臺灣博碩士論文加值系統

本研究以綠色化學的方式，利用牛血清白蛋白(Bovine serum albumin, BSA)當成保護劑及還原劑，在水溶液中以簡單的方式合成出多型態金奈米粒子。在BSA及四氯金酸反應混合物中，添加不同種金屬離子可合成出三角板、六角板、球形、八面體、十面體及二十面體等多邊形金奈米粒子。其中Cu2+與Fe3+對奈米金型態與長成速率有特別明顯之影響，因此研究中特別針對在有這二種離子的狀態下，探討BSA濃度、金屬離子濃度、反應溫度、反應時間、酸鹼度，以及二元醇碳鏈長度及添加量對金奈米粒子合成之影響。根據所得到產物的紫外可見光譜追蹤反應的進行，利用TEM及SEM影像探討金奈米粒子的大小與形狀。當Cu2+與四氯金酸莫耳數比為1：8.33、反應溫度為60 ℃時，可合成出正二十面體奈米金，產率為50.92 %，平均粒徑為141.86 ± 12.16 nm。此外，在有Fe3+及少量1, 5-pentanediol的狀況下，以高溫使反應混合液迴流，可生成粒徑均勻之花形團狀奈米金，平均粒徑為139.49 ± 15.07 nm，因粒徑均勻度高且保護劑毒性低，後續於生醫及分析化學等領域之應用具有相當潛力。

In this study, we used bovine serum albumin (BSA) both as the capping agent and reducing agent to synthesize polyhedral gold nano- particles in aqueous solutions based on a simple one-pot strategy. The method used was in compliance with the green chemistry principles. The syntheses of gold nanoparticles were influenced by metal ions. To synthesize polyhedral gold nanoparticles, metal ions were added to the mixtures of BSA and chloroauric acid (HAuCl4). The resulting polyhedral gold nanoparticles included triangular plates, hexagonal plates, spherical particles, octahedrons, decahedrons, and icosahedrons. Among the metal ions screened, copper (Ⅱ) ion and iron (Ⅲ) ion had significant effects on both the morphology and growing rate of gold nanoparticles. Thus, the influences of several factors that affected the synthesis of polyhedral gold nanoparticles in the presence of copper (Ⅱ) and iron (Ⅲ) ions were investigated. The factors studied included the BSA concentration, metal ion concentration, temperature, reaction time, pH of solution, and amount of various diols added. The proceedings of synthesis were monitored based on the UV-Vis spectra of the reaction mixtures. The shapes and size of gold nano- particles synthesized were confirmed with transmission electron microscopy (TEM) and scanning electron microscopy (SEM).
When the molar ratio of Cu2+ and HAuCl4 was 1 to 8.33, icosahedral gold nanoparticles were the major product at 60 ℃. In this reaction condition, the average yield was 50.92 %, and the average size of nanoparticle was 141.86 ± 12.16 nm. In addition, flower-shaped gold nanoparticles was synthesized by refluxing the reaction mixture in the presence of 1, 5-pentane and Fe3+. The average diameters of the resulting gold nano- particles were 139.49 ± 15.07 nm. Since the polyhedral gold nano- particles synthesized were highly uniform and the toxicity of the capping agent used was low, this one-pot strategy had the great potential to synthesize the polyhedral gold nanoparticles with high biocompatibility which can then be used in biomedicine and bioanalysis.

