簡易檢索 / 詳目顯示

回結果列表
研究生： 黃筱媛
Huang, Hsiao-Yuan
論文名稱： 分子模板應用於鄰苯二甲酸酯類分析技術之研發
Development of Molecular Imprinting Polymers for the Analysis of Phthalate Esters
指導教授： 林達昌
Lin, Ta-Chang
學位類別： 碩士
Master
系所名稱： 工學院 - 環境工程學系
Department of Environmental Engineering
論文出版年： 2011
畢業學年度： 99
語文別： 中文
論文頁數： 107
中文關鍵詞： 鄰苯二甲酸酯類 、分子模板 、固相萃取 、氣相層析儀
外文關鍵詞： phthalate esters, MIP, SPE, GC-MS
相關次數： 點閱：141  下載：0 
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報

    • 鄰苯二甲酸酯類（Phthalate esters, PAEs）為環境中微量化學物質，因分布廣泛且環境介質中成分複雜，造成其分析上的困難，樣品的前處理過程繁雜費時。
    本研究結合以DEHP為目標分子所製備之分子模板（Molecular imprinting polymers, MIP）與固相萃取（Solid phase extraction, SPE）技術，沖提後之溶液再以GC-MS分析，目的為提高分子模板吸附DEHP回收率及專一性，能有效去除環境樣品中干擾分析效果之雜訊並提高前處理效率。
    本研究參考文獻並依據現行較佳的分子模板製備比例，目標分子、官能基單體、交聯劑與起始劑之毫莫爾比製備五種不同比例之模板，隨後進行吸附容量測試（capacity）、吸附因子測試（imprinting factor, IF）、SEM表面觀察、選擇性吸附容量測試（capacity of selectivity）、選擇性吸附因子測試（IF of selectivity）、重複使用性測試以及環境樣品測試。
    實驗結果顯示， M5（目標分子、官能基、交聯劑、起始劑毫莫爾比約為1: 4: 30: 0.2）吸附容量最大，為613.3 ± 30.7 µg/g；製備為MISPE-5時回收率為90.9 ± 1.8 %。M4（目標分子、官能基、交聯劑、起始劑毫莫爾比約為1: 6: 20: 0.2）吸附因子最大，於initial conc. 為15 ppm時，IF值為1.95，但製備為MISPE-4時其回收率僅46.8 ± 1.9 %，表示M4可能不適合用於SPE，但可供之後研究做為參考。

    Phthalate esters are widely used. Due to their extremely low concentrations, tedious sample preparation must be done before the final analysis by a GC-MS. These procedures are not only time- and solvent-consuming, but also inappropriate to removing interferences.
    In this study, di-(2-ethylhexyl) phthalate was selected as the template molecule. Molecular imprinting polymers (MIP) and solid phase extraction were combined as the sample pretreatment instrument – MISPE. Samples were extracted by MISPE, and then the extracts were analyzed with a GC-MS.
    Five different ratios of template (DEHP), functional monomer (methacrylic acid), cross-linker (ethylene glycol dimethacrylate), initiator (2,2-azobis(2-isobutyronitrile)) and porogenic solvent (acetonitrile) of MIPs as well as the corresponding molecular imprinting polymers without template (NIPs) were synthesized. The polymers were tested for the material characteris¬tics of capacity, imprinting factor, capacity of selectivity, IF of selectivity, recovery, and finally tested for environmental sampling.
    The results showed that the MIP, tagged as M5 (template: monomer: cross-linker: initiator = 1:4:30:0.2), provided the best capacity (613.3 ± 30.7 μg/g) and the recovery of DEHP was about 90.9 ± 1.8 %. M4 (template: monomer: cross-linker: initiator = 1:6:20:0.2) showed the best IF (1.95 when initial concentration was 15 ppm). However, the recovery of M4 for DEHP was only 46.8 ± 1.9 %, which means it was not appropriate for M4 to be used as MISPE.
    All the experimental results suggest that MISPE-5 showed good recovery of DEHP among the 3 different PAEs in mixture and the aqueous samples used in this study, and reduce pretreatment time and background interferences when analyzed by GC-MS.

