Fluorescence Ratiometric Sensor for Trace Vapor Detection of Hydrogen Peroxide

Abstract

Trace vapor detection of hydrogen peroxide (H2O2) represents a practical approach to nondestructive detection of peroxide-based explosives, including liquid mixtures of H2O2 and fuels and energetic peroxide derivatives, such as triacetone triperoxide (TATP), diacetone diperoxide (DADP), and hexamethylene triperoxide diamine (HMTD). Development of a simple chemical sensor system that responds to H2O2 vapor with high reliability and sufficient sensitivity (reactivity) remains a challenge. We report a fluorescence ratiometric sensor molecule, diethyl 2,5-bis((((4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl)oxy)carbonyl)amino)terephthalate (DAT-B), for H2O2 that can be fabricated into an expedient, reliable, and sensitive sensor system suitable for trace vapor detection of H2O2. DAT-B is fluorescent in the blue region, with an emission maximum at 500 nm in the solid state. Upon reaction with H2O2, DAT-B is converted to an electronic "push-pull" structure, diethyl 2,5-diaminoterephthalate (DAT-N), which has an emission peak at a longer wavelength centered at 574 nm. Such H2O2-mediated oxidation of aryl boronates can be accelerated through the addition of an organic base such as tetrabutylammonium hydroxide (TBAH), resulting in a response time of less than 0.5 s under 1 ppm of H2O2 vapor. The strong overlap between the absorption band of DAT-N and the emission band of DAT-B enables efficient Förster resonance energy transfer (FRET), thus allowing further enhancement of the sensing efficiency of H2O2 vapor. The detection limit of a drop-cast DAT-B/TBAH film was projected to be 7.7 ppb. By combining high sensitivity and selectivity, the reported sensor system may find broad application in vapor detection of peroxide-based explosives and relevant chemical reagents through its fabrication into easy-to-use, cost-effective kits.

Sensors, Imaging Agents, and Theranostics to Help Understand and Treat Reactive Oxygen Species Related Diseases

“…Initial efforts using boronate groups for H 2 O 2 include an arylboronic ester‐based fluorescent probe that uses coumarin as the fluorescent reporter to detect H 2 O 2 in solution due to the structural cleavage to release the fluorescence of coumarin . Recently, Zang and co‐workers constructed fluorescent probes that were capable of detecting trace H 2 O 2 in vapor. A small‐molecular fluorescent “turn‐on” probe, based on an arylboronic ester naphthalimide unit for H 2 O 2 sensing was utilized .…”

“…A small‐molecular fluorescent “turn‐on” probe, based on an arylboronic ester naphthalimide unit for H 2 O 2 sensing was utilized . Subsequently, a ratiometric fluorescent probe was synthesized, exhibiting a subtle emission change in fluorescence intensity by H 2 O 2 ‐mediated oxidation of the boronate fluorophore ( Figure ). The presence of H 2 O 2 resulted in a redshift in fluorescence emission intensity.…”

“…Oxidation of a probe DAT‐B to produce DAT‐N caused in the presence of H 2 O 2 vapor, inducing fluorescence emission change. Reproduced with permission . Copyright 2014, American Chemical Society.…”

Bifunctional Diaminoterephthalate Fluorescent Dye as Probe for Cross‐Linking Proteins

“…[8] These compounds are powerful chromophores with remarkable fluorescence properties, [9] which found different applications in the last years. [10] We have recently introduced diaminoterephthalates as colored moleculars caffolds bearing up to four sites for orthogonal functionalization. [11] Furthermore, withp rerequisite functionalization, the fluorescencec an be switched on by ac hemical reaction and therefore, thesec ompounds can be used as "turn-on" probes for biochemical applications.…”

Ultrasensitive electrospun fluorescent nanofibrous membrane for rapid visual colorimetric detection of H2O2

“…Recent studies have indicated the emergence of fluorescence-based methods, attracting great interest because of their sensitivity, selectivity, fast response, and ease of use [9][10][11]. However, there still exists a challenge of developing a simple, highly sensitive, and inexpensive platform for the rapid detection of H 2 O 2 [12,13].…”