Graphene Oxide/Zinc Phthalocyanine Selective Singlet Oxygen Visible-Light Nanosensor for Raman-Inactive Compounds

Abstract

A novel phthalocyanine-based hybrid nanofilm is for the first time successfully applied as an oxidative platform for surface enhanced Raman spectroscopy (SERS) sensing to fine-resolve Raman-inactive compounds. The hybrid is formed by self-assembly of zinc(II) 2,3,9,10,16,17,23,24-Octa[(3′,5′-dicarboxy)-phenoxy]phthalocyaninate (ZnPc*) with the solid-supported monolayer of graphene oxide (GO) mediated by zinc acetate metal cluster. Atomic force microscopy, UV–vis and fluorescence spectroscopies confirm that this simple coordination motive in combination with molecular structure of ZnPc* prevents contact quenching of the light-excited triplet state through aromatic stacking with GO particles. Fluorescence probing with Sensor Green and terephthalic acid as specific indicators of active oxygen intermediates shows that the hybrid nanofilm initiates selective singlet oxygen generation under visible light. Direct one-electron oxidation of tetramethylbenzidine (TMB) (1.0×10⁻⁷ m) on the hybrid surface in the presence of 100 nm silver nanoparticles as plasmonic hot-spots under 450–640-nm light irradiation yields well-resolved resonance Raman spectrum of the oxidized form TMB⁺¹. Using these hybrid nanofilms as visible light platforms for redox reaction of target analytes without additional oxidizing agents, the range of Raman-detectable compounds can be significantly expanded through a rapid ultrasensitive SERS screening of substances currently considered Raman-inactive.