電漿子光觸媒材料在近年來是一個非常熱門的主題，利用貴金屬奈米粒子及半導體的特 性:表面電漿共振(LSPR)及蕭特基屏障(Schottky junction)來提昇光觸媒效率，此兩大特色能 夠使得材料有許多優點包含:可見光-紅外光驅動、電子電洞對分離、 表面電場的增強等。
在本論文中，我們利用水溶膠(Sol-gel method)合成了紅外光驅動的奈米材料:奈米啞鈴 (ND)，是由金以及二氧化鈦組成，能夠輕易的利用控制奈米金棒(AuNRs)的長寬比控制ND 的特徵吸收峰。啞鈴型結構能夠使兩組成材料與溶液接觸提升效率，且此複合材料的能階位 置能夠在紅外光驅動下產生氫氧自由基。在此使用電子自旋共振光譜的技術直接偵測系統中 所產生的活性氧化物(ROS)，以及使用磷光放光光譜偵測單重態氧氣。
由於光療中所用的到光敏劑的穩定性和光源穿深度的問題，目前僅能夠使用在皮膚表層 的癌症治療。在章節3-3中利用ND來對具有抗藥性的癌細胞進行第一型光動力治療(ROS)及 光熱治療，由於ND具有蕭特基屏障因此在毒殺癌細胞具有較好的效果;章節3-4及3-5中利用 表面電場的增強的性質，應用在表面拉曼增強光譜及催化對硝基苯酚還原反應。

Recently, plasmonic photocatalyst is popular in the field of nanotechnology and it widely made use of the noble metal nanoparticles and semiconductors, which possesses two unique features; localized surface plasmonic resonance (LSPR) and Schottky junction. These properties assert to have advantages in the plasmonic photocatalyst, such as broad UV-visible-NIR absorbance, forced charge carrier separation, and enhanced local electromagnetic field.
In this scenario, we use a sol-gel method to prepare a nanomaterial, nanodumbbells (ND), which can be activated by NIR light. It is made of the combination of gold and TiO2. Moreover, by changing the ratio of the length and width of the gold nanorods (AuNRs), we can easily control the tunable absorption band position of the ND. The unique property of nanodumbbell material could enhance the photocatalytic efficiency due to proper band position and generation of hydroxyl radical (・OH) upon NIR light illumination. We have utilized the electron paramagnetic resonance
spectrometer and phosphorescence emission spectra techniques to measure the ROS generated during the reaction.
Simultaneously, in chapter 3-3 we have employed the nanodumbbell (ND) for PDT/PTT therpeutuic reagent (such as type -1 PDT) for the killing of drug resistant cancer cells (NCI-H23) upon 980 nm light irradiation and similarly, the schottky junction has better killing efficiency comparing with AuNRs upon the light irradiation. Therefore, broad UV-visible NIR absorbance with high molar extinction-coefficient could penetrate the deep tissue as well as better photo stability. In chapter 3-4 and 3-5, we have utilized the enhanced local electromagnetic field to catalyze the reduction reaction of 4-Nitrophenol and surface-enhanced Raman spectroscopy(SERS).

1. Werner, D.; Hashimoto, S.; Uwada, T., Langmuir 2010, 26 (12), 9956-9963.
2. Arico, A. S.; Bruce, P.; Scrosati, B.; Tarascon, J.-M.; van Schalkwijk, W., Nat Mater. 2005, 4 (5), 366-377.
3. Reddy, K. G.; Deepak, T. G.; Anjusree, G. S.; Thomas, S.; Vadukumpully, S.; Subramanian, K. R. V.; Nair, S. V.; Nair, A. S., Phys. Chem. Chem. Phys. 2014, 16 (15), 6838-6858.
4. Bose, S.; Garcia-Garcia, A. M.; Ugeda, M. M.; Urbina, J. D.; Michaelis, C. H.; Brihuega, I.; Kern, K., Nat. Mater. 2010, 9 (7), 550-554.
