在本研究中我們使用簡單一步驟的水熱合成方法成功的製備出不對稱結構的Janus (金/PSMA)奈米顆粒，此不對稱結構是由每個PSMA高分子球包覆單一個金奈米粒子所組成。我們也藉由FT-IR光譜分析材料的高分子球的組成、利用XRD對材料作結構鑑定含有面心立方堆疊的金結構存在，以及使用HR-TEM傾斜不同的角度與SEM 3D影像輔助觀察材料的形貌，對Janus (金/PSMA)奈米顆粒的形貌有更進一步的瞭解，得知金奈米粒子是被PSMA高分子球包覆在內部的非對稱球體的形貌。對Janus(金/PSMA)奈米顆粒的形成過程我們也隨著時間變化作觀察，發現在水熱15小時，會經過一個過渡態的結構，PSMA高分子比較喜歡包覆在聚集成為長條狀的金奈米粒子的單邊異向成長為Janus的結構。
我們也探討Janus(金/PSMA)奈米顆粒的反應機制，發現金奈米粒子具有催化誘導氧化還原反應的進行，促進金/高分子Janus奈米顆粒的形成。我們在反應機制探討中推測金奈米粒子具有催化活性，實驗將原本使用球形金奈粒子當前驅物換成以二十面體金奈米粒子來取代，比較高分子球的生成率，結果得知二十面體比球形金奈米粒子有比較高的高分子轉化率，二十面體的金奈米粒子具有比球形金奈米粒子更高的催化活性，而小粒徑的金奈米粒子有更高的催化活性。我們也利用製備出來的材料Janus(金/PSMA)的奈米顆粒，在PSMA球上嫁接上葉酸分子以及利用金奈米粒子的光學活性，同時作為標定癌細胞以及光學診斷的探針應用。

Here we report a simple and one-step method to synthesize Janus (gold/PSMA) NPs via a hydrothermal procedure. The asymmetric hybrid nanopaticle was composed of a PSMA bead and a single gold NP. We analyzed the component of polymer beads of Janus (gold/PSMA) NPs by FT-IR. The crystal structure of Janus (gold/PSMA) NPs was also studied by X-ray diffraction (XRD), by which the gold structure in Janus (gold/PSMA) NPs was characterized by its fcc structure. Then we studied the morphology of Janus (gold/PSMA) NPs by HR-TEM with different tilt angle and 3D images of SEM. We realized that gold NPs were covered in polymer beads and formed eccentric Au/PSMA NPs. The evolution of Janus (gold/PSMA) structure formation was monitored with time. It was found that the nanoparticle formed a transient structure after 15 hours of hydrothermal treatment, at which time the PSMA polymer preferred to wrap only one side of the rod-like aggregated gold nanoparticles, leading to the Janus structure. We also studied the formation mechanism of the Janus (gold/PSMA) NPs, we found that gold NPs acted as catalyst and induced oxidation-reduction reaction, facilitating the formation of Janus (gold/PSMA) NPs. We therefore replaced the sphere-like gold NPs by icosahedral gold NPs as precursor and compared the conversion yield of polymer. The results showed that the icosahedral gold NPs have higher catalytic activity than sphere-like gold NPs, and gold nanoparticles in small size catalyzed the reaction more efficiently. Janus (gold/PSMA) NPs conjugated with folic acid for targeting, then due to the strong optical property of gold nanoparticles of Janus (gold/PSMA) NPs, we can utilize the Janus (gold/PSMA) NPs as tumor-specific targeting ligand and opticle probes for biological applications.

1.馬振基, 奈米材料科技原理及應用, 全華科技圖書股份有限公司, 台北市, 1-9, 2004.
2.Petroski, J. M.; Green, T. C.; El-Sayed, M. A. 「 Shape Transformation and Surface Melting of Cubic and Tetrahedral Platinum Nanocrystals 」 J. Phys. Chem. B 102( 32), 6145- 6151, 1998.
3.Medintz, I. L.; Uyeda, H. T.; Goldman, E. R.; Mattoussi, H. 「 Quantum Dot Bioconjugates for Imaging, Labelling and Sensing 」 Nature materials 4, 435-446, 2005.
4.王崇人, 科學發展月刊, 354, 48-51, 2002.
5.張立德, 奈米材料, 五南出版, 台北市, 2002.
6.Xu, X.; H. N.; Yeung, E. S. 「 Onset of Catalytic Activity of Gold Clusters on Titania with the Appearance of Nonmetallic Properties 」 Science 281, 1647-1650, 1988.
7.Kelly, K. L.; Coronado, E.; Zhao, L. L.; Schatz, G. C. 「 The Optical Properties of Metal Nanoparticles: the Influence of Size, Shape, and Dielectric Environment 」 J. Phys. Chem. B 107, 668-677, 2003.
