Evaluation of a retention model in comprehensive two-dimensional gas chromatography

Modeling the retention in comprehensive two-dimensional gas chromatography (GC x GC) was achieved using retention indices obtained in conventional GC. Predicted results were compared with experimental data obtained in the two-dimensional separation of a synthetic hydrocarbon mixture. This proved to be helpful in optimizing the operating conditions of GC x GC separation of a complex petroleum sample and in identifying chemical families.     

Avoiding Carbothermal Reduction: Distillation of Alkoxysilanes from Biogenic,Green, and Sustainable Sources

The direct depolymerization of SiO₂ to distillable alkoxysilanes has been explored repeatedly without success for 85 years as an alternative to carbothermal reduction (1900 °C) to Si_met, followed by treatment with ROH. We report herein the base‐catalyzed depolymerization of SiO₂ with diols to form distillable spirocyclic alkoxysilanes and Si(OEt)₄. Thus, 2‐methyl‐2,4‐pentanediol, 2,2,4‐trimethyl‐1,3‐pentanediol, or ethylene glycol (EGH₂) react with silica sources, such as rice hull ash, in the presence of NaOH (10 %) to form H₂O and distillable spirocyclic alkoxysilanes [bis(2‐methyl‐2,4‐pentanediolato) silicate, bis(2,2,4‐trimethyl‐1,3‐pentanediolato) silicate or Si(eg)₂ polymer with 5–98 % conversion, as governed by surface area/crystallinity. Si(eg)₂ or bis(2‐methyl‐2,4‐pentanediolato) silicate reacted with EtOH and catalytic acid to give Si(OEt)₄ in 60 % yield, thus providing inexpensive routes to high‐purity precipitated or fumed silica and compounds with single Si−C bonds.     

A study of the copolymerization of hydroxyethyl methacrylate and tetrahydrofurfuryl methacrylate

The free radical copolymerizations of hydroxyethyl methacrylate and tetrahydrofurfuryl methacrylate have been investigated at 50°C. The compositions of polymers prepared at low conversions have been determined using ¹³C-NMR, and the glass transition temperatures determined by DSC. The copolymerizations were found to be best described by a terminal model with reactivity ratios of r_H = 1.79 and r_T = 0.76. The triad fraction sequence distributions have been calculated based on the terminal model and the calculated reactivity ratios. The glass transitions have been fitted to the Gordon–Taylor equation. The best value of the Gordon–Taylor constant was found to be k_H = 1.42 ± 0.2, indicating nonideal mixing of the two monomer components in the copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3730–3737, 1999     

Determination of the light-induced degradation rate of the solar cell sensitizer N719 on TiO2 nanocrystalline particles

The oxidative degradation rate, kdeg, of the solar cell dye (Bu4N+)2[Ru(dcbpyH)2(NCS)2]2-, referred to as N719 or [RuL2(NCS)2], was obtained by applying a simple model system. Colloidal solutions of N719-dyed TiO2 particles in acetonitrile were irradiated with 532-nm monochromatic light, and the sum of the quantum yields for the oxidative degradation products [RuL2(CN)2], [RuL2(NCS)(CN)], and [RuL2(NCS)(ACN)], Phideg, was obtained at eight different light intensities in the range of 0.1-16.30 mW/cm2 by LC-UV-MS. The Phideg values decreased from 3.3 x 10-3 to 2.0 x 10-4 in the applied intensity range. By using the relation kdeg = Phidegkback and back electron-transfer reaction rates, kback, obtained with photoinduced absorption spectroscopy, it was possible to calculate an average value for the oxidative degradation rate of N719 dye attached to TiO2 particles, kdeg = 4.0 x 10-2 s-1. The stability of N719 dye during solar cell operation was discussed based on this number, and on values of the electron-transfer rate between [Ru(III)L2(NCS)2] and iodide ion that are available in the literature.     

Synthesis of novel tryptamine and β-carboline derivatives via palladium-catalyzed reaction of bromotryptamine with organic boronic acids

New tryptamine 5, 7 and β-carboline derivatives 3 were preparated by palladium-catalyzed coupling reaction of 5-bromotryptamine 1 with aryl boronic acids. Dedicated to Professor András Lipták on his 70^th birthday.     

Determination of k-factors by thermal neutron activation technique

The k_{o, Au}-factors of 10 elements have been determined by irradating the samples with thermal neutrons in the reactor thermal column. The proposed method has the advantage of eliminating the errors induced by the uncertainties of the neutron spectrum parameters and the nuclear data. The results obtained are in good agreement with the literature data.     

Fast determination of the tin content in cassiterite ores by photon activation method

Photon activation analysis has been success-fully applied to the fast and non-destructive analysis of tin in cassiterite ores based on the 159.7 keV gamma line of^123mSn produced in the¹²⁴Sn/γ, n/^123mSn reaction. In order to improve the accuracy of analytical results, corrections for self-absorption and pile-up effects were performed. Under typical conditions /15 μA electron beam current, 15 MeV bremsstrahlung energy, 5 min irradiation time and 10 min measurement/ the sensitivity of the analysis is 10 ppm. The proposed method can be used for routine analysis of tin in geological samples.     

Proton affinities by reactant ion monitoring: Triphenyl group Va compounds

Proton affinities of a series of triphenyl Group Va compounds have been determined by bracketing using reactant ion monitoring: (C₆H₅)₃N = 904 ± 8 kJ mol^?1, (C₆H₅)₃P = 968 ± 5 kJ mol^?1, (C₆H₅)₃As = 904 ± 8 kJ mol^?1 and (C₆H₅)₃Sb = 846 ± 8 kJ mol^?1. The large difference in substituent effect of phenyl for hydrogen between As or P and N may result from overlap of the 2p orbitals of N with the sp² orbitals on the ring carbons and lack of overlap for P or As. Proton affinities of phenylalkylphosphine oxides are essentially the same, 904 ± 8 kJ mol^?1, independent of alkyl group.