請用此 Handle URI 來引用此文件：
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/101718完整後設資料紀錄
| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 彭之皓 | zh_TW |
| dc.contributor.advisor | Chi-How Peng | en |
| dc.contributor.author | 陳雨謙 | zh_TW |
| dc.contributor.author | Yu-Chien Chen | en |
| dc.date.accessioned | 2026-02-26T16:58:41Z | - |
| dc.date.available | 2026-02-27 | - |
| dc.date.copyright | 2026-02-26 | - |
| dc.date.issued | 2026 | - |
| dc.date.submitted | 2026-01-26 | - |
| dc.identifier.citation | (1) Chen, Y.-C.; Huang, X.-F.; Hsu, H.-T.; Wu, E.-T.; Peng, C.-H.; Huang, M. H. Photocatalyzed dimethylacrylamide polymerization in an aqueous solution using 4-nitrophenylacetylene-modified Cu2O crystals. Journal of Materials Chemistry A 2024, 12 (24), 14792–14800.
(2) Shelef, O.; Gnaim, S.; Shabat, D. Self-Immolative Polymers: An Emerging Class of Degradable Materials with Distinct Disassembly Profiles. Journal of the American Chemical Society 2021, 143 (50), 21177–21188. (3) Li, Q.; Huang, J. D.; Liu, T.; van der Pol, T. P. A.; Zhang, Q.; Jeong, S. Y.; Stoeckel, M. A.; Wu, H. Y.; Zhang, S.; Liu, X.; Woo, H. Y.; Fahlman, M.; Yang, C. Y.; Fabiano, S. A Highly Conductive n-Type Conjugated Polymer Synthesized in Water. Journal of the American Chemical Society 2024, 146 (23), 15860–15868. (4) Zhao, H.; Prine, N.; Kundu, S.; Ma, G.; Gu, X. Effect of Thermal Stress on Morphology in High-Performance Organic Photovoltaic Blends. Journal of the American Chemical Society Au 2024, 4 (11), 4334–4344. (5) Kumar, A.; von Wolff, N.; Rauch, M.; Zou, Y. Q.; Shmul, G.; Ben-David, Y.; Leitus, G.; Avram, L.; Milstein, D. Hydrogenative Depolymerization of Nylons. Journal of the American Chemical Society 2020, 142 (33), 14267–14275. (6) Garcia-Meseguer, R.; Orti, E.; Tunon, I.; Ruiz-Pernia, J. J.; Arago, J. Insights into the Enhancement of the Poly(ethylene terephthalate) Degradation by FAST-PETase from Computational Modeling. Journal of the American Chemical Society 2023, 145 (35), 19243–19255. (7) McNeeley, A.; Liu, Y. A. Assessment of Nylon-66 Depolymerization for Circular Economy: Kinetic Modeling, Purification, and Sustainable Design. Industrial & Engineering Chemistry Research 2025, 64 (8), 4179–4203. (8) Schwartz, J. J. Additive manufacturing: Frameworks for chemical understanding and advancement in vat photopolymerization. MRS Bulletin 2022, 47 (6), 628–641. (9) Ginell, R.; Simha, R. On the Kinetics of Polymerization Reactions. I. First Order Initiation Reaction1. Journal of the American Chemical Society 2002, 65 (4), 706–715. (10) Soulé, E. R.; Borrajo, J.; Williams, R. J. J. Kinetics of the Free-Radical Polymerization of Isobornyl Methacrylate in the Presence of Polyisobutylenes of Different Molar Masses. Macromolecules 2005, 38 (14), 5987–5994. (11) Moehrke, J.; Vana, P. Termination Kinetics of Surface-Initiated Radical Polymerization Measured by Time-Resolved ESR Spectroscopy after Laser-Pulse Initiation. Macromolecules 2015, 48 (10), 3190–3196. (12) Greszta, D.; Matyjaszewski, K. TEMPO-mediated polymerization of styrene: Rate enhancement with dicumyl peroxide. Journal of Polymer Science Part A: Polymer Chemistry 1997, 35 (9), 1857–1861. (13) Alonso, R. C. B.; Brandt, W. C.; Souza-Junior, E. J. C.; Puppin-Rontani, R. M.; Sinhoreti, M. A. C. Photoinitiator