOF- MS). The DVA-MSPD extraction factors were screened by means of a multilevel categorical design and a Box-Behnken Design plus with response surface methodology was used to overcome the challenges related to different experimental conditions.
The optimal conditions of DVA-MSPD were: powdered vegetable sample 0.2 g was dispersed with 0.2 g C18 adsorbent by vortex- homogenized for 1 min (without using mortar/pestle), and 8 mL of methanol (as an extractant) was added, and the content was thoroughly vortex-extracted for 5 min(SPE-column-free). Then for 15 min, the phase was separated by centrifugation at 5500 rpm. The supernatant was evaporated to dryness, and re-dissolved in a 200 μL of methanol. The extract 3 μL was then directly injected into UHPLC-QTOF-MS for detection.
The developed method was validated, and provided low limits of quantification (LOQs) ranging from 1 to 9.5 ng/g ; high precisions for both repeatability and reproducibility ranging from 2 to 14 %; and high accuracy (mean extraction recovery) ranging from 67 to 120 % at two spiked concentration levels. The developed method was then successfully applied for the analysis of BPs in marketed vegetables.
Alfonso, D.M.; Paola, F.; Danilo, A.B.; Roberto, D.; Serenella, S.; Patrizia, M., Application of solid-phase extraction and liquid chromatography–mass spectrometry to the determination of neonicotinoid pesticide residues in fruit and vegetables, Journal of Chromatography A 2006, 1108, 1-6.
Anderson, W.A.C.; Castle, L., Benzophenone in cartonboard packaging materials and the factors that influence its migration into food, Food Additives & Contaminants 2015, 20, 607-618.
Armin, Z.; Hansruedi, S.; Karl, F., Simultaneous trace determination of nine organic UV-absorbing compounds (UV filters) in environmental samples, Journal of Chromatography A 2008, 1202, 64-74.
Barker, S.A.; Kappel, L.C.; Short, C.R, Tissue distribution and clearance of the cephalosporin cefquinome in the bovine, EuroResidueⅡ, 1993, 165-169.
Blasco, C.; Font, G.; Picó, Y., Comparison of microextraction procedures to determine pesticides in oranges by liquid chromatography–mass spectrometry, Journal of Chromatography A 2002, 970, 201-212.
Blüthgen, N.; Sara, Z.; Karl, F., Effects of the UV filter benzophenone-3 (oxybenzone) at low concentrations in zebrafish (Danio rerio), Toxicology and Applied Pharmacology 2012, 263, 184-194.
Bryden, A.M.; Moseley, H.; Ibbotson, S.H., Photopatch testing of 1155 patients: results of the UK multicentre photopatch study group, British Journal of Dermatology 2006, 155, 737–747.
Box, G. E. P.; Behnken, D. W.: Some new three level designs for the study of quantitative variables, Technometrics 1960, 2, 455-475.
Chen, H.C.; Chang, J.W.; Sun, Y.C.; Chang, W.T.; Huang, P.C., Determination of Parabens, Bisphenol A and Its Analogs, Triclosan, and Benzophenone-3 Levels in Human Urine by Isotope-Dilution-UPLCMS/MS Method Followed by Supported Liquid Extraction, Toxics 2022, 10, 21.
Chen, M.L.; Chen, C.H.; Huang, Y.F.; Chen, H.C.; Chang, J.W., Cumulative Dietary Risk Assessment of Benzophenone-Type Photoinitiators from Packaged Foodstuffs, Foods 2022, 11, 152.
Christin, J.W.; Petra, Y.; Kunz, A.K.; Zenker, K.F., Effects of the UV filter benzophenone-2 on reproduction in fish, Toxicology and Applied Pharmacology 2007, 225, 255-266.
Chung, W.H.; Tzing, S.H.; Ding, W.H., Optimization of dispersive micro solid-phase extraction for the rapid determination of benzophenone-type UV absorbers in aqueous samples, Journal of Chromatography A 2015, 1411, 12-17.
