Stimuli-Chromic Oxazolidine Latex Nanoparticles for Dual-Responsive pH-Sensors and Rewritable Halochromic Papers: A Physicochemical Study on Colorimetric and Fluorimetric Signals

Abstract

Oxazolidine is a new category of stimuli-chromic compounds that has unique intelligent behaviors such as halochromism, hydrochromism, solvatochromism, and ionochromism, all of which have potential applications for designing and constructing chemosensors by using functionalized-polymer nanocarriers. Here, the poly(MMA-co-HEMA) based nanoparticles were synthesized by emulsion copolymerizing methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) in different copolymer compositions. The poly(MMA-co-HEMA) based nanoparticles were modified physically with tertiary amine-functionalized oxazolidine (as an intelligent pH-responsive organic dye) to prepare halochromic latex nanoparticles. Investigation of optical properties including absorbance and emission by spectroscopic methods indicates that the halochromic behavior of the oxazolidine in nanoparticles is influenced significantly by the particle size, morphology, and concentration of hydroxyl groups. To develop optical chemosensors for the detection of pH, the pH-responsivity of halochromic latex nanoparticles in aqueous solutions with different pHs in the wide range of 1–14 were studied by UV–vis and fluorescence spectroscopies, and these results confirmed the successful photodetection of pH in a fast and facile manner. The investigation of the solid-state optical properties and pH-responsivity of halochromic nanoparticles by impregnation of latex-coated cellulosic papers with solutions having different pHs indicates the halochromic nanoparticles maintained their optical properties after incorporation to cellulose matrix and displayed notable colorimetric and fluorimetric pH-responsivity. Hence, the paper-based pH-sensors were prepared from halochromic papers and the investigation of their pH-responsivities showed the halochromic papers constructed from halochromic nanoparticles with HEMA concentration above 20 wt % have the best pH-responsivity with high resolution, high contrast, and high-intensity color change and fluorescence emission change. In addition, the halochromic papers were used as rewritable hydrochromic papers for hand-writing and stamp-printing by using acid and base solutions as inks, in which papers based on halochromic nanoparticles with a HEMA concentration above 20 wt % have maximum printability, resolution, and intensity. This study proposed the significant effects of polarity and concentration of functional groups on the halochromic properties of oxazolidine molecules and the unique role of functionalized polymer nanoparticles as a carrier of oxazolidine for its protection toward environmental degradations. These parameters should be considered in future studies on the development of halochromic papers for intelligent pH-sensor and rewritable papers.