基于激发态光酸调控光响应动态系统的研究与进展
Research and Progress on Light-Responsive Dynamic Systems Regulated by Excited-State Photoacids
DOI: 10.12677/jocr.2025.134043, PDF,   
作者: 羊天高:浙江师范大学化学与材料科学学院,浙江 金华
关键词: 激发态光酸自组装自驱动纳米结构器件催化Excited-State Photoacid Self-Assembly Self-Driven Nanostructured Devices Catalysis
摘要: 激发态光酸是一类独特的分子,其在光激发后能够释放质子,并表现出基态与激发态之间显著差异的pKa变化。这一特性赋予光酸在调控多种动态过程中的独特优势,使其成为构建光响应体系的重要工具。本文综述了近年来基于光酸特性发展的光驱动功能动态系统,重点探讨了光激发条件下光酸向特定化学基团发生质子转移所引发的体系平衡移动及其所导致的动态响应行为。具体内容涵盖了光酸在纳米结构自组装、液滴自驱动运动、二氧化碳捕获催化、酶介导纳米器件以及质子传导型离子载体与材料性能调控等方面的应用。最后,本文总结了光酸在实际应用中的设计原则,讨论了当前存在的主要挑战,并展望了未来的发展方向。
Abstract: Excited-state photoacids represent a unique class of molecules capable of releasing protons upon photoexcitation, accompanied by a pronounced shift in pKa between the ground and excited states. This distinctive property endows photoacids with powerful advantages in modulating diverse dynamic processes, thereby establishing them as versatile tools for the construction of photoresponsive systems. This review summarizes recent advances in photoacid-regulated, light-driven dynamic systems, with particular emphasis on how photoinduced proton transfer from photoacids to specific functional groups shifts system equilibria and subsequently induces dynamic responses. Applications discussed include photoacid-mediated regulation of nanoscale self-assembly, self-propelled droplet motion, catalytic carbon dioxide capture, enzyme-mediated nanodevices, and proton-conducting ion carriers and functional materials. Finally, design principles for practical photoacid applications are outlined, current challenges are analyzed, and future research directions are proposed.
文章引用:羊天高. 基于激发态光酸调控光响应动态系统的研究与进展[J]. 有机化学研究, 2025, 13(4): 446-457. https://doi.org/10.12677/jocr.2025.134043

参考文献

[1] Guo, H., Zhang, Z., Chen, Y., Yang, H., Deng, L., Dai, J., et al. (2025) All-In-One Photoacid Generators with Green/Red‐light Responsiveness and Cooperative Functionality. Angewandte Chemie International Edition, 64, e202425313. [Google Scholar] [CrossRef] [PubMed]
[2] Alabiso, W., Sölle, B., Reisinger, D., Guedes de la Cruz, G., Schmallegger, M., Griesser, T., et al. (2023) On‐Demand Activation of Transesterification by Chemical Amplification in Dynamic Thiol‐Ene Photopolymers. Angewandte Chemie International Edition, 62, e202311341. [Google Scholar] [CrossRef] [PubMed]
[3] Alfaraidi, A.M., Kudisch, B., Ni, N., Thomas, J., George, T.Y., Rajabimoghadam, K., et al. (2023) Reversible CO2 Capture and On-Demand Release by an Acidity-Matched Organic Photoswitch. Journal of the American Chemical Society, 145, 26720-26727. [Google Scholar] [CrossRef] [PubMed]
[4] Wimberger, L., Rizzuto, F.J. and Beves, J.E. (2023) Modulating the Lifetime of DNA Motifs Using Visible Light and Small Molecules. Journal of the American Chemical Society, 145, 2088-2092. [Google Scholar] [CrossRef] [PubMed]
[5] Pines, D. and Pines, E. (2006) Solvent Assisted Photoacidity. In: Hynes, J.T., Klinman, J.P., Limbach, H.H. and Schowen, R.L., Eds., Hydrogen-Transfer Reactions, Wiley, 377-415. [Google Scholar] [CrossRef
[6] Agmon, N. (2004) Elementary Steps in Excited-State Proton Transfer. The Journal of Physical Chemistry A, 109, 13-35. [Google Scholar] [CrossRef] [PubMed]
[7] Pines, E. (2003) UV-Visible Spectra and Photoacidity of Phenols, Naphthols and Pyrenols. In: Rappoport, Z., Ed., The Chemistry of Phenols, Wiley, 491-527. [Google Scholar] [CrossRef
[8] Elsaesser, T. and Becker, H.J. (2002) Ultrafast Hydrogen Bonding Dynamics and Proton Transfer Processes in the Condensed Phase. Springer, 155-184.
