Sloping convection: A paradigm for large-scale waves and eddies in planetary atmospheres?

In laboratory studies and associated theoretical and numerical work covering a very wide range of conditions (as specified by the key dimensionless parameters of the systems used) the phenomenon of sloping convection in rotating fluids can manifest itself in one of several spatial forms (waves, closed eddies, and combinations thereof), but all with strong local gradients (fronts, jet streams) and exhibiting various types of temporal behavior [steady, periodic vacillation, aperiodic (geostrophic) turbulence]. These general properties were first discovered in cylindrical (annular) systems, but they do not depend critically on geometry; differences between spherical and cylindrical systems are largely to be found in quantitative details. In all cases, the raison d'e tre of sloping convection is horizontal advective transfer, a process accompanied by upward advective heat transfer, which affects and may control vertical potential density gradients. It has been argued that sloping convection is the basic dynamical process underlying a wide variety of large-scale flow phenomena seen in planetary atmospheres (e.g., irregular waves in the Earth's atmosphere, regular waves in the Martian atmosphere, the Jovian Great Red Spot and other long-lived eddies seen in the atmospheres of the giant planets). In this review the extent to which this paradigm is upheld in the atmospheres of the major planets by recent work is discussed.     

Simple high-performance liquid chromatographic method for the determination of medroxyprogesterone acetate in human plasma

The high-performance liquid chromatographic (HPLC) method was developed as a simple, reliable alternative to available methods for measuring plasma concentrations of medroxyprogesterone acetate (MPA). The HPLC method has been successfully automated and is suitable for the rapid, inexpensive analysis of large batches of plasma samples. The best approach involves a solvent extraction followed by HPLC separation and analysis. MPA can be efficiently extracted, at all pH values, by nonpolar solvents. The Spherisorb 5-ODS2 HPLC column provides excellent separation of MPA from endogenous steroids of similar structure and from extraneous plasma blank peaks. A batch of 30-40 samples can be prepared by HPLC analysis in 2-3 hours, with a chromatographic run time of 10 minutes/sample. Calibration curves between 5-250 ng/ml show a good correlation between peak height ratio and MPA concentration, even at low levels. Plasma concentrations of MPA in patients receiving 1 g/day were between 12.6-270 ng/ml in this study, suggesting that the sensitivity of this method, 10 ng/ml, is sufficient for monitoring therapeutic concentrations of MPA. The results show a wide individual variation in plasma concentrations following similar dosing schedules--a finding reported by other workers.     

Synthesis of a 1,8-naphthyridin-5-one derivative via an intramolecular 1,3-dipolar cycloaddition reaction

Synthesis of a 1,8-naphthyridin-5-one derivative [(5,6,7,8-tetrahydro-(3-chloro-6-hydroxymethyl-8-methyl)-1,8-naphthyridin-5-one (9) ] is described starting from 2-chloronicotinic acid using an intramolecular 1,3-dipolar cycloaddition reaction as the key step.     

Kinetics and Mechanism of the Ferrate Oxidation of Thiosulfate and Other Sulfur-Containing Species

The kinetics of the reaction of ferrate, FeO(4)(2-), with several sulfur-containing species in aqueous media have been investigated, and the results are reported. It was found that, when the reductant is in excess, ferrate rapidly oxidizes thiosulfate to sulfite, benzenesulfinate to benzenesulfonate, methionine to its corresponding sulfoxide, and dimethyl sulfoxide to dimethyl sulfone. The rate law for each reaction is first order with respect to each reactant and first order with respect to the hydrogen ion concentration. A mechanism for each oxidation reaction is discussed.     

Detection of trace levels of trichothecene mycotoxins in human urine by gas chromatography-mass spectrometry

A method is described for the simultaneous detection of the trichothecene mycotoxins T-2, HT-2, T-2 tetraol, diacetoxyscirpenol, 15-monoacetoxyscirpendiol, scirpentriol, nivalenol and deoxynivalenol, in human urine. Samples were extracted from Clin Elut columns and cleaned up using reversed-phase Sep-Pak C18 cartridges. Trichothecenes were derivatised as their heptafluorobutyryl esters, and detected by gas chromatography-mass spectrometry-selected-ion monitoring using electron impact ionisation. The method was validated by the analysis of 22 urine samples, spiked and submitted "blind" for analysis by another laboratory. An alternative gas chromatography-mass spectrometry method using negative ion chemical ionisation is also described and a preliminary comparison of the two methods made. The methods enabled levels down to 1 ppb to be detected, with confirmation of identity at levels between 2 and 5 ppb, depending on the toxin.     