    第一章 前言 ......................................1 1.1 研究動機 ......................................1 1.2 研究目的 ......................................2 第二章 文獻回顧 ......................................3 2.1 微量分析之概念與應用 ......................3 2.1.1 微量分析與樣品前處理 ......................3 2.1.2 固相萃取法之概念與應用 ......................5 2.2 分子模板之概念與應用 ......................7 2.2.1 分子模板概念 ..............................7 2.2.2 分子模板之合成 ..............................8 2.3 鄰苯二甲酸酯類(Phthalate Esters, PAEs) .....12 2.3.1 環境荷爾蒙 .............................12 2.3.2 國內外相關法規 .............................13 2.3.3 鄰苯二甲酸酯類之特性 .....................19 2.3.4 環境流佈 .....................................24 2.3.5 暴露途徑及危害 .............................26 2.3.6 現行環境污染物分析方法 .....................28 第三章 實驗方法與設備 .............................35 3.1 分子模板製備 .............................38 3.2 分子模板材料測試 .............................41 3.2.1 吸附容量與吸附因子測試 .....................42 3.2.2 選擇性測試 .............................43 3.2.3 掃描式電子顯微鏡觀察 .....................43 3.3 分子模板結合固相萃取管柱(MISPE)測試 .............45 3.3.1 DEHP回收率測試 .............................49 3.3.2 選擇性測試 .............................49 3.3.3 重複使用性測試 .............................51 3.4 環境樣品結合MISPE測試 .....................52 3.4.1 環境樣品之處理 .............................53 3.4.2 MISPE結合環境樣品測試 .....................54 3.4.3 鄰苯二甲酸酯類之分析 .....................54 第四章 數據分析之品質保證與控制 .....................56 4.1 空白試驗 .....................................56 4.1.1 溶劑空白試驗 .............................56 4.1.2 程序空白試驗 .............................56 4.2 分析程序之QA/QC .............................57 4.2.1 方法偵測極限 .............................57 4.2.2 準確度及精密度建立 .............................58 4.2.3 滯留時間測試 .............................59 4.2.4 標準品檢量線之建立 .............................59 第五章 結果與討論 .............................63 5.1 分子模板材料測試結果 .....................63 5.1.1 吸附容量與吸附因子測試結果 .....................63 5.1.2 選擇性測試結果 .............................71 5.1.3 掃描式電子顯微鏡觀察結果 .....................74 5.1.4 小結 .....................................81 5.2 MISPE測試結果 .............................82 5.2.1 DEHP回收率測試結果 .............................82 5.2.2 MISPE之選擇性測試結果 .....................85 5.2.3 小結 .....................................88 5.2.4 MISPE重複使用性測試 .....................90 5.3 MISPE結合環境樣品測試 .....................91 第六章 結論與建議 .............................98 6.1 結論 .....................................98 6.2 建議 ....................................101 參考文獻 ............................................102 自述 ............................................107

    AgPU (2006). "Plastizicers market data, Arbeitsgemeinschaft PVC und Umwelt e.V., Bonn, Germany.".
    Arshady, R., Ed. (1994). Polymer synthesis via activated esters - a new dimension of creativity in macromolecular chemistry. Polymer Synthesis. Berlin, Springer-Verlag Berlin.
    ATSDR, A. f. T. S. a. D. R. (1995). "Toxicological Profile for diethyl phthalate, Public Health Service, U.S." Department of Health and Human Services, Atlanta.
    ATSDR , A. f. T. S. a. D. R. (1997). "Toxicological Profile for di-n-butyl phthalate phthalate, Public Health Service, U.S." Department of Health and Human Services, Atlanta.
    ATSDR , A. f. T. S. a. D. R. (2001). "Toxicological Profile for di-n-butyl phthalate phthalate, Public Health Service, U.S." Department of Health and Human Services, Atlanta.
    ATSDR , A. f. T. S. a. D. R. (2002). "Toxicological Profile for di-(2-ethylhexyl) phthalate, Public Health Service, U.S." Department of Health and Human Services, Atlanta.
