研究生: |
黃偉庭 Wei-ting Huang |
---|---|
論文名稱: |
過渡金屬摻雜於CuInS2/ZnS量子點的製備及其生物應用 Synthesis of Transition Metal doped CuInS2/ZnS Quantum dots and Their Bio-applications |
指導教授: |
張家耀
Jia-yaw Chang |
口試委員: |
麥富德
Fu-der Mai 蔡伸隆 Shen-long Tsai |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2013 |
畢業學年度: | 101 |
語文別: | 中文 |
論文頁數: | 118 |
中文關鍵詞: | I-III-VI族量子點 、過渡金屬 、摻雜 、水相量子點 、細胞毒性 |
外文關鍵詞: | Quantum dots, doping, transition metal, water phase quantum dots, cytotoxicity |
相關次數: | 點閱:390 下載:0 |
分享至: |
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
第一部分:我們使用殼層成長摻雜法(shell growth doping)成功地將Mn、Co、Ni等三種過渡金屬分別摻雜於CuInS2/ZnS核殼結構量子點中,並以不同摻雜量作為主要的參數調整,接著利用TEM、XRD、UV、PL、EPR與SQUID來進行摻雜量子點的組成、結構、光學性質與磁性分析。從中可以發現Mn與Ni確實是以摻雜的方式與CuInS2/ZnS量子點結合並展現出順磁特性與新的發光機制;而Co則是與CuInS2/ZnS形成合金量子點,此量子點隨著Co含量的增加可將其發光顏色從橘黃光調控制綠光並於室溫下顯現出順磁特性。
第二部分:以摻雜量子點作為基礎材料,並藉由兩性物質月桂酸的包覆,賦予其表面擁有大量的親水性羧酸基團而能形成溶解度佳且無毒性的水相量子點。接著再利用EDC/ NHS共價交聯系統對水相量子點進行葉酸功能化修飾,使其能與HeLa癌細胞表面的葉酸受之間有良好的親和力。此外,結合量子點優越的發光特性,能成功地製備出具有癌細胞螢光顯影與標靶的雙功能量子點材料。
Part I:In this work, we have used shell growth doping strategy for the synthesis of transition metal ion doped CuInS2/ZnS quantum dots (QDs). CuInS2 QDs was utilized to be a host and followed by depositing thin ZnS shell for the attachment of transition metal ions (such as Mn2+, Ni2+, and Co2+). We report the effect of the different transition metal doped CuInS2/ZnS QDs on the optical properties (such as photoluminescence [PL] quantum yield, PL full width at half-maximum, and wavelength of maximum PL emission) of QDs. The presented materials were characterized by HRTEM, XRD, EPR, and SQUID instruments. Mn and Ni doped QDs can appear paramagnetism property and new luminescence mechanism. Co doped QDs becomed alloyed QDs which can be tuned from orange-yellow light to green light and showed room temperature paramagnetism property.
Part II: We used dodecanoic acid (DDA) capping agent to interdigitate with hydrophobic and protective agents on the surface of different transition metal doped CuInS2/ZnS QDs, that allow phase transfer of hydrophobic QDs from the organic phase into the aqueous phase. To demonstrate their potential biomedical application, the resulting water-soluble QD were further conjugated with folate via EDS/NHS protocol for staining in HeLa cancer cells. Confocal imaging characterization revealed that folate-conjugated QDs could target specifically and effectively HeLa cells via folate receptor-mediated targeted delivery.
[1] 王崇人, “科學發展月刊",2002,345,48.
[2] 蘇品書(1999),超微粒子材料技術,復漢出版社, 台灣.
[3] 賴炤銘(2003),奈米材料的特殊效應與應用,The Chinese Chem Soc,61,585.
[4] G. Sun,The Intersubband Approach to Si-based Lasers,Advances in Lasers and Electro Optics,Nelson Costa and Adolfo Cartaxo (Ed.),2010.
[5] A. P. Alivisatos, Science, 1996, 271, 933-937.
[6] 馬振基(2005),奈米材料科技原理應用,全華圖書圖書股份有限公司, 台灣.
[7] J. M. Klostranec and W. C. W. Chan, Adv. Mater., 2006, 18, 1953-1964.
[8] T. Omata, K. Nose and S. Otsuka-Yao-Matsuo, J. Appl. Phys., 2009, 105, 73106.
[9] H. J. Simmons and S. P. Kelly,Optical Materials,San Diego,Academic Press,2000.
[10] A. H. Kitai,Solid State Luminescence,New York,Chapman&Hall,1993.
