Boronate-Based Fluorescence Probes for the Detection of Hydrogen Peroxide.

Emma V Lampard,Samantha C Hewins,Adam C Sedgwick,Tony D James,Katherine L Filer,Xiaolong Sun,Juyoung Yoon,Gyoungmi Kim,Steven D Bull

doi:10.1002/open.201700189

Abstract

In this work, we synthesized a series of boronate ester fluorescence probes (E)‐4,4,5,5‐tetramethyl‐2‐(4‐styrylphenyl)‐1,3,2‐dioxaborolane (STBPin), (E)‐N,N‐dimethyl‐4‐(4‐(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)styryl)aniline (DSTBPin), (E)‐4‐(4‐(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)styryl)benzonitrile (CSTBPin), (E)‐2‐(4‐(4‐methoxystyryl)phenyl)‐4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolane (MSTBPin), (E)‐N,N‐dimethyl‐4‐(4‐(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)styryl)naphthalen‐1‐amine (NDSTBPin), and N,N‐dimethyl‐4‐(2‐(4‐(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)phenyl)oxazol‐5‐yl)aniline (DAPOX‐BPin) for the detection of hydrogen peroxide (H2O2). DSTBPin and MSTBPin displayed an “Off–On” fluorescence response towards H2O2, owing to the loss of the intramolecular charge transfer (ICT) excited state. Whereas, CSTBPin displayed a decrease in fluorescence intensity in the presence of H2O2 owing to the introduction of an ICT excited state. STBPin, on the other hand, produced a small fluorescence decrease, indicating the importance of an electron‐withdrawing or electron‐donating group in these systems. Unfortunately, the longer wavelength probe, NDSTBPin, displayed a decrease in fluorescence intensity. Oxazole‐based probe DAPOX‐BPin produced a “turn‐on” response. Regrettably, DAPOX‐BPin required large concentrations of H2O2 (>3 mm) to produce noticeable changes in fluorescence intensity and, therefore, no change in fluorescence was observed in the cell imaging experiments.

Highlights

In this work, we synthesized a series of boronate ester fluorescence probes (E)-4,4,5,5-tetramethyl-2-(4-styrylphenyl)-1,3,2-dioxaborolane (STBPin), (E)-N,N-dimethyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)styryl)aniline (DSTBPin), (E)-4-(4(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)styryl)benzonitrile (CSTBPin), (E)-2-(4-(4-methoxystyryl)phenyl)-4,4,5,5-tetramethyl1,3,2-dioxaborolane (MSTBPin), (E)-N,N-dimethyl-4-(4-(4,4,5,5tetramethyl-1,3,2-dioxaborolan-2-yl)styryl)naphthalen-1-amine (NDSTBPin), and N,N-dimethyl-4-(2-(4-(4,4,5,5-tetramethyl-1,3,2dioxaborolan-2-yl)phenyl)oxazol-5-yl)aniline (DAPOX-boronate pinacol ester (BPin)) for the detection of hydrogen peroxide (H2O2)
We are interested in the development of small-molecule fluorescent probes,[8,9,10,11,12] as they are well suited to meet the need of tools to map the spatial and temporal distribution of H2O2 in living cells
Chang and co-workers[13,14] as well as others[15] have developed a range of probes for the selective detection of H2O2 based on the well-known hydrogen-peroxide-mediated oxidation of arylboronates to phenols

Summary

Introduction

We synthesized a series of boronate ester fluorescence probes (E)-4,4,5,5-tetramethyl-2-(4-styrylphenyl)-1,3,2-dioxaborolane (STBPin), (E)-N,N-dimethyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)styryl)aniline (DSTBPin), (E)-4-(4(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)styryl)benzonitrile (CSTBPin), (E)-2-(4-(4-methoxystyryl)phenyl)-4,4,5,5-tetramethyl1,3,2-dioxaborolane (MSTBPin), (E)-N,N-dimethyl-4-(4-(4,4,5,5tetramethyl-1,3,2-dioxaborolan-2-yl)styryl)naphthalen-1-amine (NDSTBPin), and N,N-dimethyl-4-(2-(4-(4,4,5,5-tetramethyl-1,3,2dioxaborolan-2-yl)phenyl)oxazol-5-yl)aniline (DAPOX-BPin) for the detection of hydrogen peroxide (H2O2). J. Yoon Department of Chemistry and Nanoscience, Ewha Womans University Seoul 120–750 (Korea) Supporting Information and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/ open.201700189. We decided to utilize this strategy for the development of ratiometric fluorescent probes for the detection of H2O2.

Results

Conclusion