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Bioprocess 2025
振动强耦合体系中溶剂–离子协同效应对ATP水解的调控作用
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Abstract:
振动强耦合(vibrational strong coupling, VSC)通过溶剂–离子–光子协同作用重塑三磷酸腺苷(adenosine triphosphate, ATP)水解动力学。通过将法布里–珀罗腔与水的O-H振动(3404 cm？1)耦合，我们发现，在富含Ca2？的磷酸盐缓冲液中，VSC使水解速率提升2.4倍，优于纯水体系(1.6倍)。Ca2？通过中和ATP磷酸基团的负电荷减少静电排斥，同时VSC诱导的振动杂化(拉比分裂能735 cm？1)通过重构氢键网络优化质子传递路径，二者协同优化了酶–底物结合构象。红外光谱研究表明，VSC重构了氢键网络，优化了质子转移。这一“溶剂–离子–振动强耦合”三元模型为光控酶工程开辟了新途径，可应用于高效生物能源系统及纳米医学。
Vibrational strong coupling (VSC) reshapes adenosine triphosphate (ATP) hydrolysis kinetics through solvent-ion-photonic synergy. Using a Fabry-Pérot cavity coupled to water’s O-H vibration (3404 cm？1), we reveal that VSC in Ca2？-enriched phosphate-buffered saline (PBS) boosts hydrolysis rates by 2.4-fold, outperforming pure water (1.6-fold). Ca2？ mitigate electrostatic repulsion by neutralizing the negative charges on ATP’s phosphate groups. Concurrently, VSC induces vibrational hybridization—evidenced by a Rabi splitting energy of 735？cm？1, which reconstructs the hydrogen-bond network and facilitates proton transfer. This synergistic effect between Ca2？ and VSC optimizes the enzyme-substrate binding conformation. Infrared spectroscopy confirms that VSC reorganizes the hydrogen-bonding landscape to promote efficient proton transfer. This integrated “solvent-ion-VSC” triad model offers a novel strategy for light-regulated enzyme engineering and holds promise for applications in high-efficiency bioenergy systems and nanomedicine.
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