Fluorescent Terpolymers Using Two Non-Emissive Monomers for Cr(III) Sensors, Removal, and Bio-Imaging

• Published in: ACS biomaterials science & engineering 2020-03, Vol.6 (3), p.1397-1407
• Main Authors: Dutta, Arnab, Mahapatra, Manas, Deb, Mousumi, Mitra, Madhushree, Dutta, Sayanta, Chattopadhyay, Pijush Kanti, Banerjee, Snehasis, Sil, Parames C, Maiti, Dilip K, Singha, Nayan Ranjan
• Format: Article
• Language: English
• Subjects: Adsorption; Coloring Agents; Humans; Macromolecular Substances; Polymerization; Polymers
• ISSN: 2373-9878; 2373-9878
• DOI: 10.1021/acsbiomaterials.9b01849

The nonconventional purely aliphatic intrinsically fluorescent multifunctional terpolymers, such as 2-acrylamido-2-methylpropane sulfonic acid-co-2-(3-acrylamidopropylamido)-2-methylpropane sulfonic acid-co-acrylamide (AMPS-co-APMPS-co-AM, 1), acrylic acid-co-3-acrylamidopropanoic acid-co-acrylamide (AA-co-APA-co-AM, 2), and methacrylic acid-co-3-acrylamido-2-methyl propanoic acid-co-acrylamide (MAA-co-AMPA-co-AM, 3), were synthesized via N–H functionalized multi-C–C/N–C coupled in situ attachments of fluorophore monomers, that is, APMPS, APA, and AMPA, in solution polymerization of two non-fluorescent monomers. These terpolymers were suitable for selective Cr­(III) sensors, high-performance exclusions of Cr­(III), and fluorescence imaging of human osteosarcoma cancer cells. The structures of 1, 2, and 3, in situ attachments of fluorescent amino acid monomers, locations of fluorophores, aggregation-induced enhanced emissions, and the superadsorption mechanism were understood via microstructural analyses. The geometries, electronic structures, and the low-lying singlet–singlet absorption and emission of 1, 2, and 3 were explored using density functional theory (DFT), time-dependent DFT, and natural transition orbital analyses. The ionic and variable interactions of 1, 2, and 3 with Cr­(III) were envisaged via analyses of adsorbed microstructures, fitting of kinetics data to a pseudo-second-order model, and the measurements of activation energies. For 1/2/3, limit of detection values and adsorption capacities were 1.88 × 10–7/3.75 × 10–7/1.25 × 10–7 M and 1316.35/1431.40/1372.18 mg g–1, respectively, at pHi = 7.0, 303 K, and 1000 ppm. The better overall properties made 3 to be more suitable in sensing and cell imaging.