The effect of N2O on the isotopic composition of air-CO2 samples

The ionisation efficiencies of N2O vs. CO2 as well as their ratios were measured in detail introducing clean N2O and CO2 into the electron impact ion source of an isotope ratio mass spectrometer. Changes in the ionisation efficiency ratio (IER) were found for different electron energy settings and compared with the ratios of literature ionisation cross-section values for pure N2O and CO2. To establish the influence of mixtures of N2O and CO2 in a mass spectrometer, artificial air mixtures were prepared by mixing different amounts of N2O and CO2 from well-calibrated spike cylinders with CO2-free air. The mixing ratios varied from 8-512 ppb for N2O and from 328-744 ppm for CO2. With these mixtures the effects of varying N2O concentrations on apparent CO2 isotope ratios in air samples were determined. After applying a mass balance correction the delta13C results were consistent within small error margins. The data seemed almost independent from a particular choice for the IER of N2O vs. CO2 in the correction algorithm. For delta18O a small effect of the ionisation efficiency ratio of N2O vs. CO2 was found. Several sets of calculations were made varying the IER between 0.88 and 0.62. The dependence of delta18O was the smallest with an adopted IER of 0.68-0.72 in the mass balance correction equation for isotopic analysis of CO2 in air. For high-precision measurements of the CO2 stable isotope ratios in air samples a careful assessment of the mass spectrometer performance is necessary. Different ion sources, even different ion source settings, alter the IER of N2O vs. CO2 which is used in the N2O correction algorithm. Preferably, the specific mass spectrometric behaviour should be established with clean N2O/CO2 mixtures or with air mixtures covering a larger range of N2O concentrations.     

Der geschwindigkeitsbestimmende Schritt bei der Decarboxy-lierung von 2,4-Dihydroxybenzoesäure in mässig konzentrierter wässeriger Salzsäure

The decarboxylation kinetics of 2,4-dihydroxybenzoic acid have been studied in 0.1–8 N aqueous HCl at 50°. At low HCl concentrations, the observed first order rate constant, k, increases with increasing acidity of the solution. In solutions with 3.5–6 N HCl, k remains constant. The D₂O solvent isotope effect decreases from ^kH₂O/^kD₂O = 2.0 in 1N HCl to 1.3 in 5 N HCl, and it remains unchanged at 1.3 if the HCl concentration is increased further to 8 N. It is concluded that an increase of the acidity of the solution causes a change of the rate determining step from slow proton transfer to rate limiting C? C bond cleavage.     

Pore morphologies in disordered nanoporous thin films

Materials with nanometer size heterogeneities are commonplace in the chemical and biological sciences (e.g, polymer blends, microemulsions, gels) and often exhibit complex morphologies. Although this morphology has a dramatic effect on the materials' properties, it is often difficult to accurately characterize. We describe a method, using small-angle X-ray scattering data, of generating representative three-dimensional morphologies of isotropic two-phase materials where the morphology is disordered, and we apply this to thin films containing nanometer sized pores with a range of porosities (4-44%). These representations provide a visualization of the pore morphology, give the pore size scale and extent of interconnection, and permit the determination of the transitions from closed pore to interconnected pores to bicontinuous morphology.     

Correspondence between de Saint-Venant and Boussinesq. 1: Birth of the Shallow–Water Equations

The Shallow–Water Equations (SWEs), also referred to as the de Saint-Venant equations, constitute the current governing mathematical tool for free-surface water flows. These include, e.g., flood flows in rivers and in urban zones, flows across hydraulic structures as dams or wastewater facilities, flows in the environmental fields, glaciology, or meteorology. Despite this attractiveness, the system of two partial differential equations has an exact mathematical solution only for a limited number of problems of practical relevance.This historical work on the SWEs is based on a correspondence between two 19th-century scientists, de Saint-Venant and Boussinesq. Their well-known papers are thus commented from the point of development of their theory; the input of both scientists is evidenced by their writings, and comments of both to each other that led to what is commonly known as the SWEs. Given the age difference of the two of 45 years, the experienced engineer de Saint-Venant, and the mathematician Boussinesq, two eminent researchers, met to discuss not only problems in hydraulics, but in physics generally. In addition, their correspondence embraced also questions in ethics, religion, history of sciences, and personal news.The results of the SWEs cease to hold if streamline curvature effects dominate; this includes breaking waves, solitary and cnoidal waves, or non-linear waves in general. In most other cases, however, the SWEs perfectly apply to typical flows in engineering practice; they are considered the fundamental system of equations describing open channel flows. This work thus provides a background to its birth, including lots of comments as to its improvement, physical meanings, methods of solution, and a discussion of the results. This paper also deals with the steady flow equations, gives a short account on the main persons mentioned in the Correspondence, and provides a summary of further developments of the SWEs until 1920.     

High alpha/beta-anomer selectivity in molecular recognition of carbohydrates by artificial receptors

[structure: see text] New effective, acyclic, pyridine-based receptors 1-3 show remarkable alpha/beta binding selectivity in the recognition of monosaccharides. They are able to participate in cooperative and bidentate hydrogen bonds with sugar hydroxyls as well as in CH-pi interactions with CH's of sugar molecules.     

Macroscopic evidence of soliton formation in multiterawatt laser-plasma interaction

A novel physical phenomenon has been observed following the interaction of an intense (10(19) W/cm(2)) laser pulse with an underdense plasma. Long-lived, macroscopic bubblelike structures have been detected through the deflection that the associated electric charge separation causes in a proton probe beam. These structures are interpreted as the remnants of a cloud of relativistic solitons generated in the plasma by the ultraintense laser pulse. This interpretation is supported by an analytical study of the soliton cloud evolution, by particle-in-cell simulations, and by a reconstruction of the proton-beam deflection.