Yury G. Yatluk

N-(2-Carboxyethyl)chitosans: regioselective synthesis, characterisation and protolytic equilibria

N-(2-Carboxyethyl)chitosans were obtained by reaction of low molecular weight chitosan with a low degree of acetylation and 3-halopropionic acids under mild alkaline media (pH 8-9, NaHCO3) at 60 degrees C. The chemical structure of the derivatives obtained was determined by 1H and 13C NMR spectroscopies. It was found that alkylation of chitosan by 3-halopropionic acids proceeds exclusively at the amino groups. The products obtained are described in terms of their degrees of carboxyethylation and ratio of mono-, di-substitution and free amine content. The protonation constants of amino and carboxylate groups of a series of N-(2-carboxyethyl)chitosans were determined by pH-titration at ionic strength 0.1 M KNO3 and 25 degrees C.

Evaluation of various chitin-glucan derivatives from Aspergillus niger as transition metal adsorbents.

A number of chelating resins were prepared by chemical derivatization of the chitin-glucan (CG) complex isolated from Aspergillus niger biomass, namely chitosan-glucan (CsG), O-carboxymethyl-chitin-glucan (CM-CG), O-(2-sulfoethyl)chitin-glucan (SE-CG), and N-(2-carboxyethyl)chitosan-glucan (CE-CsG). The chemical modification was confirmed by FT-IR and elemental analysis. Nanosecond electron beam irradiation was used to produce insoluble resins and to preserve the reactive functional groups. Batch experiments were carried out to evaluate the adsorption selectivity and capacity of the resins toward transition metal ions (Cu(2+), Ni(2+), Co(2+), Zn(2+)). The resins showed good adsorption capability with the following selectivity series: Co(2+)Zn(2+). The total metal adsorption capacities of CG, CsG, CM-CG, SE-CG, and CE-CsG resins at pH 6.5 (ammonium acetate buffer) were found to be 0.205, 0.382, 1.752, 0.319, and 0.350 mmol g(-1), respectively. Our results suggest that, depending on the type of chemical modification, the chitin-glucan complexes can be used either for selective Cu(2+) removal (CsG) or for total transition metal adsorption (CM-CG) from aqueous effluents.

Carboxyalkylation of chitosan in the gel state.

This study presents a new approach for direct carboxyalkylation of chitosan in the gel state by using aza-Michael addition and substitution reactions. Various reagents were applied including acrylic and crotonic acids, and α-, β-, γ-, δ-, and ɛ-halocarboxylic acids. The reaction of chitosan with γ- and δ-halocarboxylic acids showed no target product formation either in solution or in the gel state. In the case of acrylic, crotonic, α- and β-halocarboxylic acids, the reaction performed in the gel state (concentration of chitosan 20-40%) shows higher degree of substitution at lower reaction time and temperature than in diluted solutions (concentration of chitosan 0.5-2%). The results were discussed in terms of kinetics of the target and side reactions. (1)H and (13)C NMR confirmed that in all cases the carboxyalkylation of chitosan proceeds exclusively at the amino groups.

Bis[N-(2-hydroxyethyl)-β-alaninato]-copper(II)

The Cu(II) ion in the title complex, [Cu(C5H10NO3)2] or [Cu(He-ala)2] [He-ala = N-(2-hydroxyethyl)-beta-alaninate], resides at the inversion centre of a square bipyramid comprised of two facially arranged tridentate He-ala ligands. Each He-ala ligand binds to a Cu(II) ion by forming one six-membered beta-alaninate chelate ring in a twist conformation and one five-membered ethanolamine ring in an envelope conformation, with Cu-N = 2.017 (2) angstroms, Cu-O(COO) = 1.968 (1) angstroms and Cu-O(OH) = 2.473 (2) angstroms. The [Cu(He-ala)2] molecules are involved in a network of O-H...O and N-H...O hydrogen bonds, forming layers parallel to the (10-1) plane. The layers are connected into a three-dimensional structure by van der Waals interactions, so that the molecular centres form pseudo-face-centered close packing.