(I)建立新型水揚酸羥化酶專一隱藏式螢光分子探針生化檢測平台 (II)合成新化合物苯並咪唑衍生物電解液之添加劑提升敏化染料太陽能電池的光電轉換效率η (%)

(I)Characterization and Application of New Salicylate Hydroxylase Targeted Latent Fluorophore (II)New Bis-benzimidazole derivatives as the electrolytic additives for enchancing the dye-sensitized solar cell photo-electric convection efficiency η (%)

李玉慧(Yu-Hui Lee)

指導教授 ： 黃聲東

國立臺北科技大學/工程學院/生物科技研究所/碩士(2010年)

https://doi.org/10.6841/NTUT.2010.00442

摘要

本論文為分兩個研究，分別為建立生化檢測系統平台、電解液添加劑用於敏化染料太陽能電池提升效率。第一部分水揚酸羥化酶（Salicylate hydoxylase, SHL）屬於黃素酵素(flavoenzyme)利用NADH及 O2進行水揚酸去碳酸基反應（decarboxylation）和羥基化反應（hydroxylation reaction）產生Catechol.。已有文獻報導偵測(SHL)活性使用電化學的方式觀察氧化還原電位做檢測，但電極製程耗時及酵素不易保存，造成使用不易。本論文使用高壓液相層析法(HPLC)和螢光光譜儀(Fluorescence Spectrophotometer)詳細探討(SF) 的螢光釋放機制於(SHL)、O2及NADH情況下做研究，實驗證實了隱藏式螢光探針的螢光釋放機.。(SF) 對生理環境中的各種氧化還原物質做穩定度觀察，(SF) 具有高穩定性，具專一性不會有螢光分子釋放.。本論文也利用新穎的(SF) 與(SHL)搭配脫氫酵素3-hydroxybutyrate dehydrogenase (HBDH) 建立新生物檢測平台，可偵測到微量之3-hydroxybutyrate、膽固醇(100∼800 nΜ)。本研究有助於開發未來活體內之微量生化檢測系統(Biosensor)同時具有高靈敏度及專一性。
第二部分敏化染料太陽能電池【Dye-sensitized solar cells（DSSC）】具有低花費、高效能等優勢，可成為發展新一代太陽能電池之主流。若在電解液中額外添加促進劑(additives)例如4–TBP (4-tert-butyl-pyridine)、benzimidazole、1-methylben- zimidazole可提高電池光電轉換效率(η％)，但會造成Jsc下降是經由多篇報導已證實。本研究在電解液中添加添加劑做改良以benzimidazole、2-（1-hydroxyethyl）benzimidazole做衍生合成12個新穎的化合物，簡單合成僅需一步驟將碳氫鏈poly(alky)基團、聚乙二醇pole(ethylene glycol)基團連結在benzimidazole、2-(1-hydroxyethyl)benzimidazole形成二聚物(dimer)以bis-benzimidazole alky系列和bis-benzimidazole ethylene glycol系列。比較Voc、Jsc、FF、η％的研究數值及電池光電轉換效率η (％)，結果顯示(bis-benzimidazole)alky】系列在低濃度0.02M添加入0.5M 4–TBP的電解液中混不但造成Jsc上升還具有比benzimidazole(0.5M)更好電池光電轉換效率η (％)提升至30％以上。以benzimidazole做衍生新的化合物將會改進敏化染料太陽能電池【Dye-sensitized solar cells（DSSC）】電池光電轉換效率η (％)

關鍵字

水揚酸羥化酶隱藏式螢光探針 ； 生化檢測系統 ； 敏化染料太陽能電池 ； 苯並咪唑 ； 開路電壓 ； 短路電流密度 ； 填充因子 ； 光電轉換效率η％

並列摘要

In this study two, establishing new biosensor and dye-sensitized solar cell (DSSC) are the main projects of this thesis. The first part is the characterzation and application of new latent flourophore. Salicylate hydoxylase (SHL) is flavoenzyme catalyzes a stoichiometric conversion of salicylic acid (SA) to catechol in the presence of NADH and oxygen. .Our laboratory prepared a new latent flourogenic probe, Salicylate hydoxylase Latent fluorophore (SF) for real time monitor the SHL activities in the presence of NADH aerobe condition. The fluorogenic chemical transformation of SF triggered by SHL is through a tandem reaction, decarboxylation, hydroxylation, and quinion-methide-rearrangment reaction. In this study, we fully characterzed the fluorescence revealed of this new latent flourophore, SF, by flourescences spectrofluorometer and HPLC. Further more, the fluorescence response of SF does not influences by the presences of redox agents. Finally, we demonstrated that SF, is applicalle as a part of biosensor for analytes determination in the SHL-coupled dehydrogenases assay by including NAD+. This novel assay platform demonstrates a good relationship in detecting 3-hydroxybutyrate and cholesterol in 200 to 800 nM range, and is applicable for the construction of fiber-optic biosensors in the future clinical diagnostic.
The second part of this thesis is the improving of Dye-sensitized solar cells (DSSCs) efficiency by incorporation novel electrolyte additive. DSSC have been intensively studied over the past decade and regarded as a promising low-cost alternative to the conventional solid-state devices. Recently many research have identified electrolytic additive which can improve the photoelectric convection efficiency of DSSC additives drastically increased the Voc but reduce Jsc.
A series of 12 new bis-bezimidazole derivatives had been prepared and evaluated their influences as additives the in electrolyte DSSC. There 12 benzimidazole additives in DSSC electrolyte were by meaning the photo to electric conventional efficiency η (%) of DSSC. We had identified 2 additives which we out performed the current electrolytic additives (4-TBP).

並列關鍵字

quinion-methide-rearrangment ； Latent fluorophore ； Salicylate hydoxylase ； benzimidazole ； Voc ； Jsc ； FF ； photo to electric convection efficiency.

參考文獻

[2] Gao, W. ; X, B .; Tsien, R. Y.; Rao, J. "Novel Fluorogenic Substrates for Imaging β-Lactamase Gene Expression, " Journal of the American Chemical Society 125, 2003, pp. 11146-11147.

[3] Huanga, S. T.; Tinga, K. N.; 〝 Wang, K. L. "Development of a long-wavelength fluorescent probe based on quinone–methide-type reaction to detect physiologically significant thiols, " Analytica chimica acta, Vol 620, 2008, pp. 120–126.

[5] Benjamin G. Milagres, G. O. Netoa, L.; T. Kubotaa , H. Y.; "A new amperometric biosensor for salicylate based on salicylate hydroxylase immobilized on polipyrrole, " Analytica Chimica Acta, Vol. 347, 1997, pp. 35-41,

[7] Wolfbeis, O. S.; Koller, E; Hochmuth, P. "The Unusually Strong Effect Of a 4-Cyano Group upon Electronic Spectra and Dissociation Constants of 3-Substituted 7-Hydroxycoumarin. Bull, " Chem. Soc. Jpn. Vol. 58, 1985, pp. 731-734.

[8] Cosnier, S.; Gondran, C. ; and Jean-Christophe.; "Watelet A Polypyrrole -Bienzyme Electrode (Salicylate Hydroxylase- Polyphenol Oxidase) for the Interference-Free Determination of Salicylate," Electroanalysis, Vol. 13, No. 11, 2oo1, pp 906-910.