8.Njoki, P. N.; Lim, I-Im S.; Mott, D.; Park, H.-Y.; Khan, B.; Mishra, S.;
Sujakumar, R.; Luo, J.; Zhong, C.-J. 「 Size Correlation of Optical and Spectroscopic Properties for Gold Nanoparticles 」 J. Phys. Chem. C 111(40), 14664-14669, 2007.
9.De Gennes, P. G. 「 Soft matter 」 rev. mod. phys. 64, 645 – 648, 1992.
10.Wooley, K. L.; Hawker, C. J.; Fréchet, J. M. J. 「 Unsymmetrical Three-Dimensional Macromolecules: Preparation and Characterization of Strongly Dipolar Dendritic Macromolecules 」 J. Am. Chem. Soc. 115, 11496–11505, 1993.
11.Heroguez, V.; Gnanou Y.; Fontanille, M. 「 Novel Amphiphilic Architectures by Ring-Opening Metathesis Polymerization of Macromonomers 」 Macromolecules, 30, 4791–4798, 1997.
12.Hadjichristidis, N.; Pitsikalis, M.; Pispas S.; Latrou, H. 「 Polymers with Complex Architecture by Living Anionic Polymerization 」 Chem. Rev. 101, 3747–3792, 2001.
13.Binks, B. P. 「 Particles as surfactants-similarities and differences 」
Curr.opin.colloid Interf. Sci. 7, 21-41, 2002.
14.Binks, B. P.; Fletcher, P. D. I. 「 Adsorbed at the Oil-Water Interface: A Theoretical Comparison between Spheres of Uniform Wettability and 「Janus」 Particles 」 Langmuir, 17, 4708-4710, 2001.
15.Perro, A.; Reculusa, S.; Ravaine, S.; Elodie, B. L.; Duguet, E. 「 Design and synthesis of Janus micro- and nanoparticles 」 J. Mater. Chem. 15, 3745–3760, 2005.
16.Takei, H.; Shimizu, N. 「 Gradient Sensitive Microscopic Probes Prepared by Gold Evaporation and Chemisorption on Latex Spheres 」 Langmuir, 13, 1865-1868, 1997.
17.Cayre, O.; Paunov, V. N.; Velev, O. D. 「 Fabrication of Dipolar Colloid Particles by Microcontact Printing 」 Chem. Commun. 2296–2297, 2003.
18.Paunov, V. N.; Cayre, O. J.「 Supraparticles and 「Janus」 Particles Fabricated by Replication of Particle Monolayers at Liquid Surfaces Using a Gel Trapping Technique 」 Adv, Mater. 16 (9-10), 788-791, 2004.
19.Fujimoto, K.; Nakahama, K.; Shidara, M.; Kawaguchi, H. 「 Preparation of Unsymmetrical Microspheres at the Interfaces」 Langmuir, 15(13), 4630-4635, 1999.
20.https://www.abo.fi/student/en/media/ 11284/lbbild2.jpg
21.Mulvaney, P.; Giersig, M.; Ung, T.; Liz-Marzhn, L. M.; Mulvaney, P. 「 Direct Observation of Chemical Reactions in Silica-Coated Gold and Silver Nanoparticles 」 Adv. Mater. 9(7), 570–575, 1997.
22.Gu, H.; Zheng, R.; Zhang, X.; Xu, B. 「 Facile One-Pot Synthesis of Bifunctional Heterodimers of Nanoparticles: A Conjugate of Quantum Dot and Magnetic Nanoparticles 」 J. Am. Chem. Soc. 126, 5664-5665, 2004.
23.Yu, H.; Chen, M.; Rice, P. M.; Wang, S. X.; White R. L.; Sun, S. 「 Dumbbell-like Bifunctional Au-Fe3O4 Nanoparticles 」 Nano. Lett. 5(2), 379–382, 2005.
24.Gao, X.; Yu, L.; MacCuspie, R. I.; Matsui, H. 「 Controlled Growth of Se Nanoparticles on Ag Nanoparticles in Different Ratios 」 Adv. Mater. 17(4), 426–429, 2005.
25.Perro, A.; Reculusa, S.; Pereira, F.; Delville, M. H.; Mingotaud, C.; Duguet, E.; Elodie, B. L.; Ravaine, S. 「 Towards Large Amounts of Janus Nanoparticles through a Protection–Deprotection Route 」 Chem. Commun. 5542–5543, 2005.
26.Chen, T.; Yang, M.; Wang, X.; Tan, L. H.; Chen, H. 「 Controlled Assembly of Eccentrically Encapsulated Gold Nanoparticles 」 J. Am. Chem. Soc. 130, 11858–11859, 2008.
