Department of Chemistry , Pohang University of Science and Technology (POSTECH) , 77 Cheongam-Ro, Nam-Gu , Pohang , Gyungbuk 37673 , Republic of Korea.
Institute of Advanced Studies and Research , JIS University , Kolkata 700091 , India.
Acc Chem Res. 2019 Sep 17;52(9):2571-2581. doi: 10.1021/acs.accounts.9b00314. Epub 2019 Aug 30.
The promising features of fluorescence spectroscopy have inspired a quest for fluorescent probes for analysis and monitoring of molecular interactions in biochemical, medical, and environmental sciences. To overcome the competitive supramolecular interactions in aqueous media encountered with conventional molecular-recognition-based probes, the use of reaction-based probes that involve making or breaking of covalent bonds has emerged as a complementary sensing strategy to realize higher selectivity and sensitivity with larger spectroscopic changes. In spite of the enormous efforts, the development of reaction-based fluorescent probes meets with certain challenges in terms of their practical applications, demanding "intelligent design" of probes with an appropriate fluorophore attached to an efficient reactive moiety at the right place. This Account summarizes the results of our efforts made in the development and fine-tuning of reaction-based fluorescent probes toward those goals, classified by the type of analyte (anions, metal cations, and biomolecules) with notes on the challenges and achievements. The reaction-based approach was demonstrated to be powerful for the selective sensing of anions (cyanide and (amino)carboxylates) for the first time, and later it was extended to develop two-photon probes for bisulfite and fluoride ions. The reaction-based approach also enabled selective sensing of noble metal ions such as silver, gold, and palladium along with toxic (methyl)mercury species and paramagnetic copper ions. Furthermore, microscopic imaging and monitoring of biologically relevant species with reaction-based two-photon probes were explored for hydrogen sulfide, hypochlorous acid, formaldehyde, monoamine oxidase enzyme, and ATP.
荧光光谱学的有前途的特点激发了对荧光探针的研究，以分析和监测生物化学、医学和环境科学中的分子相互作用。为了克服在水相介质中遇到的常规基于分子识别的探针的竞争性超分子相互作用，使用涉及形成或断裂共价键的基于反应的探针已经成为一种互补的传感策略，以实现更高的选择性和更大的光谱变化的灵敏度。尽管付出了巨大的努力，但基于反应的荧光探针的发展在实际应用方面仍面临一定的挑战，需要“智能设计”探针，将合适的荧光团附着在适当位置的有效反应部分上。本综述总结了我们在开发和微调基于反应的荧光探针方面的努力，根据分析物的类型（阴离子、金属阳离子和生物分子）进行分类，并附有对挑战和成就的说明。事实证明，基于反应的方法对于首次选择性检测阴离子（氰化物和（氨基）羧酸根）非常有效，后来又扩展到开发用于亚硫酸根和氟离子的双光子探针。基于反应的方法还能够选择性地检测贵金属离子，如银、金和钯，以及有毒的（甲基）汞物种和顺磁性铜离子。此外，还探索了基于反应的双光子探针对生物相关物种的微观成像和监测，用于硫化氢、次氯酸、甲醛、单胺氧化酶酶和 ATP。
