Kinetic studies on the solvolysis and axial ligand substitutions of bis-triphenylphosphine(cyclohexane-1,2-dione-dioximato)ruthenium(II) in non-aqueous solvents

Kinetic studies of ligand substitutions of the six-coordinated Ru^II pseudo-macrocyclic complex [Ru(CHDH)₂- (PPh₃)₂] (CHDH=cyclohexanedione-dioximato) have been spectrophotometrically investigated in a variety of solvents and at 70, 80, 85 and 90°C. The reactions studied are of the form:[(PPh₃)Ru(CHDH)₂(PPh₃)] + L =[(PPh₃)Ru(CHDH)₂L] + PPH₃ where L is imidazole, pyridine, piperidine or thiophene or a solvent molecule (PhCl, PhMe, MeCN, DMSO or DMF). The solvolysis reactions with chlorobenzene and toluene proceed to an equilibrium position favoring the bis-triphenylphosphine complex. All other reactions proceed to completion. From a mechanistic point of view the reactions were found to proceed through the formation of a five coordinate intermediate that possesses little or no discriminating ability towards the incoming nucleophiles. The rate data were thus interpreted in terms of a dissociative (D) or dissociative interchange (Id) mechanism. Activation parameters H and S are reported. Preliminary studies on the solvatochromic behavior of [Ru(CHDH)₂(PPh₃)₂] and the corresponding mixed complexes are discussed.     

Rapid micellar HPLC analysis of loratadine and its major metabolite desloratadine in nano-concentration range using monolithic column and fluorometric detection: application to pharmaceuticals and biological fluids

Background

Loratadine is a commonly used selective non-sedating antihistaminic drug. Desloratadine is the active metabolite of loratadine and, in addition, a potential impurity in loratadine bulk powder stated by the United States Pharmacopeia as a related substance of loratadine. Published methods for the determination of both analytes suffer from limited throughput due to the time-consuming steps and tedious extraction procedures needed for the analysis of biological samples. Therefore, there is a strong demand to develop a simple rapid and sensitive analytical method that can detect and quantitate both analytes in pharmaceutical preparations and biological fluids without prior sample extraction steps.

Results

A highly-sensitive and time-saving micellar liquid chromatographic method is developed for the simultaneous determination of loratadine and desloratadine. The proposed method is the first analytical method for the determination of this mixture using a monolithic column with a mobile phase composed of 0.15 M sodium dodecyl sulfate, 10% n-Butanol and 0.3% triethylamine in 0.02 M phosphoric acid, adjusted to pH 3.5 and pumped at a flow rate of 1.2 mL/min. The eluted analytes are monitored with fluorescence detection at 440 nm after excitation at 280 nm. The developed method is linear over the concentration range of 20.0–200.0 ng/mL for both analytes. The method detection limits are 15.0 and 13.0 ng/mL and the limits of quantification are 20.0 and 18.0 ng/mL for loratadine and desloratadine, respectively. Validation of the developed method reveals an accuracy of higher than 97% and intra- and inter-day precisions with relative standard deviations not exceeding 2%.

Conclusions

The method can be successfully applied to the determination of both analytes in various matrices including pharmaceutical preparations, human urine, plasma and breast milk samples with a run-time of less than 5 min and without prior extraction procedures. The method is ideally suited for use in quality control laboratories. Moreover, it could be a simple time-saving alternative to the official pharmacopeial method for testing desloratadine as a potential impurity in loratadine bulk powder.

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Graphical abstract Typical chromatogram of loratadine and its major metabolite desloratadine using the proposed micellar HPLC method

     

A self-consistent boundary element, parametric dislocation dynamics formulation of plastic flow in finite volumes

We present a self-consistent formulation of 3-D parametric dislocation dynamics (PDD) with the boundary element method (BEM) to describe dislocation motion, and hence microscopic plastic flow in finite volumes. We develop quantitative measures of the accuracy and convergence of the method by considering a comparison with known analytical solutions. It is shown that the method displays absolute convergence with increasing the number of quadrature points on the dislocation loop and the surface mesh density. The error in the image force on a screw dislocation approaching a free surface is shown to increase as the dislocation approaches the surface, but is nevertheless controllable. For example, at a distance of one lattice parameter from the surface, the relative error is less than 5% for a surface mesh with an element size of 1000×2000 (in units of lattice parameter), and 64 quadrature points. The Eshelby twist angle in a finite-length cylinder containing a coaxial screw dislocation is also used to benchmark the method. Finally, large scale 3-D simulation results of single slip behavior in cylindrical microcrystals are presented. Plastic flow characteristics and the stress-strain behavior of cylindrical microcrystals under compression are shown to be in agreement with experimental observations. It is shown that the mean length of dislocations trapped at the surface is the dominant factor in determining the size effects on hardening of single crystals. The influence of surface image fields on the flow stress is finally explored. It is shown that the flow stress is reduced by as much as 20% for small single crystals of size less than .     