Core-shell technology, https://www.chromservis.eu/i/core-shell-technology/c/stationary-phases-overview
El-Dareer, S.M.; Kalin, J.R.; Tillery, K.F.; Hill, D.L., Disposition of 2‐hydroxy‐4‐ methoxybenzophenone in rats dosed orally, intravenously, or topically, Journal of Toxicology and Environmental Health 1986, 19, 491–502.
Fent, K.; Kunz, P.Y.; Gomez, E., UV Filters in the Aquatic Environment Induce Hormonal Effects and Affect Fertility and Reproduction in Fish, CHIMIA 2008, 62, 368-375.
Fernández Moreno, J.L.; Arrebola Liébanas, F.J.; Garrido Frenich, A.J.; Martínez Vidal, L., Evaluation of different sample treatments for determining pesticide residues in fat vegetable matrices like avocado by low-pressure gas chromatography–tandem mass spectrometry, Journal of Chromatography A 2006, 1111, 97-105.
Finkel, P.; Formulierung, K.S.; Seifen, O.F.W., Occurrence of UV filter compounds from sunscreens in surface waters., Chemosphere 1996, 7, 543–548.
Gago-Ferrero, P.; Díaz-Cruz, M.S.; Barceló, D., Fast pressurized liquid extraction with in-cell purification and analysis by liquid chromatography tandem mass spectrometry for the determination of UV filters and their degradation products in sediments. Analytical and Bioanalytical Chemistry 2011, 400, 2195–2204.
Gałuszka, A.; Konieczka, P.; Migaszewski, Z.M.; Namies´nik, J., Analytical Eco-Scale for assessing the greenness of analytical procedures, Trends in Analytical Chemistry 2012, 37, 61-72.
Gao, L.; Yuan, T.; Zhou, C.; Cheng, P.; Bai, Q.; Ao, J.; Wang, W.; Zhang, H., Effects of four commonly used UV filters on the growth, cell viability and oxidative stress responses of the Tetrahymena thermophila, Chemosphere 2013, 93, 2507-2513,
Hayden, C.G.J.; Roberts, M.S.; Benson, H.A.E., Systemic absorption of sunscreen after topical application, The Lancet 1997, 350, 863–864.
Ho, Y.C.; Ding, W.H., Solid-phase Extraction Coupled Simple On-line Derivatization Gas Chromatography Tandem Mass Spectrometry for the Determination of Benzophenone-type UV Filters in Aqueous Samples, Journal of the Chinese Chemical Society 2012, 59, 107-113.
Hongxia, G.; William E.; Brewer, S.T.; Garris, S.L.M., Disposable pipette extraction for the analysis of pesticides in fruit and vegetables using gas chromatography/mass spectrometry, Journal of Chromatography A 2010, 1217, 1867-1874.
Irene, A.; Julia, M.; Concepción, A.; Juan, L.S.; Esteban, A., Determination of household and industrial chemicals, personal care products and hormones in leafy and root vegetables by liquid chromatography-tandem mass spectrometry, Journal of Chromatography A 2018, 1533, 49-56.
Janjua, N.R.; Kongshoj, B.; Andersson, A.M.; Wulf, H.C., Sunscreens in human plasma and urine after repeated whole-body topical application, Journal of the European Academy of Dermatology and Venereology 2008, 22, 456–461.
Janjua, N.R.; Mogensen, B.; Andersson, A.M.; Petersen, J.H.; Henriksen, M.; Skakkebaek, N.E., Systemic absorption of the sunscreens benzophenone-3, octyl-methoxycinnamate, and 3-(4-methyl-benzylidene) camphor after whole-body topical application and reproductive hormone levels in humans, Journal of Investigative Dermatology 2004, 123, 57–61.
Jeon, H.K.; Chung, Y.; Ryua, J.C., Simultaneous determination of benzophenone-type UV filters in water and soil by gas chromatography–mass spectrometry, Journal of Chromatography A 2006, 1131, 192-202.
Jessica, H.U.; Jessica, R.C., Migration of food contact substances into dry foods: A review, Food Additives & Contaminants 2021, 38, 1044-1073.
