Peak area determination and energy dependence of gamma- and X-ray peak tailing

Two analytical shape functions representing the shapes of - and characteristic X-ray photopeak sides obtained with a Ge(Li) detector are described. The photopeak centroid is accurately determined by using these functions. Energy dependence of photopeak tailing at the lower energy side of the photopeaks are obtained by the least-squares fitting method. The present method can be used for the analysis of partly overlapped photopeaks, one side of which is well resolved, with a sufficient accuracy.     

Measurement of L&agr; and Lß X-ray fluorescence cross sections in Er, Ta, W and Au by 16.896–59.543 keV photons

La and Lb X-ray fluorescence cross sections in Er, Ta, W and Au at excitation energies of 16.896, 22.581, 25.770, 32.890, 38.184, 43.949, 50.214 and 59.5 keV were investigated. Measurements were made using a low energy Si(Li) detector coupled to a model 4096 computerized multi-channel analyser. The experimental results were compared with the theoretically calculated values of L X-rays fluorescence cross sections and other experimental results. Good agreement was observed between experimental and theoretical values.     

Quantum calculations of vibrational harmonic energy transfer in collinear collisions of X2Y2 + A and X2Y2 + A2

Quantum calculations of translational-vibrational energy transfer in atom-four-atom and diatom-four-atom collinear collisions are reported. Energy transfer shows a strong dependence on the reduced mass of the collision system and on whether the incoming particle is an atom or a molecule. Atom-molecule collisions are more efficient for energy transfer purposes.     

Thermosensitive mucoadhesive gel formulation loaded with 5-Fu: cyclodextrin complex for HPV-induced cervical cancer

Human Papilloma Virus (HPV) infections are the major cause of cervical cancers. To achieve a better therapeutic efficacy and patient compliance in the treatment for HPV-induced cervical cancers, anticancer agent 5-fluorouracil has been formulated in a vaginal gel using the thermosensitive polymer Pluronic^® F127 together with alternative mucoadhesive polymers e.g., hyaluronic acid, Carbopol 934 and hydroxypropylmethylcellulose. To increase its aqueous solubility and to achieve the complete release of 5-FU from the gel, the drug was incorporated as its inclusion complex with 1:1 molar ratio with either β-cyclodextrin or hydroxypropyl-β-cyclodextrin. Following the characterization of drug:CD complexes, thermosensitive gel formulations containing different mucoadhesive polymers and the drug in free or complexed form were characterized in vitro by determining the gelation temperature and the rheological behavior of different formulations along with the in vitro release profiles of these formulations in pH 5.5 citrate buffer. It was observed that complexation with cyclodextrin accelerated the release of 5-FU with the exception of formulation containing Carbopol 934 as mucoadhesive polymer. As far as rheological properties are concerned, favorable thermosensitive in situ gelling properties were obtained with formulations containing HPMC as mucoadhesive polymer. Complete release of 5-FU from gels were obtained with both complexes of β-CD and HP-β-CD and cytotoxicity studies against HeLa human cervical carcinoma cells demonstrated that 1% 5-FU:CD complexes were equally effective as 1% free 5-FU indicating better therapeutic efficacy with lower dose.     

Metallophthalocyanines with rod-shaped substituents

4-(4′-Dioctylaminocarbonylbiphenyloxy) phthalonitrile was synthesized from 4-(4′-carboxybiphenyloxy)phthalonitrile and dioctylamine in the presence of Et₃N. Metallophthalocyanines (Zn, Co and Cu) substituted with four dioctylaminocarbonyl biphenyloxy groups on the peripheral positions were prepared from 4-(4′-dioctylaminocarbonylbiphenyloxy)phthalonitrile and the corresponding divalent metal salts (Zn(CH₃COO)₂, CoCl₂ and CuCl₂). The new phthalocyanines are soluble in common organic solvents. These compounds were characterised by ¹H-NMR, ¹³C-NMR, FT-IR, UV-Vis and mass spectroscopies.     

