The reaction of NO and H 2 S to form HNO is a classical pathway in physiological conditions. The reported single recognition-type fluorescent probes are difficult to track precisely the relationships of H 2 S and HNO. It is necessary to develop a bifunctional fluorescence probe ( NJA ) for monitoring simultaneously the production of endogenous HNO and H 2 S. Using 7-Nitrobenzofurazan (NBD) and 2-(diphenylphosphine) benzoate as recognition sites, the obatined NJA can detect specifically HS − and HNO. The detection limit of HS − and HNO are 0.46 μM and 1.42 μM, respectively. Based on the dual recognition sites and input signals of the probe, a molecular “AND” logic gate was established to detect successfully H 2 S and HNO in MCF-7 cells. NJA based on “AND logic” provided a simple and robust tool for monitoring the production of endogenous HNO correlative with H 2 S and NO in living cells.
Xiaoyu Lv,Kaihong Chen,Guiling Shi,Wenjun Lin,Hongzhen Bai,Haoran Li,Guping Tang,Congmin Wang
Developing ionic liquid (IL) drugs broaden new horizons in pharmaceuticals. The tunable nature endows ILs with capacity to delivery active ingredients. However, the tunability is limited to screen ionic components, and none realizes the kinetic tuning of drug release, which is a key challenge in the design of IL drugs. Here, a series of ILs are developed using biocompatible ionic components, which realizes absorption of gaseous NO to yield IL-NONOates. These IL-NONOates serve as HNO donors to release active ingredient. The release kinetics can be tuned through configuring the geometric construction of ILs (release half-lives, 4.2 to 1061 min). Mechanism research indicates that the tunability depends on the strength of intramolecular hydrogen bond. Furthermore, the IL-based HNO donors exert pharmacological potential to inhibit tumor progression by regulating intratumoral redox state. Coupled with biosafety, these IL-based HNO donors with facile preparation and tunable functionalization can be promising candidates for pharmaceutical application.
Yang Zhou,Jiajun Chen,Yunxi Cui,Lingjuan Tang,Peixuan Wu,Peng Yu,Kun Fu,Zhicheng Sun,Yuanyuan Liu
The precise release and characterization of nitroxyl (HNO) gas signaling molecule remain a challenge due to its short lifetime to date. To solve this issue, an azobenzene-based HNO donor (Azo-D1) was proposed as a colorimetric and fluorometric chemosensor for HNO releasing, to release both HNO and an azobenzene fluorescent reporter together. Specifically, the Azo-D1 has an HNO release half-life of ∼68 min under physiological conditions. The characteristic color change from the original orange to the yellow color indicated the decomposition of the donor molecule. In addition, the stoichiometry release of HNO was qualitatively and quantitatively verified through the classical phosphine compound trap. As compared with the donor molecule by itself, the decomposed product demonstrates a maximum fluorescence emission at 424 nm, where the increase of fluorescence intensity by 6.8 times can be applied to infer the real-time concentration of HNO. Moreover, cellular imaging can also be achieved using this Azo-D1 HNO donor through photoexcitation at 405 and 488 nm, where the real-time monitoring of HNO release was achieved without consuming the HNO source. Finally, the Azo-D1 HNO donor would open a new platform in the exploration of the biochemistry and the biology of HNO.