Salt effects in the aqueous alkaline hydrolysis of N-hydroxyphthalimide. Kinetic evidence for the ion-pair formation

The effects of the concentrations of LiCl, NaCl, KCl, CsCl, Na₂CO₃, BaCl₂, and Me₄NCl on the rates of reactions of hydroxide ion with ionized N-hydroxyphthalimide (NHP) at 30°C and in a H₂O–MeCN solvent containing 98%, v/v, H₂O reveal a nonlinear increase in observed rate constants with increase in salt concentrations. The observed rate constants are highly sensitive to the valence state of cations and almost insensitive to the valence state of anions of the salts. These observations are explained in terms of ion-pair formation between cations and NHP^?.     

Incremental unknowns preconditioning for solving the Helmholtz equation

An efficient preconditioner is developed for solving the Helmholtz problem in both high and low frequency (wavenumber) regimes. The preconditioner is based on hierarchical unknowns on nested grids, known as incremental unknowns (IU). The motivation for the IU preconditioner is provided by an eigenvalue analysis of a simplified Helmholtz problem. The performance of our preconditioner is tested on the iterative solution of two‐dimensional electromagnetic scattering problems. When compared with other well‐known methods, our technique is shown to often provide a better numerical efficacy and, most importantly, to be more robust. Moreover, for the best performance, the number of IU levels used in the preconditioner should be designed for the coarsest grid to have roughly two points per linear wavelength. This result is consistent with the conventional sampling criteria for wave phenomena in contrast with existing IU applications for solving the Laplace/Poisson problem, where the coarsest grid comprises just one interior point. © 2007 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2007     

Influence of Relative Permeability on the Stability Characteristics of Immiscible Flow in Porous Media

Relative permeability functions for immiscible displacements in porous media show a wide range of profiles. Although, this behavior is well known, its impact on the stability of the displacement process is unexplored. Our analysis clearly demonstrates for the first time that the viscous instability characteristics of two-phase flows are governed not only by their end point values, but are strongly dependent on the actual profile of relative permeability functions. Linear stability analysis predicts the capacity of the flow to develop large scale fingers which can result in substantial bypassing of the resident fluid. It is observed that relative permeability functions attributed to drainage processes yield a more unstable displacement as compared to functions related to imbibition processes. Moreover, instability is observed to increase for those relative permeability functions which result from increased wettability of the wetting fluid. High accuracy numerical simulations show agreement with these predictions and demonstrate how large amplitude viscous fingers result in significant bypassing for certain relative permeability functions. In the nonlinear regime, the finger amplitude grows at a rate ∝ t^1/2 initially, drops to t^1/4 at a later time and finally grows ∝ t. The basic mechanisms of finger interaction, however, are not substantially influenced by relative permeability functions.     

The influence of synthetic conditions on the stability of methotrexate-monoclonal antibody conjugates determined by reversed phase high performance liquid chromatography.

Methotrexate (MTX) has been convalently attached to an IgG-type monoclonal antibody (791T/36) directed to tumour-associated antigen gp72. Conjugates were synthesized by the active ester method using MTX N-succinimidyl ester at various pH values (7.5-10.5). Following purification by gel filtration, high performance liquid chromatography was used to assess the free drug or its derivatives in samples of MTX-791T/36 conjugates previously treated (or not) with hydroxylamine. Quantitative analysis, performed on a reversed phase column (pore size 300 A) with isocratic acetonitrile-sodium acetate buffer (pH 4.8) as mobile phase, indicated no detectable amount of free methotrexate in hydroxylamine-treated conjugates even six months after their preparation. Similar observations were made with conjugates, whose synthesis were performed at pH greater than or equal to 10. In contrast, the presence of increasing amounts of drug/metabolite could be demonstrated in samples produced at lower pH values. Based on these findings, the pH-dependent kinetics of MTX release has been determined and used to design conditions under which stable MTX-791T/36 conjugates could be prepared without hydroxylamine reaction.     

Headspace SPME–GC Method for Acetone Analysis and its Biomedical Application

A new method for extraction and analysis of acetone in human urine based on headspace solid phase microextraction using a mixture of activated carbon and zeolite as sorbents in a PVC matrix coated on a silver wire and its application to the determination of ketone bodies is described. Unlike commercial fibers, which are coated on fused silica, the coating adheres strongly to the silver wire and is thermally stable up to 250 °C. After optimization of coating composition and microextraction conditions the fiber was used for the analysis of acetone in human urine.     

Studies on recoil proton tracks in NTA films with the T(d,n)He reaction

Recoil proton tracks in nuclear emulsion are counted by scanning them using strip, square or circular field of view of optical microscope. In this paper, the overestimate due to the edge effects in counting recoil proton tracks at different neutron energies produced from the T(d,n)⁴He reaction has been determined by measuring the true track density in NTA film. The overestimate has also been calculated using the measured value of the mean projected track length (L) in the film. The percentage of measured overestimates has been compared with those obtained by calculation and the results agree reasonably well. Fading effect in NTA film has been studied and found to be 22% more in the summer than in the winter season. A great reduction in fading rate could be achieved if the films are desiccated and sealed in highly pure dry nitrogen maintained at an over-pressure of 1000 Pa to reduce water vapour ingress. After the edge effect correction, the sensitivity of NTA film has been calculated from (1.72±0.08)×10⁻³ tracksn⁻¹ to (1.97±0.16)×10⁻³ tracksn⁻¹ in the neutron energy ranges from 15.91 to 18.88 MeV. The response was found to be from 0.24±0.02 trackscm⁻² permSv to 0.26±0.01 trackscm⁻² permSv in the same energy range.