Chemiluminescent Detection of Enzymatically Produced H2S

Abstract

Hydrogen sulfide (H2S) has emerged as an important biological signaling molecule. To better understand the multifaceted biological roles of H2S, the development of selective and sensitive biocompatible assays for H2S is becoming increasingly important. Motivated by these challenges, our laboratory is developing new methods to further detect and monitor biological H2S. Here, we describe in detail our recent advances in the development and the use of chemiluminescence-based H2S sensors to assist other investigators with use of these chemical tools. We highlight the use of these tools use by displaying their selectivity and high sensitivity toward H2S and provide examples of assays we have developed to detect enzymatically produced H2S.

A chemiluminescent probe for cellular peroxynitrite using a self-immolative oxidative decarbonylation reaction

“…As part of a program to develop chemical probes for imaging reactive sulphur, 29 , 37 oxygen, 30 , 38 , 39 and nitrogen species, our laboratory has previously reported that isatin reacts with ONOO – via an oxidative decarbonylation reaction to generate anthranilic acid. 40 19 F NMR probes, 5-fluoroisatin and 6-fluorisatin, have been developed for selective detection of ONOO – that utilize this newly discovered transformation.…”

“…Chemiluminescent probes based on sterically hindered 1,2-dioxetanes offer opportunities to incorporate specific reaction-based triggers and have already been applied for detection of analytes in cellular systems and for live animal imaging. 30 – 34 One fruitful design strategy uses Schaap's adamantylidene-dioxetane attached to an analyte-specific reactive handle. 35 A striking substituent effect for Schaap's 1,2-dioxetanes has been reported, where incorporation of an electron withdrawing group such as an acrylonitrile at the ortho position of the phenol results in a significant increase in the overall chemiluminescent quantum yield of 1,2-dioxetanes.…”

Nitric Oxide and Hydrogen Sulfide Regulation of Ischemic Vascular Growth and Remodeling

“…However, the inherent photosensitive azide functional group may reduce the accuracy to detect H 2 S and limit its application. To address the limitation of H 2 S-mediated azide probe, a chemiluminescent scaffold was developed to avoid unwanted photoactivation, such as azide-masked luminol compounds CLSS-1 and CLSS-2(340). Unmasking of the azide to release the free amine liberates luminol (for CLSS-1) or Isoluminol (for CLSS-2).…”