Pd-catalysed amidation of 2,6-dihalopurine nucleosides. Replacement of iodine at 0 °C

Pd-catalysed reactions of 2-Cl, 2-Br and 2-I derivatives of a 6-chloropurine nucleoside with benzamide have been compared, using Pd₂dba₃, Xantphos and Cs₂CO₃ in toluene, between 20 and 80 °C. The reactivity order was 2-I > 2-Br > 6-Cl ? 2-Cl. The 2-I substituent could be replaced even at 0 °C, under conditions disclosed here for the first time. On the other hand, the replacement of the chlorine atom at position 2 (2-Cl) required 110 °C.     

Preparation of Bi2Fe4O9 particles by hydrothermal synthesis and functional properties

In the present study, particles with different Bi₂Fe₄O₉ micro/nanostructures with a few particular morphologies (flower-like nanoplatelets, hierarchical microstructures, perfectly square platelets single crystals, etc.) obtained under specific hydrothermal synthesis conditions were investigated. The role of the processing parameters (such as NaOH concentration, reaction temperature, and reaction duration time) on the phase formation mechanism and on the microstructural characteristics was investigated. All the Bi₂Fe₄O₉ morphologies showed orthorhombic symmetry with space group Pbam. The photocatalytic properties and magnetic behavior as a function of the micro/nanostructural characteristics of various Bi₂Fe₄O₉ powders were determined. In the presence of Bi₂Fe₄O₉, a degradation rate of Rose Bengal in the range of 52–61% was determined after 180?min under UV light irradiation (λ?=?254?nm). Magnetic activity with antiferromagnetic behavior and a transition at ～240?K slightly dependent on the microstructures was found. The role of Bi₂Fe₄O₉ microstructures in the photocatalytic activity and magnetic properties was discussed.     

Sur une classe d'espaces d'Einstein

Résumé Soit un espace pseudoriemannien M muni d'une 1-forme ω. Dans [11], chaque fibré F en droites sur M est considéré, de manière naturelle, comme un espace pseudoriemannien F(M, ω, ɛ) avec ɛ=± 1 et on étudie le cas où celui-ci est un espace d'Einstein. Dans la Section 1 nous déduisons quelques propriétés générales de ces espaces d'Einstein et nous indiquons une méthode de construction pour les 1-formes ω correspondantes. Dans la Section 2 nous déterminons tous les espaces d'Einstein F(M, ω, ɛ) pour lesquels M est une forme spatiale sphérique. Nous étudions aussi le cas dual où M est une certaine forme spatiale hyperbolique. Dans la Section 3 nous acceptons, comme conséquence de cette dualité, l'existence en relativité générale de l'ainsi nommée ? comatière ?, dans laquelle la vitesse de la lumière admet une limite inférieure non nulle. Nous proposons un modèle de coexistence matière-comatière, avec une frontière de séparation correspondant aux singularités du champ gravitationnel. Nous étudions la possibilité de communication entre ces deux zones opposées à l'aide de la lumière. A la mémoire du ProfesseurBruno Finzi Entrata in Redazione il 20 gennaio 1975.     

High-Resolution Transmission Electron Microscopy Study of LiNi<Subscript>x</Subscript>Co<Subscript>1−x</Subscript>O<Subscript>2</Subscript> Synthesized by Unconventional Methods

Single phase LiNi_xCo_1–xO₂ (x=0.3) with fine particles were prepared by two low-temperature methods: the modified Pechini sol-gel method and the Self-Propagating Combustion Synthesis (SPCS). It was found that bulk quantities of nano-sized particles of layered LiNi_xCo_1–xO₂ could be obtained at temperatures below 400°C by these solutions technique. The synthesized products were characterized by structural (XRD) and thermal (DTA-TG) analyses. HRTEM was used to evaluate the purity and the phase composition of LiNi_xCo_1–xO₂. Lattice plane images give information about crystal structure and SAED patterns help us to identify the phase. Nano-crystals were obtained with minimum mean diameter about 5nm for both methods.     

Polarization quantum beat spectroscopy of HCF(A1A"). I. 19F and 1H hyperfine structure and Zeeman effect

To further investigate the (19)F and (1)H nuclear hyperfine structure and Zeeman effect in the simplest singlet carbene, HCF, we recorded polarization quantum beat spectra (QBS) of the pure bending levels 2(0) (n) with n = 0-7 and combination bands 1(0) (1)2(0) (n) with n = 1-6 and 2(0) (n)3(0) (1) with n = 0-3 in the HCF A(1)A(")<--X(1)A(') system. The spectra were measured under jet-cooled conditions using a pulsed discharge source, both at zero field and under application of a weak magnetic field (<30 G). Analysis yielded the nuclear spin-rotation constants C(aa) and weak field Lande g(aa) factors. Consistent with a two-state model, the majority of observed vibrational levels exhibit a linear correlation of C(aa) and g(aa), and our analysis yielded effective (a) hyperfine constants for the (19)F and (1)H nuclei (in MHz) of 728(23) and 55(2), respectively. The latter was determined here owing to the high resolving power of QBS. The vibrational state selectivity of the (19)F hyperfine constants is discussed, and we suggest that the underlying Renner-Teller interaction may play an important role.     

