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.     

TSL and EPR studies of SrBPO5 doped with CeO2and co-doped with CeO2 and Sm2O3

Thermally stimulated luminescence (TSL) and electron paramagnetic resonance (EPR) investigations were carried out on gamma irradiated SrBPO₅ samples doped with CeO₂ and co-doped with CeO₂ and Sm₂O₃. On gamma-irradiation at room temperature, BO₃ ^2–, O₂ ^– and O^– radicals were produced. It was seen that the O^– radical ion disappeared in the sample annealed at 500 K. It is proposed that the recombination between trapped electrons and O^– radical ions results in transfer of recombination energy to the impurity centre Ce³⁺ resulting in TSL glow peak at 485 K. In the case of co-doped samples energy transfer occurs between Ce³⁺ to Sm³⁺ resulting in increase in the intensity of glow peak at 485 K.The authors are grateful to Dr. V. K. Manchanda, Head, Radiochemistry Division, BARC for his keen interest and encouragement during the course of this work.     

Contact angle hysteresis of liquid drops as means to measure adhesive energy of zein on solid substrates

Adhesion of zein to solid substrates has been studied using surface energy profiles as indices and by adhesion mapping using atomic force microscopy (AFM). Different plasticizers like glycerol and sorbitol have been used to form mixed films with zein and properties of these films are studied using surface energy profiles. Comparison of the results from the different mixed samples with those from the pure zein films showed that force mapping could identify areas rich in protein. The adhesion maps produced were deconvoluted from sample topography and contrasted with the data obtained from contact angle measurements. A comparison of the two methods shows that the extent of contact angle hysteresis is indicative of both hydrophobicity of the surface as well as the force of adhesion. Mechanical properties and microstructure of zein films prepared by casting from solutions and using Langmuir-Blodgett film technique have been investigated. Pure zein seemed brittle and exhibited an essentially linear relationship between stress and strain. Films with plasticizer were tougher than these films. In general, mixed films showed better mechanical properties than pure films and had higher ultimate tensile strength and increased per cent elongation. Further, the mixed films of zein showed a higher force of adhesion compared to the pure films.     

Tuning size and catalytic activity of nano-clusters of cobalt oxide

Cobalt oxides were prepared by three different methods: (1) by reacting cobalt nitrate with oxalic acid, (2) co-precipitating cobalt nitrate with sodium carbonate, and (3) using sodium dodecyl sulphate as organic surfactant. All three samples were characterized before and after calcination by solvent extraction and the resulting products examined by IR spectroscopy. In the case of method 3, the removal of surfactant was followed by TGA studies. Products from all three methods were identified by XRD. Peaks in low angle XRD indicate the porous nature of the oxides. The morphology of the pores was studied by transmission electron microscopy. Some irregular pore structures were obtained for samples from methods 1 and 2, with an average size of 4–6 nm. Only the product from method 3 using SDS as template showed ordered structure and optimum size, and Brunauer-Emmet-Teller surface areas of the as-prepared, as well as the treated samples, exhibited H3 type hysteresis. The samples from the three methods were used as catalysts in the oxidation reaction of cyclohexane under mild conditions and the catalytic efficiency of the cobalt oxide was comparable with mesoporous cobalt oxides.     

Simple high-performance liquid chromatographic method for the concurrent determination of the amine metabolites vanillylmandelic acid, 3-methoxy-4-hydroxyphenylglycol, 5-hydroxyindoleacetic acid, dihydroxyphenylacetic acid and homovanillic acid in urine using electrochemical detection

A simple method for the concurrent analysis of the noradrenaline metabolites vanillylmandelic acid and 3-methoxy-4-hydroxyphenylglycol, the dopamine metabolites dihydroxyphenylacetic acid and homovanillic acid, and the serotonin metabolite 5-hydroxyindoleacetic acid in human urine is described. Following organic extraction of the metabolites from acidified urine, they are separated by single-step gradient elution high-performance liquid chromatography on a reversed-phase column. Detection and quantification are achieved with an electrochemical detector using a carbon-paste electrode; samples can be injected at 40-min intervals. Optimisation of analytical parameters is described, and examples of the application of the method in the fields of clinical chemistry and clinical neuroscience are given. This provides a convenient method for the concurrent study of the metabolism of three major biogenic amines, and is readily adaptable for studies on cerebrospinal fluid and brain tissue.     

N-benzamidosalicylaldimine complexes of copper(II), nickel(II), cobalt(II), iron(II), manganese(II), oxyvanadium(IV) and oxytitanium(IV)

Summary N-benzamidosalicylaldimine (H₂L) complexes of Cu^II, Ni^II, Co^II, Fe^II, Mn^II. VO_IV and TiO_IV have been prepared. The ligand probably coordinates to the metal from the hydroxyl, carbonyl and imino groups.     

Design,synthesis and characterization of peptidyl boronate analogues as effective antimicrobial agents

Research on Chemical Intermediates - Antibiotic-resistant penicillin binding protein (PBPs) production is one of the reasons why bacteria develop resistance to β-lactam antibiotics, and this...