Joseph, C.D.N.; Craig, A.D., Dermatological and Environmental Toxicological Impact of the Sunscreen Ingredient Oxybenzone/Benzophenone-3, Journal of Cosmetic Dermatology 2017, 17, 15-19.
Karl, F.; Armin, Z.; Maja, R., Widespread occurrence of estrogenic UV-filters in aquatic ecosystems in Switzerland, Environmental Pollution 2010, 158, 1817-1824.
Ke, H.; Anne, T.; Lee B., Simultaneous determination of UV-filters and estrogens in aquatic invertebrates by modified quick, easy, cheap, effective, rugged, and safe extraction and liquid chromatography tandem mass spectrometry, Journal of Chromatography A 2017, 1509, 91-101.
Kunisue, T.; Chen, Z.; Louis, G.M.B.; Sundaram, R.; Hediger, M.L.; Sun, L.; Kannan, K., Urinary Concentrations of Benzophenone-type UV Filters in U.S. Women and Their Association with Endometriosis, Environmental Science & Technology 2012, 46, 4624-4632.
Lihuan, H.; Miaomiao, T.; Wenxia, F.; Huiyu, H.; Yuanhong, W.; Li, Y., Sensitive detection of benzophenone-type ultraviolet filters in plastic food packaging materials by sheathless capillary electrophoresis–electrospray ionization–tandem mass spectrometry, Journal of Chromatography A 2019, 1604, 460-469.
Liu, H.; Sun, P.; Liu, H.; Yang, S.; Wang, L.S.; Wang, Z.Y., Acute toxicity of benzophenone-type UV filters for Photobacterium phosphoreum and Daphnia magna: QSAR analysis, interspecies relationship and integrated assessment, Chemosphere 2015, 135, 182-188.
Mao, F.; You, L.; Reinhard, M.; He, Y.; Gin, K.Y.H., Occurrence and Fate of Benzophenone-Type UV Filters in a Tropical Urban Watershed, Environmental Science & Technology 2018, 52, 3960-3967.
Mateus, H.P.K.; Kosjek, T.; Krajnc, U.; Heath, E., Trace analysis of benzophenone-derived compounds in surface waters and sediments using solid-phase extraction and microwave-assisted extraction followed by gas chromatography–mass spectrometry, Analytical and Bioanalytical Chemistry 2014, 406, 3179-3190.
Minuț, M.; Rosca, M.; Cozma, P.; Catrinescu, C; Gavrilescu, M., Ecological and Human Health Risks Generated by Organic UV Filters, E-Health and Bioengineering Conference 2019, 1-4.
Negreira, N.; Rodríguez, I.; Ramil, M.; Rubí, E.; Cela, R., Solid-phase extraction followed by liquid chromatography–tandem mass spectrometry for the determination of hydroxylated benzophenone UV absorbers in environmental water samples, Analytica Chimica Acta 2009, 654, 162-170.
Negreira, N.; Rodríguez, I.; Rubí, E.; Cela, R., Optimization of pressurized liquid extraction and purification conditions for gas chromatography–mass spectrometry determination of UV filters in sludge, Journal of Chromatography A 2011, 1218, 211-217.
Okereke, C.S.; Kadry, A.M.; Abdel-Rahman, M.S.; Davis, R.A.; Friedman, M.A., Metabolism of benzophenone-3 in rats, Drug Metabolism and Disposition 1993, 21, 788–91.
Pablo, G.F.M.; Silvia, D.C.; Damià, B., Multi-residue method for trace level determination of UV filters in fish based on pressurized liquid extraction and liquid chromatography–quadrupole-linear ion trap-mass spectrometry, Journal of Chromatography A 2013, 1286, 93-101.
Palm, M.D.; O'Donoghue, M.N., Update on photoprotection., Dermatology Therapy 2007, 20, 360–376.
Sánchez-Brunete, C.; Ester, M.; Beatriz, A.; José, T., Analysis of salicylate and benzophenone-type UV filters in soils and sediments by simultaneous extraction cleanup and gas chromatography-mass spectrometry, Journal of Chromatography A 2011, 1218, 4291-4298.
