Theoretical studies on the conformation of saccharides

Conformations of 2-methoxytetrahydropyran as a model for the six-membered ring in aldopyranosides have been calculated by the PCILO method using the algorithm of the conjugated gradient to optimize the geometry. The calculated geometry of the fourteen basic forms of 2-methoxytetrahydropyran was found to be in agreement with the available data obtained by X-ray diffraction of pyranosides. The results indicate differences in the geometry of 2-methoxytetrahydropyran resulting from the change of the axial vs. equatorial position of the methoxyl group. These changes are particularly meaningful in the values of bond angles and they are in agreement with the anomeric and exoanomeric effects. The experimentally found differences in the energies of an axial (⁴ C ₁) and equatorial (¹ C ₄) conformer, G = 2.9–3.7 kJ/mol, and the dipole moment, = 1.20 ± 0.05 D (1D = 3.33 10^–30mAs) agree well with the calculated values E = 3.18 kJ/mol and <> = 1.18 D which, in turn, suggest that the axial conformer is preferred over the equatorial one by a ratio a:e = 78:22.     

Coulometrische Wismutometrie

Zusammenfassung Durch elektrolytische Oxydation einer Bi-Anode in gesättigter NaCl-Lösung können Bi³⁺-Ionen in Lösung gebracht werden. Dieser Prozeß ermöglicht die coulometrische Bestimmung anwesender Anionen, die schwerlösliche Bi-Verbindungen bilden.Es wurden Semimikro- und Mikrobestimmungen von Phosphationen durch elektrolytisch erzeugte Bi³⁺-Ionen bei konstanter Stromstärke ausgeführt. Die Endpunktbestimmung erfolgte amperometrisch bei konstantem Potential mit einer Indikatorelektrode — tropfende Quecksilberelektrode — und mit einer gesättigten Kalomelelektrode als Bezugselektrode. Die coulometrische Wismutometrie bietet eine weitere Möglichkeit der coulometrischen Eichung volumetrischer Lösungen im Sinne des seinerzeitigen Vorschlags vonTutundi.

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Summary Bi³⁺ ions can be brought into solution through electrolytic oxidation of a Bi-anode in saturated NaCl solution. This process makes possible the coulometric determination of the anions present that yield difficulty soluble bismuth compounds.Semimicro- and micro-determinations of phosphate ions were made via Bi³⁺-ions produced electrolytically at constant current strength. The endpoint was determined amperometrically at constant potential with an indicator electrode-dropping mercury electrode-and with a saturated calomel electrode as reference electrode. The coulometric bismuthometry affords a further possibility of the coulometric standardization of volumetric solutions in the sense of the proposal previously advanced byTutundi.

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Résumé On peut utiliser les ions Bi³⁺ en solution par oxydation électrolytique d'une anode en bismuth, en solution de chlorure de sodium saturée. Ce procédé permet le dosage coulométrique des anions présents qui forment des composés peu solubles avec le bismuth.On a mis au point le dosage semimicro et micro des ions phosphates par les ions Bi³⁺ formés électrolytiquement sous intensité constante. On détermine par ampérométrie le point équivalent à potentiel constant à l'aide d'une électrode indicatrice — électrode de mercure à goutte pendante —et avec une électrode au calomel saturée comme électrode de référence. La «bismuthométrie» coulométrique offre de grandes possibilités pour l'étalonnage coulométrique de solutions volumétriques, suivant l'idée queTutundi a émise en son temps.

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Vorgetragen beim Symposium für analytische Chemie in Graz, 29. September bis 1. Oktober 1965.

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Wir danken Herrn Dipl.-Ing.Vladimir Pantovi für seine Hilfe bei unserer experimentellen Arbeit.     

Binary mixtures based on polycaprolactone and cellulose derivatives

Pyrolytic process has a promising potential for the environmentally friendly upgrading of lignocellulosic and plastic waste. Thermogravimetry and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) were used to get information about the reactive decomposition of PCL in binary mixtures with microcrystalline cellulose (MC) or sisal fibres (SF). Preliminary thermogravimetric investigation showed that biomass is thermally degraded at lower temperatures than PCL and this process has a predominant influence on the thermal behaviour of the mixtures. Discrepancies between the experimental and predicted TG/DTG profiles were considered as a measurement of the extent of interactions occurring on co-pyrolysis. It was found that reactivity of PCL was slightly increased in PCL-SF binary mixtures. Evolution of acidic products from cellulose and hemicelluloses decomposition may promote PCL degradation in binary mixtures with SF. It seems that the co-pyrolysis process could have potential for the environmentally friendly transformation of biocomposites.     

A viscometric study of poly(methyl methacrylate) in 2-alkoxyethanols

θ-Conditions, the temperature coefficient of unperturbed dimensions of the macromolecules and the thermodynamic interaction parameters ψ and κ were determined for solutions of poly(methyl methacrylate) in 2-alkoxyethanols (methoxy, ethoxy and butoxy). The results for this series of solvents fit the data reported for other solvents and dln $\text{r}{}_0{}^2\text{/}\text{d}\text{T = 2.6 × 10}{}^{\mathrm{?3}}\text{K}{}^{\mathrm{?1}}$. The dependence of parameters ψ and κ exhibited deviations from the theoretical dependence, mainly near the limiting value ψ = 0.5.     