總目錄
摘要 I
謝誌 IV
總目錄 V
圖目錄 VII
表目錄 XIII
第一章 序論 1
1-1 奈米材料介紹 1
1-2 金奈米粒子介紹與應用發展 5
1-3 金奈米粒子主要合成方法 7
1-4 正多面體(Platonic AuNPs)金奈米合成簡介 11
1-5 金奈米粒子之綠色化學合成法介紹 14
1-6 牛血清白蛋白介紹 16
1-7 研究動機 17
第二章 實驗部分 19
2-1 藥品與材料 19
2-2 偵測儀器 20
2-3 實驗步驟 24
2-3-1 不同金屬離子對合成BSA保護金奈米粒子之影響 24
2-3-2 Fe3+離子對合成BSA保護金奈米粒子之影響 25
2-3-3 Cu2+離子對合成BSA保護金奈米粒子之影響 27
2-3-4 合成二十面體奈米金之最適化條件 29
2-4 BSA 保護金奈米粒子之鑑定與分析 30
第三章 結果與討論 31
3-1 不同金屬離子對合成BSA保護金奈米粒子之影響 31
3-2 Fe3+離子對合成BSA保護金奈米粒子之影響 44
3-3 Cu2+離子對合成BSA保護金奈米粒子之影響 63
3-4 合成二十面體奈米金之最適化條件 70
文獻結果比較與機制探討 73
結論 79
補充資料 81
第四章 參考文獻 82

1. Carrow, J. K.; Gaharwar, A. K. Macromol. Chem. Phys. 2015, 216, 248−264.
2. 曾賢德(2010)：金奈米粒子的表面電漿共振特性：耦合、應用與樣品製作。物理雙月刊，32卷2期。臺北市：中華民國物理學會。
3. Cammarata R.C. Prog. Surf. Sci. 1994, 46, 1-38.
4. 葉晨聖(2007)：生醫奈米技術。台南市：生醫奈米科技教學資源中心。
5. Huang, X.; Jain, P. K.; El-Sayed, I. H.; El-Sayed, M. A. Laser. Med. Sci. 2008, 23, 217-228.
6. Patra, C. R.; Bhattacharya, R.; Mukhopadhyay, D.; Mukherjee, P. Adv. Drug. Deliver. Rev. 2010, 62, 346–361.
7. Aillon, K. L.; Xie, Y.; El-Gendy, N.; Berkland, C. J.; Forrest, M. L. Adv. Drug. Deliver. Rev. 2009, 61, 457–466.
8. Lal, S.; Clare, S. E.; Halas, N. J. Accounts Chem. Res. 2008, 41, 1842-1851.
9. Murph, y, C. J.; Gole, A. M.; Stone, J. W.; Sisco, P. N.; Alkilany, A. M.; Goldsmith, E. C.; Baxter, S. C. Accounts Chem. Res. 2008, 41, 1721-1730.
10. Burda, C.; Chen, X.; Narayanan, R.; El-Sayed, M. A. Chem. Rev. 2005, 105, 1025-1102.
11. Yin, Y.; Alivisatos, A. P. Nature 2005, 437, 664-670.
12. Ou, Y.-Y.; Huang, M. H. J. Phys. Chem. B 2006, 110, 2031-2036.
13. Corma, A.; Serna, P. Science 2006, 313, 332.
14. Li, N.; Zhao, P.; Astruc, D. Angew. Chem.-Int. Edit. 2014, 53, 1756-1789.
15. 郭清癸、黃俊傑、牟(2001)：中原金屬奈米粒子的製造。物理雙月刊，23卷6期。臺北市：中華民國物理學會。
16. Bradley, J. S. (1994). In Clusters and Colloids; Schmid, G., Ed. The Chemistry of Transition Metal Colloids. (pp. 459-537). New York, (USA): VCH Publishers.
17. Okitsu, K.; Bandow, H.; Maeda, Y. Chem. Mater. 1996, 8, 315-317.
18. Reetz, M. T.; Helbig, W. J. Am. Chem. Soc. 1994, 116, 7401-7402.
19. Svedberg T. (1921). The Formation of Colloids, Monographs on Physics and Chemistry of Colloids. London(England)：J&A Churchill.
20. Sharma, V.; Park, K.; Srinivararao, M. Mater. Sci. Eng. R-Rep. 2009, 65, 1-38.
21. Faraday, M. Phil. Trans. R. Soc. Lond. 1857, 147, 145-181.
22. Frens, G. Nature 1973, 241, 20-22.
23. Wilcoxon, J. P.; Williamson, R. L.; Baughman, R. J. chem. Phys. 1993, 98, 9933-9950.
24. Brust, M.; Walker, M.; Bethell, D.; Schiffrin, D. J.; Whyman, R. J. Chem. Soc. Chem. Comm. 1994, 801-802.
25. Jana, N. R.; Gearheart, L.; Murphy, C. J. Adv. Mater. 2001, 13, 1389-1393.
26. Iravani, S. Green. Chem. 2011, 13, 2638-2650.
27. Kim, F.; Connor, S.; Song, H.; Kuykendall, T.; Yang, P. Angew. Chem.-Int. Edit. 2004, 43, 3673-3677.
28. Li, C.; Shuford, K. L.; Park, Q.-H.; Cai, W.; Li, Y.; Lee, E. J.; Cho, S. O. Angew. Chem.-Int. Edit. 2007, 46, 3264-3268.