concentration and modulated photoactivation: influence on polymerization characteristics of experimental composites. Applied Adhesion Science 2014, 2 (1), (14) Otsu, T.; Yoshida, M. Efficient synthesis of two or multi component block copolymers through living radical polymerization with polymeric photoiniferters. Polymer Bulletin 1982, 7 (4), 197–203. (15) Moad, G.; Rizzardo, E.; Thang, S. H. Toward living radical polymerization. Accounts of Chemical Research 2008, 41 (9), 1133–1142. (16) Jenkins, A. D.; Jones, R. G.; Moad, G. Terminology for reversible-deactivation radical polymerization previously called "controlled" radical or "living" radical polymerization (IUPAC Recommendations 2010). Pure and Applied Chemistry 2009, 82 (2), 483–491. (17) Wayland, B. B.; Peng, C.-H.; Fu, X.; Lu, Z.; Fryd, M. Degenerative Transfer and Reversible Termination Mechanisms for Living Radical Polymerizations Mediated by Cobalt Porphyrins. Macromolecules 2006, 39 (24), 8219–8222. (18) Mandal, I.; Kilbinger, A. F. M. A Versatile Reversible, Degenerative Chain Transfer Mechanism for the Catalytic Living Ring-Opening Metathesis Polymerization. Angewandte Chemie International Edition in English 2024, 63 (40), e202409781. (19) Wang, J.-S.; Matyjaszewski, K. Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes. Journal of the American Chemical Society 1995, 117 (20), 5614–5615. (20) Kato, M.; Kamigaito, M.; Sawamoto, M.; Higashimura, T. Polymerization of Methyl Methacrylate with the Carbon Tetrachloride/Dichlorotris- (triphenylphosphine)ruthenium(II)/Methylaluminum Bis(2,6-di-tert-butylphenoxide) Initiating System: Possibility of Living Radical Polymerization. Macromolecules 1995, 28 (5), 1721–1723. (21) Kamigaito, M. Recent developments in metal-catalyzed living radical polymerization. Polymer Journal 2010, 43 (2), 105–120. (22) Xue, Z.; He, D.; Xie, X. Iron-catalyzed atom transfer radical polymerization. Polymer Chemistry 2015, 6 (10), 1660–1687. (23) Grishin, I. D.; Grishin, D. F. Ruthenium complexes in the controlled synthesis of macromolecules. Russian Chemical Reviews 2008, 77 (7), 633–648. (24) Veregin, R. P. N.; Georges, M. K.; Kazmaier, P. M.; Hamer, G. K. Free radical polymerizations for narrow polydispersity resins: electron spin resonance studies of the kinetics and mechanism. Macromolecules 1993, 26 (20), 5316–5320. (25) Sciannamea, V.; Jerome, R.; Detrembleur, C. In-situ nitroxide-mediated radical polymerization (NMP) processes: their understanding and optimization. Chemical Reviews 2008, 108 (3), 1104–1126. (26) Benoit, D.; Chaplinski, V.; Braslau, R.; Hawker, C. J. Development of a Universal Alkoxyamine for “Living” Free Radical Polymerizations. Journal of the American Chemical Society 1999, 121 (16), 3904–3920. (27) Marchand, J.; Autissier, L.; Guillaneuf, Y.; Couturier, J.-L.; Gigmes, D.; Bertin, D. SG1 Nitroxide Analogues: a Comparative Study. Australian Journal of Chemistry 2010, 63 (8), 1237–1244. (28) Abreu, C. M. R.; Mendonça, P. V.; Serra, A. C.; Noble, B. B.; Guliashvili, T.; Nicolas, J.; Coote, M. L.; Coelho, J. F. J. Nitroxide-Mediated Polymerization of Vinyl Chloride at Low Temperature: Kinetic and Computational Studies. Macromolecules 2016, 49 (2), 490–498. (29) Nguyen, N. H.; Wu, X.; Guillaneuf, Y.; Spangenberg, A.; Gigmes, D.; Clément, J.