Solubilities, in deuterium oxide

Clarke, E.C.W. and D.N. Glew (1971), Aqueous nonelectrolyte solutions, Part VIII. Deuterium and hydrogen sulfides solubilities in deuterium oxide and water, Can. J. Chem., 49, 691-698. Corsi, R.L., S. Birkett, H. Melcer, and J. Bell (1995), Control of VOC emissions from sewers A multi-parameter assessment, Water Sci. Tech, 31(7), 147-157. 

Part VIII. Deuterium and Hydrogen Sulfides Solubilities in Deuterium Oxide and Water," Can. J. Chem., 1971, 49, 691-98. 

The resolution of the spectra of dextrans having low solubility in deuterium oxide might, conceivably, be improved by recording the spectra in sodium deuteroxide, or deuterated metbyl sulfoxide. Com-... 

Ketoconazole 68 is a potent, orally active, broad-spectrum antifungal agent. It is marketed as a racemic mixture of the cis-(2S,4R)- and c/5 -(2R,45()-enantiomers. A method for determining the enantiomeric purity of 68 in deuterium oxide using (3-cyclodextrin has been developed. Enantiomeric discrimination is observed in many resonances in the H and NMR spectrum. (+)-L-tartaric acid is added to the solution to form a salt with 68 that facilitates its solubility in deuterium oxide. 

The spectrum of a compound containing rapidly exchangeable protons can be simplified, and the exchangeable proton absorption removed, simply by shaking the solution with excess deuterium oxide or by obtaining a spectrum in deuterium oxide solution if the compound is soluble. A peak resulting from HOD will appear, gen-... 

Ramette, R.W. and Spencer, J.B. Electrolyte effects on silver bromate solubility in protium and deuterium oxide solutions at 25 °. Evidence for association of silver and nitrate ions, J. Am. Chem. Soc., 67(4) 944-946, 1963. 

This material has several advantages it is chemically inert, symmetrical, volatile (bp 27°C), and soluble in most organic solvents it gives a single, intense, sharp, absorption peak, and its protons are more shielded than almost all organic protons. When water or deuterium oxide is the solvent, TMS can be used as an external reference in a concentric capillary or the methyl protons of the water-soluble sodium 2, 2-dimethyl-2-silapentane-5-sulfonate (DSS), (CH3)3SiCH2CH2CH2S03Na, are used as an internal reference (0.015 ppm). 

For samples of low polarity, carbon tetrachloride, deuterated chloroform, CDClj and deuterated benzene C D, are often used. On the other hand if the sample is soluble only in polar solvents, deuterium oxide (D O), acetone -(CDjCOCDj), or dimethyl sulfoxide - [(003)280] are often employed. 

Deuterium oxide (D2O) alone or mixed with DMSO-dfi is suitable for dissolving lignosulfonates (Hassi 1984) that are not completely soluble in any other solvents. 

The NMR analysis of this compound was extremely challenging both experimentally and in data interpretation. Only 3 mg of sample were available, which was low given the relatively high molecular weight. Sample concentration was further limited by very poor solubility. The final solvent chosen was deuterium oxide, doped with a small amount of sodium hydroxide to adjust the pH to a more basic environment. The use of a protic solvent eliminated the ability to detect labile protons, including what proved to be a critical N-H group involved in a newly formed molecular bridge. The parent... 

LC/MS of the isolated impurity indicated the presence of two peaks, corresponding to a dimer-like degradant and the parent drug. A full set of NMR experiments was performed to elucidate the structure. Despite having an adequate amount of sample, sensitivity was limited by low solubility. Deuterium oxide as the solvent eliminated the ability to detect exchangeable protons, although this was not deemed to be a significant limitation for this structural elucidation. The NMR analysis confirmed that there were two primary components present in a ratio of approximately 2.5 to 1,... 

The chemical properties of deuterium oxide do not differ greatly from the chemical properties of H2 0. However, its reactivity is generally lower, and the reactions are usually slower similarly to H2 0, it reacts with a number of compounds. For example, the reaction with respective anhydrides gives a heavy sulphuric acid (D2SO4) and phosphoric acid (D3PO4). From the chemical viewpoint the differences in the solubility of isotope compounds are of great importance. The solubility of some inorganic compounds in pure and heavy waters are shown in Table 3.2 [2]. 

Fig. 12.25. The infrared spectra of the deoxynucleo-sides with and without addition of copperfll). Deuterium oxide solutions contained 0.015M deoxy-nucleosides, in the case of the less soluble dG, only 0.0075M. Matched cells of fluorite and of a thickness of 0.005cm were used. The curves I, III, V, and VII are the infrared spectra of the deoxynucleosides dT, dA, dG, and dC, respectively. The curves II, IV, VI, and VIII are the corresponding infrared spectra of the deoxynucleotides with addition of approximately 20 moles CUSO4 per mole of deoxynucleosides. The distance between the index lines on the ordinate corresponds to a change of absorbance of 4%. For greater clarity the spectra are shifted against one another in the ordinate direction. The spectral slit-width was 15 cm . (Fritzsche and Zimmer, 1968.)...

Cosgrove BA, WalMey J (1981) Solubilities of gases in water and deuterium oxide. J Chromatogr 216 161-167... 

Woessner DE (1964) Molecular reorientation in liquids. Deuteron quadrupole relaxation in liquid deuterium oxide and perdeuterobenzene. J Chem Phys 40 2341-2348 Xenides D, Randolf BR, Rode BM (2006) Hydrogen bonding in liquid water an ab initio QM/MM MD simulation study. J Mol Liquids 123 61-67 Yalkowsky SH, Baneijee S (1992) Aqueous solubility. Dekker, New York Yalkowsky SH, Valvani SC (1980) Solubility and partitioning I solubility of nonelectrolytes in water. J Pharm Sci 69 912-922... 

Effect of Impurities on the Critical Solution Temperature. The addition of even a small amount of a third component to a two-liquid system will ordinarily alter the C.S.T. considerably. Thus, for example, the addition of 0.2 per cent of water to glacial acetic acid raises the C.S.T. with cyclohexane from 4.2 to approximately 8.2 C. Useful methods of analysis have been devised based on such observations. For example, the amount of deuterium oxide in water can be estimated by measuring the C.S.T. with phenol and the aromatic hydrocarbon content of petroleum fractions by the C.S.T. with aniline. In general, the C.S.T. will be raised if the added component is highly soluble in only one of the original components (salting out) and lowered if it is highly soluble in both. Such systems properly must be considered as three-component mixtures, however. 

All modern NMR spectrometers operate in the pulsed Fourier transform (FT) mode for technical reasons, this means that deuterated solvents must be used. Deuterochloroform, CDCI3, is the most common such solvent, although a number of other, albeit generally more expensive, solvents such as acetone-d, (CDj)2CO, dimethyl sulfoxide-d, CD3SOCD3, and benzene-d, C D are also available. Deuterium oxide, D2O, may be used if the sample is water-soluble. 

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