Role of Au(III) coordination by polymer in "green" synthesis of gold nanoparticles using chitosan derivatives.

Here we report "green" synthesis of gold nanoparticles in solutions of heterocyclic chitosan derivatives (N-(4-imidazolyl)methylchitosan (IMC), N-2-(2-pyridyl)ethylchitosan (2-PEC), and N-2-(4-pyridyl)ethylchitosan (4-PEC)) and show how efficiency of Au(III) binding to polymer influences the Au(III) reduction rate and the size of the gold nanoparticles formed using only the reducing power of these chitosan derivatives. Rheology measurements and (1)H NMR spectroscopy data have confirmed that cleavage of glycosidic bond is a common mechanism of reducing species generation in solutions of chitosan and its N-heterocyclic derivatives. However, the emerging additional reducing species in 2-PEC and 4-PEC solutions due to vinylpyridine elimination promotes Au(III) reduction and gold nanoparticles growth despite lower efficiency of glycosidic bond cleavage in pyridyl derivatives.

Chitosan and Its Derivatives as Highly Efficient Polymer Ligands.

The polyfunctional nature of chitosan enables its application as a polymer ligand not only for the recovery, separation, and concentration of metal ions, but for the fabrication of a wide spectrum of functional materials. Although unmodified chitosan itself is the unique cationic polysaccharide with very good complexing properties toward numerous metal ions, its sorption capacity and selectivity can be sufficiently increased and turned via chemical modification to meet requirements of the specific applications. In this review, which covers results of the last decade, we demonstrate how different strategies of chitosan chemical modification effect metal ions binding by O-, N-, S-, and P-containing chitosan derivatives, and which mechanisms are involved in binding of metal cation and anions by chitosan derivatives.

Imidazolyl derivative of chitosan with high substitution degree: Synthesis, characterization and sorption properties.

A method of synthesis of chitosan imidazolyl derivative - N-(5-methyl-4-imidazolyl)methylchitosan (IM-chitosan) with high degree of substitution (DS) via reaction with 5-methyl-4-imidazolylmethanol has been developed. This method enables one to obtain polymers with the DS up to 1.35 with simultaneous cross-linkage of the matrix.

Crystal structure of (2Z)-2-{(5Z)-5-[3-fluoro-2-(4-phenyl-piperidin-1-yl)benzyl-idene]-4-oxo-3-(p-tol-yl)-1,3-thia-zolidin-2-yl-idene}-N-(p-tol-yl)ethane-thio-amide dimethyl sulfoxide monosolvate.

The title compound, C37H34FN3OS2·C2H6OS, was obtained by the Knoevenagel condensation. The thia-zolidine ring is essentially planar (r.m.

Application of chitosan and its N-heterocyclic derivatives for preconcentration of noble metal ions and their determination using atomic absorption spectrometry.

Chitosan and its N-heterocyclic derivatives N-2-(2-pyridyl)ethylchitosan (2-PEC), N-2-(4-pyridyl) ethylchitosan (4-PEC), and N-(5-methyl-4-imidazolyl) methylchitosan (IMC) have been applied in group preconcentration of gold, platinum, and palladium for subsequent determination by atomic absorption spectroscopy (AAS) in solutions with high background concentrations of iron and sodium ions. It has been shown that the sorption mechanism, which was elucidated by XPS, significantly influences the sorption capacity of materials, the efficiency of metal ions elution after preconcentration, and, as a result, the accuracy of metal determination by AAS. We have shown that native chitosan was not suitable for preconcentration of Au(III), if the elution step was used as a part of the analysis scheme.

Selective adsorption of silver(I) ions over copper(II) ions on a sulfoethyl derivative of chitosan.

This study presents a simple and effective method of preparation of N-(2-sulfoethyl) chitosan (NSE-chitosan) that allows obtaining a product with a degree of modification up to 1.0. The chemical structure of the obtained polymers was confirmed by FT-IR and 1H NMR spectroscopies.

Mechanism of Au(III) reduction by chitosan: comprehensive study with 13C and 1H NMR analysis of chitosan degradation products.

The mechanism of Au(III) reduction by chitosan has been proposed on the basis of comprehensive study of kinetics of Au(III) reduction and chitosan chain degradation using UV-vis spectroscopy and viscosimetry, and identification of reaction products using colloid titration and (13)C, (1)H NMR spectroscopy. We have shown that formation of gold nanoparticles in H[AuCl4]/chitosan solutions starts with hydrolysis of chitosan catalyzed by Au(III). The products of chitosan hydrolysis rather than chitosan itself act as the main reducing species.

Simple synthesis and chelation capacity of N-(2-sulfoethyl)chitosan, a taurine derivative.

This study presents a simple and effective synthesis method of N-(2-sulfoethyl)chitosan (NSE-chitosan) via a reaction between sodium 2-bromoethanesulfonate and chitosan that allows polymer transformation without using additional reagents and organic solvents. The chemical structure of the obtained NSE-chitosan was characterized by FT-IR and (1)H NMR spectroscopies. Thermogravimetric study of NSE-chitosan coupled with FT-IR analysis has shown stability of the polymer up to 200 °C, which almost does not change with the increase of degree of substitution (DS).

N-(2-(2-pyridyl)ethyl)chitosan: Synthesis, characterization and sorption properties.

The method of producing N-2-(2-pyridyl)ethylchitosan (PE-chitosan) with substitution degrees (DS) up to 1.2 has been developed using the "synthesis in gel" approach for direct addition reaction between 2-vynilpyridine and chitosan. Investigation of sorption properties has revealed significantly higher affinity of pyridylethyl fragments to Pt(IV)) and Pd(II) ions compared to the unsubstituted amino groups of chitosan.

Mechanism of structural networking in hydrogels based on silicon and titanium glycerolates.

Formation of organic/inorganic hydrogels based on silicon- and titanium-glycerol precursors synthesized by transesterification of alkoxy derivatives in excess of glycerol was investigated. The precursors in excess of glycerol and obtained gels were studied by chemical and physical methods including gelation kinetics, IR spectroscopy, XRD, dynamic and electrophoretic light scattering, mechanical deformation, which disclosed the basic difference in the gelation mechanism and structure of network in the hydrogels. Due to this difference, the gelation time of silicon- and titanium-glycerol precursors depended on pH or electrolyte addition in an opposite way.

Bis[N-(2-hydroxyethyl)-beta-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.