-L. Synthesis of novel D–π–A-based photosensitive alkoxyamine: application of two-photon polymerization via nitroxide-mediated photopolymerization. Polymer Chemistry 2025, 16 (11), 1248–1255. (30) Chiefari, J.; Chong, Y. K.; Ercole, F.; Krstina, J.; Jeffery, J.; Le, T. P. T.; Mayadunne, R. T. A.; Meijs, G. F.; Moad, C. L.; Moad, G.; Rizzardo, E.; Thang, S. H. Living Free-Radical Polymerization by Reversible Addition−Fragmentation Chain Transfer: The RAFT Process. Macromolecules 1998, 31 (16), 5559–5562. (31) Lu, H.; Huang, Y.; Zhang, E.; Liu, Y.; Lv, F.; Liu, L.; Ma, Y.; Wang, S. Photocontrolled RAFT Polymerization Catalyzed by Conjugated Polymers under Aerobic Aqueous Conditions. ACS Macro Letters 2021, 10 (8), 996–1001. (32) Lee, Y.; Kwon, Y.; Kim, Y.; Yu, C.; Feng, S.; Park, J.; Doh, J.; Wannemacher, R.; Koo, B.; Gierschner, J.; Kwon, M. S. A Water-Soluble Organic Photocatalyst Discovered for Highly Efficient Additive-Free Visible-Light-Driven Grafting of Polymers from Proteins at Ambient and Aqueous Environments. Advanced Materials 2022, 34 (14), e2108446. (33) Yeow, J.; Chapman, R.; Xu, J.; Boyer, C. Oxygen tolerant photopolymerization for ultralow volumes. Polymer Chemistry 2017, 8 (34), 5012–5022. (34) Perrier, S. 50th Anniversary Perspective: RAFT Polymerization—A User Guide. Macromolecules 2017, 50 (19), 7433–7447. (35) Xu, J.; Jung, K.; Atme, A.; Shanmugam, S.; Boyer, C. A robust and versatile photoinduced living polymerization of conjugated and unconjugated monomers and its oxygen tolerance. Journal of the American Chemical Society 2014, 136 (14), 5508–5519. (36) Xu, J.; Jung, K.; Boyer, C. Oxygen Tolerance Study of Photoinduced Electron Transfer–Reversible Addition–Fragmentation Chain Transfer (PET-RAFT) Polymerization Mediated by Ru(bpy)3Cl2. Macromolecules 2014, 47 (13), 4217–4229. (37) Xu, J.; Shanmugam, S.; Duong, H. T.; Boyer, C. Organo-photocatalysts for photoinduced electron transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization. Polymer Chemistry 2015, 6 (31), 5615–5624. (38) Dadashi-Silab, S.; Doran, S.; Yagci, Y. Photoinduced Electron Transfer Reactions for Macromolecular Syntheses. Chemical Reviews 2016, 116 (17), 10212–10275. (39) Allegrezza, M. L.; Konkolewicz, D. PET-RAFT Polymerization: Mechanistic Perspectives for Future Materials. ACS Macro Letters 2021, 10 (4), 433–446. (40) Moad, G.; Rizzardo, E.; Thang, S. H. Living Radical Polymerization by the RAFT Process – A Third Update. Australian Journal of Chemistry 2012, 65 (8), 985–1076. (41) Chang, C.-W.; Jen, Y.-Y.; Tang, S.-C.; Zhang, P.; Chen, C.; Peng, C.-H. Reversible-deactivation radical polymerization of vinyl acetate mediated by tralen, an organomediator. Polymer Chemistry 2021, 12 (36), 5159–5167. (42) Benchaphanthawee, W.; Jen, Y.-Y.; Yang, Z.-W.; Peng, C.-H. Troponoid-Mediated Radical Polymerization of Vinyl Monomers. Macromolecules 2025, 58 (12), 6178–6189. (43) Chang, I. H.; Lin, T. Y.; Lai, P. T.; Adhidjaja, E. C.; Peng, C. H. Troponoid-mediated radical polymerization in aqueous medium. Polymer Chemistry 2025, 16 (34), 3864–3874. (44) Chang, I. H.; Adhidjaja, E. C.; Peng, C. H. Synthesis of Poly(vinyl acetate)-Based Block Copolymers for Highly Stretchable Film by Troponoid-Mediated Radical Emulsion Polymerization. Macromolecular Chemistry and