5. Wang, F.; Cheng, S.; Bao, Z.; Wang, J., Angew. Chem., Int. Ed. 2013, 52 (39), 10344-8.
6. Hoffmann, M. R.; Martin, S. T.; Choi, W.; Bahnemann, D. W., Chem. Rev. 1995, 95 (1), 69-96.
7. Chen, H. M.; Chen, C. K.; Lin, C. C.; Liu, R.-S.; Yang, H.; Chang, W.-S.; Chen, K.-H.; Chan, T.-S.; Lee, J.-F.; Tsai, D. P., J. Phys. Chem. C 2011, 115 (44), 21971-21980.
8. Mokari, T.; Rothenberg, E.; Popov, I.; Costi, R.; Banin, U., Science 2004, 304 (5678), 1787-1790.
9. Saunders, A. E.; Popov, I.; Banin, U., J. Phys. Chem. B 2006, 110 (50), 25421-25429.
10. Kwon, S. G.; Krylova, G.; Phillips, P. J.; Klie, R. F.; Chattopadhyay, S.; Shibata, T.; Bunel, E. E.; Liu, Y.; Prakapenka, V. B.; Lee, B.; Shevchenko, E. V., Nat. Mater. 2015, 14 (2), 215-223.
11. Kramer, D.; Viswanath, R. N.; Weissmüller, J., Nano Lett. 2004, 4 (5), 793-796.
12. Milliron, D. J.; Hughes, S. M.; Cui, Y.; Manna, L.; Li, J.; Wang, L.-W.; Paul
Alivisatos, A., Nature 2004, 430 (6996), 190-195.
68
13. Zhang, X.; Chen, Y. L.; Liu, R. S.; Tsai, D. P., Rep. Prog. Phys. 2013, 76 (4), 046401.
14. Mubeen, S.; Hernandez-Sosa, G.; Moses, D.; Lee, J.; Moskovits, M., Nano Lett. 2011, 11 (12), 5548-5552.
15. Wu, K.; Chen, J.; McBride, J. R.; Lian, T., Science 2015, 349 (6248), 632-635.
16. Kim, S. M.; Lee, H.; Goddeti, K. C.; Kim, S. H.; Park, J. Y., J. Phys. Chem. C 2015,
119 (28), 16020-16025.
17. Kim, S. M.; Lee, S. J.; Kim, S. H.; Kwon, S.; Yee, K. J.; Song, H.; Somorjai, G. A.; Park, J. Y., Nano Lett. 2013, 13 (3), 1352-1358.
18. Naskar, S.; Schlosser, A.; Miethe, J. F.; Steinbach, F.; Feldhoff, A.; Bigall, N. C., Chem. Mater. 2015, 27 (8), 3159-3166.
19. LaMer, V. K.; Dinegar, R. H., J. Am. Chem. Soc. 1950, 72 (11), 4847-4854.
20. Xia, Y.; Xiong, Y.; Lim, B.; Skrabalak, S. E., Angew. Chem., Int. Ed. 2009, 48 (1),
60-103.
21. Ye, X.; Zheng, C.; Chen, J.; Gao, Y.; Murray, C. B., Nano Lett. 2013, 13 (2), 765-71.
22. Boles, M. A.; Ling, D.; Hyeon, T.; Talapin, D. V., Nat. Mater. 2016, 15 (2), 141-153.
23. Konan, Y. N.; Gurny, R.; Allémann, E., J. Photochem. Photobiol., B 2002, 66 (2),
89-106.
24. Niedre, M.; Patterson, M. S.; Wilson, B. C., Photochem. Photobiol. 2002, 75 (4),
382-391.
25. Vankayala, R.; Sagadevan, A.; Vijayaraghavan, P.; Kuo, C. L.; Hwang, K. C., Angew.
Chem., Int. Ed. 2011, 50 (45), 10640-4.
