Additive Positive Stable Frailty Models

In this article, we describe an additive stable frailty model for multivariate times to events data using a flexible baseline hazard, and assuming that the frailty component for each individual is described by additive functions of independent positive stable random variables with possibly different stability indices. Dependence properties of this frailty model are investigated. To carry out inference, the likelihood function is derived by replacing high-dimensional integration by Monte Carlo simulation. Markov chain Monte Carlo algorithms enable estimation and model checking in the Bayesian framework.      

Substitution of aqua ligands fromcis-diaqua-bis(bipyridyl) ruthenium(II) by 1, 10-phenanthroline in aqueous medium

The kinetics of aqua ligand substitution fromcis-[Ru(bipy)₂(H₂O)₂]²⁺ by 1, 10-phenanthroline (phen) have been studied spectrophotometrically in the 35 to 50°C temperature range. We propose the following rate law for the reaction within the 3.65 to 5.5 pH range:

The reaction kinetics of NiCl2 in silica-alumina gel matrix

Insitu isothermal reduction of NiCl₂ by dextrose in silica-alumina gel matrix has been carried out between 800 and 950 °C under nitrogen atmosphere. The predominant mechanism of reaction is found to be nucleation and growth. X-ray diffraction (XRD) analyses of reacted samples confirm the presence of metallic Ni, nickel aluminate and finely dispersed alumina in the reacted samples. The average particle size of nickel has been determined by transmission electron micrograph (14 nm) as well as XRD (17±2 nm).     

Fluorescence resonance energy transfer from tryptophan in human serum albumin to a bioactive indoloquinolizine system

The interaction between a bioactive molecule, 3-acetyl-4-oxo-6,7-dihydro-12H indolo-[2,3-a] quinolizine (AODIQ), with human serum albumin (HSA) has been studied using steady-state absorption and fluorescence techniques. A 1:1 complex formation has been established and the binding constant (K) and free energy change for the process have been reported. The AODIQ-HSA complex results in fluorescence resonance energy transfer (FRET) from the tryptophan moiety of HSA to the probe. The critical energy-transfer distance (R ₀) for FRET and the Stern-Volmer constant (K _sv) for the fluorescence quenching of the donor in the presence of the acceptor have been determined. Importantly, K _SV has been shown to be equal to the binding constant itself, implying that the fluorescence quenching arises only from the FRET process. The study suggests that the donor and the acceptor are bound to the same protein at different locations but within the quenching distance.     

Relativistic Ornstein–Uhlenbeck Process

We wish to shed some light on the problem of thermodynamic irreversibility in the relativistic framework. Therefore, we propose a relativistic stochastic process based on a generalization of the usual Ornstein–Uhlenbeck process: we introduce a relativistic version of the Langevin equation with a damping term which has the correct Galilean limit. We then deduce relativistic Kramers and Fokker–Planck equations and a fluctuation-dissipation theorem is derived from them. Finally, numerical simulations are used to check the equilibrium distribution in momentum space and to investigate diffusion in physical space.     

Synthesis,characterization, and antimicrobial activity of some novel poly(ether ketone)s

Low molecular weight poly(ether ketone)s were synthesized from phenol, 1,4‐phenylenedioxy diacetylchloride, chloroacetylchloride, and dichloroalkanes [1,2‐dichloroethane and dichloromethane] by a Friedel–Crafts reaction with anhydrous aluminum chloride as a catalyst and carbon disulfide as a solvent. The conditions for the preparation of the poly(ether ketone)s and the chlorine contents obtained with the Carius method were examined, and a reaction scheme for each resin was established. The molecular weights and polydispersities of the resins were obtained by gel permeation chromatography. The polyketones were characterized by IR spectroscopy. The characteristic frequencies due to different functional groups were assigned. The thermal properties of the resins were studied with thermogravimetry and differential scanning calorimetry. The characteristic temperatures of thermal degradation for the poly(ether ketone)s were evaluated with thermogravimetric analysis. The kinetic parameters for the decomposition reactions of the resins were obtained with Broido and Doyle's method, and the heats of fusion were obtained from differential scanning calorimetry thermograms. The polyketones were thermally stable up to 200 °C. All the polyketones were tested for their microbial properties against bacteria, fungi, and yeast. The effect of poly(ether ketone)s on the growth of these microorganisms was investigated, and the polyketones were found to inhibit the growth of the microorganisms to a considerable extent. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2335–2344, 2003     

Reaction of 2-(arylazo)pyridine complexes of type [OsX2L2] (X = Cl or Br) with heterocyclic bases (B): spectra and electrochemistry of [OsX(B)L2]ClO4·H2O

