An "off-on-off" fluorescence chemosensor for the sensitive detection of Cu2+ in aqueous solution based on multiple fluorescence emission mechanisms.

ABSTRACT

A new organosiloxane precursor ((E)-3-hydroxy-4-((2-(2-hydroxy-4-(3-(3-(triethoxysilyl)propyl)ureido)benzoyl)hydrazono)methyl)phenyl(3-(triethoxysilyl)propyl)carbamate, hereinafter referred to as AHBH-Si) and tetraethylorthosilicate (TEOS) were mixed as the mixed Si source, and bridged periodic mesoporous organic silica (AHBH-PMOs) nanoparticles were obtained through the co-condensation reaction. AHBH-PMO nanoparticles possess mechanisms of "Aggregation Induced Emission" (AIE) and "Intramolecular Charge Transfer" (ICT), which originate from the molecular structure of AHBH having "C[double bond, length as m-dash]N" bond, ortho hydroxyl groups, etc.. Therefore, the optical properties of AHBH are excellent with respect to the solvent effect and enhanced fluorescence. For hybrid materials, the silica framework provides a rigid environment that restricts the rotation of AHBH, thereby turning on the fluorescence of AHBH due to the regulation by the AIE effect. In particular, AHBH-PMOs are no longer restricted by organic solvents and could really achieve the response to Cu2+ with high sensitivity and selectivity in aqueous solutions of a wide pH range. In addition, the detection limit is as low as 3.26 × 10-9 M. Methods such as Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and high-resolution mass spectrometry have shown the coordination interaction between AHBH and Cu2+. The Gaussian 09 software of density functional theory to calculate the reducing changes of energy gaps among AHBH and AHBH-Si before and after the addition of Cu2+ showed that coordination interaction exists in the system. These results indicate that AHBH-PMO hybrid materials have potential applications in the field of environmental monitoring.