26. Montalti, M.; Cantelli, A.; Battistelli, G., Chem. Soc. Rev. 2015, 44 (14), 4853-4921.
69
27. Huang, X.; El-Sayed, I. H.; Qian, W.; El-Sayed, M. A., J. Am. Chem. Soc. 2006, 128 (6), 2115-2120.
28. C. M. Penney , L. M. G. M. L., Nature Physical Science 1972, 235, 110-112.
29. Kastrup, L.; Hell, S. W., Angew. Chem., Int. Ed. 2004, 43 (48), 6646-9.
30. Fleischmann, M.; Hendra, P. J.; McQuillan, A. J., Chem. Phys. Lett. 1974, 26 (2),
163-166.
31. Sutherland, W. S.; Laserna, J. J.; Angebranndt, M. J.; Winefordner, J. D., Anal.
Chem. 1990, 62 (7), 689-693.
32. Sha, M. Y.; Xu, H.; Natan, M. J.; Cromer, R., J. Am. Chem. Soc. 2008, 130 (51),
17214-17215.
33. Flood, A. H.; Stoddart, J. F.; Steuerman, D. W.; Heath, J. R., Science 2004, 306
(5704), 2055-2056.
34. Kleinman, S. L.; Ringe, E.; Valley, N.; Wustholz, K. L.; Phillips, E.; Scheidt, K. A.;
Schatz, G. C.; Van Duyne, R. P., . Am. Chem. Soc. 2011, 133 (11), 4115-4122.
35. Brosseau, C. L.; Rayner, K. S.; Casadio, F.; Grzywacz, C. M.; Van Duyne, R. P.,
Anal. Chem. 2009, 81 (17), 7443-7447.
36. Hsu, K. C.; Chen, D. H., ACS Appl. Mater. Interfaces 2015, 7 (49), 27571-9.
37. Ma, L.; Huang, Y.; Hou, M.; Xie, Z.; Zhang, Z., Sci. Rep. 2015, 5, 15442.
38. Ren, B.; Lin, X.-F.; Yang, Z.-L.; Liu, G.-K.; Aroca, R. F.; Mao, B.-W.; Tian, Z.-Q., J.
Am. Chem. Soc. 2003, 125 (32), 9598-9599.
39. Frontiera, R. R.; Dasgupta, J.; Mathies, R. A., J. Am. Chem. Soc. 2009, 131 (43),
15630-15632.
40. Bailo, E.; Deckert, V., Angew. Chem., Int. Ed. 2008, 47 (9), 1658-1661.
41. Zheng, Z.; Tachikawa, T.; Majima, T., J. Am. Chem. Soc. 2015, 137 (2), 948-57. 70

42. Lou, Z.; Fujitsuka, M.; Majima, T., ACS Nano 2016, 10 (6), 6299-305.
43. Wang, G.; Xiao, X.; Li, W.; Lin, Z.; Zhao, Z.; Chen, C.; Wang, C.; Li, Y.; Huang, X.; Miao, L.; Jiang, C.; Huang, Y.; Duan, X., Nano Lett. 2015, 15 (7), 4692-8.
44. Mamak, M.; Choi, S. Y.; Stadler, U.; Dolbec, R.; Boulos, M.; Petrov, S., J. Mater. Chem. 2010, 20 (44), 9855.
45. Mattox, T. M.; Bergerud, A.; Agrawal, A.; Milliron, D. J., Chem. Mater. 2014, 26 (5), 1779-1784.
46. Choi, J.; Moon, K.; Kang, I.; Kim, S.; Yoo, P. J.; Oh, K. W.; Park, J., Chem. Eng. J. 2015, 281, 236-242.
47. Fang, C.; Jia, H.; Chang, S.; Ruan, Q.; Wang, P.; Chen, T.; Wang, J., Energy Environ. Sci. 2014, 7 (10), 3431-3438.
48. Gao, J.; Bender, C. M.; Murphy, C. J., Langmuir 2003, 19 (21), 9065–9070.
49. Fan, H.; Lopez, G. P.; Brinker, C. J.; Lu, Y., 2005, US 6913832 B2.
50. Thierry, B.; Ng, J.; Krieg, T.; Griesser, H. J., Chem. Commun. (Camb) 2009,
(13),
1724-6.