[11] K. D,Mielenz. Optical Radiation Measurements,New York, Academic Press,1982.
[12] H. Kissel, U. Müller, C. Walther, W. T. Masselink, Y. I. Mazur, G. G. Tarasov and M. P. Lisitsa, Phys. Rev. B, 2000, 62, 7213-7218.
[13] J. Wan, G. L. Jin, Z. M. Jiang, Y. H. Luo, J. L. Liu and K. L. Wang, Appl. Phys. Lett., 2001, 78, 1763-1765.
[14] 簡有廷(2010),I-III-VI族量子點製備與鑑定,台灣科技大學碩士論文, 台灣.
[15] H. Ohno, Science, 1998, 281, 951-956.
[16] P. Wu and X.-P. Yan, Chem. Soc. Rev., 2013, 42, 5489-5521.
[17] J. A. Smyder and T. D. Krauss, Mater. Today, 2011, 14, 382-387.
[18] R. Gill, M. Zayats and I. Willner, Angew. Chem. Int. Ed., 2008, 47, 7602-7625.
[19] A. M. Smith, H. Duan, A. M. Mohs and S. Nie, Adv. Drug Delivery Rev., 2008, 60, 1226-1240.
[20] I. L. Medintz, H. T. Uyeda, E. R. Goldman and H. Mattoussi, Nat Mater, 2005, 4, 435-446.
[21] W. Zheng, K. Singh, Z. Wang, J. T. Wright, J. van Tol, N. S. Dalal, R. W. Meulenberg and G. F. Strouse, J. Am. Chem. Soc., 2012, 134, 5577-5585.
[22] L. Deng, Y. Shan, J.-J. Xu and H.-Y. Chen, Nanoscale, 2012, 4, 831-836.
[23] Y. Chen, L. Huang, S. Li and D. Pan, J. Mater. Chem. C, 2013, 1, 751-756.
[24] S. Jana, B. B. Srivastava, S. Acharya, P. K. Santra, N. R. Jana, D. D. Sarma and N. Pradhan, Chem. Commun., 2010, 46, 2853-2855.
[25] D. A. Schwartz, N. S. Norberg, Q. P. Nguyen, J. M. Parker and D. R. Gamelin, J. Am. Chem. Soc., 2003, 125, 13205-13218.
[26] P. V. Radovanovic and D. R. Gamelin, J. Am. Chem. Soc., 2001, 123, 12207-12214.
[27] S. Acharya, D. D. Sarma, N. R. Jana and N. Pradhan, J Phys Chem Lett, 2009, 1, 485-488.
[28] P. Yang, M. Lü, G. Zhou, D. Yuan and D. Xu, Inorg. Chem. Commun., 2001, 4, 734-737.
[29] S. Jana, B. B. Srivastava and N. Pradhan, J Phys Chem Lett, 2011, 2, 1747-1752.
[30] R. Buonsanti and D. J. Milliron, Chem. Mater., 2013, 25, 1305-1317.
[31] N. Pradhan and D. D. Sarma, J Phys Chem Lett, 2011, 2, 2818-2826.
[32] G. M. Dalpian and J. R. Chelikowsky, Phys. Rev. Lett., 2006, 96, 226802.
[33] A. Nag, S. Chakraborty and D. D. Sarma, J. Am. Chem. Soc., 2008, 130, 10605-10611.
[34] D. J. Norris, N. Yao, F. T. Charnock and T. A. Kennedy, Nano Lett., 2000, 1, 3-7.
[35] N. Pradhan, D. Goorskey, J. Thessing and X. Peng, J. Am. Chem. Soc., 2005, 127, 17586-17587.
[36] Y. Yang, O. Chen, A. Angerhofer and Y. C. Cao, J. Am. Chem. Soc., 2006, 128, 12428-12429.
[37] D. Chen, R. Viswanatha, G. L. Ong, R. Xie, M. Balasubramaninan and X. Peng, J. Am. Chem. Soc., 2009, 131, 9333-9339.
[38] R. Beaulac, P. I. Archer, X. Liu, S. Lee, G. M. Salley, M. Dobrowolska, J. K. Furdyna and D. R. Gamelin, Nano Lett., 2008, 8, 1197-1201.
[39] R. Beaulac, P. I. Archer and D. R. Gamelin, Journal of Solid State Chemistry, 2008, 181, 1582-1589.
[40] W. Chen, R. Sammynaiken, Y. Huang, J.-O. Malm, R. Wallenberg, J.-O. Bovin, V. Zwiller and N. A. Kotov, J. Appl. Phys., 2001, 89, 1120-1129.