New liquid chromatographic-chemometric approach for the determination of sunset yellow and tartrazine in commercial preparation

A new liquid chromatographic (LC)-chemometric approach was developed for the determination of sunset yellow (SUN) and tartrazine (TAR) in commercial preparations. This approach uses LC and chemometric calibration methods, i.e., classical least-squares (CLS), principal component regression (PCR), and partial-least squares (PLS), simultaneously. The combined LC-chemometric approaches, denoted as LC-CLS, LC-PCR, and LC-PLS, are based on photodiode array (PDA) detection at multiple wavelengths. Optimum chromatographic separation of SUN and TAR with allura red as the internal standard (IS) was obtained by using a Waters Symmetry C18 column, 5 microm, 4.6 x 250 mm, and 0.2 M acetate buffer (pH 5)-acetonitrile-methano-bidistilled water (55 + 20 + 15 + 10, v/v) as the mobile phase at a flow rate of 1.9 mL/min. The LC data sets consisting of the ratios of analyte peak areas to the IS peak area were obtained by using PDA detection at 5 wavelengths (465, 470, 475, 480, and 485 nm). LC-chemometric calibrations for SUN and TAR were separately constructed by using the relationship between the peak-area ratio and the training sets for each colorant. LC-chemometric approaches were tested for different synthetic mixtures containing SUN and TAR in the presence of the IS. These LC-chemometric calibrations were applied to a commercial preparation of the 2 colorants. The experimental results of the LC-chemometric approaches were compared with those obtained by a developed classical LC method using single-wavelength detection.     

Thermal oxidation of cellulose investigated by chemiluminescence. The effect of magnesium and calcium carbonates and of different pHs

Whatman cellulose impregnated with calcium and magnesium carbonates was oxidized and chemiluminescence accompanying this oxidation has been measured. It was shown that magnesium ions in deacidified cellulose pulp promote the light emission significantly. On the other hand, acid papers give the more pronounced light signals at temperatures close to ambient. The relation between chemiluminescence runs and paper degradation has been implicated, with an attempt to extrapolate half-lives of paper samples to conditions close to ambient. To cite this article: J. Rychlý et al., C. R. Chimie 9 (2006).     

Synthese von 4H-Pyrano[2,3-d]pyrimidinen

Summary Good yields of substituted 5-(5R-2-furyl)-4H-pyrano[2,3-d]pyrimidines4 were obtained in the reaction of 2-ethoxymethyleneamino-3-cyano-4H-pyranes2 with ammonia. Compounds2 were prepared by the condensation of the starting 2-amino-5-acetyl-3-cyano-6-methyl-4H-pyranes1 with ethyl orthoformate. Spectral properties of the bicyclic system4 in relation to compounds3 are discussed.

     

Die Reduktion von Ammoniumpolyuranat zu Urandioxid

Zusammenfassung Es werden die Resultate des isothermen Zerfalles und der Reduktion vonstandardisiertem Ammoniumpolyuranat im Bereich von 285 bis 463° C (in Wasserstoff) wiedergegeben. Der Zerfall zu UO₃ wurde schon bei einer Temp. unter 290° C festgestellt, diese Phase blieb jedoch darauf stabil bis 320° C. Zwischen 320° C und 380° C verläuft die Reduktion zu U₃O₈, über 380° C aber zu UO₂. Die Aktivierungsenergien bei der Reduktion von UO₃ zu U₃O₈ und von U₃O₈ zu UO₂ wurden berechnet, und zwar 32,2 kcal/g-mol und 41,7 kcal/g-mol. Die Ergebnisse können mit den Literaturangaben für die Reduktion der einzelnen Phasen UO₃ und U₃O₈ verglichen werden. Die beobachteten Unterschiede weisen auf den Einfluß der Aktivität der Präparate hin.

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The isothermal decomposition and reduction of ammonium polyuranate (ADU) was investigated in the temperature interval 285–463° C in hydrogen. The formation of UO₃ was noticed below 290° C and this product was stable up to 320° C. U₃O₈ was stable from this temperature on up to 380° C, where the reduction to UO₂ was observed. The activation energies 32,2 Kcal/mole and 41.7 Kcal/mole were calculated for the reduction of UO₃ to U₃O₈ and for the reduction of U₃O₈ to UO₂, respectively. The results are comparable with the published data on reduction of separate phases UO₃ and U₃O₈. Some differences noticed show the influence of the activities of the products.

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Mit 4 Abbildungen     

Microwave-promoted cross-coupling of acid chlorides with arylboronic acids: a convenient method for preparing aromatic ketones

Simple catalytic systems for cross-coupling reactions of acyl chlorides with arylboronic acids under microwave conditions were tested. Microwave irradiation facilitated the reaction course. Mild reaction conditions afford the symmetrical and unsymmetrical aryl ketones in reasonable to high yields within a short time. A wide range of substrates bearing an electron-donating or an electron-withdrawing substituent on aryl ring of acid chloride as well as on boronic acid were examined and high yields of ketones were produced.