Temperature dependence of the rate constants for reactions of the carbonate radical with organic and inorganic reductants

Rate constants have been measured by pulse radiolysis for the reactions of the carbonate radical, CO₃^·?, with a number of organic and inorganic reactants as a function of temperature, generally over the range 5 to 80°C. The reactants include the substitution-inert cyano complexes of Fe^II, Mo^IV, and W^IV, the simple inorganic anions SO₃^2?, ClO₂^?, NO₂^?, I^?, and SCN^?, several phenolates, ascorbate, tryptophan, cysteine, cystine, methionine, triethylamine, and allyl alcohol. The measured rate constants ranged from less than 10⁵ to 3 × 10⁹ M^?1 s^?1, the activation energies ranged from ?11.4 to 18.8 kJ mol^?1, and the pre-exponential factors ranged from log A = 6.4 to 10.7. The activation energies for the metal complexes and inorganic anions generally decrease with increasing driving force for the reaction, as expected for an outer sphere electron transfer. For highly exothermic reactions, however, the activation energy appears to increase, probably reflecting the temperature dependence of diffusion. For many of the organic reactants, the activation energies were low and independent of driving force, suggesting that the oxidation is via an inner sphere mechanism.     

Structure of fullerene-containing soot at different formation stages of arc discharge vaporization of graphite

Electron microscopy is used in a study of nanoclusters of the carbon soot deposited on a probe in different areas of arc discharge during graphite vaporization under conditions favorable for fullerene synthesis. It is found that the spatial network of soot nanoclusters consists of alternating regions of higher density or associates of carbon particles. Two types of nanoclusters have been identified with the correlation radii of the associates equal to 0.6–0.8 and 1.6–2.2 nm, respectively. Type I nanoclusters are dominant in the soot microparticles, and their structure shows practically no variations with increasing separation r of the soot collector from the discharge axis over the range of distances studied, r=1–9 cm. The effective radius R ₀ of the “elementary” particles making up the associates in the soot nanoclusters of Type I calculated with the use of scaling relationships is 0.15–0.17 nm and is close to the gas-kinetic radius of carbon atoms. Type II nanoclusters have been identified in soot collected at r>3 cm. Values of R ₀ calculated in this case are 0.6–0.9 nm and decrease with increasing r, which indicates the presence of fullerene molecules in these nanocluster associates.     

Higher order radiative corrections to the QED Compton events at HERA

We estimate the higher order QED corrections to the QED Compton events at HERA employing the leading logarithmic approximation to all orders in α. The Compton events are events of the typee+p→e′+γ+ Hadrons, wheree′ and γ have nearly balancedp _T .     

Analysis of barbiturates in human serum and urine by high-performance capillary electrophoresis-micellar electrokinetic capillary chromatography with on-column multi-wavelength detection

The analysis of barbiturates in human serum (or plasma) and urine by high-performance capillary electrophoresis-electrokinetic capillary chromatography with on-column fast-scanning multi-wavelength detection is discussed. The use of a buffer of ca. pH 8 and containing sodium dodecyl sulphate provides a medium suitable for fast and high-resolution separations of barbiturates. Seven barbiturates are characterized by their retention and absorption spectra between 195 and 320 nm. Comparison of these computer-stored data with those of unknown samples is shown to allow the identification of barbiturates in samples of patients undergoing pharmacotherapy and in toxicological urine and serum specimens. Three-dimensional electropherograms provide reliable information on the requirement and suitability of sample pretreatment procedures. With urine, extraction of barbiturates prior to analysis is necessary. With human serum several barbiturates, including phenobarbital, are shown to elute in an interference-free window in front of uric acid and the proteins, allowing these substances to be determined by direct sample injection. The need for multi-wavelength detection over a relatively wide wavelength range as a means of peak confirmation in electrokinetic capillary analyses is demonstrated and limitations of this technique for compounds with similar retention behaviour and absorption spectra are discussed.     

Plant processing by simultaneous lactic acid fermentation and enzyme hydrolysis

Traditional ensiling of plant material by anaerobic lactic acid fermentation was combined with enzymatic hydrolysis (ENLAC for short) with cell wall degrading enzymes (hemicellulases, cellulases, and pectinases) to increase fiber digestibility or to increase the recovery of cell content from plants. Such findings were made using 0.015% (w/w, wet basis) Phylacell® enzyme preparation by ENLAC of corn and corn-sorghum mixtures, but not of forage grasses. Addition to alfalfa of a mixture of cell wall degrading enzymes, such as NOVO Viscozyme® together with NOVO Celluclast® each at 0.2–1.0% (w/w, wet basis), resulted in more rapid ensiling and improvement of rumen digestibility of silage by 20%. After 20 d of ensiling at 25 °C when the same enzymes were added to alfalfa at the 1.0% level, protein recovery by pressing increased by 35%, β-carotene recovery by 80%, and chlorophyll/xanthophyll recovery by 30%. ENLAC with the same enzymes also increased the recovery of sclareol from muscatel sage by 400%.

     

How should one define a (weak) crystal?

We compare two proposals for the study of positional long-range order: one in terms of the spectrum of the translation operator, the other in terms of the Fourier spectrum. We point out that only the first one allows for the consideration of molecular, as opposed to atomic, (weakly) periodic structures. We illustrate this point on the Thue-Morse system.