In Situ Attachment of Acrylamido Sulfonic Acid-Based Monomer in Terpolymer Hydrogel Optimized by Response Surface Methodology for Individual and/or Simultaneous Removal(s) of M(III) and Cationic Dyes

Abstract

Herein, grafting of starch (STR) and in situ strategic inclusion of 2-(3-(acrylamido)propylamido)-2-methylpropane sulfonic acid (APMPS) via solution polymerization of 2-(acrylamido)-2-methylpropanesulfonic acid (AMPS) and acrylamide (AM) have resulted in the synthesis of smart STR-grafted-AMPS- co -APMPS- co -AM (i.e., STR- g -TerPol) interpenetrating terpolymer (TerPol) network hydrogels. For fabricating the optimum hydrogel showing excellent physicochemical properties and recyclability, amounts of ingredients and temperature of synthesis have been optimized using multistage response surface methodology. STR- g -TerPol bearing the maximum swelling ability, along with the retention of network integrity, has been employed for individual and/or simultaneous removal(s) of metal ions (i.e., M(III)), such as Bi(III) and Sb(III), and dyes, such as tris(4-(dimethylamino)phenyl)methylium chloride (i.e., crystal violet) and (7-amino-8-phenoxazin-3-ylidene)-diethylazanium dichlorozinc dichloride (i.e., brilliant cresyl blue). The in situ strategic protrusion of APMPS, grafting of STR into the TerPol matrix, variation of crystallinity, thermal stabilities, surface properties, mechanical properties, swellability, adsorption capacities (ACs), and ligand-selective superadsorption have been inferred via analyses of unadsorbed and/or adsorbed STR- g -TerPol using Fourier transform infrared (FTIR), 1 H/ 13 C NMR, UV–vis, thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, field emission scanning electron microscopy, energy-dispersive X-ray, dynamic light scattering, and rheological analyses and measuring the lower critical solution temperature, % gel content, pH at point of zero charge (pH PZC ), and network parameters, such as ρ c and M c . The prevalence of covalent, ionic (I), and variegated interactions between STR- g -TerPol and M(III) has been understood through FTIR analyses, fitting of kinetics data to the pseudosecond-order model, and by the measurement of activation energies of adsorption. The formation of H-aggregate type dimers and hypochromic and hypsochromic shifts has been explained via UV–vis analyses during individual and/or simultaneous removal(s) of cationic dyes. Several isotherm models were fitted to the equilibrium experimental data, of which Langmuir and combined Langmuir–Freundlich models have been best fitted for individual Bi(III)/Sb(III) and simultaneous Sb(III) + Bi(III) removals, respectively. Thermodynamically spontaneous chemisorption processes have shown the maximum ACs of 1047.39/282.39 and 932.08/137.85 mg g –1 for Bi(III) and Sb(III), respectively, at 303 K, adsorbent dose = 0.01 g, and initial concentration of M(III) = 1000/30 ppm. The maximum ACs have been changed to 173....

Multi‐C−C/C−N‐Coupled Light‐Emitting Aliphatic Terpolymers: N−H‐Functionalized Fluorophore Monomers and High‐Performance Applications

“…The higher adsorption capacities ( q max ) of 1 and 2 compared with 5 have been ascribed to the better binding affinity of Cu II to the nitrogen and oxygen donor atoms compared with the sulfur donor. As the separation factors ( R L ), given by Equation , vary in the range 0–1, the adsorption process is spontaneous …”

“…than pseudo‐first‐order kinetics [Eq. ] suggests chemisorption (see Table S19) through variable coordinative and strong ionic interactions of the oxygen donors in ‐COOH/‐COO − and ‐SO 3 H/‐SO 3 − in 1 / 2 and 5 with Cu II , respectively. Moreover, the activation energies ( E a ) calculated by using the Arrhenius Equation are 24.88, 22.55, and 25.65 kJ mol −1 for Cu II – 1 , Cu II – 2 , and Cu II – 5 , respectively, which indicates the feasibility of chemisorption (see Figure S18d).…”

“…[13,15] Additionally,C u II has severe detrimental effects on the environment, andt hus Cu II exclusion is crucial forits betterment. [16] In view of this, five nonconventional, purely aliphatic, intrinsiccally fluorescent, multifunctionalt erpolymersh ave been prepared fort he first time by the CÀC/CÀN-coupled, NÀ H-functionalized polymerization of two non-emissive monomers with in situ generated protrusions of af luorescent tertiary amide monomer for use in four-in-one applications, namely Cu II sensing, high-performancer emoval of Cu II ,l ogic gates, and Madin-Darby canine kidney (MDCK) cell imaging. The five terpolymers are methacrylic acid-co-3-(N-isopropylacrylamido)-2-methylpropanoic acid-co-N-isopropylacrylamide (MAA-co-NIPAMPA-co-NIPA, 1), acrylic acid-co-3-(N-isopropylacrylamido)propanoica cid-co-N-isopropylacrylamide (AA-co-NIPAPA-co-NIPA, 2), butyl acrylate-co-butyl 3-(N-isopropylacrylamido)propanoate-co-N-isopropylacrylamide( BA-co-BNIPAP-co-NIPA, 3), hydroxyethyl methacrylate-co-hydroxyethyl 3-(N-isopropylacrylamido)-2-methylpropanoate-co-N-isopropylacrylamide (HEMA-co-HENIPAMP-co-NIPA, 4), and 2-acrylamido-2-methylpropanesulfonic acid-co-2- [3-(N-isopropylacrylamido)propylamido]-2-methylpropanesulfonic acid-co-N-isopropylacrylamide (AMPS-co-NIPAPAMPS-co-NIPA, 5).…”

Structures, Properties, and Performances—Relationships of Polymeric Membranes for Pervaporative Desalination

“…Similarly, for SSA crosslinked PVA film, the peaks at 1030 cm −1 and 1226 cm −1 represent asym and sym str. S=O of the sulfonic acid group, respectively [122,184,185]. For GO hybridized CS membrane, reaction between primary –NH 2 of CS with epoxy group of GO was identified from the increase in N–H bending, along with the weakening of primary –NH 2 peak at 1651 cm −1 [136,186,187,188].…”

Removal of 3-Chloroaniline from aqueous solution by Treated Coffee Waste: Isotherm Modelling and Thermodynamic Studies

“…of 26 Many approaches are currently being used to remove chloroaniline compounds from wastewater effluents, for instance photodegradation [21,22], hydrodechlorination [23], oxidation [24,25], biodegradation [26], electrochemical oxidation [27] and sorption [28][29][30]. Amongst all, sorption is a reliable method that has been applied widely because of its effectiveness, simplicity, rapidness, cost effectiveness and the possibility of organic pollutants being recovered as reuse resources [31][32][33][34][35].…”