Mass-spectrometric studies on alkylated 6-thiopurines

6-Thiopurine and its N- or C-alkyl derivatives all form an [M – 1]-ion upon fragmentation. In the 7-alkyl derivatives, this ion represents the major component of the spectrum. This is ascribed to formation of a five-membered thiazoline-like ring. Similar ring formation stabilises the [M – 1]-ion in the 7-methyl derivatives of hypoxanthine, adenine and 6-selenopurine.     

Aqueous solutions—A new perspective. Amorphous carbohydrates: Science and application technology

At a recent meeting of the International Symposium on Solution Chemistry I presented a paper dealing with aqueous solutions in which water was present not in excess but as one component of a supersaturated solution with polyhydroxy compounds. In response to a request from the Editor of this Journal I have submitted this article in which I outline my general interest in the subject and its importance as a new direction for solution chemists.     

Radiochemical solvent extraction of Au(III) using thionalide in ethyl methyl ketone/iso buthyl methyl ketone

A radiochemical method for the determination of gold using¹⁹⁸Au, has been developed. It is based on the synergistic extraction of Au(III) with thionalide (TA) in ethyl methyl ketone (EMK) or isobuthyl methyl ketone (IBMK) at pH 5.0.Effect of various parameters such as pH, nature of solvent and interferences due to other radionuclides have been studied. The method can be used up to 25 ng of Au.     

Radiochemical solvent extraction of Mn(II) using54Mn tracer

A radiochemical solvent extraction method has been developed for the determination of Mn(II) using⁵⁴Mn tracer. Mn(II) is complexed with 2-thenoyltrifluoroacetone (TTA) at pH 8.5 and extracted in isobutyl methyl ketone (IBMK). Different parameters affecting the extraction, and interferences due to diverse ions have been studied. The method can be used for the determination of Mn in microgram amounts.     

Formation and stability of N-heterocyclic carbenes in water: the carbon acid pKa of imidazolium cations in aqueous solution

We report second-order rate constants kDO (M-1 s-1) for exchange for deuterium of the C(2)-proton of a series of simple imidazolium cations to give the corresponding singlet imidazol-2-yl carbenes in D2O at 25 degrees C and I = 1.0 (KCl). Evidence is presented that the reverse protonation of imidazol-2-yl carbenes by solvent water is limited by solvent reorganization and occurs with a rate constant of kHOH = kreorg = 10(11) s-1. The data were used to calculate reliable carbon acid pK(a)s for ionization of imidazolium cations at C(2) to give the corresponding singlet imidazol-2-yl carbenes in water: pKa = 23.8 for the imidazolium cation, pKa = 23.0 for the 1,3-dimethylimidazolium cation, pKa = 21.6 for the 1,3-dimethylbenzimidazolium cation, and pKa = 21.2 for the 1,3-bis-((S)-1-phenylethyl)benzimidazolium cation. The data also provide the thermodynamic driving force for a 1,2-hydrogen shift at a singlet carbene: K12 = 5 x 10(16) for rearrangement of the parent imidazol-2-yl carbene to give neutral imidazole in water at 298 K, which corresponds to a favorable Gibbs free energy change of 23 kcal/mol. We present a simple rationale for the observed substituent effects on the thermodynamic stability of N-heterocyclic carbenes relative to a variety of neutral and cationic derivatives that emphasizes the importance of the choice of reference reaction when assessing the stability of N-heterocyclic carbenes.     

Neutron activation analysis of geological and biological samples using short-term reactor irradiation and successive counting

Short-term reactor irradiation followed by successive counting over long periods has been used for the nondestructive determination of more the 20 elements in geological and biological samples. The samples, along with USGS standards and NBS SRMs, were irradiated for 5 m, 10 m, 15 m, 1 h, 2.5 h, and 10 h, followed by counting on a Ge/Li/ gamma-ray spectrometer. The technique has been employed for the determination of several major, minor, and trace constituents in geological, biological and environmental samples.     

A comparative study of trace elements in water from various sources in surrounding areas of Nagpur city (India) by instrumental neutron activation analysis

Instrumental neutron activation analysis (INAA) has been used for the determination of 27 elements (Ag, Au, Ba, Br, Ce, Co, Cr, Cs, Eu, Fe, Ga, Hg, Hf, K, La, Mn, Na, Sb, Sc, Se Sr, Th, P, Ta, Tb, Zn and Zr) in 15 water samples collected from different sources (reservoirs, well, borewell, sewage tank, river, rain) in and around Nagpur city (central India) including doubly distilled and a sea water sample from Bombay. Sample residues after evaporation were irradiated at a thermal neutron flux of 10¹²–10¹³ n·cm^–2·s^–1 for 10 min, 1d and 1wk and counted using a HPGe detector and an 4k MCA at different intervals. Several environmental standards from NIST (USA), NIES (Japan) and USGS rock were also analysed for quality assurance. Wide variations in elemental concentrations have been observed in water samples from different sources. Most elemental concentrations in drinking water from various sources, are within ISI/WHO limits. Sea water showed very high concentrations of Ba, Cr, Co, Fe, Hg, Sb, Se and Zn. For doubly distilled and rain waters, however, very low elemental concentrations of Ba, Ce, Fe, Sc, Hg, Se, Sr and Th were observed.     

Elemental composition studies of fugitive and ambient air dust particulates from a thermal power station by instrumental neutron activation analysis

In order to assess the source of pollutants and the atmosphere quality in and around a thermal power plant, fugitive dust particulates from seven different locations and ambient air dust from six locations have been analyzed for 32 elements (As, Au, Ba, Br, Ce, Cl, Co, Cr, Cs, Cu, Eu, Fe, Ga, Hg, Hf, K, La, Lu, Mg, Mn, Na, P, Rb, Sb, Sc, Se, Ta, Tb, Te, Th, W and Yb) by employing instrumental neutron activation analysis (INAA). The method involves the irradiation of samples and comparator standards in a thermal neutron flux range of 10¹²–10¹³ n·cm^–2·s^–1 in a nuclear reactor for 10 min and 1 day followed by high resolution -spectrometry. Wide differences have been observed in the mean elemental concentrations of Fe, Co, Br, Mn, As, P. Ba and Cu in fugitive and ambient dust particulates coliected from these different locations. Further, a comparison of the elemental contents of the dust particulates from the plant with environmental standards (Urban Particulate Matter, Coal Fly Ash, Vehicle Exhaust and Coal) show significantly lower or comparable amounts of toxic and pollutant elements in the environmental samples.     

Low power upconversion using MLCT sensitizers

Selective low energy excitation of the metal-to-ligand charge transfer (MLCT) transition in [Ru(dmb)(3)](2+)(dmb = 4,4'-dimethyl-2,2'-bipyridine) in the presence of anthracene or 9,10-diphenylanthracene yields easily visualized upconverted singlet fluorescence resulting from triplet-triplet annihilation at low excitation power.     

Aporphines 24. The synthesis of N-alkylderivatives of bulbocapnine and isoeorydine

The synthesis of three new racemic aporphine alkaloids ( 1b, 1c and 2 ) is reported and these alkaloids are fully characterized. The method of synthesis involved either a Bischler-Napieralski-Psehorr sequence or a Reissert alkylation-Pschorr cyclization route. The Pschorr cyclization also gave the morphinandienones 7a and 7b , respectively.