29. Seo, D.; Park, J. C.; Song, H. J. Am. Chem. Soc. 2006, 128, 14863-14870.
30. Xia, Y.; Xiong, Y.; Lim, B.; Skrabalak, S. E. Angew. Chem.-Int. Edit. 2008, 48, 60-103.
31. Lee, S. J.; Scotti, N.; Ravasio, N.; Chung, I. S.; Song, H. Cryst. Growth Des. 2013, 13, 4131-4137.
32. Xu, J.; Li, S.; Weng, J.; Wang, X.; Zhou, Z.; Yang, K.; Liu, M.; Chen, X.; Cui, Q.; Cao, M.; Zhang, Q. Adv. Funct. Mater. 2008, 18, 277-284.
33. Kwon, K.; Lee, K. Y.; Lee, Y. W.; Kim, M.; Heo, J.; Ahn, S. J.; Han, S. W. J. Phys. Chem. C 2007, 111, 1161-1165.
34. Chen, L.; Leong, G. J.; Schulze, M.; Dinh, H. N.; Pivovar, B.; Hu, J.; Qi, Z.; Fang, Y.; Prikhodko, S.; Pozuelo, M.; Kodambaka, S.; Richards, R. M. ChemCatChem 2012, 4, 1662-1667.
35. Anastas, P. T.; Warner, J. C. (1998). Green chemistry: theory and practice. Oxford (England); New York: Oxford University Press.
36. Anastas, P. T.; Kirchhoff, M. M. Accounts Chem. Res. 2002, 35, 686-694.
37. Anastas, P.; Eghbali, N. Chem. Soc. Rev. 2010, 39, 301-312.
38. 趙宙興、李中光、林麗惠、邱惠敏(2014)：淺談綠色化學及其實際應用。環保簡訊，12期，34-38。
39. Chiang, C. L. J. Colloid Interface Sci. 2001, 239, 334-341.
40. Raveendran, P.; Fu, J.; Wallen, S. L. J. Am. Chem. Soc. 2003, 125, 13940-13941.
41. Turkevich, J.; Stevenson, P. C.; Hillier, J. Discuss. Faraday Soc. 1951, 11, 55-75.
42. Engelbrekt, C.; Sørensen, K. H.; Zhang, J.; Welinder, A. C.; Jensen, P. S.; Ulstrup, J. J. Mater. Chem. 2009, 19, 7839-7847.
43. Larsen, M. T.; Kuhlmann, M.; Hvam, M. L.; Howard, K. A. Molecular and Cellular Therapies 2016, 4, 1-12.
44. Yoo, C. I.; Seo, D.; Chung, B. H.; Chung, I. S.; Song, H. Chem. Mater. 2009, 21, 939-944.
45. Lu, X.; Xia, Y.; Tuan, H.-Y.; Korgel, B. A. Chem. Eur. J. 2008, 14, 1584-1591.
46. Liu, M.; Guyot-Sionnest, P. J. Phys. Chem. B 2005, 109, 22192-22200.
47. Wiley, B.; Sun, Y.; Xia, Y. Langmuir 2005, 21, 8077-8080.
48. Wu, Z.; Zhao, H.; Xue, Y.; Cao, Q.; Yang, J.; He, Y.; Li, X.; Yuan, Z. Biosens. Bioelectron.2011, 26, 2574-2578.
49. Zhou, M.; Chen, S.; Zhao, S. J. Phys. Chem. B 2006, 110, 4510-4513.
50. Kuai, L.; Geng, B.; Wang, S.; Zhao, Y.; Luo, Y.; Jiang, H. Chem. Eur. J. 2011, 17, 3482-3489.