[9] Joung, J.F., Jeong, M. and Park, S. (2022) Reliable Experimental Method for Determination of Photoacidity Revealed by Quantum Chemical Calculations. Physical Chemistry Chemical Physics, 24, 21714-21721. [Google Scholar] [CrossRef] [PubMed]
[10] Gould, E., Popov, A.V., Tolbert, L.M., Presiado, I., Erez, Y., Huppert, D., et al. (2012) Excited-State Proton Transfer in N-Methyl-6-Hydroxyquinolinium Salts: Solvent and Temperature Effects. Physical Chemistry Chemical Physics, 14, 8964-8973. [Google Scholar] [CrossRef] [PubMed]
[11] Simkovitch, R., Karton-Lifshin, N., Shomer, S., Shabat, D. and Huppert, D. (2013) Ultrafast Excited-State Proton Transfer to the Solvent Occurs on a Hundred-Femtosecond Time-Scale. The Journal of Physical Chemistry A, 117, 3405-3413. [Google Scholar] [CrossRef] [PubMed]
[12] Simkovitch, R., Akulov, K., Shomer, S., Roth, M.E., Shabat, D., Schwartz, T., et al. (2014) Comprehensive Study of Ultrafast Excited-State Proton Transfer in Water and D2O Providing the Missing Ro···H+ Ion-Pair Fingerprint. The Journal of Physical Chemistry A, 118, 4425-4443. [Google Scholar] [CrossRef] [PubMed]
[13] Kim, T.G. and Topp, M.R. (2004) Ultrafast Excited-State Deprotonation and Electron Transfer in Hydroxyquinoline Derivatives. The Journal of Physical Chemistry A, 108, 10060-10065. [Google Scholar] [CrossRef
[14] Presiado, I., Karton-Lifshin, N., Erez, Y., Gepshtein, R., Shabat, D. and Huppert, D. (2012) Ultrafast Proton Transfer of Three Novel Quinone Cyanine Photoacids. The Journal of Physical Chemistry A, 116, 7353-7363. [Google Scholar] [CrossRef] [PubMed]
[15] Simkovitch, R., Shomer, S., Gepshtein, R. and Huppert, D. (2014) How Fast Can a Proton-Transfer Reaction Be Beyond the Solvent-Control Limit? The Journal of Physical Chemistry B, 119, 2253-2262. [Google Scholar] [CrossRef] [PubMed]
[16] Tolbert, L.M. and Haubrich, J.E. (1994) Photoexcited Proton Transfer from Enhanced Photoacids. Journal of the American Chemical Society, 116, 10593-10600. [Google Scholar] [CrossRef
[17] Solntsev, K.M., Huppert, D., Agmon, N. and Tolbert, L.M. (2000) Photochemistry of “Super” Photoacids. 2. Excited-State Proton Transfer in Methanol/Water Mixtures. The Journal of Physical Chemistry A, 104, 4658-4669. [Google Scholar] [CrossRef
[18] Solntsev, K.M., Huppert, D. and Agmon, N. (1999) Photochemistry of “Super”-Photoacids. Solvent Effects. The Journal of Physical Chemistry A, 103, 6984-6997. [Google Scholar] [CrossRef
[19] Agmon, N., Rettig, W. and Groth, C. (2002) Electronic Determinants of Photoacidity in Cyanonaphthols. Journal of the American Chemical Society, 124, 1089-1096. [Google Scholar] [CrossRef] [PubMed]
[20] Choi, Y., Kim, H. and Kwon, O. (2022) Acid-Base Reaction of a Super-Photoacid with a Cooperative Amide Hydrogen‐Bonded Chain. Bulletin of the Korean Chemical Society, 43, 501-507. [Google Scholar] [CrossRef
