On the Parametrization of the Afocal Stable Distributions

Thanks to Hall's documentation of a situation he described asa ‘Comedy of errors’ in the earlier literature onstable distributions, there is now general agreement as to theparametrization of these distributions when standardized asto location and scale. However, two subtly different parametrizationsof location and scale remain current in the afocal stable cases,defined as those with characteristic exponent = 1 and skewnessparameter ß 0. The more widely used parametrization,adopted by Hall and two recent monographs, lacks the linearityproperty that is ordinarily expected of location and scale parameters.This note shows that the alternative parametrization has thislinearity property, and compares the implications of the twoparametrizations for properties of stable distributions. A thirdrecent monograph seeks to avoid these issues by denying thatthe afocal stable distributions are stable at all, but it isshown that they are, in fact, integral members of the stablefamily.     

Microporous hypercrosslinked polystyrene Styrosorb as a restricted access packing in sample clean-up for high performance liquid chromatography. Part I: Evaluation of restricted access properties

Summary Styrosorb is a beaded microporous polystyrene with particle sizes between 2 and 4 m. In spite of hypercrosslinkage the material was seen to swell in organic solvents. The native material is functionalized with Tris-groups at the outer surface of the particles. The average pore diameter was determined as 1.45±0.3 nm from size exclusion data using polystyrene and polyethylene standards in THF. The reversed phase behavior of the restricted access phase Styrosorb was investigated by injection of two test mixtures. Mixture I contained five aromatic amines, mixture II consisted of Amperozide^R and four related compounds. The optimum range of mobile phase composition was assessed so that analytes were separated whilst any proteins present were eluted unretained. Due to the small particle size short columns of 29×4 mm can be used for both sample clean-up and analytical separation of Amperozide^R and its metabolite.     

ULTRAVIOLET LIGHT-INDUCED FREE RADICAL FORMATION IN SKIN: AN ELECTRON PARAMAGNETIC RESONANCE STUDY

It has been suggested that ultraviolet light induces free radical formation in skin, leading to photoaging and cancer. We have demonstrated by electron paramagnetic resonance that the ascorbate free radical is naturally present in unexposed skin at a very low steady state level. When a section of SKH-1 hairless mouse skin in an EPR cavity is exposed to UV light (4,500 J m⁻²−1, Xe lamp, 305 nm cutoff and IR filters), the ascorbate free radical signal intensity increases. These results indicate that UV light increases free radical oxidative stress, consistent with ascorbate's role as the terminal, small-molecule antioxidant. The initial radicals produced by UV light would have very short lifetimes at room temperature; thus, we have applied EPR spin trapping techniques to detect these radicals. Using α-[4-pyridyl 1-oxide]-N- tert -butyl nitrone (POBN), we have for the first time spin trapped a UV light-produced carbon-centered free radical from intact skin. The EPR spectra exhibited hyperfine splittings that are characteristic of POBN/alkyl radicals, a^N= 15.56 G and a^H= 2.70 G, possibly generated from membrane lipids as a result of β-scission of lipid alkoxyl radicals. Iron can act as a catalyst for free radical oxidative reactions; chronic exposure of skin to UV radiation causes increased iron deposition. Using our spin trapping system, we have shown that topical application of the iron-chelator, Desferal, to a section of skin reduces the UV light-induced POBN adduct radical signal. These results provide direct evidence for free radical generation and a role for iron in UV light-induced dermatopathology. We suggest that iron chelators can serve as photoprotective agents by preventing these oxidations.     

Microstructured cocultures of cardiac myocytes and fibroblasts: a two-dimensional in vitro model of cardiac tissue.

