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PubMed2001

Spectroscopic study of the interactions of alkali fluorides with D-xylose.

The interactions of alkali fluorides with D-xylose have been studied by X-ray diffraction (XRD), infrared spectroscopy (IR), nuclear magnetic resonance (NMR, 1H and 13C) and atomic absorption spectrophotometry. KF and CsF form complexes with D-xylose in a 1:1 molar ratio. These complexes can be obtained by solid state milling the reactants in an agate mortar or from methanolic solutions of the sugar and the salt. LiF and NaF do not form complex with D-xylose. IR and XRD prove the identical nature of the complexes obtained by milling and from solution. IR spectra indicate strong perturbation of the OH stretching vibrations with considerable shifts to lower frequencies, which must be caused by strong hydrogen bond formation to the fluorine anion. The perturbations of C-O bond are weak, indicating that cation binding to the oxygen atoms is not the main interaction responsible for the complex formation. 1H NMR spectra of the D-xylose-KF complex dissolved in deuterium oxide is equal to that of pure D-xylose, indicating the destruction of the complex in solution. The complex is stable in DMSO, and 13C spectra of the complex in DMSO-d6 and in solid state (CPMAS) spectra are in accordance with the observed interactions in the IR spectra. As far as we know, this is the first report of a sugar-halide salt complex in which the anion instead of the cation provides the binding forces.

Alcohols↗
PubMed1993

On the mechanism of sodium ion translocation by oxaloacetate decarboxylase of Klebsiella pneumoniae.

Proteoliposomes reconstituted with purified oxaloacetate decarboxylase of Klebsiella pneumoniae catalyzed the uptake of Na+ ions upon oxaloacetate decarboxylation. The degree of coupling between the chemical and the vectorial reaction is dependent on the reconstitution conditions, and with the best preparations approaches a stoichiometry of two Na+ ions per decarboxylation of one oxaloacetate. This coupling ratio is observed only in the absence of a delta mu Na+, immediately after oxaloacetate addition. The ratio gradually declines during development of the electrochemical Na+ ion gradient and becomes zero in the steady state. The Na+ pump, however, continued to decarboxylate oxaloacetate and to catalyze Na+ influx at the apparent stoichiometry of two Na+ ions per decarboxylation event. During the steady state, this influx must be compensated by Na+ efflux of the same size. The efflux is catalyzed by the Na+ pump upon oxaloacetate decarboxylation, because in the absence of the substrate the efflux rate dropped to less than 10%. Proteoliposomes loaded with Na2SO4 catalyzed a bicarbonate-dependent uptake of 22Na+ that was completely abolished after incubation with avidin. These results suggest coupling of Na+ translocation to the carboxylation/decarboxylation of the biotin prosthetic group without the requirement for the oxaloacetate/pyruvate interconversion. The oxaloacetate-dependent transport of Na+ into proteoliposomes was inhibited by the additional presence of the beta + gamma subunits of oxaloacetate decarboxylase. A model of Na+ translocation by oxaloacetate decarboxylase based on these experimental results is proposed.

Avidin↗
PubMed2003

Polymeric enzyme mimics: catalytic activity of ribose-containing polymers for a phosphate substrate.

The polymers containing ribose rings: poly(5'-acrylamido-5'-deoxy-1',2'-O-isopropylidene-alpha-D-ribose) (11), poly(5'-acrylamido-5'-deoxy-alpha-D-ribose) (12) and poly(5'-acrylamido-5'-deoxy-1'-O-methyl-D-ribose) (13) were prepared as enzyme mimics. Polymers 12 and 13 with free vic-cis-diol groups catalyzed the hydrolysis of phosphodiester (ethyl p-nitrophenyl phosphate and N-methylpyridinium 4-tert-butylcatechol cyclic phosphate) and phosphomonoester substrates with a rate acceleration of 10 approximately equal to 10(3) compared with the uncatalyzed reaction. They also catalyzed the reverse reactions, i.e., the esterification of phosphomonoester to phosphodiester and the phosphorylation of alcohols with phosphate ions. The catalytic activity was attributable to the vic-cis-diols of riboses on polymer chains, which formed hydrogen bonds with two phosphoryl oxygen atoms of phosphates so as to activate the phosphorus atoms to be attacked by nucleophiles. The catalytic activity was negligible for polymer 11 where vic-cis-diol groups were blocked with isopropylidene groups. The catalytic activity was attributable to the vic-cis-diols of riboses on polymer chains, which formed hydrogen bonds with two phosphoryl oxygen atoms of phosphates so as to activate the phosphorus atoms to be attacked by nucleophiles.

Catalysis↗
PubMed1998

Electrostatic inhibition of hemolysis induced by organotin compounds.

The effect of cations on the kinetics of hemolysis caused by organotin compounds was studied. The ions used in the investigation diminish or totally inhibit hemolysis of red cells induced by organotin compounds. The degree of inhibition depends both on the kind of ion and the compounds that induce hemolysis. The ions Zn2+, Co2+, and Cd2+ present in the medium at 50 microM concentration totally protect the erythrocytes against hemolysis induced by the compound (C3H7)3SnCl. The study has also shown the monovalent ions K+ and trimethyldodecylammonium bromide are less potent inhibitors of hemolysis than divalent ions, which is not the case for two non-ionic organotin compounds only. The studies performed indicate that hemolysis induced by organotin compounds is inhibited due to electrostatic interaction between the cations selected and erythrocyte membrane.

Animals↗
PubMed2002

Optically and thermally stimulated luminescence of KMgF3:Ce3 and NaMgF3:Ce3+.

The potentialities of optically stimulated luminescence (OSL) for personal dosimetry of ionising radiation have stimulated the search for new synthetic materials with good dosimetric properties. The sensitivity of two new OSL materials KMgF3 and NaMgF3 doped with Ce3+ ions has been evaluated and found to be of the same order of magnitude as that of Al2O3:C. Several other characteristics have also been investigated. Promising results for KMgF3:Ce are the high sensitivity and the low fading. However, this material suffers from a high self-dose due to the presence of 40K. NaMgF5:Ce is sensitive as well but shows strong fading. Interesting information on the mechanism has been obtained by correlating the signals of OSL and TL. Furthermore, the different bleachabilities under blue LED illumination of the strongly overlapping glow peaks allowed the extraction of one single peak for KMgF3:Ce3+. The results demonstrate new possibilities offered by the combination of TL and OSL.

Cerium↗