[21] Nho, H., Adhikari, A. and Kwon, O. (2022) Ultrafast Excited-State Proton Transfer of a Cationic Superphotoacid in a Nanoscopic Water Pool. The Journal of Physical Chemistry B, 126, 1275-1283. [Google Scholar] [CrossRef] [PubMed]
[22] Raucci, U., Chiariello, M.G. and Rega, N. (2020) Modeling Excited-State Proton Transfer to Solvent: A Dynamics Study of a Super Photoacid with a Hybrid Implicit/Explicit Solvent Model. Journal of Chemical Theory and Computation, 16, 7033-7043. [Google Scholar] [CrossRef] [PubMed]
[23] Simkovitch, R., Shomer, S., Gepshtein, R., Roth, M.E., Shabat, D. and Huppert, D. (2014) Comparison of the Rate of Excited-State Proton Transfer from Photoacids to Alcohols and Water. Journal of Photochemistry and Photobiology A: Chemistry, 277, 90-101. [Google Scholar] [CrossRef
[24] Finkler, B., Spies, C., Vester, M., Walte, F., Omlor, K., Riemann, I., et al. (2014) Highly Photostable “Super”-Photoacids for Ultrasensitive Fluorescence Spectroscopy. Photochemical & Photobiological Sciences, 13, 548-562. [Google Scholar] [CrossRef] [PubMed]
[25] Nandi, R. and Amdursky, N. (2022) The Dual Use of the Pyranine (HPTS) Fluorescent Probe: A Ground-State pH Indicator and an Excited-State Proton Transfer Probe. Accounts of Chemical Research, 55, 2728-2739. [Google Scholar] [CrossRef] [PubMed]
[26] Yucknovsky, A., Rich, B.B., Westfried, A., Pokroy, B. and Amdursky, N. (2021) Self‐Propulsion of Droplets via Light‐stimuli Rapid Control of Their Surface Tension. Advanced Materials Interfaces, 8, Article ID: 2100751. [Google Scholar] [CrossRef
[27] Szczepanik, B. (2015) Protolytic Dissociation of Cyano Derivatives of Naphthol, Biphenyl and Phenol in the Excited State: A Review. Journal of Molecular Structure, 1099, 209-214. [Google Scholar] [CrossRef
[28] Karton-Lifshin, N., Presiado, I., Erez, Y., Gepshtein, R., Shabat, D. and Huppert, D. (2011) Ultrafast Excited-State Intermolecular Proton Transfer of Cyanine Fluorochrome Dyes. The Journal of Physical Chemistry A, 116, 85-92. [Google Scholar] [CrossRef] [PubMed]
[29] Ireland, J.F. and Wyatt, P.A.H. (1976) Acid-Base Properties of Electronically Excited States of Organic Molecules. Advances in Physical Organic Chemistry, 12, 131-221. [Google Scholar] [CrossRef
[30] Beens, H., Grellmann, K.H., Gurr, M. and Weller, A.H. (1965) Effect of Solvent and Temperature on Proton Transfer Reactions of Excited Molecules. Discussions of the Faraday Society, 39, 183. [Google Scholar] [CrossRef
[31] Weller, A. (1959) Outer and Inner Mechanism of Reactions of Excited Molecules. Discussions of the Faraday Society, 27, 28-33. [Google Scholar] [CrossRef
[32] Weller, A. (1958) Zeitschrift für Phys. Chemie, Protolytische Reaktionenangeregter Oxyverbindungen, 17, 224-245.