Summary The synthesis and characterization of a series of complexes of the type [OsX(B)L₂] ⁺ (X = Cl or Br, B = pyridine (py) and pyrazine (pyz), L = 2-(phenylazo)pyridine (L¹) or 2-(m-tolylazo)pyridine (L²)) is described. The cations have been isolated as crystalline perchlorate monohydrates after purification by column chromatography. The diamagnetic compounds display several spin-allowed and spin-forbidden m.l.c.t. transitions in the visible region. The metal-centred oxidations and ligand-based reductions of the complexes are studied electrochemically in MeCN. Two consecutive one-electron oxidations corresponding to Os^III/Os^II and Os^IV/Os^III couples occur at ca. 1.3 and ca. 2.3 V versus s.c.e. respectively. Four successive azo-reductions are observable in the potential range -0.4 to -2.4V.     

Efficient Entrapment of Dye in Hollow Silica Nanoparticles: Direct Evidence Using Fluorescence Spectroscopy

Using hollow silica nanoparticles we demonstrate a simple and highly efficient way of removing hydrophilic dye (Rhodamine B) from water by encapsulation within these hollow spheres. The hollow silica spheres were obtained by using a surfactant templated procedure. Using fluorescence spectroscopy, we also show the evidence of the dye being absorbed within the hollow core of the silica shell (which is crucial for many applications) and differentiate from the adsorption of dye on the surface of the silica shell. It was found that that up to 94 % of the hydrophilic dye could be entrapped using these hollow shells within 72 h of exposure. Fluorescence spectroscopy shows a red shift in the dye encapsulated in the hollow silica which is due to aggregation of the dye and enables us to follow quantitatively the uptake of the dye molecules by the silica shells with time. The evidence for the encapsulation of the dye in these hollow spheres was reinforced by carrying out a comparative study, using solid silica particles.

An investigation into flow mode transition and pressure fluctuations for fluidized dense-phase pneumatic conveying of fine powders

This paper presents the results of an ongoing investigation into the fluctuations of pressure signals due to solids-gas flows for dense-phase pneumatic conveying of fine powders.Pressure signals were obtained from pressure transducers installed along different locations of a pipeline for the fluidized dense-phase pneumatic conveying of fly ash(median particle diameter 30μm;particle density 2300kg/m~3;loosepoured bulk density 700kg/m~3) and white powder(median particle diameter 55 u.m;particle density1600kg/m~3;loose-poured bulk density 620kg/m~3) from dilute to fluidized dense-phase.Standard deviation and Shannon entropy were employed to investigate the pressure signal fluctuations.It was found that there is an increase in the values of Shannon entropy and standard deviation for both of the products along the flow direction through the straight pipe sections.However,both the Shannon entropy and standard deviation values tend to decrease after the flow through bend(s).This result could be attributed to the deceleration of particles while flowing through the bends,resulting in dampened particle fluctuation and turbulence.Lower values of Shannon entropy in the early parts of the pipeline could be due to the non-suspension nature of flow(dense-phase),i.e.,there is a higher probability that the particles are concentrated toward the bottom of pipe,compared with dilute-phase or suspension flow(high velocity),where the particles could be expected to be distributed homogenously throughout the pipe bore(as the flow is in suspension).Changes in straight-pipe pneumatic conveying characteristics along the flow direction also indicate a change in the flow regime along the flow.     

Homogeneous Palladium Nanoparticles Surface Hosts Catalyzed Reduction of the Chromophoric Azo (–N=N–) Group of Dye,Acid Orange 7 by Borohydride in Alkaline Media

In alkaline media, well‐characterized gelatin‐stabilized palladium (GPd) nanoparticles catalyze the reduction of the azo group containing pollutant dye, Acid Orange 7 (AO7) by sodium borohydride (NaBH₄) to 1‐amino‐2‐napthol and sulfanilic acid. Kinetic observations and detailed FTIR studies suggests that the reaction follows Langmuir–Hinshelwood kinetic model, where during the reaction both AO7 and borohydride are adsorbed on the GPd surface. Plots of lnk_o versus ln[AO7] or ln[NaBH₄] show that the order of reaction with respect to AO7 and NaBH₄ remains almost same over different molar ratios of [NaBH₄]/[AO7]. The catalyzed reaction shows an initial induction period (t₀) due to a surface‐restructuring process of GPd nanoparticles, and (1/t₀) can be defined as the rate of surface restructuring. The activation energy of the catalyzed reaction and energy of the surface‐restructuring process of GPd are estimated as 22 ± 3 and 25 ± 7 kJ M^?1, respectively.