A. V. Pestov

Imidazole-containing chitosan derivative: a new synthetic approach and sorption properties

A novel method for the synthesis of a hetaryl-containing chelate amino polymer, namely, N-(4(5)-imidazolylmethyl)chitosan (IMC), with a degree of substitution up to 0.3 was proposed. The “synthesis in gel” approach involves direct substitution of the hydroxyl group in 4(5)-imidazolylmethanol. The structures of these polymers were confirmed by 1H NMR data. For sorption studies, IMC samples were crosslinked with epichlorohydrin and diglycidyl ethers of ethylene glycol and diethylene glycol. The degrees of swelling and sorption properties of the polymers largely depend on the crosslinking agent and the degree of crosslinking. The sorption capacities of IMC for AuIII, PtIV, and PdII ions are higher than those of the nonmodified polymer. The extraction of noble metal ions from chloride solutions becomes more selective with increasing degree of crosslinking. The sorption capacity of IMC for CoII and NiII ions is higher than those of chitosan and its known N-heterocyclic derivatives.

Synthesis in a gel and sorption properties of N-2-sulfoethyl chitosan

A new procedure was developed for preparation of chelate amino-containing polymer N-2-sulfoethyl chitosan by synthesis in a gel through the reaction between chitosan and sodium 2-bromoethanesulfonate, yielding a polymer with the degree of substitution of up to 0.5. The structure of the resulting polymers was confirmed by 1H NMR spectroscopy. The sorption characteristics with respect to transition and alkaline-earth metal ions were determined for the cross-linked polymers.

N-2-(2-pyridyl)ethyl chitosan: Synthesis in gel and sorption properties

A procedure was developed for preparing a new heterocyclically substituted chelating aminopolymer, N-2-(2-pyridyl)ethyl chitosan, by direct addition of 2-vinylpyridine to chitosan under the conditions of synthesis in gel. The resulting polymer has the degree of substitution of up to 1. The ability of the samples obtained to sorb transition and noble metal ions was evaluated.

Gel-synthesis, structure, and properties of sulfur-containing chitosan derivatives

The possibility of using the thermochemical approach to thermal decomposition of solids, previously developed by the author, to interpretation of the mechanism and kinetics of reduction of metal oxides with hydrogen was studied. Many properties of NiO reduction with hydrogen, including formation of metal nuclea, the nature of induction period, autocatalysis effect, equimolar and isobaric periods of reduction, the character of the effect of hydrogen pressure on reduction rate, and the nanocrystalline structure of a reduced metal, were explained in terms of the given approach.

Copper and nickel chelate complexes with polydentate N,O-ligands: structure and magnetic properties of polynuclear complexes*

A comparative analysis of the structures of copper(II) and nickel(II) chelate complexes with N-substituted 2-aminoethanols, 3-aminopropan-1-ols, glycines and -alanines is performed. It is shown that tetradentate ligands based on 3-aminopropan-1-ol and -alanine, sterically hindered 2-aminoethanol derivatives and tridentate enamino ketone derivatives tend to form oligonuclear copper(II) and nickel(II) complexes. Glycine derivatives do not provide the formation of oligonuclear copper(II) and nickel(II) complexes. The magnetic properties of a number of polynuclear complexes are compared.The bibliography includes 182 references.

Application of chitosan and its derivatives for solid-phase extraction of metal and metalloid ions: a mini-review

Here we review chitosan-based materials for solid-phase extraction of metal and metalloid ions prior to their determination by atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry, mass spectrometry, and some other spectrometric techniques. We show that nearly zero affinity of chitosan and its derivatives to alkali and alkali-earth metal ions is very beneficial for separation of analytes from the salt matrix, which is always present in natural waters, waste streams, and geological samples and interferes with analytical signals. Applicability of chitosan to selective recovery of different metal and metalloid ions can be significantly improved via functionalization with N-, S-, and O-containing groups imparting chitosan with additional electron donor atoms and capability to form stable five- and six-membered chelate rings with metal ions. Among most promising materials for analytical preconcentration, we discussed chitosan-based composites; carboxyalkyl chitosans; chitosan derivatives containing residues of aminoacids, iminodiacetic acid, ethylenediaminetetraacetic and diethylenetriaminepentaacetic acids; chitosans modified with aliphatic and aromatic amines, heterocyclic fragments (pyridyl, imidazole), and crown ethers. We have shown that most chitosan derivatives provide only group selectivity toward metal ions; however, optimization of recovery conditions allows metals and metalloids speciation and efficient separation of noble and transition metal ions.

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. The group preconcentration of Au(III), Pd(II), and Pt(IV) with subsequent quantitative elution using 0.1M HCl/1M thiourea solution was possible only on IMC and 4-PEC. Application of IMC for analysis of the national standard quartz ore sample proved that gold could be accurately determined after preconcentration/elution with the recovery above 80%.

Chemical properties of N-2-Sulfoethylchitosan with a medium degree of substitution

A method was developed for the preparation of N-2-sulfoethylchitosan (SECH) via synthesis in a gel with the use of the reaction of chitosan and sodium 2-bromoethanesulfonate. This method makes it possible to conduct a polymer-like transformation without any acid or base. The structures of the obtained polymers were confirmed via IR and 1H NMR spectroscopy. The study of the sorption of Ag+, Cu2+, Zn2+, Ni2+, Co2+, Cd2+, Pb2+, Mn2+, Mg2+, Ca2+, Sr2+, and Ba2+ ions that were crosslinked by SECH during their joint presence in an ammonia-acetate buffer solution showed high values of selectivity in relation to those of silver(I) and copper(II). The selectivity of the sorption of silver(I) ions with respect to copper(II) ions increased with an increase in the degree of substitution of SECH.

Preparation of a sorbent for metal ions based on N-(5-methylimidazol-4-ylmethyl) chitosan with medium degree of substitution

A procedure was developed for preparing a heterocycle-containing chelating amino polymer, N-(5-methylimidazol-4-ylmethyl) chitosan, by polymer-analogous transformations of chitosan in reaction with 4-chloromethyl-5-methylimidazole. The procedure allows synthesis of the polymer with the degree of substitution of up to 0.8, with simultaneous formation of the cross-linked structure. The structure of the polymers prepared was proved by IR and 13C NMR spectroscopy. The ability of N-(5-methylimidazol-4-ylmethyl) chitosan with the degree of substitution of 0.54 to sorb Cu2+ and Ni2+ ions was evaluated. According to the sorption isotherms, the sorption capacity of this derivative exceeds that of the unmodifi ed polymer by a factor of 5.

Synthesis of poly[N-(2,3-dihydroxypropyl)aminostyrene], a new sorbent for boron(III) ions

A procedure was developed for preparation of poly[N-(2,3-dihydroxypropyl)aminostyrene] via successive stages of nitration, reduction, and glycidol treatment of polystyrene, which gives the polymer with a maximal degree of functionalization. The composition and structure of the intermediates and end products of the polymer-analogous reactions were characterized by elemental analysis, IR spectroscopy, and solid-state 13C NMR spectroscopy. The sorption characteristics of poly[N-(2,3-dihydroxypropyl)aminostyrene] toward boroncontaining ions were assessed.