Department of Chemistry, ‡Biophysics Program, §Department of Biomedical Engineering, and ∥Department of Radiology, University of Michigan , Ann Arbor, Michigan 48109, United States.
Anal Chem. 2017 Aug 1;89(15):7943-7949. doi: 10.1021/acs.analchem.7b00930. Epub 2017 Jul 12.
Ion-selective optodes (ISOs), the optical analog of ion-selective electrodes, have played an increasingly important role in chemical and biochemical analysis. Here we extend this technique to ion-selective photoacoustic optodes (ISPAOs) that serve at the same time as fluorescence-based ISOs, and apply it specifically to potassium (K). Notably, the potassium ion is one of the most abundant cations in biological systems, involved in numerous physiological and pathological processes. Furthermore, it has been recently reported that the presence of abnormal extracellular potassium concentrations in tumors suppresses the immune responses and thus suppresses immunotherapy. However, unfortunately, sensors capable of providing potassium images in vivo are still a future proposition. Here, we prepared an ion-selective potassium nanosensor (NS) aimed at in vivo photoacoustic (PA) chemical imaging of the extracellular environment, while being also capable of fluorescence based intracellular ion-selective imaging. This potassium nanosensor (K NS) modulates its optical properties (absorbance and fluorescence) according to the potassium concentration. The K NS is capable of measuring potassium, in the range of 1 mM to 100 mM, with high sensitivity and selectivity, by ISPAO based measurements. Also, a near infrared dye surface modified K NS allows fluorescence-based potassium sensing in the range of 20 mM to 1 M. The K NS serves thus as both PA and fluorescence based nanosensor, with response across the biologically relevant K concentrations, from the extracellular 5 mM typical values (through PA imaging) to the intracellular 150 mM typical values (through fluorescence imaging).
离子选择性光声光纤(ISPAO),是光学领域中离子选择性电极的对应物,在化学和生物化学分析中发挥着越来越重要的作用。在此,我们将该技术扩展到离子选择性光声光纤(ISPAO),它同时充当基于荧光的 ISO,并将其特别应用于钾(K)离子。值得注意的是,钾离子是生物系统中最丰富的阳离子之一,参与了许多生理和病理过程。此外,最近有报道称,肿瘤中外周钾离子浓度异常会抑制免疫反应,从而抑制免疫疗法。然而,令人遗憾的是,能够提供体内钾离子图像的传感器仍在未来的探索中。在这里,我们制备了一种离子选择性钾纳米传感器(NS),旨在对细胞外环境进行体内光声(PA)化学成像,同时也能够进行基于荧光的细胞内离子选择性成像。这种钾纳米传感器(K NS)根据钾浓度调节其光学性质(吸光度和荧光)。K NS 能够通过 ISPAO 测量,在 1 mM 至 100 mM 的范围内,以高灵敏度和选择性测量钾。此外,表面修饰有近红外染料的 K NS 允许在 20 mM 至 1 M 的范围内进行基于荧光的钾传感。因此,K NS 既是 PA 也是基于荧光的纳米传感器,其响应范围涵盖了从细胞外 5 mM 的典型值(通过 PA 成像)到细胞内 150 mM 的典型值(通过荧光成像)的整个生物相关钾浓度。