Chitosan Cross-Linking with Acetaldehyde Acetals.

Here we demonstrate the possibility of using acyclic diethylacetal of acetaldehyde (ADA) with low cytotoxicity for the fabrication of hydrogels via Schiff bases formation between chitosan and acetaldehyde generated in situ from acetals in chitosan acetate solution. This approach is more convenient than a direct reaction between chitosan and acetaldehyde due to the better commercial availability and higher boiling point of the acetals. Rheological data confirmed the formation of intermolecular bonds in chitosan solution after the addition of acetaldehyde diethyl acetal at an equimolar NH2: acetal ratio. The chemical structure of the reaction products was determined using elemental analysis and 13C NMR and FT-IR spectroscopy. The formed chitosan-acetylimine underwent further irreversible redox transformations yielding a mechanically stable hydrogel insoluble in a broad pH range. The reported reaction is an example of when an inappropriate selection of acid type for chitosan dissolution prevents hydrogel formation.

Carboxyalkylchitosan-based hydrogels with "imine clip": Enhanced stability and amino acids-induced disassembly under physiological conditions.

Here we report on the properties of hydrogels of carboxyalkylchitosans-salicylimines depending on the salicylaldehyde (SA) grafting density, type of carboxyalkyl substitution, pH, and presence of amino acids. The mechanism of SA grafting has been investigated using 13C NMR and FT-IR spectroscopy and elemental analysis. We have found that, despite lower SA grafting density to carboxyalkylchitosans, gelation in these solutions occurred at much lower SA:polymer molar ratios than for chitosan-salicylimines, being the highest for a N-carboxyethylchitosan with a medium substitution degree. Controlled disassembly of supramolecular architecture of hydrogel of N-carboxyethylchitosan-salicylimine at physiological pH was achieved via the transimination reaction in the presence of amino acids with the efficiency decreased in the order: lysine > arginine ≥ serine. Application of carboxyalkylchitosans opens a new window for development of salicylimine-based hydrogels with lower SA grafting density, better mechanical properties, and reversibility in a broader pH range than it was earlier known for chitosan-based biodynamers.

Cryogels of carboxyalkylchitosans as a universal platform for the fabrication of composite materials.

Here we report a new simple method for fabrication of supermacroporous beads and monoliths via cross-linking of carboxyalkylated chitosan derivatives with hexamethylene diisocyanate in aqueous solution at subzero temperature. These materials provide high filtration rate and good mass-transfer that in combination with high binding capacity toward metal ions allows their application as a universal platform for fabrication of composite catalysts, sorbents, and metal-affine chromatography stationary phases. Using N-(2-carboxyethyl)chitosan (CEC), we have demonstrated that optimum chitosan carboxylation degree for cryogels synthesis is close to 1.0. Cu(II)-chelated CEC cryogels have shown high efficiency as metal-affinity sorbents for ciprofloxacin recovery. Co(II)-chelated CEC cryogels have been used for fabrication of Co(II) ferrocyanide-containing composite with the distribution coefficient for 137Cs of 140,000 ml/g and the adsorption capacity of ˜1 mmol/g. Composite Pd-catalysts supported on CEC cryogel provided tenfold higher reaction rate in 4-nitrophenol reduction in comparison with Pd-catalyst supported on chitosan beads.

Chitosan Gels and Cryogels Cross-Linked with Diglycidyl Ethers of Ethylene Glycol and Polyethylene Glycol in Acidic Media.

Here we show that the efficacy of the chitosan interaction with diglycidyl ethers of glycols significantly depends on pH and the nature of acid used to dissolve chitosan. In solutions of hydrochloric acid, cross-linking with diglycidyl ethers of ethylene glycol (EGDGE) and polyethylene glycol (PEGDGE) at room and subzero temperatures yields mechanically stable chitosan gels and cryogels, while in acetic acid solutions only weak chitosan gels can be formed under the same conditions. A combination of elemental analysis, FT-IR spectroscopy, and solid state 13C and 15N NMR spectroscopy was used to elucidate possible differences in the mechanism of chitosan cross-linking in alkaline and acidic media at room and subzero temperatures. We have proved that in acidic media diglycidyl ethers of glycols interacted with chitosan mainly via hydroxyl groups at the C6 position of the glucosamine unit. Besides, not only cross-linkages but also grafts were formed at room temperature. The cryo-concentration effect facilitates cross-linkages formation at -10 °C and, despite lower modification degrees compared to those of gels obtained at room temperature, supermacroporous chitosan cryogels with Young's moduli up to 90 kPa can be fabricated in one step. Investigations of chitosan cryogels biocompatibility in a mouse model have shown that a moderate inflammatory reaction around the implants is accompanied by formation of a normal granulation tissue. No toxic, immunosuppressive, and sensitizing effects on the recipient's tissues have been observed.

Fluxional seven-coordinated fluorido- and oxofluoridotantalates.

Seven-coordinated (NH4)2TaF7, Rb2TaF7 and Rb3TaOF6 were synthesized in single-crystal form and their structures were determined. A monocapped trigonal prism (CTP) or a pentagonal bipyramid (PB) of the TaF72- anion are stereochemically nonrigid and coexist in the first two compounds as a result of strong intraspheric dynamics. Upon cooling, tetragonal Rb2TaF7 undergoes a first-order phase transition at 145 K and the seven-coordinated polyhedron transforms into a regular CTP. The seven-coordinated polyhedron in (NH4)2TaF7 approaches the PB configuration as the temperature decreases. Cubic elpasolite-like Rb3TaOF6 is characterized by the simultaneous two-state coexistence of TaOF63- of the PB shape as rigidly reoriented and as fluxional. In the former case, the central atom is disordered over the octahedron in the unit cell, allowing the determination of the short Ta-O distance, whereas in the latter case, tantalum remains in the polyhedron center, resulting in synchronous Ta-O and Ta-F stretching vibrations appearing as the infrared band at 723 cm-1.

Bonding and structure of oxofluoroniobate-based glasses.

Glasses based on the oxofluoroniobate anion have been characterized by vibrational and solid-state NMR spectroscopy. The mechanism of glass formation in the systems K2NbOF5-MF3 (M = Al, In) has been suggested. A glass network is built from the chains of corner-sharing octahedra through -Nb-F(O)-M- and -Nb-F-Nb- bridges. Isolated NbOF5(2-) octahedra are also present, which is consistent with the glass composition. The high ionic mobility of NbOF5(2-) due to its fast reorientations results in equalization of the Nb-O and Nb-F distances, which is reflected in the appearance of the IR band at 700-800 cm(-1) not observed in the Raman spectrum. Its assignment to bridging -Nb-O-Nb- species accepted in the literature was not proven.