X-ray and IR spectroscopic studies of specific intermolecular interactions inN′-substituted isonicotinohydrazides

_N-Thenylidene- andN-(o-nitrobenzylidene)hydrazides of isonicotinic acid have been studied by X-ray structural analysis and IR spectroscopy. In the crystalline state, these molecules are linked through intermolecular N—H ... Np_y hydrogen bonds. Carbonyl groups are not involved in intermolecular hydrogen bonds. However, it was found that the C=O group participates in an attractive interaction with the sulfur atom of the thiophene group. The energy of this interaction is comparable with the energies of intermolecular C=O ... H—N hydrogen bonds in amides.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 896–900, April, 1996.     

Thermal Decomposition of Bi(III), Cd(II), Pb(II) and Cu(II) Thiocyanates

Thermal decomposition of Bi(SCN)₃, Cd(SCN)₂, Pb(SCN)₂ and Cu(SCN)₂ has been studied. The thermal analysis curves and the diffraction patterns of the solid intermediate and final products of the pyrolysis are presented. The gaseous products of the decomposition (SO₂ and CO₂) were detected and quantitatively determined. Thermal, X-ray and chemical analyses have been used to establish the nature of the reactions occurring at each stage in the decomposition.This revised version was published online in November 2005 with corrections to the Cover Date.     

Determination of acidic sites and binding toxic metal ions on cumin surface using nonideal competitive adsorption model

A fundamental study of the application of cumin biomass in the recovery of Cu and Zn metal ion uptake from food and drinks is carried out at different pH's and at fixed ionic strength. The chemical characteristics of protein in cumin seeds were investigated. Results showed that cumin contains 18.25% crude protein, which includes 18 amino acids. The main reactive groups on protein cumin are amino and carboxylic groups of dicarboxylic amino acids, leading to a pH-dependent charge. Therefore, the cumin surface is considered as a heterogeneous system. To describe protonation behavior in a heterogeneous cumin biomass (cumin/0.1 M NaNO(3)) system, acid-base titrations have been performed with conductometric and potentiometric titration. Measurement of the reactivity of cumin surface in the adsorption of Cu and Zn metal ions and determination of metal binding at different pH's were also carried out. To solve broad and ill-defined titration curves, a simplified version of nonideal competitive analysis (NICA) by Plette et al.) was applied. The results show that the sorption of the bivalent metal ions onto the whole surface of cumin could be attributed to a monodentate binding to one site mainly carboxylic-type site.     

Supercritical Propanol-Water Synthesis and Comprehensive Size Characterisation of Highly Crystalline anatase TiO2 Nanoparticles

Highly crystalline anatase TiO₂ nanoparticles have been synthesised in less than 1 min in a supercritical propanol-water mixture using a continuous flow reactor. The synthesis parameter space (T, P, concentration) has been explored and the average particle size can be accurately controlled within 10-18 nm with narrow size distributions (2-3 nm). At subcritical conditions amorphous products are obtained, whereas a broad range of T and P in the supercritical regime gives 11-14 nm particles. At high temperature and pressure, the particles size increase to 18 nm. The nanoparticles have been extensively characterised with powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) with excellent agreement on size and size distribution parameters. The SAXS analysis suggests disk-shaped particles with diameters that are approximately double the height. For comparison, a series of conventional autoclave sol-gel syntheses have been carried out. These also produce phase-pure anatase nanoparticles, but with much broader size distributions and at much longer synthesis times (hours). The study demonstrates that synthesis in supercritical fluids is a very promising method for manipulating the size and size distribution of nanoparticles, thus removing one of the key limitations in many applications of nanomaterials.     

