Methane activation on Ni(1 1 1): Effects of poisons and step defects

We have, theoretically and experimentally, investigated the dissociation of methane on the terraces and steps of a Ni(1 1 1) surface. Using Density Functional Theory (DFT) total energy calculations combined with Ultra High Vacuum (UHV) experiments, we find that the steps exhibit a higher activity than the terraces. We have, furthermore, investigated how carbon and sulfur present on the surface will deactivate the steps, leaving only the terraces active. We find the intrinsic sticking probabilities of methane on the steps and terraces at 500 K to be 2.8 × 10⁻⁷ for the steps and 2.1 × 10⁻⁹ for the terraces, in complete agreement with our calculated difference in activation energy of 17 kJ/mol.     

Enthalpies of sorption of linear hydrocarbons (C2–C8) and chloroderivatives of methane and ethylene on the surface of hydrotalcite

Differential molar adsorption enthalpies (DMAE) were determined by gas chromatographic measurements of specific retention volume of vapors on the surface of two forms of Mg–Al hydrotalcite. A linear dependence of the DMAE on the number of the carbon atoms in hydrocarbons was observed for both form of hydrotalcite. The dependence of the differential molar adsorption enthalpies on the number of chlorine atoms in organic molecules is discussed. A linear dependence of DMAE on the molecular weight of chloroderivatives of methane and ethylene on the basic form in an order monochloromethane < dichloromethane < trichloromethane or vinylidene chloride < 1,1-dichloroethylene < trichloroethylene was found.     

New Interfaces for Coupling TLC with TOF SIMS

JPC – Journal of Planar Chromatography – Modern TLC - Two interfaces have been tested for coupling thin-layer chromatography (TLC) with time-of-flight secondary-ion mass spectrometry...     

Fluorimetric determination of the levels of urinary neopterin and serum thiobarbituric acid reactive substances in the nonagenarians

Twelve self-sustaining nonagenarians, 10 women and two men, aged 94+/-3 years, and eight institutionalised nonagenarians, eight women, aged 91+/-1 year as well as 11 control subjects, seven women and four men, aged 84+/-5 years entered the study. Urinary neopterin, an indicator of systemic immune activation, and serum thiobarbituric acid reactive substances (TBARS), a marker of lipoperoxidation, were determined initially, and collection of the blood and urine samples was repeated at 3-month interval. Neopterin was measured in the urine specimens by reversed-phase high performance liquid chromatography. A C(18) reversed-phase column 3.3x150 mm, 5 mum-diameter packing Separon SGX was used. Potassium phosphate buffer (15 mmol l(-1), pH 6.4) at flow rate of 0.8 ml min(-1) was used as mobile phase. After centrifugation (5 min, 1300xg) and diluting 100 mul of urine specimens with 1.0 ml of mobile phase containing 2 g of disodium-EDTA per litre, a 20 mul sample was injected on a column. Neopterin was identified by its native fluorescence (353 nm excitation, 438 nm emission). Creatinine was determined by Jaffé kinetic reaction after dilution of sample 1:50 (v/v). The concentration of neopterin in urine was expressed as neopterin/creatinine ratio (mumol mol(-1) creatinine). TBARS were determined spectrofluorometrically using LS-5 spectrofluorimeter (excitation wavelength 528 nm, emission wavelength 558 nm) after extraction with n-butanol treatment with thiobarbituric acid. The significance of differences between nonagenarians and control group was examined by ANOVA-Kruskal-Wallis tests, using statistical software NCSS 6.0.21 (Kaysville, UT, 1996). The decision on significance was based on P=0.05. Urinary neopterin was significantly higher in institutionalised compared to self-sustaining subjects and controls (625+/-565 vs. 203+/-63 mumol mol(-1) creatinine, and 198+/-128 mumol mol(-1) creatinine, respectively, P=0.006). The serum TBARS were higher in both groups of nonagenarians (3.23+/-1.16 mumol l(-1) and 2.69+/-0.39 vs. 2.12+/-0.83 mumol l(-1) for the self-sustaining, institutionalised and controls, respectively, P=0.023). We conclude that the fluorimetric determinations of urinary neopterin and serum TBARS can be useful for the monitoring health status in the elderly patients.     

An exponential lower bound to the size of bounded depth frege proofs of the pigeonhole principle

We prove lower bounds of the form exp(n^{ε d}), ε_d > 0, on the length of proofs of an explicit sequence of tautologies, based on the Pigeonhole Principle, in proof systems using formulas of depth d, for any constant d. This is the largest lower bound for the strongest proof system, for which any superpolynomial lower bounds are known.     

A class of polynomial variable metric algorithms for linear optimization

In the paper, the behaviour of interior point algorithms is analyzed by using a variable metric method approach. A class of polynomial variable metric algorithms is given achieving O ((n/β)L) iterations for solving a canonical form linear optimization problem with respect to a wide class of Riemannian metrics, wheren is the number of dimensions and β a fixed value. It is shown that the vector fields of several interior point algorithms for linear optimization is the negative Riemannian gradient vector field of a linear a potential or a logarithmic barrier function for suitable Riemannian metrics. Research Partially supported by the Hungarian National Research Foundation, Grant Nos. OTKA-T016413 and OTKA-2116.     

Model of free charge generation in polymers

A time solution of the excimer-ion pair system is presented here with a special attention to the time asymptote. Presented at the Czech-Israeli-German Symposium “Dynamical Processes in Condensed Molecular Systems”, Prague, Czech Republic, 26–30 May 1997. This work was supported by the grant No. C 1050601 of the Grant Agency of the Academy of Sciences of the Czech Republic.