pH-Regulated Optical Performances in Organic/Inorganic Hybrid: A Dual-Mode Sensor Array for Pattern-Recognition-Based Biosensing

Dual-mode optical assays are becoming more popular and attractive because they would provide robust detailed information in biochemical analysis. We herein unveil a novel dual-mode optical (i.e., UV vis absorption and fluorescence) method for multifunctional sensing of phosphate compounds (PCs) (e.g., nucleotides and pyrophosphate),based on pattern recognition, which innovatively employs only one kind of porphyrin/lanthanide-doped upconversion nanoparticles (Ln-UCNPs) hybrid integrated with a facile pH-regulated strategy as the sensor array. An easy-to-obtain porphyrin hydrate (tetraphenylporphyrin tetrasulfonic acid hydrate, TPPS) can assemble onto the ligand-free Ln-UCNPs to construct the organic/inorganic hybrid (TPPS/Ln-UCNPs), leading to a new absorption band to quench the upconversion fluorescence of Ln-UCNPs due to fluorescence resonance energy transfer (FRET). The dual-mode optical performances of TPPS/Ln-UCNPs are characteristically correlated with the pH in aqueous solution. Thus, as a proof-of concept design, three types of TPPS/Ln-UCNPs (TPPS/Ln-UCNPs(4), TPPS/Ln-UCNPs(4.5), and TPPS/Ln-UCNPs(5)) were prepared by using buffers with different pH (at 4, 4.5, and 5) to form our proposed sensor array, which would result in individual dual-mode optical response patterns upon being challenged with PCs for their pattern recognition through a competitive mechanism between TPPS and PCs. The results show that three TPPS/Ln-UCNPs(n) sensors can successfully permit the sensitive detection of 14 PCs and differentiate them between different concentrations, as well as a mixture of them. The pH-dependent TPPS/Ln-UCNPs promises the simple, yet powerful discrimination of PCs via pattern recognition, would prospectively stimulate and expand the use of organic/inorganic hybrid toward more biosensing applications.