Crystallochemical causes of the different thermal properties of [Cu(py)2(NCS)2] and [Cu(4-Mepy)2(NCS)2] complexes

The crystal structures and thermal behaviour of [Cu(py)₂(NCS)₂] (at 293) and [Cu(4-Mepy)₂(NCS)₂] and 180 K) complexes have been compared with their different temperature behaviour. It was found that the thermal stability of coordinated thiocyanate ligands in the course of thermal decomposition depends not only on the properties of the ligand L, but it is related to the arrangement of the thiocyanatocopper chains in the crystal structures.     

Studies on the refolding of the reduced-denatured insulin with size exclusion chromatography

The refolding of the reduced-denatured insulin from bovine pancreas was investigated with the size exclusion chromatography (SEC). It was shown that the reduced-denatured insulin originally denatured with 7.0 mol L^?1 guanidine hydrochloride (GuHCI) or 8.0 mol L^?1 urea could not be refolded with a non-oxidized mobile phase. Although the oxidized and reduced glutathione (GSSG and GSH) were employed in the oxidized mobile phase, the reduced-denatured insulin still could not be renatured. However, in the presence of 2.0 mol L^t-1 urea in the oxidized mobile phase employed, the reduced-denatured insulin can be refolded with SEC, and the aggregation of denatured insulin can be diminished by urea. In addition, the disulfide exchange of reduced-denatured insulin also can be accelerated with GSSG/GSH in the oxidized mobile phase. The three disulfide bridges of insulin were formed correctly and the reduced-unfolded insulin can be renatured completely. The results were further tested with reversed-phase liquid chromatography (RPLC) and hydrophobic interaction chromatography (HIC).     

Competitive adsorption and desorption of a bi-solute mixture: effect of activated carbon type

This study aims to clarify the effects of carbon activation type and physical form on the extent of adsorption capacity and desorption capacity of a bi-solute mixture of phenol and 2-chlorophenol (2-CP). For this purpose, two different PACs; thermally activated Norit SA4 and chemically activated Norit CA1, and their granular countertypes with similar physical characteristics, thermally activated Norit PKDA and chemically activated Norit CAgran, were used. The thermally activated carbons were better adsorbers for phenol and 2-CP compared with chemically activated carbons, but adsorption was more reversible in the latter case. 2-CP was adsorbed preferentially by each type of activated carbon, but adsorption of phenol was strongly suppressed in the presence of 2-CP. The simplified ideal adsorbed solution (SIAS) model underestimated the 2-CP loadings and overestimated the phenol loadings. However, the improved and modified forms of the SIAS model could better predict the competitive adsorption. The type of carbon activation was decisive in the application of these models. For each activated carbon type, phenol was desorbed more readily in the bi-solute case, but desorption of 2-CP was less compared with single-solute. This was attributed to higher energies of 2-CP adsorption.     

Partial Least-Squares Study of the Effects of Organic Modifier and Physicochemical Properties on the Retention of Some Thiazoles

JPC – Journal of Planar Chromatography – Modern TLC - Reversed-phase (RP) HPTLC with aqueous ammonia-organic modifier (acetonitrile, dioxane, acetone) mobile phases has been used to...     

Mechanism of the thermal decomposition of hydrophosphites of lithium,sodium and potassium

The thermal decomposition of some M ₂ ^I HPO₃ (M-Li, Na, K) phosphites under nitrogen atmosphere was investigated. A stepwise mechanism of thermal decomposition has been proposed.

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Zusammenfassung Es wurde die thermische Zersetzung von Phosphiten M ₂ ^I HPO₃ (M-Li, Na, K) in Stickstoffatmosphere untersucht. Die Schritte des Mechanismus der thermischen Zersetzung wurden vorgeschlagen.

     

Cadmium and zinc determination by neutron activation analysis and biochemical tests in tissues of workers professionally exposed to cadmium

Cadmium and zinc levels in urine, serum, hair obtained from workers professionally exposed to cadmium oxide dust and from a control, nonoccupationally exposed group were determined by neutron activation analysis. The study was completed by biochemical monitoring tests such as the ₂ (₂-MG) determination in urine and serum and the -aminolevulinic acid dehydratase (ALAD) determination in blood. Significantly increased levels of cadmium in urine, serum, and hair, ₂-MG in urine and serum, ALAD in blood and decreased levels of zinc in serum were found in the exposed group compared to the control group. The most distinct differences of the parameters studied were observed for cadmium in hair. Correlations among the parameters were preliminary evaluated, too. For quality assurance purposes, the cadmium and zinc concentrations were determined in biological (standard) reference materials NBS SRM-1577 Bovine Liver, Bowen's Kale, IAEA A-11 Milk Powder, and IAEA H-8 Horse Kidney.