51. Sim, H. R.; Wark, A. W.; Lee, H. J., Analyst 2010, 135 (10), 2528-32.
52. Vigderman, L.; Zubarev, E. R., Adv. Drug Deliv. Rev. 2013, 65 (5), 663-76.
53. Walther, A.; Muller, A. H., Chem. Rev. 2013, 113 (7), 5194-261.
54. Vijayaraghavan, P.; Liu, C. H.; Vankayala, R.; Chiang, C. S.; Hwang, K. C., Adv.
Mater. 2014, 26 (39), 6689-95.
55. Murphy, C. J.; Sau, T. K.; Gole, A. M.; Orendorff, C. J.; Gao, J.; Gou, L.; Hunyadi,
S. E.; Li, T., J. Phys. Chem. B 2005, 109 (29), 13857-13870.
56. Shi, Y.; Luo, H. Q.; Li, N. B., Spectrochim. Acta. A Mol. Biomol. Spectrosc. 2011,
78 (5), 1403-7.
71
57. Cassaignon, S.; Koelsch, M.; Jolivet, J.-P., J. Phys. Chem. Solids 2007, 68 (5-6), 695-700.
58. Yoon, I.; Li, J. Z.; Shim, Y. K., Clin. Endosc. 2013, 46 (1), 7-23.
59. Hervier, A.; Renzas, J. R.; Park, J. Y.; Somorjai, G. A., Nano Lett. 2009, 9 (11),
3930-3933.
60. Lee, H.; Nedrygailov, I. I.; Lee, C.; Somorjai, G. A.; Park, J. Y., Angew. Chem. Int. Ed. 2015, 54 (8), 2340-2344.
61. Kale, M. J.; Avanesian, T.; Christopher, P., ACS Catalysis 2014, 4 (1), 116-128.
62. Kale, M. J.; Christopher, P., Science 2015, 349 (6248), 587-588.
63. Brongersma, M. L.; Halas, N. J.; Nordlander, P., Nat. Nanotechnol. 2015, 10 (1),
25-34.
64. Johnson, P. B.; Christy, R. W., Phys. Rev. B 1972, 6 (12), 4370-4379.
65. Christensen, N. E., Phys. Rev. B 1976, 13 (6), 2698-2701.
66. Nishijima, Y.; Ueno, K.; Yokota, Y.; Murakoshi, K.; Misawa, H., J. Phys. Chem. Lett.
2010, 1 (13), 2031-2036.
67. DeRosa, M. C.; Crutchley, R. J., Coord. Chem. Rev. 2002, 233–234, 351-371.
68. Ge, J.; Lan, M.; Zhou, B.; Liu, W.; Guo, L.; Wang, H.; Jia, Q.; Niu, G.; Huang, X.;
Zhou, H.; Meng, X.; Wang, P.; Lee, C.-S.; Zhang, W.; Han, X., Nat. Commun. 2014, 5, 4596.
69. Charbouillot, T.; Brigante, M.; Mailhot, G.; Maddigapu, P. R.; Minero, C.; Vione, D.,
J. Photochem. Photobiol., A 2011, 222 (1), 70-76.
70. Zhao, T.; Shen, X.; Li, L.; Guan, Z.; Gao, N.; Yuan, P.; Yao, S. Q.; Xu, Q.-H.; Xu, G.
Q., Nanoscale 2012, 4 (24), 7712-7719.
71. Vankayala, R.; Huang, Y. K.; Kalluru, P.; Chiang, C. S.; Hwang, K. C., Small 2014,
10 (8), 1612-22.
72
72. Idris, N. M.; Gnanasammandhan, M. K.; Zhang, J.; Ho, P. C.; Mahendran, R.; Zhang, Y., Nat. Med. 2012, 18 (10), 1580-5.
73. Guo, W.; Guo, C.; Zheng, N.; Sun, T.; Liu, S., Adv. Mater. 2017, 29 (4).
74. Long, C. A.; Kearns, D. R., J. Am. Chem. Soc. 1975, 97 (8), 2018-2020.
75. Kalluru, P.; Vankayala, R.; Chiang, C.-S.; Hwang, K. C., Angew. Chem. Int. Ed.
2013, 52 (47), 12332-12336.
