含硫官能基之內環狀中孔洞矽材合成與反 丁烯二酸金屬骨架材料之酵素催化應用

鐘紹恩(Shao-En Chung)

指導教授 ： 謝發坤

國立中央大學/理學院/化學系/碩士(2015年)

摘要

本篇論文分成兩個部分：
第一部分為合成具有硫醇官能基之內環裝中孔洞材料，其是利用直接合成法得到具有硫醇官能基的中孔洞材料SBA-15-thiol，且進一步利用具有雙異氰酸酯官能基之化合物進行合環反應，達到在中孔洞材料上修飾上內環狀之結構，而合成條件在經過最佳化後反應時間進需2 小時且反應在室溫下即可進行。新合成之內環狀中孔洞材料其體表面積高達600m2/g，且孔徑大小約在60 Å ，而此材料依舊保有中孔洞矽材的高熱穩定性的特性。因此在材料擁有眾多的優勢下將其去對金屬離子做吸附實驗，期望會有相較於同類型材料有更好的的吸附能力及選擇性。
第二部分是利用水相合成反丁烯二酸金屬骨架材料 (Zr-fum MOF) 將碳酸酐酶 (Carbonic Anhydrase, CA) 以原位反應的方式包裹在材料當中，來進行碳酸酐酶催化。因材料的合成環境較酸低於蛋白可容忍的範圍，所以我們利用縮短合成時間的方式提前結束反應以保留蛋白的活性，而經由X光繞射圖及掃描式電子顯微鏡的影像可以得知在提前結束反應的材料依舊保留完好的結構與外型。在酵素活性測試中，由CA@Zr-fum MOF 可加速4-硝基苯乙酸酯的水解速度可看出，包覆在Zr-fum MOF 中的碳酸酐酶依然保有活性。

關鍵字

中孔洞矽材 ； 環狀結構 ； 重金屬吸附 ； 金屬有機骨架材料 ； 固定化酵素

並列摘要

This research is divided into two parts which are majorly focusing on the synthesis of annulated mesoporous silica and microporous material of Zr-Fumarate MOF. In the first part, a series of annulated mesoporous silica (SBA-15) with mercapto functional groups are successfully synthesized under room temperature condition. In this study, we adjust the annulated design with several diisocyanate derivatives. The as-synthesized particles were characterized by X-ray diffraction, 13C NMR, FT-IR spectra, thermogravimetric analysis, nitrogen sorption isothermal, electron microscopy. Notably, these synthesis
conditions are also moderate that the modified SBA-15 materials remain merely no change in their chemical and physical property. Moreover, we also utilized these materials as sorbents for the removal of mercury ion under aqueous solutions, and the results also reveal the exceptional consequence.
In the second part, we developed an aqueous system to synthesize Zr-Fumarate MOF and an in-situ procedure to encapsulate biomolecules such as protein. In order to limit the impact of the acidity and harshness of the synthetic environment on carbonic anhydrase, the synthesis duration was reduced from 2 hours to 15 minutes. According to the result from powder X-ray diffraction patterns (XRD) and scanning electron microscope (SEM), enzyme-encapsulated Zr-fum MOF are still with well morphology. Furthermore, the enzyme activity test showed that enzyme-encapsulated Zr-fum MOF still maintained its activity after the synthetic procedure.

參考文獻

1. McBain, J. W., The Sorption of Gases and Vapours by Solids. The Journal of Physical Chemistry 1932, 37 (1), 149-150.

2. Ciesla, U.; Schüth, F., Ordered mesoporous materials. Microporous and Mesoporous Materials 1999, 27 (2–3), 131-149.

3. Lee, C.-H.; Lin, T.-S.; Mou, C.-Y., Mesoporous materials for encapsulating enzymes. Nano Today 2009, 4 (2), 165-179.

4. Shieh, F.-K.; Hsiao, C.-T.; Wu, J.-W.; Sue, Y.-C.; Bao, Y.-L.; Liu, Y.-H.; Wan, L.; Hsu, M.-H.; Deka, J. R.; Kao, H.-M., A bioconjugated design for amino acid-modified mesoporous silicas as effective adsorbents for toxic chemicals. Journal of Hazardous Materials 2013, 260 (0), 1083-1091.

5. Appell, M.; Jackson, M. A.; Dombrink-Kurtzman, M. A., Removal of patulin from aqueous solutions by propylthiol functionalized SBA-15. Journal of Hazardous Materials 2011, 187 (1–3), 150-156.