Ratiometric Chemosensors That Are Capable of Quantifying Hydrostatic Pressure Stimulus: A Case of Porphyrin Tweezers

Seiya Ono, Tomokazu Kinoshita, Hiroshi Iwasaki, Yoshitane Imai and Gaku Fukuhara*, 
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Abstract

Investigating chemosensors that are capable of quantifying pressure in solution, particularly hydrostatic pressure, which is one of the mechanical forces, is an attractive challenge in chemistry from the viewpoint of “mechano”-science. Herein, we report the investigation of chiral porphyrin tweezers, Por-Cy and Por-DPhEt, comprising different flexible linkers; Por-Cy and Por-DPhEt displayed distinct ratiometric signaling by using the higher excited S2 state with a standard excited S1 level. A novel operative mechanism using the S1/S2 fluorescence ratio was revealed using hydrostatic pressure-ultraviolet/visible (UV/vis), fluorescence/excitation, circular dichroism spectroscopy, and lifetime measurements, which can be further controlled by the open-closed conformational change inherent in the tweezer skeleton. Furthermore, the fluorescent chiral tweezers exhibited a promising |glum| of 2.9 × 10–3, indicating that they are potential candidates for sensory applications in chiral environments. This study provides opportunities for the development of smart pressure-responsive chemosensors.

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能够量化静水压力刺激的比率化学传感器:卟啉镊子案例
从 "机械 "科学的角度来看,研究能够量化溶液中的压力(尤其是作为机械力之一的静水压力)的化学传感器是化学领域一项极具吸引力的挑战。在此,我们报告了对包含不同柔性连接体的手性卟啉镊子 Por-Cy 和 Por-DPhEt 的研究;Por-Cy 和 Por-DPhEt 通过使用较高激发 S2 态和标准激发 S1 电平,显示出不同的比率信号。利用静水压-紫外/可见光(UV/vis)、荧光/激发、圆二色性光谱和寿命测量揭示了一种利用 S1/S2 荧光比的新型工作机制,该机制可通过镊子骨架固有的开闭构象变化进一步控制。此外,荧光手性镊子的|glum|值为 2.9 × 10-3,表明它们是手性环境中感官应用的潜在候选材料。这项研究为开发智能压力响应化学传感器提供了机会。
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3.70
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期刊介绍: ACS Physical Chemistry Au is an open access journal which publishes original fundamental and applied research on all aspects of physical chemistry. The journal publishes new and original experimental computational and theoretical research of interest to physical chemists biophysical chemists chemical physicists physicists material scientists and engineers. An essential criterion for acceptance is that the manuscript provides new physical insight or develops new tools and methods of general interest. Some major topical areas include:Molecules Clusters and Aerosols; Biophysics Biomaterials Liquids and Soft Matter; Energy Materials and Catalysis
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