Physics 2025, 226 (12), 2400519. (45) Raimondi, M. T.; Eaton, S. M.; Nava, M. M.; Lagana, M.; Cerullo, G.; Osellame, R. Two-photon laser polymerization: from fundamentals to biomedical application in tissue engineering and regenerative medicine. Journal of Applied Biomaterials & Functional Materials 2012, 10 (1), 56–66. (46) Stansbury, J. W.; Idacavage, M. J. 3D printing with polymers: Challenges among expanding options and opportunities. Dental Materials 2016, 32 (1), 54–64. (47) Chiulan, I.; Heggset, E. B.; Voicu, S. I.; Chinga-Carrasco, G. Photopolymerization of Bio-Based Polymers in a Biomedical Engineering Perspective. Biomacromolecules 2021, 22 (5), 1795–1814. (48) Petko, F.; Swiezy, A.; Ortyl, J. Photoinitiating systems and kinetics of frontal photopolymerization processes - the prospects for efficient preparation of composites and thick 3D structures. Polymer Chemistry 2021, 12 (32), 4593–4612. (49) Yagci, Y.; Jockusch, S.; Turro, N. J. Photoinitiated Polymerization: Advances, Challenges, and Opportunities. Macromolecules 2010, 43 (15), 6245–6260. (50) Bagheri, A.; Jin, J. Y. Photopolymerization in 3D Printing. Acs Applied Polymer Materials 2019, 1 (4), 593–611. (51) Petko, F.; Jankowska, M.; Galek, M.; Noworyta, M.; Popielarz, R.; Ortyl, J. One-Component Stilbene-Based Iodonium Photoinitiators with Increased Photoacid Quantum Yield for Cationic Vat 3D Printing. Macromolecules 2024, 57 (24), 11639–11657. (52) Xu, J. T.; Jung, K.; Corrigan, N. A.; Boyer, C. Aqueous photoinduced living/controlled polymerization: tailoring for bioconjugation. Chemical Science 2014, 5 (9), 3568–3575. (53) Lee, Y.; Boyer, C.; Kwon, M. S. Photocontrolled RAFT polymerization: past, present, and future. Chemical Society Reviews 2023, 52 (9), 3035–3097. (54) Zhang, J.; Lalevée, J.; Hill, N. S.; Launay, K.; Morlet-Savary, F.; Graff, B.; Stenzel, M. H.; Coote, M. L.; Xiao, P. Disubstituted Aminoanthraquinone-Based Multicolor Photoinitiators: Photoinitiation Mechanism and Ability of Cationic Polymerization under Blue, Green, Yellow, and Red LEDs. Macromolecules 2018, 51 (20), 8165–8173. (55) Wang, G. N.; Hill, N. S.; Zhu, D.; Xiao, P.; Coote, M. L.; Stenzel, M. H. Efficient Photoinitiating System Based on Diaminoanthraquinone for 3D Printing of Polymer/Carbon Nanotube Nanocomposites under Visible Light. Acs Applied Polymer Materials 2019, 1 (5), 1129–1135. (56) Voutyritsa, E.; Lazou, T.; Bushi, J.; Margaritaki, S.; Charitaki, M.; Christensen, S. M.; Hatzakis, N. S.; Velonia, K. Oxygen-tolerant, eosin Y mediated synthesis of protein–polymer biohybrids and protein-coated polymer nanoparticles. Polymer Chemistry 2024, 15 (32), 3246–3255. (57) Lee, Y. B.; Lim, S.; Lee, Y.; Park, C. H.; Lee, H. J. Green Chemistry for Crosslinking Biopolymers: Recent Advances in Riboflavin-Mediated Photochemistry. Materials (Basel) 2023, 16 (3), 1218. (58) Li, K.; Gao, S.; Wang, Q.; Xu, H.; Wang, Z.; Huang, B.; Dai, Y.; Lu, J. In-Situ-Reduced Synthesis of Ti3+ Self-Doped TiO2/g-C3N4 Heterojunctions with High Photocatalytic Performance under LED Light Irradiation. ACS Applied Materials & Interfaces 2015, 7 (17), 9023–9030. (59) Acharya, R.; Parida, K. A review on TiO2/g-C3N4 visible-light- responsive photocatalysts for sustainable energy generation and environmental remediation. Journal of