Radiation effects on polymers—XI. Radiation grafting of acrylamide on to cellulose acetate reverse osmosis membranes

With the aim of improving properties of cellulose acetate membranes for reverse osmosis desalination, grafting was performed using high energy electrons. In this paper, the grafting parameters (radiation dose and method, monomer concentration, solvents, chain transfer agent and redox system) are considered; conclusions are drawn as to the grafting content and mode of grafting.     

Characterizing photolithographic linewidth sensitivity to process temperature variations for advanced resists using a thermal array

A thermal system is developed to rapidly characterize the linewidth sensitivity of advanced resists to process temperature variations in the photolithographic manufacturing sequence. This thermal array consists of a 7×7 grid of individually programmable heating zones distributed within a thermal cycling apparatus. It is used to improve the quality and quantity of data for determining the optimal thermal conditions by effectively producing equivalent operating conditions besides the spatially controlled temperature. The system is demonstrated for the optimization of the post-apply and post-exposure thermal-processing conditions for chemically amplified photoresists used in the fabrication of quartz photomasks . PACS 07.20.Hy; 81.16.Nd; 81.70.Pg     

Trapping and escape of dislocations in micro-crystals with external and internal barriers

We perform three-dimensional dislocation dynamics simulations of solid and annular pillars, having both free-surface boundary conditions, or strong barriers at the outer and/or inner surfaces. Both pillar geometries are observed to exhibit a size effect where smaller pillars are stronger. The scaling observed is consistent with the weakest-link activation mechanism and depends on the solid pillar diameter, or the annular pillar effective diameter, D_eff = D − D_i, where D and D_i are the external and internal diameters of the pillar, respectively. An external strong barrier is observed to dramatically increase the dislocation density by an order of magnitude due to trapping dislocations at the surface. In addition, a considerable increase in the flow strength, by up to 60%, is observed compared to simulations having free-surface boundary conditions. As the applied load increases, weak spots form on the surface of the pillar by dislocations breaking through the surface when the RSS is greater than the barrier strength. The hardening rate is also observed to increase with increasing barrier strength. With cross-slip, we observe dislocations moving to other glide planes, and sometimes double-cross-slipping, producing a thickening of the slip traces at the surface. Finally the results are in qualitative agreement with recent compression experimental results of coated and centrally-filled micropillars.     

Preparation of capped silver nanoparticles using sunlight and cationic surfactants and their biological activity

Silver nanoparticles were prepared in situ using sunlight and cationic surfactants. Silver nano-particles were confirmed using UV–vis spectrophotometry, transmission electron microscopy(TEM), electron diffraction, dynamic light scattering(DLS) and FTIR. Increasing the hydrophobic chain length of surfactants increase the amount of silver nano-particles formed in addition to increasing their stability.The results showed formed, uniform, well arranged hexagonal and spherical shapes. The prepared silver nanoparticles exhibit enhanced biological activity against Gram-positive, Gram-negative bacteria and sulfate reducing bacteria(SRB).     

Thermodynamic properties of 1-butyl-3-methylpyridinium tetrafluoroborate

Pressure, density, temperature (p, ρ, T) data of 1-butyl-3-methylpyridinium tetrafluoroborate [C4mpyr][BF₄] at T = (283.15 to 393.15) K and pressures up to p = 100 MPa are reported with an estimated experimental relative combined standard uncertainty of Δρ/ρ = ±(0.01 to 0.08)% in density. The measurements were carried out with a newly constructed Anton-Paar DMA HPM vibration-tube densimeter. The system was calibrated using double-distilled water, methanol, toluene and aqueous NaCl solutions. An empirical equation of state for fitting of the (p, ρ, T) data of [C4mpyr][BF₄] has been developed as a function of pressure and temperature to calculate the thermal properties of the ionic liquid (IL), such as isothermal compressibility, isobaric thermal expansibility, differences in isobaric and isochoric heat capacities, thermal pressure coefficient and internal pressure. Internal pressure and the temperature coefficient of internal pressure data were used to make conclusions on the molecular characteristics of the IL.     

Nonlinear dynamics associated with rotating magnetized electron-positron-ion plasmas

By using the hydrodynamic equations of electrons and positrons and Poisson equation with stationary ions, a three-dimensional extended Zakharov-Kuznetsov (EZK) equation is derived for small but finite amplitude nonlinear Langmuir structures (solitary and shock pulses) The EZK equation is solved analytically and the features of the nonlinear excitations are investigated numerically. Furthermore, the propagation condition for the nonlinear structures is examined.     

Radiation effects on polymers—XII. Molecular weight and molecular weight distribution of cellulose acetate-grafted polyacrylamide side-chains and homopolyacrylamide using gel permeation chromatography

Calibration of gel permeation chromatography was carried out to determine molecular weight and molecular weight distribution of the side-chains and homopolymer formed during grafting of cellulose acetate with acrylamide monomer using accelerated electrons. Polyacrylamide in side-chains and in homopolymer was found to be of very high molecular weight; the grafting event was found to be as low as 1–10 polyacrylamide chains per 10³ cellulose acetate chains.