76. Vankayala, R.; Lin, C. C.; Kalluru, P.; Chiang, C. S.; Hwang, K. C., Biomaterials
2014, 35 (21), 5527-38.
77. Vankayala, R.; Kuo, C.-L.; Nuthalapati, K.; Chiang, C.-S.; Hwang, K. C., Adv.
Funct. Mater. 2015, 25 (37), 5934-5945.
78. Kalluru, P.; Vankayala, R.; Chiang, C.-S.; Hwang, K. C., Adv. Funct. Mater. 2016, 26
(43), 7908-7920.
79. Bessho, Y.; Oguri, T.; Achiwa, H.; Muramatsu, H.; Maeda, H.; Niimi, T.; Sato, S.;
Ueda, R., Cancer Sci 2006, 97 (3), 192-8.
80. Rosi, N. L.; Giljohann, D. A.; Thaxton, C. S.; Lytton-Jean, A. K.; Han, M. S.;
Mirkin, C. A., Science 2006, 312 (5776), 1027-30.
81. Huang, X.; El-Sayed, I. H.; Qian, W.; El-Sayed, M. A., J. Am. Chem. Soc. 2006, 128
(6), 2115-2120.
82. Hu, K.-W.; Liu, T.-M.; Chung, K.-Y.; Huang, K.-S.; Hsieh, C.-T.; Sun, C.-K.; Yeh,
C.-S., J. Am. Chem. Soc. 2009, 131 (40), 14186-14187.
83. Christopher, P.; Ingram, D. B.; Linic, S., J. Phys. Chem. C 2010, 114 (19),
9173-9177.
84. Kumar, S. G.; Devi, L. G., T., J. Phys. Chem. A 2011, 115 (46), 13211-13241.
73
85. Feng, Z. V.; Lyon, J. L.; Croley, J. S.; Crooks, R. M.; Vanden Bout, D. A.; Stevenson, K. J., J. Chem. Educ. 2009, 86 (3), 368.
86. Zhu, Z.; Guo, X.; Wu, S.; Zhang, R.; Wang, J.; Li, L., Ind. Eng. Chem. Res. 2011, 50 (24), 13848-13853.
87. Khalavka, Y.; Becker, J.; Sönnichsen, C., J. Am. Chem. Soc. 2009, 131 (5), 1871-1875.
88. Lu, Y.; Mei, Y.; Drechsler, M.; Ballauff, M., Angew. Chem. Int. Ed. 2006, 45 (5), 813-816.
89. Mei, Y.; Sharma, G.; Lu, Y.; Ballauff, M.; Drechsler, M.; Irrgang, T.; Kempe, R., Langmuir 2005, 21 (26), 12229-12234.
90. Tang, S.; Vongehr, S.; Meng, X., J. Mater. Chem. 2010, 20 (26), 5436-5445.
91. Gangula, A.; Podila, R.; M, R.; Karanam, L.; Janardhana, C.; Rao, A. M., Langmuir
2011, 27 (24), 15268-15274.
92. Tian, J.; Sang, Y.; Yu, G.; Jiang, H.; Mu, X.; Liu, H., Adv. Mater. 2013, 25 (36), 5075-5080.
93. Jensen, L.; Schatz, G. C., J. Phys. Chem. A 2006, 110 (18), 5973-5977.
94. Tian, F.; Bonnier, F.; Casey, A.; Shanahan, A. E.; Byrne, H. J., Anal. Methods 2014, 6
(22), 9116-9123.
95. Bao, Z.; Sun, Z.; Xiao, M.; Chen, H.; Tian, L.; Wang, J., J. Mater. Chem. 2011, 21 (31), 11537.
96. Zheng, Z.; Tachikawa, T.; Majima, T., J. Am. Chem. Soc. 2015, 137 (2), 948-957.