螢光金奈米團簇和金複合奈米材料之合成與應用

螢光金奈米團簇和金複合奈米材料因有高靈敏度、選擇性、以及獨特光學和催化的特性，故具有應用於生物感測器、細胞顯影及生物分子辨識等之潛力。本論文主要著重於螢光金奈米團簇和金複合奈米材料的製備、鑑定及應用探討。第一章節簡述螢光金奈米團簇、金複合奈米材料和質譜學等的基礎背景知識及現況發展。第二章節，為利用碲化汞奈米材料(HgTe nanostructure)搭配表面輔助雷射脫附游離質譜法，以應用於分析聚乙二醇(polyethylene glycol)和硫醇聚乙二醇修飾金奈米粒子(thiol-PEG modified gold nanoparticles)。此分析方法能夠有效偵測聚乙二醇的分子量達42,000道爾頓，以及鑑別出硫醇聚乙二醇修飾金奈米粒子上的不同官基能 (如:羧甲基、胺基、生物素)類別，並成功建立生物分子辨識系統(生物素與抗生物素蛋白之相互作用)。第三章節，進一步製備具抗菌活性的金/銀-碲奈米材料，結果顯示此材料對於大腸桿菌、沙門氏菌和金黃色葡萄球菌等常見致病菌具有良好的抗菌能力。第四章節，藉由調控修飾於金量子點上不同密度的11-巰基十一酸，以探討不同密度的配體分子所造成的影響。另外，也將11-巰基十一酸金微奈米點成功應用在複雜的尿液、血漿以及魚類樣品中，進行無機汞和有機汞離子的檢測分析。第五章節，更進一步研究以硼氫化鈉(NaBH4)還原超分子配位聚合物[[CysAu(I)]n]後，形成光致發光L-半胱胺酸金奈米團簇的相關機制。此研究結果證明，形成光致發光的金奈米團簇過程中，硫醇配體分子間的作用力扮演著極重要的角色。總結，本論文以成功開發出具快速檢測高分子化合物的新穎性質譜法，且也證明金/銀-碲奈米材料於發展抗微生物奈米藥物中展現出巨大的潛能。另外，也成功開發出能於真實樣品中快速檢測汞離子的奈米感測器。最後，提供明確的論點，以說明由下而上合成法(bottom-up)於形成金奈米團簇的合成機制。

關鍵字

金奈米材料；螢光金奈米團簇；聚乙二醇；抗微生物藥物；表面輔助雷射脫附游離質譜法；超分子化合物

並列摘要

Gold nanomaterials (Au NMs) and luminescent noble metal nanoclusters (NCs) exhibit great potential for sensing, imaging, characterization and biorecognition, due to their high selectivity, sensitivity and because of unique optical and catalytic properties. This thesis focuses on the preparation, characterization, and application of Au NMs and Au NCs. In Chapter 1, the background of Au NMs, Au NCs and the principle of laser desorption/ionization techniques of mass spectrometry are described. In Chapter 2, the details of our work using HgTe nanostructure-based matrices for SALDI-MS for the analyses of polyethylene glycol (PEG) derivatives as well as thiol-PEG-modified gold nanoparticles (PEGAu NPs) is explained. This approach allows the determination of PEG (molecular weights: 42,000 Da), PEG-Au NP species functional groups (e.g., carboxymethyl, amine, biotin), and biotinylated-PEG-Au NPs (biotin-PEG-Au NPs) to study the biotin-avidin biorecognition. We also prepared the antimicrobial gold/silver-tellurium nanostructures (Au/Ag-Te NSs) which possessed superior antimicrobial activity toward Escherichia coli (E. coli), Salmonella enterica serovar Enteritidis (S. enteritidis), and Staphylococcus aureus (S. aureus) as described in Chapter 3. In Chapter 4, the effect of controlled ligand density of 11-mercaptoundecanoic acid (11-MUA) on the gold nanodots (Au NDs) is described. We could achieve the detection of total inorganic and organic mercury ions in complex biological urine and plasma samples, as well as in fish sample. Photoluminescent L-cysteine (Cys)-capped gold nanoclusters (CysAu NCs) via NaBH4-mediated reduction of aggregated coordination polymers (supramolecules) of [CysAu(I)]n were also synthesized as mention in Chapter 5. Based on these studies, we demonstrated that the photoluminescence and structural properties of Au NCs are mediated by the intermolecular forces of thiol ligands. Accordingly, we have demonstrated that novel SALDI-MS approach allows rapid detection of macromolecules, and suggested that Au/Ag−Te NSs holds great potential as effective antimicrobial drugs. We also developed nanosensor for the rapid determination of total Hg concentration in real sample. Finally, our study also affords insights into the bottom-up synthesis of photoluminescent Au NCs from thiol-ligandAu(I) complexes and supramolecules.

並列關鍵字

gold nanomaterials (Au NMs) ； luminescent gold nanoclusters/nanodots (Au NCs/NDs) ； polyethylene glycol (PEG) ； antimicrobial drugs ； surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) ； supramolecules

參考文獻

Chapter 1

1.4 References

(1) Yang, X.; Yang, M.; Pang, B.; Vara, M.; Xia, Y. Gold Nanomaterials at Work in Biomedicine. Chem. Rev. 2015, 115, 10410–10488.

(2) Zhou, W.; Gao, X.; Liu, D.; Chen, X. Gold Nanoparticles for In Vitro Diagnostics. Chem. Rev. 2015, 115, 10575–10636.

(3) Kim, J. E.; Choi, J. H.; Colas, M.; Kim, D. H.; Lee, H. Gold-Based Hybrid Nanomaterials for Biosensing and Molecular Diagnostic Applications. Biosens. Bioelectron. 2016, 80, 543–559.

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螢光金奈米團簇和金複合奈米材料之合成與應用

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