27.Chen, T.; Chen, G.; Xing, S.; Wu, T.; Chen, H. 「 Scalable Routes to Janus Au-SiO2 and Ternary Ag-Au-SiO2 Nanoparticles 」 Chem. Mater. 22(13), 3826–3828, 2010.
28.Wang, F.; Phonthammachai, N.; Mya, K. Y.; Tjiua,W. W.; He, C. 「 PEG-POSS Assisted Facile Preparation of Amphiphilic Gold Nanoparticles and Interface Formation of Janus Nanoparticles 」 Chem. Commun. 47, 767–769, 2011.
29.Reculusa, S.; Céline, P.-L.; Perro, A.; Duguet, E.; Mingotaud, C.; Bourgeat-Lami, E.; Ravaine, S. 「Hybrid Dissymmetrical Colloidal Particles」 Chem. Mater. 17, 3338-3334, 2005.
30.Cao, Y.; Guan, Y.; Du, J.; Luo, J.; Peng, Y.; Yipb, C. W.; Chan, A. S. C. 「 Hydrogen-Bonded Polymer Network-Poly(Ethylene Glycol) Complexes with Shape Memory Effect 」 J. Mater. Chem. 12, 2957–2960, 2002.
31.Binks, B. P. 「 Particles as Surfactants-Similarities and Differences 」 Curr.opin.colloid Interf. Sci. 7, 21-41, 2002.
32.Shen, M.; Resasco, D. E. 「 Emulsions Stabilized by Carbon Nanotube-Silica Nanohybrids 」 Langmuir, 25 (18), 10843–10851, 2009.
33.Duncan, G.-R. 「Electronic Paper Rewrites the Rulebook for Displays」 Nature Photonics, 1, 248-251, 2007.
34.Nisisako, T.; Torii, T.; Takahashi, T.; Takizawa, Y. 「Synthesis of Monodisperse Bicolored Janus Particles with Electrical Anisotropy Using a Microfluidic Co-Flow System」 Adv. Mater. 18, 1152–1156, 2006.
35.Wang, C.; Daimon, H.; Sun, S. 「 Dumbbell-like Pt-Fe3O4 Nanoparticles and Their Enhanced Catalysis for Oxygen Reduction Reaction 」 Nano Lett. 9(4), 1493-1496, 2009.
36.Crossley, S.; Faria, J.; Shen, M.; Resasco, D. E. 「 Solid Nanoparticles that Catalyze Biofuel Upgrade Reactions at the Water/Oil Interface」 Science, 327, 68-72, 2010.
37.Gu, H.; Zheng, R.; Zhang, X.; Xu, B. 「 Facile One-Pot Synthesis of Bifunctional Heterodimers of Nanoparticles: A Conjugate of Quantum Dot and Magnetic Nanoparticles 」 J. Am. Chem. Soc. 126, 5664-5665, 2004.
38.Yoshida, M.; Roh, K. H.; Lahann, J. 「 Short-term Biocompatibility of Biphasic Nanocolloids with Potential Use as Anisotropic Imaging Probes 」 Biomaterials, 28, 2446–2456, 2007.
39.Salem, A. K.; Searson, P. C.; Leong, K. W. 「 Multifunctional Nanorods for Gene Delivery 」 Nature materials, 2, 668-671, 2003.
40.Xu, C.; Wang, B.; Sun, S. 「 Dumbbell-like Au-Fe3O4 Nanoparticles for Target-Specific Platin Delivery 」 J. Am. Chem. Soc. 131, 4216–4217, 2009.
41.Xu, C.; Xie, J.; Ho, D.; Wang, C.; Kohler, N.; Walsh, E. G.; Morgan, J. R.; Chin, Y. E.; Sun, S. 「 Au–Fe3O4 Dumbbell Nanoparticles as Dual-Functional Probes 」 Angew. Chem. Int. Ed. 47, 173 –176, 2008.
42.Glaser, N.; Adams, D. J.; Boker, A.; Krausch, G. 「 Janus Particles a at Liquid-Liquid Interfaces 」 Langmuir 22, 5227-5229, 2006.
43.Hu, S.-H.; Gao, X. 「 Nanocomposites with Spatially Separated Functionalities for Combined Imaging and Magnetolytic Therapy」 J. Am. Chem. Soc. 132, 7234–7237, 2010.
44.Sheu, M. S.; El-Aasser, M. S.; Vanderhoff, J. W. 「 Uniform Nonspherical Latex Particles as Model Interpenetrating Polymer Networks 」 J. Polym. Sci., Part A: Polym. Chem. 28, 653-667, 1990.
