金屬有機骨架於固相微萃取、酵素固定化與生質能源之應用

Applications of Metal-Organic Frameworks in Solid-Phase Microextraction, Enzyme Immobilization, and Bioenergy

李傑(Stephen Berango Lirio)

指導教授 ： 黃悉雅

中原大學/理學院/化學研究所/博士(2017年)

https://doi.org/10.6840/cycu201700188

摘要

本論文以探討金屬有機骨架材料(metal-organic frameworks, MOFs)應用在分析化學、生物性催化劑、及生質能源研究，將分成三部分探討。
本研究的第一部分，以離子液體 1-hexyl-3-methylimidazolium tetrafluoroborate ([C6mim][BF4])作為溶劑，透過微波聚合單體甲基丙烯酸丁酯(butyl methacrylate, BMA)及乙二醇二甲基丙烯酸酯(ethylene dimethacrylate, EDMA)製備高分子整體成形管柱(poly(BMA-EDMA) monolith)並混摻數種鋁金屬之MOF，應用在盤尼西林的固相微萃取(solid phase microextraction, SPME)技術，其中MIL-53-poly(BMA-EDMA)展現顯著萃取效果，在最佳化條件下，此MIL-53-polymer管柱的intra-day、inter-day及column-to-column萃取效率分別介於90.5-95.7% (< 3.5% RSDs)、90.7-97.6% (< 4.2% RSDs)及89.5-93.5% (< 3.4% RSDs)。此外，其偵測極限(limit of detection, LOD)和定量極限(limit of quantification)分別為0.06-0.26 µg L-1 和 0.20-0.87 µg L-1。最後將MIL-53-polymer應用在河水及牛奶實際樣品，經添加標準品進行萃取後分別可得到回收率80.8-90.9% (< 6.7% RSDs)和81.1-100.7% (< 7.1% RSDs)。MIL-53-polymer的高穩定性，顯示其在層析分離和SPME技術方面的可行性。
第二部分中，將胺基酸及豬胰脂肪酶(porcine pancreas lipase)共固定化在MOF-1,4-NDC(Al)材料 (簡稱PP@MOF-1,4-NDC(Al))，作為異相生物性催化劑。MOF的微孔特性可避免脯胺酸(proline)在反應過程中的脫離並增加固定化酵素重複使用之催化活性。此外，胺基酸透過氫鍵與靜電交互作用使得 MOF對PPL的吸附效率提升。此生物性催化劑可成功應用在不對稱碳-碳鍵生成(asymmetric carbon-carbon bond formation)反應並可重複使用數次。
本研究最後一部分， 利用磺酸化的MOF (UiO-66-SO3H)，在離子液體存在下針對大豆油與低碳數醇類進行轉酯化反應。在最佳化的條件下，UiO-66-SO3H40%擁有最高的催化活性，在100oC下反應12小時，產率可達80.5%，Zr oxo團簇和具磺酸化的苯環可作為布朗斯特酸(Brønsted acid)和路易斯酸(Lewis acid)活性部位，提供催化劑的良好催化效果.

關鍵字

金屬有機骨架材料 ； 固相微萃取 ； 酵素固定化 ； 生質能源 ； 異相催化劑

並列摘要

In this study, the applications of metal-organic frameworks (MOFs) in analytical chemistry, biocatalysis and bioenergy were explored.
First, several aluminum-based MOFs were incorporated into the poly(butyl methacrylate-co-ethylene dimethacrylate) (poly(BMA-EDMA)) monolith via microwave polymerization of BMA and EDMA monomer solution using 1-hexyl-3-methylimidazolium tetrafluoroborate ([C6mim][BF4]) ionic liquid (IL), as reaction media. The Al-MOF-polymer monolithic columns were applied in solid-phase microextraction (SPME) of penicillins wherein the MIL-53-poly(BMA-EDMA) exhibited remarkable extraction performance. Under the optimized conditions, the extraction efficiencies of MIL-53-polymer (n=3) were in the range of 90.5-95.7% (< 3.5% RSDs), 90.7-97.6% (< 4.2% RSDs), and 89.5-93.5% (< 3.4%RSDs) for intra-day, inter-day and column-to-column, respectively. Furthermore, the limit of detections and quantifications were in the range of 0.06-0.26 µg L-1 and 0.20-0.87 µg L-1, respectively. Finally, the fabricated MIL-53-polymer was applied in real sample analysis of river water and milk by spiking with known concentration of penicillins. The extraction recoveries were in the range of 80.8-90.9% (< 6.7% RSDs) and 81.1-100.7% (< 7.1% RSDs) for river water and milk sample, respectively. With excellent stability, the as-prepared MIL-53-polymer can be useful in chromatographic science and SPME application.
Second, the amino acid and porcine pancreas lipase were co-immobilized on MOF-1,4-NDC(Al) (PP@MOF-1,4-NDC) and applied as heterogeneous biocatalyst for chemical transformation. The microporous MOF prevented the leaching of L-proline and thus contributing to enhancement of the catalytic activity of the immobilized enzyme. The incorporation of amino acid through hydrogen bonding and electrostatic interaction with PPL increased the loading efficiency of MOF. The as-prepared biocatalyst was successfully applied in asymmetric carbon-carbon bond formation and could be useful for several cycles.
Lastly, sulfonated MOF (UiO-66-SO3H) was used in the transesterification of soybean oil with short chain alcohols and ionic liquid. Under the optimized condition, the UiO-66-SO3H40% afforded the highest catalytic activity with 80.5% yield at 100 ºC for 12 h reaction time. The Zr oxo clusters and benzene functionalized SO3H provided the good performance of the catalysts, which acted as Brønsted acid and Lewis acid sites, respectively.

並列關鍵字

Metal-organic framework ； Solid-Phase Microextraction ； Enzyme Immobilization ； Bioenergy ； Heterogeneous Catalyst

參考文獻

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