Synthesis and optimization of chitosan-incorporated semisynthetic polymer/α-Fe2O3 nanoparticle hybrid polymer to explore optimal efficacy of fluorescence resonance energy transfer/charge transfer for Co(II) and Ni(II) sensing.

ABSTRACT

Initially, four synthetic fluorescent polymers (SFPs) are synthesized from α-methacrylic acid and methanolacrylamide monomers carrying -C(=O)OH and -C(=O)NH subfluorophores, respectively. Among SFPs, ∼11 incorporation of subfluorophores in the optimum SFP3 is explored by spectroscopic analyses. Subsequently, chitosan is incorporated in SFP3 to produce five semi-synthetic fluorescent polymers (SSFPs). The maximum incorporation of chitosan in SSFP4 is supported by different spectroscopies. In SSFP4, strong electrostatic interactions among polar functionalities of chitosan and synthetic polymer favor resonance-associated charge transfer (RCT) from SSFP4-(amide) to SSFP4-(canonical). Finally, three hybrid fluorescent polymers (HFPs) are fabricated encapsulating iron-oxide nanoparticle within SSFP4. The maximum proportion of hematite (α-Fe2O3) phase in HFPs is explored by spectroscopic, magnetometric, microscopic, and light scattering studies. HFP2 shows local/RCT/fluorescence resonance energy transfer (FRET) emission at 393/460/570 nm. In HFP2, FRET, RCT, and ratiometric pH-sensing within 3.0-6.5 phenomena are explored by solvent polarity effects, time-correlated single photon counting, quantum yield measurements, alongside I431/I460 vs pH plots. RCT and FRET emissions of HFP2 are utilized for selective sensing of Co(II)/Ni(II) with limits of detection of 4.990 ppb (460 nm)/4.353 ppb (570 nm) and 45.041 ppb (428 nm)/29.617 ppb (527 nm) in organic and aqueous solutions, respectively.