Synthesis of modified vitamin D precursors

Modified vitamin D precursors with oxygen-containing substituents at various positions in the side-chain were obtained using previously synthesized 20-isoxazolin-3-yl-and 20-isoxazolin-5-ylsteroids.Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, 220141 Minsk, Belarus;Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 230–235, February, 2000.     

Certification of reference materials for inorganic trace analysis: the INCT approach

This paper presents the work done by the Institute of Nuclear Chemistry and Technology (INCT), Warsaw on a procedure of the certification of matrix reference materials (CRMs) for inorganic trace analysis. The INCT has been involved in preparation and certification of that type of CRMs since 1986 till now. The certification of CRMs is performed on the basis of statistical evaluation of the data obtained from the worldwide interlaboratory comparison. The initially adopted certification procedure has been developed, and the final shape is presented and discussed. The modifications are connected with the new demands of the international standards. The results of analysis of candidate CRMs obtained by the potentially primary procedures based on radiochemical neutron activation analysis (RNAA) and results of analysis of CRM accompanying candidate RMs are applied in the certification process for quality assurance purpose.     

Preparation of a new Cd(II)-imprinted polymer and its application to determination of cadmium(II) via flow-injection-flame atomic absorption spectrometry

A new cadmium(II)-imprinted polymer based on cadmium(II) 2,2′-{ethane-1,2-diylbis[nitrilo(E)methylylidene]} diphenolate-4-vinylpyridine complex was obtained via suspension polymerization. The beads were used as a minicolumn packing for flow-injection-flame atomic absorption spectrometry (FI-FAAS) determination of cadmium(II) in water samples. Sorption effectiveness was optimal within pH range of 6.6-7.7. Nitric acid, 0.5% (v/v) was used as eluent. Fast cadmium(II) sorption by the proposed material enabled to apply sample flow rates up to 10 mL min⁻¹ without loss in sorption effectiveness. Enrichment factor (EF), concentration efficiency (CE) and limit of detection (LOD, 3σ) found for 120-s sorption time were 117, 39.1 min⁻¹ and 0.11 μg L⁻¹, respectively. Sorbent stability was proved for at least 100 preconcentration cycles (RSD = 2.9%). When compared to non-imprinted polymer the new Cd(II)-imprinted polymer exhibited improved selectivity towards cadmium(II) against other heavy metal ions, especially Cu(II) and Pb(II), as well as light metal ions. Accuracy of the method was tested for ground water and waste water certified reference materials and fortified water. The method was applied to Cd(II) determination in natural water samples.     

New look inside human breast ducts with Raman imaging. Raman candidates as diagnostic markers for breast cancer prognosis: Mammaglobin,palmitic acid and sphingomyelin

Looking inside the human body fascinated mankind for thousands of years. Current diagnostic and therapy methods are often limited by inadequate sensitivity, specificity and spatial resolution. Raman imaging may bring revolution in monitoring of disease and treatment. The main advantage of Raman imaging is that it gives spatial information about various chemical constituents in defined cellular organelles in contrast to conventional methods (liquid chromatography/mass spectrometry, NMR, HPLC) that rely on bulk or fractionated analyses of extracted components. We demonstrated how Raman imaging can drive the progress on breast cancer just unimaginable a few years ago. We looked inside human breast ducts answering fundamental questions about location and distribution of various biochemical components inside the lumen, epithelial cells of the duct and the stroma around the duct during cancer development. We have identified Raman candidates as diagnostic markers for breast cancer prognosis: carotenoids, mammaglobin, palmitic acid and sphingomyelin as key molecular targets in ductal breast cancer in situ, and propose the molecular mechanisms linking oncogenes with lipid programming.     

Interactions of polar hydrogen bond donor solvents with ions: a theoretical study

Structural Chemistry - Intermolecular interactions between molecules of protic solvents (water, methanol, formic acid, formamide, methylamine and ammonia) and monatomic ions (Li+, Na+, K+,...     

Ortho effect in the mass spectrometric behaviour of N(pyrimidin-4-yl)aminobenzoic acids and their methyl esters

Ortho-. meta- and para-isomers of N-(pyrimidin-4-yl)aminobenzoic acid and their methyl esters were investigated by electron impact mass Spectrometry. Their fragmentation was found to be strongly dependent on the position of the substituent in the aminobenzoic moiety. Two different kinds of ortho effect were studied and confirmed with the aid of deuterium-labelled derivatives.     

Determination of phenol and catechol concentrations with oxygen probes coated with immobilized enzymes or immobilized cells

The enzyme phenol 2-hydroxylase was immobilized on Sepharose and used in conjunction with an O₂ electrode for quantitating phenol. Similarly, catechol 1,2-oxygenase was used for quantitating catechol. A third probe was prepared by immobilization ofTrichosporon cutaneum cells rather than purified phenol 2-hydroxylase for phenol quantitation. The whole cell system gave results comparable to the immobilized enzyme system.     

Set-valued solutions to the Cauchy problem for hyperbolic systems of partial differential inclusions

We prove the existence of global set-valued solutions to the Cauchy problem for partial differential equations and inclusions, with either single-valued or set-valued initial conditions. The method is based on the equivalence between this problem and problem of finding viability tubes of the associated characteristic system of ordinary differential equations. As an application we construct the value function of the Mayer problem arising in control theory. Received August 25, 1995     

Estimation in the continuous time mover‐stayer model with an application to bond ratings migration

The usual tool for modelling bond ratings migration is a discrete, time‐homogeneous Markov chain. Such model assumes that all bonds are homogeneous with respect to their movement behaviour among rating categories and that the movement behaviour does not change over time. However, among recognized sources of heterogeneity in ratings migration is age of a bond (time elapsed since issuance). It has been observed that young bonds have a lower propensity to change ratings, and thus to default, than more seasoned bonds. The aim of this paper is to introduce a continuous, time‐non‐homogeneous model for bond ratings migration, which also incorporates a simple form of population heterogeneity. The specific form of heterogeneity postulated by the proposed model appears to be suitable for modelling the effect of age of a bond on its propensity to change ratings. This model, called a mover–stayer model, is an extension of a Markov chain. This paper derives the maximum likelihood estimators for the parameters of a continuous time mover–stayer model based on a sample of independent continuously monitored histories of the process, and develops the likelihood ratio statistic for discriminating between the Markov chain and the mover–stayer model. The methods are illustrated using a sample of rating histories of young corporate issuers. For these issuers the default probabilities predicted by the Markov chain and mover–stayer models are different. In particular for 1–4 years old bonds the mover–stayer model estimates substantially lower default probabilities from rating C than a Markov chain. Copyright © 2004 John Wiley & Sons, Ltd.