The first ionization constant from 25 to 200°C and 2000 bar for orthophosphoric acid

The ionization constant of orthophosphoric acid, determined by conductivity measurements, decreased from 7.11×10^–3 at 25°C to 6.2×10^–4 mol-kg^–1 at 200°C. The pressure effect to 2000 bar was also measured and the ratio K₂₀₀₀/K₁ is 2.7 at 25°C and 3.7 at 200°C. The standard partial molar volume change for the ionization at 1 bar, , changes from –16.1 at 25°C to –33.3 cm³-mol^–1 at 200°C. The partial molar compressibility change for the ionization, , varies from –3.8×10^–3 to –8.3×10^–3 cm³-mol^–1 bar^–1 over the same temperature range.     

The Approximation of the Optimal Control of Vibrations—A Geometrical Approach

In this paper we employ concepts from Banach space geometry in order to examine the problem of approximating the optimal distributed control of vibrating media whose motion is governed by a wave equation with a 2n-order self-adjoint and positive-definite linear differential operator. We show that this geometrical approach, arrived at via duality theory, provides the exact framework in which the approximation problem must be placed in order to get the correct convergence results, for it is here that the necessary and sufficient conditions for the approximate norm or time minimal control can be fully developed. Using the theory of Asplund, we are also able to improve the traditional weak^* convergence results for the more difficult case of L^∞ controls. Finally, we consider certain numerical examples which help illustrate our theoretical results.     

Calculation of scattering from stretched copolymers using the tube model: a generalisation of the RPA

There are many experimental situations in which polymer chains are constrained or localised into a small region of space (e.g. melt chains confined to a “tube”, network chains pinned by crosslinks). We show that detailed consideration of the quenched variables is vital in these experiments. This paper provides a crucial link between microscopic models with localising constraints and scattering patterns by a generalisation of the Random Phase Approximation (RPA) which allows for quenched translational variables. A method is developed which deals with correlations between the quenched variables brought about by incompressiblity (for example, in a polymer melt there are correlations between tubes because of the interaction between chains). As an example, the generalised RPA is applied to models based on the Warner-Edwards picture of the tube. Theoretical results for a melt of H-shaped copolymers are compared with experimental scattering. Early results suggest that to fit the scattering we may be forced to relax one of the central assumptions of the tube model; that the tube deforms affinely, that all chains retract by the same amount or that the tube diameter does not couple to the strain. Received 26 October 1998 and Received in final form 19 March 1999     

Planar chromatographic separation of petroleum residues and coal-derived liquids

Vacuum distillation residues from two petroleum crudes, a coal liquefaction extract and a coal tar pitch have been fractionated by planar chromatography (PC) using two solvent sequences: pyridine–acetonitrile and tetrahydrofuran (THF)–toluene. Fractions recovered from PC were examined by UV-fluorescence spectroscopy (UV-F), size-exclusion chromatography (SEC). UV-F and SEC of the whole samples showed differences in aromatic cluster size and molecular mass (MM) ranges which could be related to the different origins of the samples. The MM ranges indicated by SEC were greater for the vacuum residues than for coal-derived materials. However, the UV-F spectra of the fractions indicated that the petroleum residue fractions contained similar aromatic types, whereas the fractions from coal liquids contained significantly different aromatic types. SEC profiles of the fractions indicated a separation of coal-derived samples by increasing molecular size with increasing immobility in PC, whereas for petroleum fractions, the same trend was not apparent. MALDI-mass spectra of the set of original samples showed broadly similar ranges of MM distributions but additional work is necessary to identify appropriate matrices and procedures in order to improve the MALDI spectra.