Molecular orbital calculations on the conformation of nucleic acids and their constituents

The conformational properties of the furanose ring of purine- and pyrimidine--nucleosides and-nucleotides are studied quantum-mechanically with the help of the PCILO method, using the pseudorotational concept. The computations point to the existence of two stable conformational zones centered around the C(3)-endo and C(2)-endo conformations which in the isolated furanose ring are separated by barriers of the order of 4 kcal/mole. In nucleosides one of the barriers (the one running through the O(1)-exo-C(2)-exo path) becomes very high. A detailed study is made of the relation between the phase angle of pseudorotation, P, and the torsion angle about the glycosyl bond, _CN. A very satisfactory agreement with the available experimental data is observed.

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Zusammenfassung Die Konformationseigenschaften des Furanoserings in -Nucleosiden und Nucleotiden von Purin und Pyrimidin werden nach der PCILO-Methode unter Berücksichtigung der pseudorotatorischen Betrachtungsweise studiert. Die Rechnung läßt auf die Existenz zweier stabiler Konformationszonen schließen, die in der Umgebung der C(2)-endo und der C(3)-endo Konformationen liegen, und die im isolierten Furanosering durch Energiebarrieren der Größenordnung von 4 kcal/mol voneinander getrennt sind. In Nucleosiden wird eine der Barrieren (die durch den Weg O(1)-exo-C(2)-exo gekennzeichnete) sehr hoch. Die Relation zwischen dem Phasenwinkel der Pseudorotation, P, und dem Drehwinkel um die Glycosylbindung, _CN, wird einer eingehenden Untersuchung unterworfen. Man beobachtet eine sehr zufriedenstellende Übereinstimmung mit den verfügbaren experimentellen Daten.

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Résumé Les propriétés conformationnelles du noyau furanose des -nucleosides et nucleotides des purines et pyrimidines sont étudiées par la méthode PCILO en faisant appel au concept de la pseudorotation. Les calculs indiquent l'existence de deux zones de conformations stables, centrées autour des conformations C(2)-endo et C(3)-endo, qui sont dans le sucre isolé séparées par des barrières de l'ordre de 4 kcal/mole. Dans les nucleosides, l'une de ces barrières (celle qui passe par le chemin O(1)-exo-C(2)-exo) devient très élevée. Une étude détaillée est effectuée sur la relation entre l'angle de phase de la pseudorotation P et l'angle de torsion autour de la liaison glycosylique, _CN. Un excellent accord avec les données expérimentales disponibles est observé.

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This research was supported by the R.C.P. 173 and the A.T.P. A 655-2303 of the C.N.R.S.     

Arsenite oxidation and arsenate determination by the molybdene blue method

Based on the similarity in properties of arsenate and phosphate, the colorimetric method using the molybdene blue complex was tested in order to determine low As(V) concentration in waters. The influence of complex formation time, daylight, temperature and competitive anions (silicate and sulphate) upon complex formation was determined. Optimal complex formation was reached in 1 h at 20±1 °C and was slightly favoured when developed in daylight. The formation rate declined with decreasing reaction temperature and no influence of any of the competitive anions tested (at concentrations usually found in natural waters of granitic areas) was noted. The detection limit of this method was 20 μg As(V) l⁻¹. This simple, fast and sensitive arsenic determination method is suitable for field analysis, especially for waters containing low levels of phosphate and organic matter. Through arsenate determination, this colorimetric method allowed the arsenite oxidation efficiency of five common industrial oxidants to be compared. H₂O₂ and MnO_2(s) were not considered as effective oxidants as a high excess was necessary to ensure As(III) oxidation. NaOCl and KMnO₄ were promising oxidants as they allowed complete arsenite oxidation with a small excess for NaOCl or even less than the electron stoichiometric ratio in the case of KMnO₄. FeCl₃ was the most effective oxidant among the reagents tested here.     

Complexes acetyleniques de titane(II). Reactivite vis-a-vis de l'hydrogene moleculaire: Une nouvelle approche du titanocene

¹³C NMR measurements were performed on [Re₃(μ-H)₃(CO)₁₀]^2? at various temperatures and field strengths. Selective decoupling allowed assignments of the carbonyl resonances. Spin-lattice relaxation time measurements indicated that two mechanisms, scalar coupling and chemical shielding anisotropy, contribute to the relaxation of carbon-13. Variable temperature experiments revealed that more than one mechanism is responsible for the fluxional behaviour.     

