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Surfing the limits of cyanine photocages one step at a time

机译:一步一个脚印地探索花青光笼的极限

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摘要

Near-infrared light-activated photocages enable controlling molecules with tissue penetrating light. Understanding the structural aspects that govern the photouncaging process is essential to enhancing their efficacy, crucial for practical applications. Here we explore the impact of thermodynamic stabilization on contact ion pairs in cyanine photocages by quaternarization of the carbon reaction centers. This strategy enables the first direct uncaging of carboxylate payloads independent of oxygen, resulting in a remarkable two-orders-of-magnitude enhancement in uncaging efficiency. Our computational analyses reveal that these modifications confer a kinetic instead of thermodynamic effect, reducing ion–ion interactions and allowing complete separation of free ions while inhibiting recombination. We demonstrate that, while thermodynamic stabilization is effective in traditional chromophores operating at shorter wavelengths, it rapidly reaches its thermodynamic limitations in NIR photocages by compromising the photocage stability in the dark. Thanks to these findings, we establish that activation of cyanine photocages is limited to wavelengths of light below 1000 nm. Our work illuminates the path to improving uncaging cross-sections in NIR photocages by prioritizing kinetic trapping and separation of ions.
机译:近红外光激活光笼能够用组织穿透光来控制分子。了解控制光解离过程的结构方面对于提高其功效至关重要,这对于实际应用至关重要。在这里,我们探讨了热力学稳定通过碳反应中心的四元化对花青光笼中接触离子对的影响。这种策略实现了首次独立于氧气的羧酸盐有效载荷的直接解笼,从而使解笼效率显著提高了两个数量级。我们的计算分析表明,这些修饰赋予了动力学而不是热力学效应,减少了离子-离子相互作用并允许自由离子完全分离,同时抑制了复合。我们证明,虽然热力学稳定在以较短波长运行的传统发色团中是有效的,但它通过损害光电笼在黑暗中的稳定性,在 NIR 光电笼中迅速达到其热力学极限。由于这些发现,我们确定花青光笼的激活仅限于 1000 nm 以下的光波长。我们的工作通过优先考虑离子的动力学捕获和分离,阐明了改善 NIR 光笼中解笼横截面的道路。

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