Electric field gradient at the Hf site and the phase transition in HfV2

The electric quadrupole interaction at the Hf site in the cubic HfV₂ compound, which shows lattice instability when cooled below 120 K, has been studied using the 482 keV (5/2⁺) state in¹⁸¹Ta. The time differential perturbed angular correlation (TDPAC) studies involving (133+136)-482 keV - cascade at room temperature show that only a fraction of¹⁸¹Ta nuclei see a cubic symmetry while the remaining experience a weak, randomly oriented, electric quadrupole interaction described by a Gaussian frequency distribution with _Q=6.1±1.0 Mrad/sec and the relative width =0.5. There is a dramatic change in TDPAC pattern indicating a phase transition when the compound is cooled down to 77 K. At this temperature the quadrupole interaction frequency is found to be _Q=40.6±3.0 Mrad/sec with =0.35. The experimentally observed EFG both at the Hf and the V sites are compared to the theoretical estimates based on point charge model.     

Interaction of potassium hexacyanoferrate (II) with histidine

L-histidine substitutes cyano groups of K₄Fe (CN)₆ at pH 7·0 on irradiation with ultraviolet light. The reaction follows first order kinetics with reference to K₄Fe(CN)₆ and zero order with reference to histidine. The kinetic data shows the primary process to be aquation of Fe(CN) ₆ ^4? while the final product is formed through a rapid dark reaction of histidine with Fe(CN)₄ (H₂O) ₂ ^2? to give the product K₂Fe(CN)₂(histidine)₂. The final product has been subjected to chemical and infrared spectral analysis.     

Synthesis of chiral building blocks for cephalostatin analogues

The present paper describes the synthesis of 5‐azido‐6‐ketones (14) and 6‐hydroxy‐5‐ketone (20) from Hajos Wiechert ketone as chiral building blocks for cephalostatin analogues. The synthesis of symmetric cephalostatin analogue from 6‐hydroxy‐5‐ketone has also been reported. The characterization of the each synthesized compounds was carried out by IR, ¹H‐NMR, ¹³C‐NMR and High resolution Mass Spectrometry.     

Adsorption of phenanthrene on organoclays from distilled and saline water

Isotherms of phenanthrene adsorption on different organoclay complexes were obtained using the HPLC technique to understand the adsorption behavior and to characterize the effect of sodium chloride (NaCl) on the adsorption. The adsorbed amounts of phenanthrene on montmorillonite exchanged by organic cations such as tetraheptylammonium, benzyltrimethylammonium, hexadecyltrimethylammonium, or tetraphenylphosphonium were several times higher than those obtained using montmorillonite clay without surface modification. At the same equilibrium concentration, the adsorbed amount of phenanthrene is higher on clay modified with benzyltrimethylammonium than on clay modified with hexadecyltrimethylammonium or other cations. Adsorption of phenanthrene on clay modified with benzyltrimethylammonium increased dramatically as the concentration of NaCl increased up to 150 g/l in the aqueous solution. The shape of the curves obtained can be classified as S-type. The adsorption data obtained from salinity experiments support a mathematical model that links the Langmuir constant with the salinity constant. This model may be useful to predict the equilibrium concentration of a contaminant in saline solution. FTIR studies showed strong interactions between the aromatic rings of phenanthrene and the preadsorbed benzyltrimethylammonium on clay surfaces.     

Spectrophotometric determination of isonicotinic acid hydrazide

Summary Isonicotinic acid hydrazide reacts with 2,3,5-triphenyltetrazolium chloride in acidic medium in presence of excess of thallium(III) to give a pink-coloured formazan having maximum absorption at 480 nm. This colour reaction is used to determine isonicotinic acid hydrazide in urine and blood. The reaction is specific for isonicotinic acid hydrazide, and the visual limit of identification is1 g per ml.

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Zusammenfassung Isonikotinsäurehydrazid reagiert mit 2,3,5-Triphenyltetrazoliumchlorid in saurem Milieu bei Gegenwart von überschüssigem Thallium(III) unter Bildung eines rosa gefärbten Formazans mit dem Absorptionsmaximum bei 480 nm. Diese Farbreaktion wird zur Bestimmung von Isonikotinsäurehydrazid in Harn und Blut verwendet. Sie ist spezifisch. Ihre Erfassungsgrenze beträgt 1g/ml.

