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

Mousumi Deb; Shrestha Roy; Nadira Hassan; Deepak Chowdhury; M D Hussain Sanfui; Preetam Nandy; Dilip K Maiti; Mincheol Chang; Mostafizur Rahaman; Mohammad A Hasnat; Kamalendu Bhunia; Pijush Kanti Chattopadhyay; Nayan Ranjan Singha

doi:10.1016/j.ijbiomac.2024.135831

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

Int J Biol Macromol. 2024 Sep 28;280(Pt 4):135831. doi: 10.1016/j.ijbiomac.2024.135831. Online ahead of print.

Affiliations

¹ Advanced Polymer Laboratory, Department of Polymer Science and Technology, Government College of Engineering and Leather Technology (Post Graduate), Maulana Abul Kalam Azad University of Technology, Salt Lake City, Kolkata-700106, West Bengal, India.
² Advanced Polymer Laboratory, Department of Polymer Science and Technology, Government College of Engineering and Leather Technology (Post Graduate), Maulana Abul Kalam Azad University of Technology, Salt Lake City, Kolkata-700106, West Bengal, India; Department of Chemistry, University of Calcutta, 92, A.P.C. Road, Kolkata-700009, West Bengal, India.
³ Department of Chemistry, University of Calcutta, 92, A.P.C. Road, Kolkata-700009, West Bengal, India.
⁴ Department of Polymer Engineering, Graduate School, Chonnam National University, Gwangju 61186, South Korea.
⁵ Department of Chemistry, College of Science, King Saud University, PO Box 2455, Riyadh 11451, Saudi Arabia.
⁶ Electrochemistry & Catalysis Research Laboratory (ECRL), Department of Chemistry, School of Physical Sciences, Shahjalal University of Science and Technology, Sylhet 3114, Bangladesh.
⁷ Department of Chemical Engineering, Government College of Engineering and Leather Technology (Post Graduate), Maulana Abul Kalam Azad University of Technology, Salt Lake City, Kolkata 700106, West Bengal, India.
⁸ Department of Leather Technology, Government College of Engineering and Leather Technology (Post Graduate), Maulana Abul Kalam Azad University of Technology, Salt Lake City, Kolkata 700106, West Bengal, India.
⁹ Advanced Polymer Laboratory, Department of Polymer Science and Technology, Government College of Engineering and Leather Technology (Post Graduate), Maulana Abul Kalam Azad University of Technology, Salt Lake City, Kolkata-700106, West Bengal, India. Electronic address: [email protected].

PMID: 39349075
DOI: 10.1016/j.ijbiomac.2024.135831

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, ∼1:1 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.

Keywords: Chitosan; FRET; Fluorescent-polymer; Hematite-nanoparticle; Sensing.