[33] Loken, M.R., Hayes, J.W., Gohlke, J.R. and Brand, L. (1972) Excited-State Proton Transfer as a Biological Probe. Determination of Rate Constants by Means of Nanosecond Fluorometry. Biochemistry, 11, 4779-4786. [Google Scholar] [CrossRef] [PubMed]
[34] Agmon, N., Pines, E. and Huppert, D. (1988) Geminate Recombination in Proton-Transfer Reactions. II. Comparison of Diffusional and Kinetic Schemes. The Journal of Chemical Physics, 88, 5631-5638. [Google Scholar] [CrossRef
[35] Tolbert, L.M. and Haubrich, J.E. (1990) Enhanced Photoacidities of Cyanonaphthols. Journal of the American Chemical Society, 112, 8163-8165. [Google Scholar] [CrossRef
[36] Guardado-Alvarez, T.M., Russell, M.M. and Zink, J.I. (2014) Nanovalve Activation by Surface-Attached Photoacids. Chemical Communications, 50, 8388-8390. [Google Scholar] [CrossRef] [PubMed]
[37] Hattori H. and Ono, Y. (2018) Metal Oxides in Heterogeneous Catalysis. Elsevier, 133-209. [Google Scholar] [CrossRef
[38] Genosar, L., Cohen, B. and Huppert, D. (2000) Ultrafast Direct Photoacid-Base Reaction. The Journal of Physical Chemistry A, 104, 6689-6698. [Google Scholar] [CrossRef
[39] Arnaut, L.G. and Formosinho, S.J. (1993) Excited-State Proton Transfer Reactions I. Fundamentals and Intermolecular Reactions. Journal of Photochemistry and Photobiology A: Chemistry, 75, 1-20. [Google Scholar] [CrossRef
[40] Klajn, R., Wesson, P.J., Bishop, K.J.M. and Grzybowski, B.A. (2009) Writing Self‐Erasing Images Using Metastable Nanoparticle “Inks”. Angewandte Chemie International Edition, 48, 7035-7039. [Google Scholar] [CrossRef] [PubMed]
[41] Samanta, D. and Klajn, R. (2016) Aqueous Light‐Controlled Self‐Assembly of Nanoparticles. Advanced Optical Materials, 4, 1373-1377. [Google Scholar] [CrossRef
[42] Zhang, X., Chen, L., Lim, K.H., Gonuguntla, S., Lim, K.W., Pranantyo, D., et al. (2019) The Pathway to Intelligence: Using Stimuli‐Responsive Materials as Building Blocks for Constructing Smart and Functional Systems. Advanced Materials, 31, Article ID: 1804540. [Google Scholar] [CrossRef] [PubMed]
[43] Lagzi, I., Soh, S., Wesson, P.J., Browne, K.P. and Grzybowski, B.A. (2010) Maze Solving by Chemotactic Droplets. Journal of the American Chemical Society, 132, 1198-1199. [Google Scholar] [CrossRef] [PubMed]
[44] Merindol, R. and Walther, A. (2017) Materials Learning from Life: Concepts for Active, Adaptive and Autonomous Molecular Systems. Chemical Society Reviews, 46, 5588-5619. [Google Scholar] [CrossRef] [PubMed]
[45] Keyvan Rad, J., Balzade, Z. and Mahdavian, A.R. (2022) Spiropyran-Based Advanced Photoswitchable Materials: A Fascinating Pathway to the Future Stimuli-Responsive Devices. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 51, Article ID: 100487. [Google Scholar] [CrossRef
[46] Fedele, C., Ruoko, T., Kuntze, K., Virkki, M. and Priimagi, A. (2022) New Tricks and Emerging Applications from Contemporary Azobenzene Research. Photochemical & Photobiological Sciences, 21, 1719-1734. [Google Scholar] [CrossRef] [PubMed]
[47] Borberg, E., Zverzhinetsky, M., Krivitsky, A., Kosloff, A., Heifler, O., Degabli, G., et al. (2019) Light-Controlled Selective Collection-And-Release of Biomolecules by an On-Chip Nanostructured Device. Nano Letters, 19, 5868-5878. [Google Scholar] [CrossRef] [PubMed]
