Concentration and pH-modulated dual fluorescence in self-assembled nanoparticles of phototautomerizable biopolymeric amphiphile

A dual-emissive biopolymeric amphiphile (GC–HBO) has been prepared by densely conjugating hydrophilic glycol chitosan (GC) with a phototautomerizable hydrophobic dye (a derivative of 2-(2′-hydroxyphenyl)benzoxazole, HBO) showing excited-state intramolecular proton transfer (ESIPT). Ratiometric modulation of phototautomeric (enol–keto) dual emission, governed by the chromophoric aggregation state, was studied with a low-molecular-weight model compound (GA–HBO) and was well correlated with the nanoparticle-forming behavior of GC–HBO via amphiphilic self-assembly in water. It has been found that the promoted chromophoric aggregation at higher concentration or at basic-to-neutral pH assists the nanostructure formation to generate predominant keto emission while the enol emission is intensified at lower concentration or with decreasing pH by disintegration of self-assembled structure. The assembly-related advantageous potential of GC–HBO for probing self-concentration and surrounding pH has been demonstrated with the ratiometric determination of critical particulation concentration (0.04 kg m−3) and near-physiological pH sensitivity (pKa ∼ 5.1).

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideResearch highlights► Dual-emissive amphiphilic biopolymer self-assembles into nanoparticles. ► Phototautomerizable pendants generate the assembly-dependant dual emission. ► The dual emission modulation correlates to the concentration and pH condition. ► Ratiometric dual emission of the biopolymeric amphiphile probes the surrounding pH.