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Résumé L'hydrazide de l'acide isonicotinique réagit avec le chlorure de triphényl-2,3,5 tétrazolium, en milieu acide en présence d'un excès de thallium-III, en donnant un formazan coloré en rose dont le maximum d'absorption se situe à 480 nm. On utilise cette réaction colorée pour doser l'hydrazide de l'acide isonicotinique dans l'urine et dans le sang. La réaction est spécifique et la limite d'identification visuelle est de 1g par ml.

     

Charge-transfer photochemistry of bis(diethyl-diselenocarbamato)copper(II)

The photochemical reactions of bis(diethyl-diselenocarbamato)copper(II), Cu(Et2dsc)2, complex have been studied in toluene, CH2Cl2, CHCl3 and chloroalkane/EtOH mixed solvents. Charge-transfer irradiation induces intramolecular oxidation of the ligand and reduction of copper(II) to copper(I) as evidenced by EPR and UV-Vis spectra of the complex as well as quantum yield results. When photolysis is carried out in CHCl3 or CH2Cl2 or in the solvent mixture CHCl3/EtOH resp. CH2Cl2/EtOH of lower than 1:1 EtOH content, the primary photoproduct CuI(Et2dsc) is further oxidised in a dark reaction with the chloroalkane producing the corresponding paramagnetic mixed-ligand CuII(Et2dsc)Cl complex in equilibrium with its chloride-bridged and EPR silent, dimeric form Cu2(Et2dsc)2Cl2. At low concentration of EtOH the equilibrium is shifted to the dimeric form whereas at higher than 1:1 EtOH content in the mixed solvent CHCl3/EtOH it is shifted to CuII(Et2dsc)Cl. A reaction mechanism is proposed and the role of ethanol is discussed.     

PHOTOINDUCED DEGRADATION AND MODIFICATION OF PHOTOFRIN II IN CELLS in vitro

Abstract— Human cells of the line NHIK 3025 were incubated with Photofrin II (PII) and exposed to light. Fluorescence- and absorption spectra of PII in the cells were measured. Light exposure resulted in a degradation of PII in the cells and changes in the shape of the fluorescence spectra. These changes are probably partly due to a photochemical modification of PII and to a relocalization of PII in the cells. Notably, a destruction of binding sites for PII on or close to proteins was caused by the light exposure. The rate of the light-induced decay of the porphyrin fluorescence intensity was only slightly increasing with the PII concentration, indicating that each porphyrin molecule is mainly degraded by photoproducts originating from itself. On the other hand, the rate of the degradation of porphyrin binding sites on the proteins increased with increasing PII concentrations.
The excitation spectrum of PII in cells has a peak at285–290 nm attributed to energy transfer from proteins to porphyrins located close to the proteins. The intensity of this peak relative to the intensity of the Soret band increases with decreasing porphyrin concentrations. This might indicate that some of the binding sites close to proteins have a higher affinity for the porphyrin than binding sites at longer distances from the proteins.     

Triosmium clusters derived from the reactions of thioureas with dodecacarbonyltriosmium: Crystal structures of [Os3(CO)11{η 1-SC(NMe2)2}], [Os3(CO)9(μ-OH)(μ-OMeOCO){η 1-SC(NMe2)2}] and [(μ-H)Os3(CO)9{μ 3-NHC(S)NH2}]

