Schiff Base Substituent-Triggered Efficient Deboration Reaction and Its Application in Highly Sensitive Hydrogen Peroxide Vapor Detection.

The organic thin-film fluorescence probe, with the advantages of not polluting the analyte and fast response, has attracted much attention in explosive detection. Different with nitro explosives, the peroxide-based explosives are hardly to be detected because of their poor ultraviolet absorption and lack of an aromatic ring. As the signature compound of peroxide-based explosives, H2O2 vapor detection became more and more important. Boron ester or acid is considered to be a suitable functional group for the detection of hydrogen peroxide due to its reliable reactive activity. Its only drawback lies on its slow degradation velocity. In this work, we try to introduce some functional group to make the boron ester to be easily oxidized by H2O2. Herein, 4-(phenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amino)benzaldehyde (OTB) was synthesized and its imine derivatives, OTBXAs, were easily obtained just by putting OTB films in different primary amines vapors. OTBXAs show fast deboronation velocity in H2O2 vapor compared with OTB. The complete reaction time of (E)-N-phenyl-4-((propylimino)methyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)aniline (OTBPA) was even shortened 40 times with a response time of seconds. The detection limit for H2O2 vapor was as low as 4.1 parts per trillion (ppt). Further study showed that it is a general approach to enhance the sensing performance of borate to hydrogen peroxide (H2O2) vapor by introducing an imine into an aromatic borate molecule via a solid/vapor reaction.

Highly Efficient Multiple-Anchored Fluorescent Probe for the Detection of Aniline Vapor Based on Synergistic Effect: Chemical Reaction and PET.

A multiple-anchored fluorescent probe ((((hexane-1,6-diylbis(2,7-bis(4-formyl)-phenyl)-9H-fluorine-9,9-diyl))-bis(hexane-6,1-diyl))-bis(9H-carbazole-9,3,6-triyl))-tetrakis(benzene-4,1-diyl))-tetraformyl-(8FP-2F) with eight aldehyde groups was designed and synthesized. The molecule has four branches and highly twisted structure. Furthermore, it tends to self-assemble into nanospheres, which is beneficial for gaseous analyte penetration and high fluorescence quantum efficiency. Among gaseous analytes, detection of aniline vapor is extraordinarily important in the control of environmental issues and human diseases. Herein, 8FP-2F was introduced to detect aniline vapor with distinguished sensitivity and selectivity via simple Schiff base reaction at room temperature. After exposure to saturate aniline vapor, the 89% fluorescence of 8FP-2F was quenched in 50 s and the detection limit was as low as 3 ppb. Further study showed the suitable HOMO/LUMO energy levels and matched orbital symmetry between probe and aniline molecules ensured chemical reaction and PET process work together. The synergistic effect resulted in a significant sensing performance and fluorescence quenching toward aniline vapor. Moreover, the multiple active sites structure of 8FP-2F means it could be applied for constructing many interesting structures and highly efficient organic optoelectronic functional materials.