[48] Cardenas-Daw, C. and Gröhn, F. (2015) Photo-Induced Assembly of Nanostructures Triggered by Short-Lived Proton Transfers in the Excited-state. Journal of the American Chemical Society, 137, 8660-8663. [Google Scholar] [CrossRef] [PubMed]
[49] Zika, A. and Gröhn, F. (2021) Multiswitchable Photoacid-Hydroxyflavylium-Polyelectrolyte Nano-Assemblies. Beilstein Journal of Organic Chemistry, 17, 166-185. [Google Scholar] [CrossRef] [PubMed]
[50] Zika, A., Bernhardt, S. and Gröhn, F. (2020) Photoresponsive Photoacid-Macroion Nano-assemblies. Polymers, 12, Article 1746. [Google Scholar] [CrossRef] [PubMed]
[51] Zika, A., Agarwal, M., Schweins, R. and Gröhn, F. (2022) Joining Two Switches in One Nano‐Object: Photoacidity and Photoisomerization in Electrostatic Self‐Assembly. ChemistryA European Journal, 29, e202203373. [Google Scholar] [CrossRef] [PubMed]
[52] Gilad Barzilay, Y., Yucknovsky, A. and Amdursky, N. (2024) Light-Triggered Reversible Change in the Electronic Structure of Moo3 Nanosheets via an Excited-State Proton Transfer Mechanism. Nano Letters, 24, 1936-1943. [Google Scholar] [CrossRef] [PubMed]
[53] Yucknovsky, A., Rich, B.B., Gutkin, S., Ramanthrikkovil Variyam, A., Shabat, D., Pokroy, B., et al. (2022) Application of Super Photoacids in Controlling Dynamic Processes: Light-Triggering the Self-Propulsion of Oil Droplets. The Journal of Physical Chemistry B, 126, 6331-6337. [Google Scholar] [CrossRef] [PubMed]
[54] Peretz-Soroka, H., Pevzner, A., Davidi, G., Naddaka, V., Kwiat, M., Huppert, D., et al. (2015) Manipulating and Monitoring On-Surface Biological Reactions by Light-Triggered Local pH Alterations. Nano Letters, 15, 4758-4768. [Google Scholar] [CrossRef] [PubMed]
[55] Borberg, E., Pashko, S., Koren, V., Burstein, L. and Patolsky, F. (2021) Depletion of Highly Abundant Protein Species from Biosamples by the Use of a Branched Silicon Nanopillar On-Chip Platform. Analytical Chemistry, 93, 14527-14536. [Google Scholar] [CrossRef] [PubMed]
[56] Borberg, E., Meir, R., Burstein, L., Krivitsky, V. and Patolsky, F. (2021) Ultrafast High-Capacity Capture and Release of Uranium by a Light-Switchable Nanotextured Surface. Nanoscale Advances, 3, 3615-3626. [Google Scholar] [CrossRef] [PubMed]
[57] Zhao, G. and Wang, T. (2018) Stereoselective Synthesis of 2‐Deoxyglycosides from Glycals by Visible‐Light‐Induced Photoacid Catalysis. Angewandte Chemie International Edition, 57, 6120-6124. [Google Scholar] [CrossRef] [PubMed]
[58] Das, A., Banerjee, T. and Hanson, K. (2016) Protonation of Silylenol Ether via Excited State Proton Transfer Catalysis. Chemical Communications, 52, 1350-1353. [Google Scholar] [CrossRef] [PubMed]
[59] Seo, H., Schretter, J., Massen-Hane, M. and Hatton, T.A. (2024) Visible Light-Driven CO2 Capture and Release Using Photoactive Pyranine in Water in Continuous Flow. Journal of the American Chemical Society, 146, 26777-26785. [Google Scholar] [CrossRef] [PubMed]
[60] Lancaster, L.S., Krueger, T.D., Chen, C., Musa, E.N., Lessard, J.M., Chiu, N., et al. (2024) Ultrafast Planarization of Photoexcited Ligands in Metal-Organic Frameworks Gates Charge Transfer to Promote Photocatalysis. Chemical Physics Reviews, 5, Article ID: 021401. [Google Scholar] [CrossRef