The reaction of [Os₃(CO)₁₂] with tetramethylthiourea in the presence of a methanolic solution of Me₃NO·2H₂O at 60° yields the compounds [Os₃(CO)₁₁{η ¹-SC(NMe₂)₂}] (1) in 56% yield and [Os₃(CO)₉(μ-OH)(μ-MeOCO){η ¹-SC(NMe₂)₂}] (2) in 10% yield in which the tetramethylthiourea ligand is coordinatedvia the sulfur atom at an equatorial position. Compound2 is a 50 e^? cluster with two metal-metal bonds and the hydroxy and methoxycarbonyl ligands bridging the open metal-metal edge. In contrast, the analogous reaction of [Os₃(CO)₁₂] with thiourea gives the compounts [(μ-H)Os₃(CO)₁₀{μ-NHC(S)NH₂}] (3) in 8% yield and [(μ-H)Os₃(CO)₉{₃-NHC(S)NH₂}] (4) in 30% yield. In3, the thioureato ligand bridges two osmium atomsvia the sulfur atom, whereas in4 in addition to the sulfur bridge, one of the nitrogen atoms of thioureato moiety bonds to the remaining osmium atom. The decacarbonyl compounds 3 can also be obtained in 50% yield from the reaction of [Os₃(CO)₁₀(MeCN)₂] with thiourea at ambient temperature. Compound3 converts to4 (65%) photochemically. Compound1 reacts with PPh₃ and acetonitrile at ambient temperature to give the simple substitution products [Os₃(CO)₁₁(PPh₃)] and [Os₃(CO)₁₁(MeCN)], respectively, while with pyridine, the oxidative addition product [(μ-H)Os₃(CO)₁₀(μ-NC₅H₄] is formed at 80°C. All the new compounds are characterized by IR,¹-H-NMR and elemental analysis together with the X-ray crystal structures of1,2 and4. Compound1 crystallizes in the triclinic space group P $P\bar 1$ with unit cell parametersa = 8.626(3) Å,b = 11.639(3) Å,c = 12.568(3_ Å,α = 84.67(2)°,β = 75.36(2)°,γ = 79.49(3)°,V = 1199(1) ų, andZ = 2. Least-squares refinement of 4585 reflections gave a final agreement factor ofR = 0.0766 (R _w = 0.0823). Compound2 crystallizes in the monoclinic space group P2_1/n with unit cell parametersa = 9.149(5) Å,b = 17.483(5) Å,c = 15.094(4) Å,β = 91.75(2)°,V = 2413(2) ų, andZ = 4. Least-squares refinement of 3632 reflections gave a final agreement factor ofR = 0.0603 (R _w = 0.0802). Compound4 crystallizes in the monoclinic space group C2/c with unit cell parametersa = 13.915(7) Å,b = 14.718(6) Å,c = 17.109(6) Å,β = 100.44(3)°,V = 3446(5) ų, andZ = 8. Least-squares refinement of 2910 reflections gave a final agreement factor ofR = 0.0763 (R _w = 0.0863).     

Analysis of multiple pesticide residues in tobacco using pressurized liquid extraction, automated solid-phase extraction clean-up and gas chromatography-tandem mass spectrometry

A new method was developed for the analysis of pesticide residues in tobacco. The objective was to significantly increase the number of samples that can be processed by the laboratory and to enable the extension of the current coverage to additional pesticides. A new analytical approach was therefore defined based on two main axes, the automation of the sample preparation and the selectivity of the analyte detection using tandem mass spectrometry. This latter aspect reduces the stringency of the requirements placed on the clean-up of the extracts and on the chromatographic resolution when less selective detectors are used. The extraction of the analytes from the matrix is performed using the pressurized liquid extraction technique. Tobacco samples are extracted at elevated temperature and pressure (100 C and 100 atm; 1 atm = 101,325 Pa) using acetone as an extraction solvent. The resulting extract is then concentrated using a Vortex evaporator. Three different solid-phase extraction (SPE) procedures, adjusted to the chemical properties of the different active ingredients to be measured, are applied to the concentrated extract, thus leading to three extract fractions. The first fraction contains such main classes of active ingredients as organohalogenated and 2,6-dinitroaniline compounds while the second one collects the organophosphorus and acylalanines residues; these two fractions are analyzed by capillary gas chromatography coupled to tandem mass spectrometry using negative chemical ionization and electron impact ionization in the positive mode, respectively. The third extract fraction gathers the N-methylcarbamates residues which are analyzed by HPLC with post-column derivatization and fluorescence detection. The different sample preparation stages from extraction to SPE clean-up have been automated through the use of recent analytical technologies. In combination with the analysis by tandem mass spectrometry, this provided a potential for a high sample throughput.     

Synthesis and Structure Determination of Some New N‐Glycosides of 4,5‐Disubstituted‐1,2,4‐Triazole‐3‐Thiones

Some new N‐glycosides of 4‐(2‐phenylethyl)‐5‐pyridyl‐1,2,4‐triazole‐3‐thiones were synthesised by the coupling reaction of halo sugar with 4,5‐disubstituted 3H‐1,2,4‐triazole‐3‐thiones in the presence of mercuric cyanide and dry nitromethane as solvent, followed by deprotection using dry ammonia in methanol. All of the above compounds were fully characterized by means of infrared, ¹H NMR spectroscopy, mass spectroscopy and elemental analysis.