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  • 學位論文

以二氧化錳處理水中雙氯芬酸之研究

Diclofenac removal by manganese dioxide in water

指導教授 : 胡景堯

摘要


近年來,許多非類固醇消炎藥(Non-steroidal anti-inflammatory drugs, NSAIDs)已經被發現存在於環境中,而相關研究指出,其中一種藥物-雙氯芬酸會對人體及環境中的其他生物造成危害。二氧化錳(Manganese oxide, MnO2)是天然的氧化劑,存在於土壤與底泥中,對於含有氯酚 (chlorophenol)、酚(phenol)、苯胺(anilines) 及磷酸根(phosphonates)官能基的化合物有良好的分解效果。雙氯芬酸含有苯胺基,應該可以被二氧化錳所去除。本研究主要的目的為探討二氧化錳劑量、pH值、共存陽離子(Ca2+、Mg2+)以及輔助吸附劑(SDS、CTAB)的使用對於二氧化錳去除水中雙氯芬酸效果的影響。本研究中殘餘的藥物濃度皆以高效能液相層析儀(HPLC)進行偵測。另外,並以液相層析串聯質譜儀(Liquid Chromatography Tandem Mass Spectrometry, LC/MS/MS)分析雙氯芬酸被二氧化錳降解可能生成產物之結構。 研究結果發現二氧化錳對於雙氯芬酸有良好的去除效果,其去除率會隨者二氧化錳的劑量增加、pH值的降低而上升。此外,在水中加入鈣離子和鎂離子並不能提升去除效果。於輔助吸附劑使用的實驗中,於pH=4~9時加入陽離子型輔助吸附劑(CTAB)均較未加入輔助吸附劑之去除率高;然而,若加入陰離子型輔助吸附劑(SDS),則只有在pH=4~5時較未加入輔助吸附劑之去除率佳。 以HPLC和LC/MS/MS進行雙氯芬酸被二氧化錳降解可能生成產物分析,結果發現其中一種主要產物為雙氯芬酸結構中C-N鍵斷裂所形成雙氯苯胺,雙氯苯胺及其他二氧化錳降解後的產物是否對環境和人體健康產生更高的毒性為未來重要的研究方向。

並列摘要


In recent years, Non-steroidal anti-inflammatory drugs(NSAIDs) have been widely found in the environment. They may be toxic for human and aquatic species. Manganese dioxide is one of the most important naturally oxidants for facilitating organic pollutant transformation in soils and sediments. It is a effective oxidant for many pollutants containing chlorophenol, phenol, aniline and propionate functional groups. Diclofenac has a aniline in it’s structure. Therefore, it should be possible to remove by manganese dioxide. The objective of this study was to systematically explore the oxidation of diclofenac with manganese dioxide and to investigate the influence of manganese dioxide loading, pH, concentration of alkaline earth metal(e.g.,Ca2+, Mg2+), and surfactant(e.g.,SDS, CTAB).The residual concentration of drugs were measured by high performance liquid chromatography(HPLC). The intermediates and products formed from the reaction of diclofenac with manganese dioxide were identified using liquid chromatography tandem mass spectrometry (LC/MS/MS). Results from this study indicate that the removal efficiency was enhanced with the increase of manganese dioxide dosage, and with decrease of pH. However, metal cations (e.g.,Ca2+, Mg2+) demonstrated inhibitory effects on the oxidation of diclofenac by manganese dioxide. The diclofenac removal with manganese dioxide in the presence of CTAB was better than in the absence of CTAB. However, the diclofenac removal with manganese dioxide in the presence of SDS was only better than that in the absence of SDS at acidic condition. For the identification of the oxidation products of diclofenac was performed with HPLC and LC/MS/MS. Diclofenac may be attacked at C-N binding between the two aromatic rings. Further research is required to investigate whether the intermidiates formed from the reaction of diclofenac with manganese dioxide are harmful to human health and environment.

參考文獻


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