Causes and effects of sample loss using a dry capsule injection method for the automated gas chromatographic analysis of pesticide samples.

The automatic capsule sampling system is said to have many advantages for accurate gas chromatographic analysis. One is that the solvent may be removed by evaporation before injection, so that no solvent peak is obtained to interfere with the separation. However, working with aldrin and dieldrin, we have shown that up to 50% of the material can be lost from the capsules by air-drying at normal ambient temperature before injection. These losses occurred only with aldrin and it is suggested that they are connected with its relatively high vapour pressure. Significant amounts of material enter the top third of the capsule which is removed during the sealing process. The losses appear to be due to a combination of adsorption to the capsules, creep-up the capsule walls, co-distillation with the solvent, and direct volatilisation. Silylation of the capsules was quite effective in reducing these losses.     

Study of complexation of gliclazide with β-cyclodextrin in solution by nmr techniques

The study of complexation between GL and -CD in liquid medium has been carried out by phase-solubility,¹H and¹³C NMR studies. A formation complex is observed from the phase solubility diagram, being the average association constant of 1094 M^–1, The NMR studies revealed the preferent complexation of the aliphatic moiety of GL. The aromatic moiety is also entrapped, but in minor extent, by the CD molecules.     

Increased eumelanin expression and tanning is induced by a superpotent melanotropin [Nle4-D-Phe7]-alpha-MSH in humans

Seven normal volunteers (six males and one female) with tanning skin types III or IV (Fitzpatrick scale) were given 10 daily subcutaneous injections of a superpotent synthetic analog of alpha-melanocyte stimulating hormone (alpha-MSH) over two weeks. This agent, [Nle4-D-Phe7]alpha-MSH, also called Melanotan-I (MT-I), was administered at a dose of 0.16 mg/kg/day (Monday-Friday), over a two week period. Tanning was measured serially using computerized light reflectance. This regimen induced tanning at 3 of 8 anatomic sites including the face, neck and forearm by comparison of baseline to (1) the end of the daily dosing period, (day 14), and (2) one week later, (day 21). Shave biopsies of the forearm taken at baseline and day 21 were analyzed by high performance liquid chromatography for eumelanin content which was measured as the permanganate oxidation product, pyrrole-2,3,5-tricarboxylic acid or PTCA. Pheomelanin content was measured as the hydroiodic acid digestion product, aminohydroxyphenylalanine (AHP). Eumelanin was also measured in the forehead skin samples of three subjects. The HPLC results show that mean (+/- SD) baseline eumelanin (PTCA) levels in forehead skin (n = 3) averaged 1.38 (+/- 0.87) ng/mg of wet skin tissue weight. Higher mean baseline levels of PTCA were detected in forearm skin (2.06 +/- 0.28 ng/mg wet weight, n = 7). One week after MT-I treatments ended, there was a mean (SD) 49% (+/- 17.6%) increase in forehead skin PTCA levels compared to baseline (P = 0.019, n = 3, by paired sample T-test). The mean (SD) increase in forearm skin PTCA levels was 98% (+/- 25.4%) over the same period (P = 0.003). In contrast, forearm pheomelanin expression following MT-I treatment did not significantly change from baseline. Overall, the MT-I regimen increased the eumelanin: pheomelanin ratio in forearm skin from 51:1 at baseline to 86:1 following MT-I (P = 0.054 by paired sample T-test). These results show that the tanning induced by MT-I in the face and forearm is associated with a significant increase in the eumelanin content of the human skin.     

Stochastic binding of Ca2+ ions in the dyadic cleft; continuous vs random walk description of diffusion

Ca²⁺ signaling in the dyadic cleft in ventricular myocytes is fundamentally discrete and stochastic. In this paper we study the stochastic binding of single Ca²⁺ ions to receptors in the cleft using two different models of diffusion; a stochastic and discrete Random walk (RW) model, and a deterministic continuous model. We investigate if the latter model, together with a stochastic receptor model, can reproduce binding events registered in fully stochastic RW simulations. By evaluating the continuous model goodness-of-fit, we present evidences that it can. The large fluctuations in binding rate observed at the time level of single time steps are integrated and smoothed at the larger time scale of binding events, explaining the continuous model goodness-of-fit. With this we demonstrate that the stochasticity and discreteness of the Ca²⁺ signaling in the dyadic cleft, determined by single binding events, can be described with a deterministic model of Ca²⁺ diffusion together with a stochastic model of the binding events. Time consuming RW simulations can thus be avoided. We also present a new analytical model of bi-molecular binding probabilities that is used in the RW simulations, and in the statistical analysis. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nature of the ferroelectric-paraelectric phase transition in lithium tantalate

It is suggested that the ferroelectric phase transition in LiTaO₃ has characteristics of both displacement and order-disorder types, with peaks in the ion coordinate distribution function of the paraelectric phase at both centrosymmetric and off-center positions.     

Electrochemistry and Spectroelectrochemistry of Luminescent Europium Complexes

Fast, cost effective, and robust means of detecting and quantifying lanthanides are needed to support more efficient tracking within the nuclear, medicinal, and industrial fields. Furthermore, methods for isolating lanthanide signal from spectroscopic interferents are also needed. Applying spectroelectrochemistry to the detection of these species can meet those needs. However, application of this technique is limited by the low molar absorptivities and quantum yields of the lanthanides. These limitations can be circumvented by complexing the lanthanides with sensitizing ligands that enhance fluorescence, thereby dropping the limits of detection. Complexation will also cause changes in the electrochemical behavior of the lanthanides. To demonstrate this concept, studies were completed using europium as a model lanthanide in complexes with four different sensitizing ligands, which included 2,2′‐bipyridine and related derivatives. Results indicate that all four studied complexes demonstrate quasi‐reversible redox couples and improvements in limits of detection where electrochemical and spectroscopic characteristics showed some dependence on attached ligand. All four complexes studied display the necessary characteristics for spectroelectrochemical analysis, which was successfully and reproducibly applied to all Eu complexes.     

Total cross-sections for the scattering of positrons by helium,neon, and argon at intermediate energies

A slow positron beam time of flight system in which scattering is localised to a region of the flight path close to the slow positron source is described. Total cross-sections measured in helium, neon, and argon at intermediate energies are presented. The results for helium and neon are in agreement with the recent results of Brenton et al. While significant disagreement still exists in the argon data. The helium and neon data are in agreement with the sum rule predictions of Bransden et al.     

The discretized flow on domains of attraction: a structural stability result

It is well known that, for stepsize sufficiently small, compactattractors of ordinary differential equations persist underdiscretization. The present paper describes the structure ofthe discrete-time dynamical system obtained via discretizationon A(M_h)\M_h where M_h is the approximate attractor and A(M_h)is its domain of attraction. The existence of a smooth embeddinginto a continuous-time parallelizable flow is proved. The constructioncan be used to define sections for discretizations and can beinterpreted as a justification of the method of modified equations.