    Bornehag C-G, L. B., Weschler C.J., Sigsgaard T., Hagerhed-Engman L., Sundell J. (2005). "Phthalates in indoor dust and their association with building characteristics." Environ Health Perspect 113(10): 1399~1404.
    Bornehag C-G, S. J., Weschler C.J., Sigsgaard T., Lundgren B., Hasselgren M., Hagerhed- Engman L. (2004). "The association between asthma and allergic symptoms in children and phthalates in house dust: a nested case-control study." Environ Health Perspect 112(14): 1393~1397.
    Cousins, I. and D. Mackay (2000). "Correlating the physical-chemical properties of phthalate esters using the [`]three solubility' approach." Chemosphere 41(9): 1389-1399.
    Crocker J, S. S., Acott P. (1988). "Effects of chronic phthalate exposure on the kidney." J Toxicol Environ Health 23: 433-444.
    Davis B, M. R., Heindel J. (1994). "Di-(2-ethylhexyl) phthalate suppresses estradiol and ovulation in cycling rats." Toxicol Appl Pharmacol 128: 216-223.
    ECB, E. C. B. (2003). "European Union Risk Assessment Report for 1,2- benzenedicarboxylic acid, di-C9-11-branched alkyl esters, C10-rich and di-“isodecyl” phthalate (DIDP)."
    ECB, E. C. B. (2003). "European Union Risk Assessment Report for 1,2-benzenedicarboxylic acid, di-C8-10-branched alkyl esters, C9-rich and i-“isononyl” phthalate (DINP)."
    ECB, E. C. B. (2004). "European Union Risk Assessment Report for dibutyl phthalate."
    ECB, E. C. B. (2007). "European Union Risk Assessment Report for Benzyl Butyl Phthalate."
    ECB, E. C. B. (2008). "European Union Risk Assessment Report for Bis(2-ethylhexyl) phthalate."
    Ganning A, B. U., Dallner G. (1984). "Phthalate esters and their effect on the liver." Hepatology 4: 541-547.
    Ganning A, B. U., Edlund C, Elhammer A, Dallner G. (1987). "Effects of prolonged administration of phthalate ester on the liver." Environ Health Perspect 73: 251-258.
    Gibson T, B. W., Boone B. (1976). "Delivery of di-2-ethylhexyl phthalate to patients during hemodialysis." J Lab Clin Med 87: 519-524.
    He, J., R. H. Lv, et al. (2010). "Selective solid-phase extraction of dibutyl phthalate from soybean milk using molecular imprinted polymers." Analytica Chimica Acta 661(2): 215-221.
    He JA (He, J., Lv RH (Lv, Ruihe)1, Cheng J (Cheng, Jie)1, Li YX (Li, Yongxiang)2, Xue JF (Xue, Jianfang)2, Lu K (Lu, Kui)1, Wang FC (Wang, Fengcheng)1 (2010). "Preparation and characterization of molecularly imprinted microspheres for dibutyl phthalate recognition in aqueous environment." JOURNAL OF SEPARATION SCIENCE 33(21): 3409-3414.
    He, J. A., R. H. Lv, et al. (2010). "Preparation and characterization of molecularly imprinted microspheres for dibutyl phthalate recognition in aqueous environment." JOURNAL OF SEPARATION SCIENCE 33(21): 3409-3414.
    He, J. A., R. H. Lv, et al. (2010). "Preparation and evaluation of molecularly imprinted solid-phase micro-extraction fibers for selective extraction of phthalates in an aqueous sample." Analytica Chimica Acta 674(1): 53-58.
    Huber W, G.-K. B., Schulte-Hermann R. (1996). "Hepatocarcinogenic potential of DEHP in rodents and its implications on human risk." Crit Rev Toxicol 26: 365-481.
    Jacobson MS, K. S., Gran RJ. (1977). "Effects of a plasticizer leached from PVC on the subhuman primate: a consequence of chronic transfusion therapy." J Lab Clin Med 89: 1066-1079.
