Gamma-radiolysis of chiral molecules: R(+)-limonene, S(-)-limonene and R(-)-a-phellandrene

Three isomeric chiral terpenes, R(+)-limonene, S(-)-limonene and R(-)-a-phellandrene were γ-radiolyzed in sealed vials at room temperature with a total radiation dose of 317 kGy. The radiolyzed samples were analyzed by FT-IR, electronic absorption spectroscopy, liquid chromatography using a diode-array detector (HPLC-DAD) and by polarimetry. Despite a relatively high radiation dose used, all the chiral molecules selected have shown a low radioracemization rate. This fact and the role played by the impurities in the selective radio-degradation of one of the two enantiomers has been discussed in the context of the origin of chirality in prebiotic molecules and the chirality enhancement in a prebiotic world. The results were also discussed in the frame of the radiosterilization technique of chiral drugs, perfumes and food components. This revised version was published online in July 2006 with corrections to the Cover Date.     

Observation of vibration-electronic exchange in gas-surface collisions

Intensity increase of exoelectronic emission in the interaction of vibrationally excited hydrogen beam (v1) with emitter surface (CaSO₄) has been found. The effect proves to be due to the transfer of vibrational energy from molecules to trapped electrons, i.e. to the v-e transition in gas-surface collisions.

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- (v1) (CaSO₄). , .. v-e- -.

     

Preparation of a new carboranyl lactoside for the treatment of cancer by boron neutron capture therapy: synthesis and toxicity of fluoro carboranyl glycosides for in vivo 19F-NMR spectroscopy

The synthesis of new ortho-carboranyl lactosides 8, 17, 19 and glucosides 22 and 23 for the use in boron neutron capture therapy is reported. Carboranyl lactosides 17 and 19 as well as the glucosides 22 and 23 contain a fluorine atom to allow a noninvasive determination of these compounds in tumor cells by 19F-NMR spectroscopy. In cloning efficiency tests on human bronchial carcinoma cells the carboranyl lactosides 17 and 19 displayed almost no cytotoxicity. Thus, the considerably cytotoxic carboranyl alcohol 11 is detoxified when linked to a sugar moiety such as in carboranyl glucoside 22.     

Determination of iodide in drinking water by isotope dilution analysis

The most suitable way of determination iodine-deficiency is to measure iodine concentrations in water and urine. For this reason, a method that can determine iodide concentrations in drinking water and suitable for routine analysis, is developed. Water samples have been collected from four Aegean localities: Izmir, Salihli, Ödemis and Tire situated in the western Turkey. The method is based on substochiometric isotope dilution analysis. Iodile concentrations vary within 9.86–85.14 μg/l ranges in the analyzed samples. Mean value is 44.92±22.07 μg/l.     

Analysis of sediments for heavy metals by a rapid electrothermal atomic-absorption procedure

A rapid electrothermal atomic-absorption spectrophotometric procedure with homogenization as the only pretreatment is compared with two wet pretreatment methods followed by flame atomic-absorption, in a statistically designed experiment. Samples from the top 5 cm of sediments at three different points of the Tejo estuary were used for the tests. The results show that the electrothermal procedure performed as well as whichever was the better of the flame methods for the determination of cadmium and nickel, irrespective of the sand content of the samples; although not statistically significant, there was apparently a decrease in recovery for chromium, copper and lead by the electrothermal method as the sand content of the sample increased. For zinc the electrothermal method gave results statistically different from those of the flame procedures when the sand content was high but not when the organic content of the sample was high. Because of the limited degree of replication (5 variates) the relative differences between the average values obtained by the three methods were significant only if they exceeded 15%. The electrothermal method has the advantage of substantially greater speed.     

Coulomb energy averaged over the nlN-atomic states with a definite spin

A purely group-theoretical approach (for which the symmetric group plays a central role), based upon the use of properties of fractional-parentage coefficients and isoscalar factors, is developed for the derivation of the Coulomb energy averaged over the states, with a definite spin, arising from an atomic configuration nl^N. © 1995 John Wiley & Sons, Inc.     

Wannier-Stark effect on surface states

A recursive Green-function (RGF) technique is used to study the surface states of an electrified solid. The concatenating nature of the method leads to a continued-fraction form of the RGF, which can be expressed as a ratio of Bessel functions. The surface density of states (SDOS), derived from the RGF, reveals a quasi-Stark-ladder distribution of the energy levels at the surface atom. The dependence of the SDOS on the applied field and surface perturbation parameters is discussed.     

Kinetics and mechanism of the photodecomposition of xenon tetroxide

The of photochemical decomposition of XcO4 under the action of UV-radia(ion in the wavelength range of 200–300 nm was investigated. The quantum yield of the formation of oxygen atoms upon XeO₄ photodissociation was measured (Ф = 3.6±0.4). The results obtained point to the predominant role of the XeO₄ +hv → 4O + Xe photodissociation channel of XeO₄. The value of the rate constant of the reaction XeO₄ + O → O₂ + XeO₃ was estimated (<4.5 · 10^?16 cm² s^?1).     

Phosphinofenchol or metastable phosphorane? Phosphorus derivatives of fenchol

Not the expected phosphinofenchol 1 but phosphorane 2 is obtained after reaction of 2-lithio(diphenylphosphino)benzene with (-)-fenchone. Surprisingly, ONIOM(B3LYP/6-31G*:UFF) computations of 1 and 2 as well as B3LYP analyses of smaller model systems point to a lower thermodynamic stability of phosphoranes relative to their isomeric alkoxyphosphines. An analogue inherent instability is computed for the methylphosphorane 10, which is also synthesized and characterized by X-ray analysis. Decreasing ring size in cyclic phosphoranes, that is, from five- to four-membered ring systems, destabilizes cyclic phosphoranes even more. This computational prediction is verified experimentally by reaction of lithiomethyl(diphenylphosphine) with (-)-fenchone and subsequent isolation of the corresponding phosphinofenchol. Protonation or alkylation of phosphoranide intermediates can account for the formation of metastable phosphoranes.