45.Okubo, M.; Yamashita, T.; Minami, H.; Konishi, Y. 「 Preparation of Micron-Sized Monodispersed Highly Monomer-『『Adsorbed'』 Polymer Particles Having Snow-Man Shape by Utilizing the Dynamic Swelling Method with Tightly Crosslinked Seed Particles 」 Colloid Polym. Sci. 276(10), 887-892, 1998.
46.Ohnuma, A.; Cho, E. C.; Jiang, M.; Ohtani, B.; Xia Y. 「 Metal-Polymer Hybrid Colloidal Particles with an Eccentric Structure 」 Langmuir, 25(24), 13880–13887, 2009.
47.Grabar, K. C.; Freeman, R. G.; Hommer, M. B.; Natan, M. J. 「 Preparation and Characterization of Au Colloid Monolayers 」 Anal. Chem. 67, 735-743, 1995.
48.Tao, M.; Hu, Z.; Zhang, Z. 「 Morphology of the Poly(styrene-alt-maleic anhydride) Micelles Obtained by Radiation-Induced Emulsion Polymerization Using Anionic/Nonionic Mixed Surfactants Templates 」 Materials Letters, 62, 597–599, 2008.
49.Kuo, W.-S.; Chang, C.-N.; Chang, Y.-T.; Yang, M.-H.; Chien, Y.-H.; Chen, S.-J.; Yeh, C.-S. 「 Synthesis of Silica/Carbon-Encapsulated Core-Shell Spheres: Templates for Other Unique Core-Shell Structures and Applications in in Situ Loading of Noble-Metal Nanoparticles」 Langmuir, 24, 5024-5028, 2008.
50.Malardier-Jugroot, C.; Van de Ven, T. G. M.; Whitehead, M. A. 「 Linear Conformation of Poly(styrene-alt-maleic anhydride) Capable of Self-Assembly: A Result of Chain Stiffening by Internal Hydrogen Bonds」 J. Phys. Chem. B, 109, 7022-7032, 2005.
51.Liu, X.; Xu, B.; Haubrich, J.; Madix, R. J.; Friend, C. M. 「 Surface-Mediated Self-Coupling of Ethanol on Gold 」 J. Am. Chem. Soc. 131, 5757–5759, 2009.
52.Vinod, C. P.; Wilson, K.; Lee, A. F. 「 Recent Advances in the Heterogeneously Catalysed Aerobic Selective Oxidation of Alcohols」 J. Chem. Technol. Biotechnol. 86, 161–171, 2011.
53.Legodi, M. A.; De Waal, D.; Potgieter, J. H.; Potgieter, S. S. 「 Technical Note Rapid Determination of CaCO3 in Mixtures Utilising FT-IR Spectroscopy 」 Miner. Eng. 14(9), 1107-1111, 2001.
54.Tsunoyama, H.; Sakurai, H.; Ichikuni, N.; Negishi, Y.; Tsukuda, T. 「 Colloidal Gold Nanoparticles as Catalyst for Carbon-Carbon Bond Formation: Application to Aerobic Homocoupling of Phenylboronic Acid in Water 」 Langmuir, 20, 11293-11296, 2004.
55.Tsunoyama, H.; Ichikuni, N.; Sakurai, H.; Tsukuda, T. 「 Effect of Electronic Structures of Au Clusters Stabilized by Poly(N-vinyl-2-pyrrolidone) on Aerobic Oxidation Catalysis 」 J. Am. Chem. Soc. 131, 7086–7093, 2009.
56.Liu, H.; Liu, Y.; Li, Y.; Tang, Z.; Jiang, H. 「 Metal-Organic Framework Supported Gold Nanoparticles as a Highly Active Heterogeneous Catalyst for Aerobic Oxidation of Alcohols 」 J. Phys. Chem. C, 114, 13362–13369, 2010.
57.Kuai, L.; Geng, B.; Wang, S.; Zhao, Y.; Luo, Y.; Jiang, H. 「 Silver and Gold Icosahedra: One-Pot Water-Based Synthesis and Their Superior Performance in the Electrocatalysis for Oxygen Reduction Reactions in Alkaline Media 」 Chem. Eur. J. 17, 3482-3489, 2011.
58.Peng, S.; Lee, Y.; Wang, C.; Yin, H.; Dai, S.; Sun, S. 「 A Facile Synthesis of Monodisperse Au Nanoparticles and Their Catalysis of CO Oxidation 」 Nano Res, 1, 229-234, 2008.
59.Wang, C.; Cheng, L.; Zhuang Liu, Z. 「 Drug Delivery with Upconversion Nanoparticles for Multi-functional Targeted Cancer Cell Imaging and Therapy 」 Biomaterials, 32, 1110-1120, 2011.