Eco-friendly colorimetric nanofiber design : halochromic sensors with tunable pH-sensing regime based on 2-ethyl-2-oxazoline and 2-n-butyl-2-oxazoline statistical copolymers functionalized with alizarin yellow R

Colorimetric nanofibers provide visual, easy-to-interpret sensors for personal use as well as advanced applications. The potential of 2-n-butyl-2-oxazoline (B) and 2-ethyl-2-oxazoline (E) statistical copolymers as a universal, versatile support platform for nanofibrous halochromic sensor design is demonstrated. These polymers are electrospinnable from eco-friendly solvent systems, while wettability, moist adsorption capacity, and water-solubility of the membranes can be easily tuned by changing the B/E monomer ratio, ensuring wide applicability. The halochromic sensing functionality is introduced by incorporating the alizarin yellow R (AYR) chromophore, which is covalently modified with an ethyl ester-group or a short poly(2-n-butyl-2-oxazoline) chain, which is demonstrated to simultaneously prevent dye-leaching and allows tuning of the halochromic pH-sensing window. The colorimetric nanofibrous sensors reversibly respond toward aqueous solutions of different pH, (hydrochloric) acid and alkaline (ammonia) vapors, and several biogenic amines with detection limits as low as 5 ppb. Tunability of sensor responsivity, sensitivity, and pKa via manipulation of dye–polymer interactions, determined by support polymer structure and semi-crystallinity, as well as the chain length of the AYR-modified polymer, are discussed. Preliminary proof-of-principle studies indicate the potential of the developed sensors for sub-ppm biogenic amine vapor detection, which may serve as the basis for future applications in food packaging or breath analysis.