Thermal decomposition of cobalt nitrato compounds: Preparation of anhydrous cobalt(II)nitrate and its characterisation by Infrared and Raman spectra

The thermal decomposition of Co(NO₃)₂·6H₂O (1) as well as that one of NO[Co(NO₃)₃] (Co(NO₃)₂·N₂O₄) (2) was followed by thermogravimetric (TG) measurements, X-ray recording and Raman and IR spectra. The stepwise decomposition reactions of 1 and 2 leading to anhydrous cobalt(II)nitrate (3) were established. In N₂ atmosphere, cobalt oxides are finally formed whereas in H₂/N₂ (10% H₂) cobalt metal is produced. Rapid heating of cobalt(II)nitrate hexahydrate causes melting (formation of a hydrate melt) and therefore side reactions in the hydrate melt by incoupled reactions and evolution/evaporation of different species as, e.g., HNO₃, NO₂, etc. In case of larger amounts in dense packing in the sample container, the formation of oxo(hydoxo)nitrates is possible at higher temperature. For 2, its thermal decomposition to 3 was followed and its decomposition mechanism is proposed.     

Qualitative evaluation of aromatic herbs by direct headspace GC analysis. Applications of the method and comparison with the traditional analysis of essential oils

GC headspace analyses of various aromatizing herbs have been compared with those relating to the essential oils, obtained by steam distillation, of the same plants. In this way it was possible to establish the most significant differences between the composition of a herb flavor and that of its essential oil. In particular, we observed some very volatile compounds in the headspace samples which were absent from the essential oil; these components may make an important contribution to the herb flavor. The identification of these substances is still in progress.     

Highly selective conversion of N-aroyl-α-dehydronaphthylalaninamides into 3,4-dihydrobenzoquinolinone derivatives via photoinduced intermolecular electron transfer

The irradiation of substituted (Z)-N-aroyl-α-dehydronaphthylalaninamides [(Z)-1] in methanol containing triethylamine (TEA) with Pyrex-filtered light was found to give 3,4-dihydrobenzoquinolinone derivatives (2) in high yields along with minor amounts of 4,5-dihydrooxazole derivatives (3). Analysis of the substituent effects on product composition revealed that both the photoreactivity of 1 and the selectivity of 2 are decreased with increasing electron-withdrawing ability of the substituent introduced at the para-position on the N-benzoyl benzene ring. From the analysis of the dependence of the quantum yield for the formation of 2 on the TEA concentration, it was found that back electron transfer occurs efficiently within an (E)-1 anion radical-TEA cation radical pair intermediate.     

A Sensitive Spectrophotometric Determination of Nitrite in Water and Soil

A highly sensitive spectrophotometric method for the determination of nitrite in water and soil has been developed. The reaction of nitrite with acidified potassium iodide to liberate iodine which oxidizes leuco‐crystal violet (LCV) to form crystal violet having absorption maxima at 590 nm forms the bases of this method. In aqueous medium the system obeys Beer's law in the range of 0.1 to 1.0 μg per 25 mL (0.004–0.04 ppm), while in an extractive system the range is 0.025–0.25 μg in 100 mL (0.00025–0.0025 ppm). The molar absorptivity and Sandell's sensitivity were found to be 1.54 × 10⁶ 1 mol^?1 cm^?1 and 44 pg cm^?2, respectively.     

2-Trif luoromethyl-4H-thiochromen-4-one and 2-trif luoromethyl-4H-thiochromene-4-thione: Synthesis and reactivities

2-Trifluoromethyl-4H-thiochromene-4-thione obtained from 2-trifluoromethyl-4H-thiochromen-4-one and P₂S₅ reacts with aromatic amines, hydrazine hydrate, phenylhydrazine, and hydroxylamine at the C(4) atom of the chromene ring to give the corresponding anils, azine, hydrazones, and oxime of thiochromone. 2-Trifluoromethyl-4H-thiochromen-4-one is oxidized by hydrogen peroxide in AcOH into 4-oxo-2-trifluoromethyl-4H-thiochromene 1,1-dioxide and reduced by NaBH₄ to 2-trifluoromethyl-4H-thiochromen-4-ol or cis-2-(trifluoromethyl)thiochroman-4-ol. When treated with hydrazine hydrate, thiochromen-4-one gives 3(5)-(2-mercaptophenyl)-5(3)-trifluoromethylpyrazole. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 504–509, March, 2006.