[41] A. Nag, R. Cherian, P. Mahadevan, A. V. Gopal, A. Hazarika, A. Mohan, A. S. Vengurlekar and D. D. Sarma, J. Phys. Chem. C, 2010, 114, 18323-18329.
[42] P. A. Gonzalez Beermann, B. R. McGarvey, S. Muralidharan and R. C. W. Sung, Chem. Mater., 2004, 16, 915-918.
[43] W. B. Jian, J. Fang, T. Ji and J. He, Appl. Phys. Lett., 2003, 83, 3377-3379.
[44] S. Wang, B. R. Jarrett, S. M. Kauzlarich and A. Y. Louie, J. Am. Chem. Soc., 2007, 129, 3848-3856.
[45] G. Manna, S. Jana, R. Bose and N. Pradhan, J Phys Chem Lett, 2012, 3, 2528-2534.
[46] N. S. Karan, D. D. Sarma, R. M. Kadam and N. Pradhan, J Phys Chem Lett, 2010, 1, 2863-2866.
[47] S. Gul, J. K. Cooper, C. Corrado, B. Vollbrecht, F. Bridges, J. Guo and J. Z. Zhang, J. Phys. Chem. C, 2011, 115, 20864-20875.
[48] P. Mandal, S. S. Talwar, S. S. Major and R. S. Srinivasa, The Journal of Chemical Physics, 2008, 128, 114703-114707.
[49] R. Xie and X. Peng, J. Am. Chem. Soc., 2009, 131, 10645-10651.
[50] B. B. Srivastava, S. Jana and N. Pradhan, J. Am. Chem. Soc., 2010, 133, 1007-1015.
[51] J.-U. Kim, Y. K. Kim and H. Yang, Journal of Colloid and Interface Science, 2010, 341, 59-63.
[52] C. Corrado, Y. Jiang, F. Oba, M. Kozina, F. Bridges and J. Z. Zhang, The Journal of Physical Chemistry A, 2009, 113, 3830-3839.
[53] A. V. Isarov and J. Chrysochoos, Langmuir, 1997, 13, 3142-3149.
[54] S. Jana, B. B. Srivastava, S. Jana, R. Bose and N. Pradhan, J Phys Chem Lett, 2012, 3, 2535-2540.
[55] N. Pradhan and X. Peng, J. Am. Chem. Soc., 2007, 129, 3339-3347.
[56] S. A. Ivanov, A. Piryatinski, J. Nanda, S. Tretiak, K. R. Zavadil, W. O. Wallace, D. Werder and V. I. Klimov, J. Am. Chem. Soc., 2007, 129, 11708-11719.
[57] 許哲豪(2006),單一硒化鎘/硫化鋅膠體量子點之螢光特性,國立交通大學碩士倫文, 台灣.
[58] Y. Yang, O. Chen, A. Angerhofer and Y. C. Cao, J. Am. Chem. Soc., 2008, 130, 15649-15661.
[59] S. Shen, Y. Zhang, Y. Liu, L. Peng, X. Chen and Q. Wang, Chem. Mater., 2012, 24, 2407-2413.
[60] B. B. Srivastava, S. Jana, N. S. Karan, S. Paria, N. R. Jana, D. D. Sarma and N. Pradhan, J Phys Chem Lett, 2010, 1, 1454-1458.
[61] S. Sadhu and A. Patra, J. Phys. Chem. C, 2012, 116, 15167-15173.
[62] W.-D. Xiang, H.-L. Yang, X.-J. Liang, J.-S. Zhong, J. Wang, L. Luo and C.-P. Xie, J. Mater. Chem. C, 2013, 1, 2014-2020.
[63] C. Bresson, R. Spezia, S. Esnouf, P. L. Solari, S. Coantic and C. Den Auwer, New Journal of Chemistry, 2007, 31, 1789-1797.
[64] M. D. Regulacio and M.-Y. Han, Accounts of Chemical Research, 2010, 43, 621-630.
[65] M. Z. Fahmi and J.-Y. Chang, Nanoscale, 2013, 5, 1517-1528.
[66] J. M. Rosenholm, E. Peuhu, L. T. Bate-Eya, J. E. Eriksson, C. Sahlgren and M. Lindén, Small, 2010, 6, 1234-1241.
[67] D. Sehgal and I. K. Vijay, Analytical Biochemistry, 1994, 218, 87-91.
[68] A. Juzeniene, K. T. Stokke, P. Thune and J. Moan, Journal of Photochemistry and Photobiology B: Biology, 2010, 101, 111-116.