A series of macroporous amphoteric cryogels based on allylamine, methacrylic acid and acrylamide were synthesized by radical copolymerization of monomers in cryoconditions. The average molar composition of amphoteric cryogels was found from the potentiometric and conductimetric titration curves. The morphology of cryogels was evaluated by SEM. Cryogels are highly elastic and have continuous macroporous structure with 50-200 mm pores. The values of the isoelectric pH determined from the swelling experiments arranged between 3.5 and 4.3. Complexation of amphoteric with transition metal ions was studied. Cryogels with adsorbed copper, nickel, or cobalt ions have an intense colour due to formation of coordination and ionic bonds between metal ions and amine and/or carboxylic groups of cryogels. Metal ions entrapped within the pores of cryogels were reduced by treating aqueous solution of NaBH 4 . Formation of micron sized metals on the inner surface of cryogels was observed by SEM.
Gold nanoparticles (AuNPs) were synthesized and stabilized using the one-pot method and growth seeding, through utilization of synthetic polymers, including poly(N-vinylpyrrolidone) (PVP), poly(ethylene glycol) (PEG), and poly(vinylcaprolactame) (PVCL), as well as natural polysaccharides, including gellan, welan, pectin, and κ-carrageenan. The absorption spectra, average hydrodynamic size, ζ-potential, and morphology of the gold nanoparticles were evaluated based on various factors, such as polymer concentration, molecular mass of polymers, temperature, and storage time. The optimal polymer concentration for stabilization of AuNPs was found to be 4.0 wt % for PVP, 0.5 wt % for gellan, and 0.2 wt % for pectin, welan, and κ-carrageenan. The values of the ζ-potential of polymer-stabilized AuNPs show that their surfaces are negatively charged. Most of the AuNPs are polydisperse particles, though very monodisperse AuNPs were detected in the presence of a 0.5 wt % gellan solution. At a constant polymer concentration of PVP (4 wt %), the average size of the PVP–AuNPs decreased with the decrease of molecular weight, and in the following order: PVP 350 kDa (~25 nm) > PVP 40 kDa (~8 nm) > PVP 10 kDa (~4 nm). The combination of Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopy revealed that the functional groups of polymers that are responsible for stabilization of AuNPs are lactam ring in PVP, carboxylic groups in gellan and welan, esterified carboxylic groups in pectin, and SO2 groups in κ-carrageenan. Viscometric and proton nuclear magnetic resonance (1H NMR) spectroscopic measurements showed that the temperature-dependent change in the size of AuNPs, and the gradual increase of the intensity of AuNPs at 550 nm in the presence of gellan, is due to the rigid and disordered conformation of gellan that affects the stabilization of AuNPs. The AuNPs synthesized in the presence of water-soluble polymers were stable over a period of 36 days. Preliminary results on the synthesis and characterization of gold nanorods stabilized by polymers are also presented.
Macroporous amphoteric cryogels based on N,N-dimethylaminoethylmethacrylate and methacrylic acid p(DMAEM-co-MAA) crosslinked by N,N 0 -methylenebisacrylamide (MBAA) were synthesized by radical copolymerization of monomer mixtures in cryoconditions. The structure and morphology of cryogels were evaluated by FTIR and SEM. Cryogels exhibited interconnected porous structure with pore size ranging from 40 to 80 mm, which depended on their crosslinking degree. The value of the isoelectric point (IEP) of equimolar amphoteric cryogel determined from the water flux was equal to 4.4, while the IEP of cryogel with the excess of DMAEM units was equal to 7.1. The mechanical strength of equimolar amphoteric cryogels increases with increasing amount of crosslinking agent. The complexation ability of amphoteric cryogels with respect to surfactant, dyes, and protein was demonstrated. The adsorption isotherms with respect to anionic surfactant-sodium dodecylbenzene sulfonate (SDBS) and protein-lysozyme correspond to Langmuir equation, while adsorption isotherms of anionic and cationic dyes-methylene blue (MB) and methyl orange (MO) are well described by Freundlich equation. It was found that the binding ability of p(DMAEM-co-MAA) with respect to various low-and high-molecular weight compounds changes in the following order: SDBS > lysozyme MO > MB. The preferential adsorption of MB from the mixture of protein and MB was shown. The quantitative release of protein, surfactant and dye molecules from the matrix of cryogels takes place at the IEP of cryogel.
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