    Kavlock, R., Barr, D., Boekelheide, K., Breslin, W. et al. (2006). "NTP-CERHR expert panel update on the reproductive and developmental toxicity of di(2-ethylhexyl) phthalate." Toxicol 22: 291~399.
    Kavlock, R., Boekelheide, K., Chapin, R., Cunningham, M. et al. (2002). "NTP Center for the Evaluation of Risks to Human Reproduction: phthalates expert panel report on the reproductive and developmental toxicity of butyl benzyl phthalate." Toxicol 16: 453~487.
    Kavlock, R., Boekelheide, K., Chapin, R., Cunningham, M. et al. (2002). "NTP Center for the Evaluation of Risks to Human Reproduction: phthalates expert panel report on the reproductive and developmental toxicity of di-isodecyl phthalate." Toxicol 16: 655~678.
    Kavlock, R., Boekelheide, K., Chapin, R., Cunningham, M. et al. (2002). "NTP Center for the Evaluation of Risks to Human Reproduction: phthalates expert panel report on the reproductive and developmental toxicity of di-isononyl phthalate." Toxicol 16: 679~708.
    Kavlock, R., Boekelheide, K., Chapin, R., Cunningham, M. et al. (2002). "NTP Center for the Evaluation of Risks to Human Reproduction: phthalates expert panel report on the reproductive and developmental toxicity of di-n-butyl phthalate." Toxicol 16: 489~527.
    Kavlock, R., Boekelheide, K., Chapin, R., Cunningham, M. et al. (2002). "NTP Center for the Evaluation of Risks to Human Reproduction: phthalates expert panel report on the reproductive and developmental toxicity of di-n-hexyl phthalate." Toxicol 16: 709~719.
    Kavlock, R., Boekelheide, K., Chapin, R., Cunningham, M. et al. (2002). "NTP Center for the Evaluation of Risks to Human Reproduction: phthalates expert panel report on the reproductive and developmental toxicity of di-n-octyl phthalate." Toxicol 16: 721~734.
    Kavlock, R., Boekelheide, K., Chapin, R., Cunningham, M. et al. (2002). "NTP Center for the Evaluation of Risks to Human Reproduction: phthalates expert panel report on the reproductive and developmental toxicity of di(2-ethylhexyl) phthalate." Toxicol 16: 529~653.
    Kevy S, J. M. (1982). "Hepatic effects of a phthalate ester plasticizer leached from poly(vinyl chloride) blood bags following transfusion." Environ Health Perspect 45: 57-64.
    Kluwe, W. (1982). "Overview of phthalate ester pharmacokinetics in mammalian species." Environ Health Perspect 45: 3-10.
    Lai, J. P., M. L. Yang, et al. (2007). "Molecularly imprinted microspheres and nanospheres for di(2-ethylhexyl)phthalate prepared by precipitation polymerization." ANALYTICAL AND BIOANALYTICAL CHEMISTRY 389(2): 405-412.
    Lamb J, C. R., Teague J, Lawton A, Reel J. (1987). "Reproductive effects of four phthalic acid esters in the mouse." Toxicol Appl Pharmacol 88: 255-269.
    Lewis L, F. T., Kerkay J, Pearson K, Nakamoto S. (1978). "Bis(2-ethylhexyl) phthalate concentrations in the serum of hemodialysis patients." Clin Chem 24(5): 741-746.
    Long, J. L. A., W. A. House, et al. (1998). "Micro-organic compounds associated with sediments in the Humber rivers." SCIENCE OF THE TOTAL ENVIRONMENT 210-211: 229-253.
    Nollet, L. M. L., Ed. (2006). Chromatographic Analysis of the Environment, Taylor & Francis.
    Peters JM, T. M., Keen CL, Gonzalez FJ. (1997). "DEHP induces a functional zinc deficiency during pregnancy and teratogenesis that is independent of peroxisome proliferator-activated receptoralpha." Teratology 56: 311-316.
    Pollack G, B. J., Slaughter R, Kohll R, Shen D. (1985). "Circulating concentrations of di(2-ethylhexyl) phthalate and its deesterified phthalic acid products following plasticizer exposure
    in patients receiving hemodialysis." Toxicol Appl Pharmacol 79: 257-267.
