Synthesis and spectroscopic characterization of heterobimetallic (α-alkynyl)iron-cobalt hexacarbonyl complexes, μ-(1-σ, 2-3, η2-R2C-CCR′)][(CO)3Fe-Co(CO)3] and [μ-(1-σ, 2-3, η2-H2C-CCCH2OH)] [(CO)3Fe-Co(CO)2(PPh3)]

The title compounds have been prepared from reactions of Co₂(CO)₆(μ-HOR₂CC₂R′) or Co₂(CO)₆(μ-HOR₂CC₂CR₂OH) complexes with Fe(CO)₅ in acetone. In the latter set of reactions the homobimetallic butatriene compounds, Fe₂(CO)₆-(μ-R₂CCCCR₂), are also obtained. The striking feature of these reactions is the ability of Fe(CO)₅ to dehydroxylate the organic moiety and to replace a Co(CO)₃ unit forming mixed iron-cobalt derivatives. A direct interaction between the iron and the carbon atom, originally bearing the lost -OH group, is evident from the bulk of the spectroscopic data; thus the organic chain acts as an overall 5 electron donor, according to the E.A.N. formalism. The heterobimetallic compounds have been characterized by elemental analysis, mass spectrometry, IR spectroscopy and NMR studies. For the phosphine derivative FeCo(CO)₅(PPh₃)(H₂CC₂OH) a crudely refined X-ray analysis has been performed.     

Selective liquid phase hydrogenation of citral on Au/Fe2O3 catalysts

Gold supported on iron oxide hydrogenates citral (an alpha,beta-unsaturated aldehyde) to the corresponding alpha,beta-unsaturated alcohols (geraniol and nerol) with a selectivity higher than 95%.     

Modeling cell dynamics under mobile phone radiation

Perturbations by pulse-modulated microwave radiation from GSM mobile phones on neuron cell membrane gating and calcium oscillations have been suggested as a possible mechanism underlying activation of brain states and electroencephalographic epiphenomena. As the employ of UMTS phones seems to reveal other symptoms, a unified phenomenological framework is needed. In order to explain possible effects of mobile phone radiation on cell oscillations, GSM and UMTS low-frequency envelopes have been detected, recorded and used as input in cell models. Dynamical systems endowed with contiguous regular and chaotic regimes suitable to produce stochastic resonance can both account for the perturbation of the neuro-electrical activity and even for the low intensity of the signal perceived by high sensitive subjects. Neuron models of this kind can be employed as a reductionist hint for the mentioned phenomenology. The Hindmarsh-Rose model exhibits frequency enhancement and regularization phenomena induced by weak GSM and UMTS. More realistic simulations of cell membrane gating and calcium oscillations have been performed with the help of an adaptation of the Chay-Keizer dynamical system. This scheme can explain the suspected subjective sensitivity to mobile phone signals under the thermal threshold, in terms of cell calcium regularity mechanisms. Concerning the two kinds of emission, the stronger occupation of the ELF band of last generation UMTS phones is compensated by lower power emitted.     

Controlled crystallization and ionic conductivity of a nanostructured LiAlGePO4 glass–ceramic

A Li_1.5[Al_0.5Ge_1.5(PO₄)₃] glass composition was subjected to several crystallization treatments to obtain glass–ceramics with controlled microstructures. The glass transition (T_g), crystallization onset (T_x) and melting (T_m) temperatures of the parent glass were characterized by differential scanning calorimetry (DSC). The glass has a reduced glass transition temperature T_gr = T_g/T_m = 0.57 indicating the possibility of internal nucleation. This assumption was corroborated by the similar DSC crystallization peaks from monolithic and powder samples. The temperature of the maximum nucleation rate was estimated by DSC. Different microstructures were produced by double heat treatments, in which crystal nucleation was processed at the estimated temperature of maximum nucleation rate for different lengths of time. Crystals were subsequently grown at an intermediate temperature between T_g and T_x. Single phase glass–ceramics with Nasicon structures and grain sizes ranging from 220 nm to 8 μm were then synthesized and the influence of the microstructure on the electrical conductivity was analysed. The results showed that the larger the average grain size, the higher the electrical conductivity. Controlled glass crystallization allowed for the synthesis of glass–ceramics with fine microstructures and higher electrical conductivity than those of ceramics with the same composition obtained by the classical sintering route and reported in literature.     

Fission of gold induced by a coherent photon beam from 1 GeV electrons

Fission measurements on Au have been performed by means of a coherent bremsstrahlung photon beam from 1 GeV electrons. The photofission cross section deduced from the experimental yields by an unfolding method shows a resonance at photon energy 320 MeV.     

Structure elucidation of a novel funicone-like compound produced by Penicillium pinophilum

A novel metabolite related to the previously identified compound 3-O-methylfunicone (1) was isolated from the fungus Penicillium pinophilum and its structure elucidated by spectral analysis as 3-O-methyl-5, 6-epoxyfunicone (2).     

Differentiation of O-acetyl and O-carbamoyl

Nod factors are substituted N-acyl chito-oligomers secreted by plant symbiotic bacteria of the Rhizobium family. Substitutions on the oligosaccharide core specify their recognition by host plants. A method using tandem mass spectrometry is proposed to locate the O-acetyl and O-carbamoyl substituents on the nonreducing terminal residue of the chito-oligomers. As model compounds, all the positional isomers of monoacetyl and monocarbamoyl esters of 1-O-methyl-N-acetyl-alpha-D-glucosamine were synthesized. Oxonium ions (MH - CH3OH)+ were generated by liquid secondary ion mass spectrometry (LSIMS) and their decomposition was recorded on a tandem magnetic instrument. Large differences were observed in the relative abundances of ions resulting from elimination of water and of the O-ester substituent from metastable oxonium ions. Deuterium exchange reactions indicated parallel elimination pathways involving either exchangeable or carbon-linked hydrogens. The intensity ratios of some of the ions generated by collisions with helium atoms allowed the isomers to be distinguished. The main dissociation routes were identified. Metastable and collision-induced decomposition of the B1 ions from Nod factors of Sinorhizobium meliloti and Azorhizobium caulinodans resembled that of the 6-O-substituted N-acetylglucosamine models. Decomposition of the B1 ion from Mesorhizobium loti and Rhizobium etli Nod factors, was similar to that of 3-O-carbamoyl N-acetyl-glucosamine and different to that of the 4-O isomer. 6-O- and 3-O-carbamoylation specified by the nodU and nolO genes, respectively, of Rhizobium. sp. NGR234 were confirmed.     

Reaction of Ru3(CO)12 with styrene

The reaction of styrene with Ru₃(CO)₁₂ yields the known complex Ru₄(CO)₁₂(PhCCH) and the new cluster Ru₄(CO)₉(PhCCH)(PhEt), in which a second molecule of styrene is hydrogenated and η⁶-bonded.