Environmental Chemical Engineering 2020, 8 (4), (60) Sun, J. X.; Yuan, Y. P.; Qiu, L. G.; Jiang, X.; Xie, A. J.; Shen, Y. H.; Zhu, J. F. Fabrication of composite photocatalyst g-C3N4-ZnO and enhancement of photocatalytic activity under visible light. Dalton Trans 2012, 41 (22), 6756–6763. (61) Pourali, S.; Amrollahi, R.; Alamolhoda, S.; Masoudpanah, S. M. In situ synthesis of ZnO/g-C3N4 based composites for photodegradation of methylene blue under visible light. Scientific Reports 2025, 15 (1), 462. (62) Huang, M. H. Facet-Dependent Optical Properties of Semiconductor Nanocrystals. Small 2019, 15 (7), 1804726. (63) Huang, M. H.; Rej, S.; Chiu, C. Y. Facet-Dependent Optical Properties Revealed through Investigation of Polyhedral Au-Cu2O and Bimetallic Core-Shell Nanocrystals. Small 2015, 11 (23), 2716–2726. (64) Wu, S. C.; Tan, C. S.; Huang, M. H. Strong Facet Effects on Interfacial Charge Transfer Revealed through the Examination of Photocatalytic Activities of Various Cu2O–ZnO Heterostructures. Advanced Functional Materials 2017, 27 (9), 1604635. (65) Lee, A. T.; Tan, C. S.; Huang, M. H. Current Rectification and Photo-Responsive Current Achieved through Interfacial Facet Control of Cu2O-Si Wafer Heterojunctions. ACS Central Science 2021, 7 (11), 1929–1937. (66) Chen, T. N.; Kao, J. C.; Zhong, X. Y.; Chan, S. J.; Patra, A. S.; Lo, Y. C.; Huang, M. H. Facet-Specific Photocatalytic Activity Enhancement of Cu2O Polyhedra Functionalized with 4-Ethynylanaline Resulting from Band Structure Tuning. ACS Central Science 2020, 6 (6), 984–994. (67) Kao, J. C.; Yu, W. Y.; Chien, K. C.; Chou, P. J.; Huang, M. H.; Lo, Y. C.; Chou, J. P. Enhanced Photocatalytic Performance of Halogenated Phenylacetylene-Decorated Cu2O Surfaces via Electronic Structure Modulation: A DFT and Experimental Study. ACS Nanoscience Au 2025, 5 (4), 314–323. (68) Chan, S.-J.; Kao, J.-C.; Chou, P.-J.; Lo, Y.-C.; Chou, J.-P.; Huang, M. H. 4-Nitrophenylacetylene-modified Cu2O cubes and rhombic dodecahedra showing superior photocatalytic activity through surface band structure modulation. Journal of Materials Chemistry C 2022, 10 (21), 8422–8431. (69) Encinas, M. V.; Rufs, A. M.; Norambuena, E.; Giannotti, C. p-Nitroacetanilide in the presence of triethylamine as a photoinitiator system for vinyl polymerization. Journal of Polymer Science Part A: Polymer Chemistry 1997, 35 (15), 3095–3100. (70) Rehm, D.; Weller, A. Kinetics of Fluorescence Quenching by Electron and H‐Atom Transfer. Israel Journal of Chemistry 1970, 8 (2), 259–271. (71) Lakowicz, J. R. Principles of Fluorescence Spectroscopy; Springer, 2006. (72) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian 16 Rev. C.01; 2016. (73) Pound, G.; Eksteen, Z.; Pfukwa, R.; Mckenzie, J. M.; Lange, R. F. M.; Klumperman, B. Unexpected reactions associated with the xanthate-mediated polymerization of N-vinylpyrrolidone. Journal of Polymer Science Part a-Polymer Chemistry 2008, 46 (19), 6575–6593. (74) Kausche, T.; Sauberlich, J.; Trobitzsch, E.; Beckert, D.; Dinse, K. P. Photoreduction of 9,10-anthraquinone by triethylamine: A Fourier-transform EPR study. Chemical Physics 1996, 208 (3), 375–390. (75) DeLaive, P. J.; Sullivan, B. P.; Meyer, T. J.; Whitten, D. G. Applications of light-induced electron-transfer reactions. Coupling of hydrogen