Thermodynamic parameters for the molecular inclusion reaction of dulcin with beta-cyclodextrin. spectrofluorimetric determination of dulcin

The inclusion of dulcin in alpha- and beta-cyclodextrin has been studied by fluorescence spectroscopy. To quantitatively describe complex formation between the beta-cyclodextrin and dulcin, an association constant of 290 M(-1) at 21 degrees was obtained. The thermodynamics associated with the complex formation between dulcin and beta-cyclodextrin in aqueous solution has been studied. The obtained value of DeltaG(0) = -13.7 kJ/mole at 21 degrees , together with DeltaH(0) = -33.6 +/- 2.3 kJ/mole and DeltaS(0) = -67.2 +/-8.3 Jmole(-1) K(-1) indicate that dulcin has a very marked tendency to associate with beta-cyclodextrin in water. The inclusion complex of dulcin in beta-cyclodextrin has been used to determine dulein in the range 0.13-5 mug/ml the method has been applied to determine dulcin in soft drinks.     

Evaluation of the thermochemical changes in agricultural by-products and in the carbon adsorbents obtained from them

The thermochemical decomposition of waste products from a coconut (Cocos nucifera L.), a nut (Juglans regia L.) an apricot (Armeniaca vulgaris L.), an almond (Amygdalus communis L.var amara DC.), a grape (Vitis vinifera L.) and a cherry (Prunus avium L.), as raw materials for producing carbon adsorbents, was investigated by DTA and TG. The thermo-oxidative and decomposition processes resulting in increased number of oxygen-containing functional groups of phenolic and carbonyl type are responsible for the high adsorption capacities of the carbon adsorbents. The thermochemical changes in adsorbents based on agricultural wastes are similar to those in commercial activated carbons. The adsorbents derived from apricot stones have the highest overall thermal stability.     

Experimental and computational studies of intracomplex reactions in Mg+(primary, secondary alkylamine) complexes induced by photoexcitation of Mg+

We report herein a comprehensive study of photoinduced reactions in complexes of Mg+ with primary (n-propyl- and isopropylamine) and secondary amines (dipropyl- and diisopropylamine) in the spectral range of 230-440 nm. Similar to the methyl- and ethylamine complexes studied previously, N-H bond activation of these complexes is very unfavorable. Instead, the C(alpha)-C, C-N, and C(alpha)-H bond-cleavage photoproducts are observed after photoexcitation of the Mg+ complexes (3(2)P<--3(2)S). For Mg+(primary amine) complexes, for example, Mg+-NH2CH2CH2CH3, and Mg+-NH2CH(CH3)2, the photoproducts resulting from C(alpha)--C rupture prevail after P(z) and charge-transfer excitations, whereas the Mg+ photofragment is predominant upon P(x,y) excitation. However, with further N-alkyl substitution, as in Mg+(secondary amine) complexes, for example, Mg+-NH(CH2CH2CH3)2 and Mg+-NH[CH(CH3)2]2, a novel intracomplex C-C coupling photoreaction dominates on P(x,y) excitation of Mg+, which is believed to arise from Mg+* insertion into the C-N bond. With P(z) and charge-transfer excitation, the Mg-R elimination photoproducts, arising from C(alpha)-C bond cleavage, predominate. The energetics and possible mechanisms of the intracomplex photoreactions are analyzed in detail with the help of extensive quantum mechanics calculations.     

Stereoisomerism of N-(1-Propenyl)thiobenzamide

A prototropic rearrangement of N-prop-2-enylbenzocarbothioamide afforded two stereoisomeric N-prop-1-enylbenzocarbothioamides (IIa, b) isolated as individual compounds. The stereoisomerism is due to hindered rotation around thioamide bond C(S)-N and also to -diastereoisomerism. The configuration of the isolated isomers was investigated by IR spectroscopy, AM1 and PM3 methods. In the molecules occurs the p,-conjugation with participation of nitrogen atom and multiple bonds resulting in formation of a united delocalized MO in the planar fragment C(S)-NC = C.     

Infrared spectra of negative ions with a strong,symmetric hydrogen bond (HO...H...OH)− and (H3CO...H...OCH3)−

From the multiple attenuated total internal reflection (MATIR) infrared spectrum of an aqueous KOH solution, the spectrum of the (HO)₂H^– ion, formed by a strong, symmetric H-bond, has been segregated. The spectrum of the analogous ion (CH₃O)₂H^– has been segregated from the MATIR infrared spectrum of a solution of KOCH₃ in methanol. The segregated spectra contain large numbers of individual bands that are not present in the spectra of the original components of the solution. This may be a consequence of strong interaction of vibrations of the proton in the central strong, symmetric hydrogen bond with vibrations of other groups in the ion.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1363–1366, June, 1991.     

HPLC Determination of some antibilharzial antimonials by extraction of antimony

The antimonial drug (antimony potassium tartrate, antimony piperazine tartrate or antimony lithium thiomaleate) in aqueous solution or biological fluid is treated with sodium diethyldithiocarbamate in the presence of a suitable masking reagent, the pH is adjusted to 9 +/- 0.5. and the antimony complex extracted with n-hexane and determined by reversed-phase HPLC with an ODS column and detection at 254 nm. The limits of detection are 20 ng (for antimony potassium tartrate and antimony lithium thiomaleate) and 16 ng (for antimony piperazine tartrate).     

Meroterpenoids—III : Psoralea corylifolia linn.—3. Synthesis of (±)-bakuchiol methyl ether

A synthesis of (±)-bakuchiol methyl ether, involving Claisen rearrangement of geranyl vinyl ether as the key step, is described. Further thermal reorganisation of the intermediate 3-vinyl-citronellal is discussed.     

Selective complexometric determination of palladium, with thiourea as masking agent

A method is proposed for selective complexometric determination of palladium, thiourea being used as masking agent. An excess of EDTA is added and the surplus EDTA is back-titrated at pH 5-5.5 with lead nitrate, with Xylenol Orange as indicator. Thiourea is then added to decompose the palladium-EDTA complex and the liberated EDTA is again back-titrated with lead nitrate. The interference of various cations has been studied.     

Rapid chemical separation procedures

Fast, discontinuous separation procedures are described for zirconium, niobium, technetium and antimony from fission products. Other rapid separation methods from aqueous solutions are summarized. The combination of a gas jet recoil transport system with a continuous solvent extraction technique and with a thermochromatographic separation method is presented. The application of such procedures to the investigation of new and already known short-lived nuclides is illustrated by some examples.     

Multielement determination in tobacco leaves by photon activation analysis

A nondestructive photon activation procedure with 30 MeV bremsstrahlung followed by high-resolution gamma-spectrometry has been applied to the multielement determination in tobacco leaves and commercial cigarettes. The elements determined by this method included essential minor elements such as Ca, Cl, K and Mg, essential trace elements such as Fe, Mn and Zn, and possibly toxic elements such As and Sb. The NBS Orchard Leaves could successfully be used as a comparative standard. The method is quite simple and gives good reproducible results for at least 12 elements.