    Polyakov, M. V. (1931). "Adsorption properties and structure of silica gel. Russian Journal of Physical Chemistry." A 2: 799.
    Ritter E, S. W., Randall J, Ritter J. (1987). "Teratogenicity of di(2-ethylhexyl) phthalate, 2-ethylhexanol, 2-ethylhexanoic acid, and valproic acid, and potentiation by caffeine." Teratology 35: 41-46.
    Roth B, H. P., Lehmann H, Ohlres H, Homig H, Benz-Bohm G, Kreuder J, Younossi-Hartenstein A. (1988). "DEHP as plasticizer in PVC respiratory tubing systems: indications of hazardous effects on pulmonary function in mechanically ventilated, preterm infants." Eur J Pediatr 147: 41-46.
    Rudel R.A., C. D. E., Spengler J.D., Korn L.R., Brody J.G. (2003). "Phthalates, alkylphenols, pesticides, polybrominated diphenyl ethers, and other endocrine-disrupting compounds in indoor air and dust." Environ Sci Technol 37: 4543~4553.
    Santianni, P. G. D. L. L. L. C. D. (1994). "Organic Compounds in Surface and Deep Antarctic Snow." International Journal of Environmental Analytical Chemistry 55(1 & 4): 33~34.
    Schneider B, S. J., Truoug R, Jacobson M, Kevy S. (1989). "Exposure to di(2-ethylhexyl) phthalate in infants receiving extracorporeal membrane oxygenation." N Engl J Med 320(23): 1563.
    Stales, C. A., D. R. Peterson, et al. (1997). "The environmental fate of phthalate esters: A literature review." Chemosphere 35(4): 667-749.
    Stanley, M. K., Robillard, K. A., Staples, C. A., in: Staples, C. A. Editor, Ed. (2003). The Handbook of Environmental Chemistry. New York, Springer.
    Syracuse, Ed. (1982). Information profiles on potential occupational hazards phthalates. Prepared for National Institutes for Occupational Safety and Health.
    Tickner, J. A., T. Schettler, et al. (2001). "Health risks posed by use of di-2-ethylhexyl phthalate (DEHP) in PVC medical devices: A critical review." American Journal of Industrial Medicine 39(1): 100-111.
    Tomita I, N. Y., Yagi Y, Tutikawa K. (1982). "Teratogenicity/fetotoxicity of DEHP in mice." Environ Health Perspect 41: 71-75.
    Tomita I, N. Y., Yagi Y, Tutikawa K. (1986). "Fetotoxic effects of mono-2-ethylhexyl phthalate (MEHP) in mice." Environ Health Perspect 65: 249-254.
    Tyl RW, P. C., Marr MC, Kimmel C. (1988). "Developmental toxicity evaluation of dietary di(2-ethylhexyl) phthalate in Fischer 344 rats and CD-1 mice." Fundam Appl Toxicol 10: 395-412.
    Ward JM, P. J., Perella CM, Gonzalez FJ. (1998). "Receptor and nonreceptor mediated organ-specific toxicity of DEHP in peroxisome proliferator-activated receptor alpha-null mice." Toxicol and Pathol 26: 240-246.
    王銘駿 (2008). "室內粉塵吸附電纜線中鄰苯二甲酸二乙基己基酯(Di-(2ethylhexyl)phthalate;DEHP)之研究." 國立高雄第一科技大學碩士論文.
    何緯倫 (2011). "運用分子模板於香菸中半揮發有機物檢測方法研發." 國立成功大學環境工程系博士論文.
    衛生署 (2003). "食品器具容器包裝衛生標準."
    衛生署 (2011). "食品中鄰苯二甲酸酯類之檢驗方法."
    環保署 (2010). 「列管毒性化學物質及其運作管理事項」附表.
    環保署 (2010). "行政院環境保護署篩選認定毒性化學物質作業原則." 毒化物管理

    無法下載圖示 校內：2013-08-25公開
    校外：不公開
    電子論文尚未授權公開，紙本請查館藏目錄
    QR CODE