generation with photoreduction of ruthenium(II) complexes by triethylamine. Journal of the American Chemical Society 2002, 101 (14), 4007–4008. (76) Encinas, M. V.; Majmud, C.; Garrido, J.; Lissi, E. A. Methyl methacrylate polymerization photoinitiated by pyrene in the presence of triethylamine. Macromolecules 2002, 22 (2), 563–566. (77) Costela, A.; Garcı́a-Moreno, I.; Garcı́a, O.; Sastre, R. p-Nitronaphthylaniline in the presence of N,N-dimethylaniline as bimolecular photoinitiating system of polymerization. Journal of Photochemistry and Photobiology A: Chemistry 2000, 131 (1-3), 133–140. (78) Sun, G. D.; Huang, Y.; Li, D. P.; Chen, E. Y.; Zhong, Y. H.; Fan, G.; Shao, J. Z. Blue Light Initiated Photopolymerization: Kinetics and Synthesis of Superabsorbent and Robust Poly(N,N--dimethylacrylamide/Sodium Acrylate) Hydrogels. Industrial & Engineering Chemistry Research 2019, 58 (22), 9266–9275. (79) Carbonell, C.; Valles, D.; Wong, A. M.; Carlini, A. S.; Touve, M. A.; Korpanty, J.; Gianneschi, N. C.; Braunschweig, A. B. Polymer brush hypersurface photolithography. Nature Communications 2020, 11 (1), 1244. (80) Balcerak, A.; Kabatc, J. The photooxidative sensitization of bis(p-substituted diphenyl)iodonium salts in the radical polymerization of acrylates. RSC Advances 2019, 9 (49), 28490–28499. (81) Wu, M.; Wang, G.; Zhang, M.; Li, J.; Wang, C.; Sun, G.; Zheng, J. A tough and piezoelectric poly(acrylamide/N,N-dimethylacrylamide) hydrogel-based flexible wearable sensor. Soft Matter 2024, 20 (34), 6800–6807. (82) Chen, M.; Zhong, M.; Johnson, J. A. Light-Controlled Radical Polymerization: Mechanisms, Methods, and Applications. Chemical Reviews 2016, 116 (17), 10167–10211. (83) Zhu, M.; Wang, S.; Li, Z.; Li, J.; Xu, Z.; Liu, X.; Huang, X. Tyrosine residues initiated photopolymerization in living organisms. Nature Communications 2023, 14 (1), 3598. (84) Kuhn, A.; von Eschwege, K. G.; Conradie, J. Reduction potentials of para‐substituted nitrobenzenes—an infrared, nuclear magnetic resonance, and density functional theory study. Journal of Physical Organic Chemistry 2011, 25 (1), 58–68. (85) Gandhimathi, R.; Dheivamalar, S.; Dhanasekaran, R. Geometry optimization, HOMO and LUMO energy, molecular electrostatic potential, NMR, FT-IR and FT-Raman analyzes on 4-nitrophenol. European Physical Journal-Applied Physics 2015, 69 (1), 10202. (86) Norambuena, E.; Olea-Azar, C.; Rufs, A. M.; Encinas, M. V. Photoreduction of 4-substituted nitrobenzenes by amines. Physical Chemistry Chemical Physics 2004, 6 (6), 1230–1235. (87) Lau, N. A.; Ghosh, D.; Bourne-Worster, S.; Kumar, R.; Whitaker, W. A.; Heitland, J.; Davies, J. A.; Karras, G.; Clark, I. P.; Greetham, G. M.; Worth, G. A.; Orr-Ewing, A. J.; Fielding, H. H. Unraveling the Ultrafast Photochemical Dynamics of Nitrobenzene in Aqueous Solution. Journal of the American Chemical 2024, 146 (15), 10407–10417. (88) Efe, H.; Bicen, M.; Kahraman, M. V.; Kayaman-Apohan, N. Synthesis of 4-Acryloylmorpholine-based Hydrogels and Investigation of their Drug Release Behaviors. Journal of the Brazilian Chemical Society 2013, 24 (5), 814–820. (89) Kohsaka, Y.; Tanimoto, Y. Synthesis of Thermo-Responsive Polymer via Radical (Co)polymerization of N,N-Dimethyl-alpha-(hydroxymethyl)acrylamide with N,N-Diethylacrylamide. Polymers (Basel) 2016, 8 (10), 374. (90) Kadoma, Y.; Ishihara, M.; Yokoe, I.; Fujisawa, S. Kinetic Radical-scavenging Activity of Colchicine and Tropolone. In Vivo 2007, 21, 481–486. | - |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/101718 | - |