Experimental and theoretical study of 2,5-diaryloxazoles whose aryl are para-substituted phenyl groups

Absorption and emission properties of some phenoxy derivatives of diphenyloxazole (PPO) are presented and discussed. The photophysical properties reflect a dependence on the substituted 2 or 5 position of the oxazole ring. The experimental data were correlated with molecular parameters such as molecular flexibility, electronic structure and the singlet-triplet gap. The substitution with heteroatomic-bridged phenyls maintains the same frontier orbitals (m, m+1) as in the parent compound, but introduces a new molecular orbital, m-1, located on the terminal phenyl. The presence of the so-called band B in the absorption spectra of some diaryloxazoles was attributed to the m-1-->m+1 transition participating to the second excited state wave function. The other main component of this state, the m-->m+2 transition, was found to have a forbidden character, explaining the lack or the low intensity of band B. The decrease of the fluorescence quantum yield subsequent to substitution of PPO with phenoxy fragments was found to be due to the enhanced molecular flexibility comparing to PPO. The differences between the 2- or 5-substituted derivatives were rationalized in terms of a smaller S(1)-T(2) gap for the former, thus increasing the rate of the overall nonradiative intersystem crossing processes.     

untersuchung der Molekularassoziation des (p-Chlorbenzolsulfonamido)benzolthiophosphonsäure-O-äthylesters mit Hilfe der IR-Spektroskopie

O-Ethyl (p-chlorobenzenesulfonamido)benzenethiophosphonate (1) is shown to be associated by hydrogen-bonding by means of its i.r. spectrum in CCl₄ solution. Quantitative examination allows to determine the dissociation konstantK, the temperature dependence of which leads to a H-value of 8.3 kcal/mole. From this value it is concluded that the associated molecules are cyclic dimers2. The comparison of the H- and pK-values with the corresponding data of other compounds which form cyclic dimers, shows that the strength of the hydrogen bonding is greater in those compounds which possess smaller pK-values.

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XLIV. Mitt.:L. Almasi, N. Popovici undJ. Zsakó, Chem. Ber.106, 1384 (1973).     

Contribution of the polymer standards' polydispersity to the observed band broadening in size-exclusion chromatography

The contribution of the polydispersity of polymer standards to the observed band broadening in size-exclusion chromatography was evaluated. Initially, theoretical predictions based on an equation by Knox et al. were found to overestimate this contribution, greatly due to the fact that the polydispersity values specified by the manufacturers are upper limits and therefore too high to be applied in this context. An improved estimate of the polydispersity values was obtained from the size-exclusion chromatography results and these new values were used to reassess the polydispersity contribution to band broadening. For two of three columns tested the best molar-mass-distribution parameters, i.e. those the least affected by extra-column and intra-column band broadening effects, can be obtained for polymers with a molar mass in the effective range of the given column and at rather low mobile-phase flow rates. At those conditions, for low-molar-mass polymers, the estimated polydispersity index values approach the theoretical ones derived from a Poisson distribution.     

Recovery of Metals from Anodic Dissolution Slime of Waste from Electric and Electronic Equipment(WEEE) by Extraction in Ionic Liquids

The recovery of metals from a multi-component alloy obtained by crushing, melting and anodic dissolution of waste from electric and electronic equipment(WEEE) was investigated. The anodic dissolution of the alloy was carried out in an electrolysis cell with one copper cathode and a central cast anode, immersed in the electrolyte formed by choline chloride-ethylene glycol-iodine. The temperature of the electrolyte during the process was 343 K. Depending on the electrolysis parameters(current density and cell voltage), cathodic deposits of Sn, Pb and Zn of >99% purity were obtained. Cyclic voltammetry was used in order to determine the deposition potentials of the studied metals. The obtained metallic deposits were subject of determination of XRD, SEM/EDX and AFM in order to evidence the deposits structure and morphology. The experiments performed demonstrated the possibility of separating/selective recovery of metals from the multi-component alloy resulted from the waste from electrical and electronic equipment by anodic dissolution in ionic liquids.