Synthesis of thienothiazocinoisoindolediones and thienothiazinoisoindolones from mercaptothiophenes and chloromethylphthalimide

2-Thienylthiomethylphthalimides 3a,b were synthesized by action of Chloromethylphthalimide on 2-or 3-mercaptothiophene. Reduction of 3a,b and Wittig reaction using carbethoxycarbonyltriphenyl-phosphorane gave the corresponding acetic acids 5a,b which cyclized under Friedel and Crafts conditions to lead the thienothiazocinoisoindolediones 6a,b. Thienothiazinoisoindolones 7a,b were obtained from hydroxyisoindolones derivatives 4a,b in acid conditions via an acyliminium ion.     

Anderson localization for multi-dimensional systems at large disorder or large energy

We prove that discrete Schrödinger operators on ^d with a random-potential have almost-surely only pure point spectrum and exponentially decaying eigenfunctions for large disorder or large energy. This is the first proof of localization for multi-dimensional Anderson models.Groupe de recherche 048 du CNRS     

Comparative study of reflectance cells for PLS-FTIR determination of sugars in soft drinks

A comparative study has been carried out between a horizontal Attenuated Total Reflectance (h-ATR) cell and a Cylindrical Internal Reflection (CIR) cell (CIRCLE cell). Both cells were employed for the determination of glucose, fructose, sucrose and total sugar in soft drinks and fruit juices using absorbance measurements at two resolution values (4 and 8 cm^–1). Data were processed by Partial Least Squares regression (PLS). Using a resolution of 4 cm^–1, mean relative errors of prediction from 0.6% to 1.3% were obtained using the horizontal-ATR and from 0.6% to 2.8% using the CIRCLE cell resulting in a limit of detection from 0.03% in the case of sucrose to 0.21% for total sugar for the h-ATR and from 0.06% for sucrose to 0.13% for glucose using the CIRCLE cell. Both cells provided appropriate figures of merit, but the analytical sensitivity obtained using the h-ATR cell was three times higher than that obtained using the CIRCLE cell.     

Synthesis of new 4-(1-ethylthio-2,2,2-trifluoroethyl)-6-methylpyridazin-3(2H)-ones starting from S-ethyl 4-oxo-2-(pentafluoroethyl)pentanethiolate and hydrazines

The paper presents a one-pot conversion of γ-keto-α-pentafluoroethyl thioester into new pyridazin-3-ones and α,β-unsaturated lactams. The structures of all new compounds were ascribed using 1D (¹⁹F, ¹H, ¹³C) and 2D (¹H-¹⁵N) NMR data, and X-ray diffraction analysis. Two possible competitive reaction mechanisms for the synthesis of pyridazin-3-ones and lactams are presented.     

Two new 5-deoxyflavones from Albizia odoratissima

Two new 5-deoxyflavones, 7,8-dimethoxy-3',4'-methylenedioxyflavone (1) and 7,2',4'-trimethoxyflavone (2) together with a known flavone, 7,4'-dimethoxy-3'-hydroxyflavone (3) were isolated from the rootbark of Albizia odoratissima. The structures of these new compounds were elucidated by electrospray ionization mass spectrometry (ESI-MS) and 1D and 2D-NMR spectral studies including (1)H-(1)H correlation spectroscopy (COSY), heteronuclear single quantum coherence (HSQC), heteronuclear multiple bond connectivity (HMBC) and nuclear Overhauser enhancement spectroscopy (NOESY).     

Multicomponent coupling approach to (+/-)-frondosin B and a ring-expanded analogue

[reaction: see text] A recently discovered multicomponent coupling reaction is used to give direct access to a late intermediate in the synthesis of frondosin B. This intermediate can also be efficiently converted to a ring-expanded analogue of frondosin B by sustained heating of the reaction mixture. An unprecedented tandem 1,7-hydrogen shift, 8pi-electrocyclization is proposed to explain the formation of this ring-expanded species.