Sancho, J.V.; Ibáñez, M.; Grimalt, S.; Pozo, Ó.J.; Hernández, F., Residue determination of cyromazine and its metabolite melamine in chard samples by ion-pair liquid chromatography coupled to electrospray tandem mass spectrometry, Analytica Chimica Acta 2005, 530, 237-243.
Santos Delgado, M.J.; Barroso, S.R.; Toledano, G.; Fernández-Tostado, L.; Polo-Dı́ez, M., Stability studies of carbamate pesticides and analysis by gas chromatography with flame ionization and nitrogen–phosphorus detection, Journal of Chromatography A 2001, 921, 287-296.
Schlumpf, M.; Schmid, P.; Durrer, S., Endocrine activity and developmental toxicity of cosmetic UV filters-an update, Toxicology 2004, 205, 113-122.
Shen, D.; Lian, H.; Ding, T., Determination of low-level ink photoinitiator residues in packaged milk by solid-phase extraction and LC-ESI/MS/MS using triple-quadrupole mass analyzer, Analytical and Bioanalytical Chemistry 2009, 395, 2359-2370.
Valle, S.J.; Molins, D.D.; Díaz, M.; Ibáñez, L.; Barceló, D.M.; Díaz, S.C., Determination of parabens and benzophenone-type UV filters in human placenta, Environment International 2016, 88, 243-249.
Vela-Soria, F.; Ballesteros, O.; Zafra-Gómez, A.; Ballesteros, L.; Navalón, A., A new method for the determination of benzophenone-UV filters in human serum samples by dispersive liquid–liquid microextraction with liquid chromatography–tandem mass spectrometry, Talanta 2014, 121, 97-104.
Vela-Soria, F.; Jiménez-Díaz, I.; Rodríguez-Gómeza, R.; Zafra-Gómeza, A.; Ballesterosa, O.; Navalóna, A.; Vílcheza, J.L.; Fernándezb, M.F.; Olea, N., Determination of benzophenones in human placental tissue samples by liquid chromatography–tandem mass spectrometry, Talanta 2011, 85, 1848-1855.
Wang, T.E.; Guo, M.; Song, W.L.; Zhang, Y.D.; Du, X.Z., A new nitrogen-containing carbon nanoparticles coated stainless steel fiber for selective solid-phase microextraction of ultraviolet filters, Analytical Methods 2015, 7, 3385-3394.
Wasserstein, R.L.; Lazar, N.A., The ASA's statement on p-values: context, process, and purpose. The American Statistician 2016, 70, 129-133.
Yoko, W.; Hiroyuki, K.; Shinji, T.; Naoto, U.; Seigo, S.; Kazumi, S.; Shigeyuki, K.; Shigeru, O., Metabolism of UV-filter benzophenone-3 by rat and human liver microsomes and its effect on endocrine-disrupting activity, Toxicology and Applied Pharmacology,Volume 2015, 282, 119-128.
Zhang, Q.; Maa, X.; Dzakpasua, M.; Wanga, X.C., Evaluation of ecotoxicological effects of benzophenone UV filters: Luminescent bacteria toxicity genotoxicity and hormonal activity, Ecotoxicology and Environmental Safety 2017, 142, 338- 347.
Zhang, T.; Sun, H.; Qin, X.; Wu, Q.; Zhang, Y.; Jing, M.; Kannan, K., Benzophenone-type UV filters in urine and blood from children, adults, and pregnant women in China: Partitioning between blood and urine as well as maternal and fetal cord blood, Science of The Total Environment 2013, 461–462, 49-55.
Zhang, Z.; Ren, N.; Li, Y.F.; Kunisue, T.; Gao, D.; Kannan, K., Determination of Benzotriazole and Benzophenone UV Filters in Sediment and Sewage Sludge, Environmental Science & Technology 2011, 45, 3909–3916.
行政院環境保護署毒物及化學物質局,陳亭瑋,環境荷爾蒙就在你身邊? 2017, https://www.tcsb.gov.tw/cp-263-2723-6359e-1.html