| dc.description.abstract | 在本實驗室先前研究中，我們發現將 4-硝基苯乙炔 (4-NA) 修飾於半導體氧化亞銅 (Cu2O) 表面後，能有效催化水相中N,N-二甲基丙烯醯胺 (DMA) 的光聚合反應。進一步研究指出，即使不倚賴半導體材料，單獨使用含硝基芳香環結構的有機分子，也展現出啟動自由基聚合的潛力。
基於此發現，本研究進一部探討4-硝基苯乙炔 (4-NA) 是否能作為一種可回收、無金屬添加的水相光引發劑，針對多種具三級胺結構的醯胺類單體 (如N,N-二甲基丙烯醯胺、4-丙烯醯嗎啉、N,N-二乙基丙烯醯胺) 及常見水溶性單體進行聚合實驗，並藉由轉化率與反應性差異，推論其可能的光引發機制。 實驗結果顯示，僅有三級胺類單體 (N,N-二甲基丙烯醯胺、4-丙烯醯嗎啉) 在4-硝基苯乙炔 (4-NA) 光激發後具聚合活性，推測其可能與激發態4-硝基苯乙炔發生電子轉移，生成α-胺基烷基自由基 (α-aminoalkyl radical)，進而加成至單體雙鍵並啟動聚合反應。為佐證此推論，我們進一步利用密度泛函理論 (DFT) 模擬激發態過程，並計算電子轉移與自由基加成步驟的能量變化。特別針對N,N-二甲基丙烯醯胺及4-丙烯醯嗎啉的α-胺基烷基自由基加成步驟執行本徑反應座標 (IRC) 追蹤，成功建立完整的能量路徑與合理的反應能障。此外，透過引入可逆加成－斷裂鏈轉移聚合 (RAFT) 策略，初步觀察到聚合反應之分子量可隨轉化率調控，且分子量分佈趨於狹窄，顯示本系統具備進一步發展為光控可逆－失活自由基聚合 (RDRP) 之潛力。 綜合而言，本研究驗證了以4-硝基苯乙炔作為綠色有機光引發劑的可行性，並揭示其可在無金屬的條件下引發水相聚合反應，對於未來開發環境友善之光控聚合系統提供了嶄新方向。 | zh_TW |
| dc.description.abstract | In our laboratory’s previous research, we found that surface modification of cuprous oxide (Cu2O) nanoparticles with 4-nitrophenylacetylene (4-NA) can effectively catalyze the photopolymerization of N,N-dimethylacrylamide (DMA) in aqueous solution. Further investigations revealed that even in the absence of semiconductor materials, organic molecules containing a nitroaromatic structure alone also exhibit potential in initiating radical polymerization.
Building upon this finding, this study explores the feasibility of using 4-NA as a recyclable, metal-free photo-initiator for aqueous-phase polymerization. We conducted polymerization experiments with various amide-based monomers bearing tertiary amine groups (e.g., N,N-dimethylacrylamide, 4-acryloylmorpholine, N,N-diethylacrylamide) and other common water-soluble monomers. Differences in conversion rates and reactivity were analyzed to infer the possible photo-initiation mechanism. The results show that only tertiary amide monomers (N,N-dimethylacrylamide and 4-acryloylmorpholine) exhibited polymerization activity under 4-NA photoexcitation. We propose that this is due to an electron transfer from the monomer to the excited-state 4-NA, generating α-aminoalkyl radicals that subsequently add to the monomer’s double bond, initiating polymerization. To support this hypothesis, density functional theory (DFT) was employed to simulate the excitation process, and energy changes during electron transfer and radical addition were calculated. In particular, intrinsic reaction coordinate (IRC) calculations were carried out for the α-aminoalkyl radical addition step for N,N-dimethylacrylamide and 4-acryloylmorpholine, successfully establishing a complete energy profile and a reasonable activation barrier. In addition, by incorporating a reversible addition–fragmentation chain transfer (RAFT) strategy, preliminary results revealed that the polymer molecular weight could be regulated as a function of monomer conversion, accompanied by relatively narrow molecular weight distributions, indicating the potential of this system to be further developed into a light-controlled reversible-deactivation radical polymerization (RDRP) platform. In conclusion, this study demonstrates the potential of 4-NA as a green, metal-free organic photo-initiator capable of initiating aqueous-phase polymerizations. This work offers a promising strategy for developing environmentally friendly photo-controlled polymerization systems. | en |