Cardiac myocytes and fibroblasts are essential elements of myocardial tissue structure and function. In vivo, myocytes constitute the majority of cardiac tissue volume, whereas fibroblasts dominate in numbers. In vitro, cardiac cell cultures are usually designed to exclude fibroblasts, which, because of their maintained proliferative potential, tend to overgrow the myocytes. Recent advances in microstructuring of cultures and cell growth on elastic membranes have greatly enhanced in vitro preservation of tissue properties and offer a novel platform technology for producing more in vivo-like models of myocardium. We used microfluidic techniques to grow two-dimensional structured cardiac tissue models, containing both myocytes and fibroblasts, and characterized cell morphology, distribution, and coupling using immunohistochemical techniques. In vitro findings were compared with in vivo ventricular cyto-architecture. Cardiac myocytes and fibroblasts, cultured on intersecting 30-microm-wide collagen tracks, acquire an in vivo-like phenotype. Their spatial arrangement closely resembles that observed in native tissue: Strands of highly aligned myocytes are surrounded by parallel threads of fibroblasts. In this in vitro system, fibroblasts form contacts with other fibroblasts and myocytes, which can support homogeneous and heterogeneous gap junctional coupling, as observed in vivo. We conclude that structured cocultures of cardiomyocytes and fibroblasts mimic in vivo ventricular tissue organization and provide a novel tool for in vitro research into cardiac electromechanical function.     

Stabilisation of [Fe2(CO)9] and [Ru2(CO)9] bu substitution with bridging diphosphorus ligands

Reaction of [Fe₂(CO)₉] with a half molar amount of R₂PYPR₂ (Y = CH₂, R = Ph, Me, OMe or OPrⁱ; Y = N(Et), R = OPh, OMe or OCH₂; Y = N(Me), R = OPrⁱ or OEt) leads to the ready formation of a product which on irradiation with ultraviolet light rapidly decarbonylates to the heptacarbonyl derivative [Fe₂(μ-CO)(CO)₆{μ-R₂PYPR₂}]. Treatment of the latter with a slight excess of the appropriate ligand results, under photochemical conditions, in the formation of the dinuclear pentacarbonyl complex [Fe₂(μ-CO)(C))₄{μ-R₂PYPR₂}₂] but under thermal conditions in the formation of the mononuclear species [Fe(CO)₃{R₂PYPR₂}]. Reaction of [Ru₃(CO)₁₂] with an equimolar amount of (RO)₂PN(R′)P(OR)₂ (R′ = Me, R = Prⁱ or Et; R′ = Et, R = Ph or Me) under either thermal or photochemical conditions produces [Ru₃(CO)₁₀{μ-(RO)₂PN(OR)₂}] which reacts further with excess (RO)₂PN(R′)P(OR)₂ on irradiation with ultraviolet light to afford the dinuclear compound [Ru₂(μ-CO)(CO₄{μ-(RO)₂PN(R′)P(OR)₂}₂]. The molecular structure of [Ru₂(μ-CO)(CO)₄{μ-(MeO)₂PN(Et)P(OMe)₂}₂], which has been determined by X-ray crystallography, is described.     

The U.S. Department of Energy (DOE) Sampling and Analytical Chemistry Guide: Doe Methods for Evaluating Environmental and Waste Management Samples

Abstract

DOE Methods for Evaluating Environmental and Waste Management Samples (DOE Methods) is a guidance/methods document to support sampling and analysis activities at DOE sites. DOE Methods is intended to supplement existing guidance documents (e.g., EPA's Test Methods for Evaluating Solid Waste, SW-846), which generally apply to low-level or nonradioactive samples. DOE Methods targets the complexities of DOE radioactive mixed waste and environmental samples. The document contains quality assurance (QA), quality control (QC), safety, sampling, organic analysis, inorganic analysis, and radioanalytical guidance as well as sampling and analytical methods. An addendum is distributed every six months (April and October) with updated guidance and additional methods.

DOE Methods provides a vehicle for technology transfer within the environmental restoration (ER) and waste management (WM) (collectively known as EM) community. As DOE Methods evolves, its usefulness and applicability are anticipated to grow to meet the demands of the DOE/EM mission. At the present time, DOE Methods contains methods and guidance information supplied by DOE sites. Because the EM activities in DOE are not unique to the United States, the international environmental community could benefit from the information gathered for the DOE program. This information could provide additional resources for their EM activities.     

Gibbs Sampling with Diffuse Proper Priors: A Valid Approach to Data-Driven Inference?

Abstract

This article demonstrates by example that the use of the Gibbs sampler with diffuse proper priors can lead to inaccurate posterior estimates. Our results show that such inaccuracies are not merely limited to small sample settings.