| dc.description.provenance | Submitted by admin ntu (admin@lib.ntu.edu.tw) on 2026-02-26T16:58:41Z No. of bitstreams: 0 | en |
| dc.description.provenance | Made available in DSpace on 2026-02-26T16:58:41Z (GMT). No. of bitstreams: 0 | en |
| dc.description.tableofcontents | 口試委員會審定書 i
誌謝 ii 中文摘要 iii Abstract iv 目 次 vi 圖 次 viii 表 次 xii 式 次 xiv 第一章 緒論 1 1.1 傳統聚合反應 1 1.2 自由基聚合反應 3 1.3 可逆－失活自由基聚合反應 (Reversible-Deactivation Radical Polymerization, RDRP) 5 1.3.1 原子轉移自由基聚合反應 (Atom Transfer Radical Polymerization, ATRP) 8 1.3.2 氮氧自由基聚合反應 (Nitroxide Mediated Radical Polymerization, NMP) 10 1.3.3 可逆加成－斷裂鏈轉移聚合反應 (Reversible Addition−Fragmentation Chain-Transfer Polymerization, RAFT) 12 1.3.4 環庚三烯酮及其衍生化合物應用於可逆－失活自由基聚合反應 14 1.4 光引發聚合技術 16 1.4.1 可見光在聚合反應中的應用 17 1.4.2 奈米半導體材料應用於光催化聚合反應 19 1.5 研究動機 20 第二章 實驗及藥品 23 2.1 化學藥品 23 2.2 實驗儀器 23 2.3 實驗方法 25 一般光聚合反應 25 螢光猝熄實驗 25 理論計算方法 26 第三章 實驗結果與討論 27 3.1 4-硝基苯乙炔於可見光誘導聚合反應之應用 27 3.1.1 單體結構對聚合效率之控制實驗 30 3.1.2 不同比例條件對聚合反應之影響 33 3.1.3 時間控制光照實驗 35 3.1.4 反應過程中溶液pH變化之量測與分析 36 3.1.5 光引發劑之可回收性測試 37 3.1.6 聚合物鏈尾端結構分析 39 3.1.7 螢光淬熄實驗 42 3.2 反應機制之密度泛函理論 (DFT) 探討 45 3.2.1 能階圖與電子轉移機制推演 47 3.2.2 過渡態 (Transition State) 及本徑反應座標追踪 (Intrinsic Reaction Coordinate) 計算 50 3.3 4-硝基苯乙炔應用於光誘導可逆－失活自由基聚合反應探討 54 3.3.1 引發劑比例與環庚三烯酮對可逆－失活自由基聚合反應的影響 55 3.3.2 環庚三烯酮於可見光照射下之光化學行為探討 57 3.3.3 可逆加成－斷裂鏈轉移聚合於4-硝基苯乙炔光引發系統中的應用探討 58 3.4 結論 61 第四章 附錄 63 4.1 1H NMR光譜圖 63 4.2 反應過程顏色變化之原始圖像 67 4.3 聚合原始數據 67 4.4 DFT計算之原始座標 70 參考文獻 93 | - |
| dc.language.iso | zh_TW | - |
| dc.subject | 可見光光聚合 | - |
| dc.subject | 水相環境 | - |
| dc.subject | 可回收光引發劑 | - |
| dc.subject | 電子轉移機制 | - |
| dc.subject | 綠色化學 | - |
| dc.subject | 可逆加成－斷裂鏈轉移聚合反應 | - |
| dc.subject | Visible-light photopolymerization | - |
| dc.subject | Aqueous medium | - |
| dc.subject | Electron transfer mechanism | - |
| dc.subject | Green chemistry | - |
| dc.subject | Reversible Addition−Fragmentation Chain-Transfer Polymerization | - |
| dc.subject | Recyclable photoinitiator | - |
| dc.title | 利用4-硝基苯乙炔於水相中引發可見光誘導的自由基聚合反應 | zh_TW |
| dc.title | Visible-Light-Induced Radical Polymerization initiated by 4-Nitrophenylacetylene in Aqueous Phase | en |
| dc.type | Thesis | - |
| dc.date.schoolyear | 114-1 | - |
| dc.description.degree | 碩士 | - |
| dc.contributor.oralexamcommittee | 陳浩銘;邱昱誠 | zh_TW |
| dc.contributor.oralexamcommittee | Hao-Ming Chen;Yu-Cheng Chiu | en |
| dc.subject.keyword | 可見光光聚合,水相環境可回收光引發劑電子轉移機制綠色化學可逆加成－斷裂鏈轉移聚合反應 | zh_TW |
| dc.subject.keyword | Visible-light photopolymerization,Aqueous mediumElectron transfer mechanismGreen chemistryReversible Addition−Fragmentation Chain-Transfer PolymerizationRecyclable photoinitiator | en |
| dc.relation.page | 104 | - |
| dc.identifier.doi | 10.6342/NTU202600017 | - |
| dc.rights.note | 同意授權(限校園內公開) | - |
| dc.date.accepted | 2026-01-27 | - |
| dc.contributor.author-college | 理學院 | - |
| dc.contributor.author-dept | 化學系 | - |
| dc.date.embargo-lift | 2029-01-20 | - |
| 顯示於系所單位： | 化學系 | |
文件中的檔案：
| 檔案 | 大小 | 格式 | |
|---|---|---|---|
| ntu-114-1.pdf 未授權公開取用 | 5.93 MB | Adobe PDF | 檢視/開啟 |
系統中的文件，除了特別指名其著作權條款之外，均受到著作權保護，並且保留所有的權利。