OFFGEL isoelectric focusing and polyacrylamide gel electrophoresis separation of platinum-binding proteins

In this work a 2D electrophoretic separation procedure able to maintain the integrity of platinum-protein bonds has been developed. The method is based on the use of sequential OFFGEL isoelectric focussing (IEF) and PAGE. A systematic study of the reagents used for PAGE, for OFFGEL-IEF separation, and post-separation treatment of gels (such as enzymatic digestion and sample preparation for MS analysis) was tackled regarding their suitability for the identification of platinum binding proteins using standard proteins incubated with cisplatin. The distribution of platinum in high and low molecular weight fractions (separated by cut-off filters) was determined by ICP-MS, which allows evaluating platinum-protein bond stability under the conditions studied. SDS-PAGE in the absence of β-mercaptoethanol or dithiotreitol preserved the platinum-protein bonds. In addition, neither the influence of the electric field during the electrophoretic separation, nor the processes of fixing, staining and destaining of proteins in the gel did result in the loss of platinum from platinum binding proteins. SDS-PAGE under non-reducing conditions provides separation of platinum-binding proteins in very narrow bands with quantitative recoveries. Different amounts of platinum-bound proteins covering the range 0.3-2.0 μg were separated and mineralised for platinum determination, showing good platinum linearity. Limits of detection for a mixture of five standard proteins incubated with cisplatin were between the range of 2.4 and 13.9 pg of platinum, which were satisfactory for their application to biological samples. Regarding OFFGEL-IEF, a denaturing solution without thiourea and without dithiotreitol is recommended. The suitability of the OFFGEL-IEF for the separation of platinum binding proteins of a kidney cytosol was demonstrated.     

Quantifying temperature and flow rate effects on the performance of a fixed-bed chromatographic reactor

Chromatographic reactors are based on coupling chemical reactions with chromatographic separation in fixed-beds. Temperature and flow rate are important parameters for the performance of such reactors. Temperature affects mainly adsorption, chemical equilibria, mass transfer and reaction kinetics, whereas flow rate influences residence time and dispersion. In order to evaluate the mentioned effects, the hydrolysis reactions of methyl formate (MF) and methyl acetate (MA) were chosen as case studies. These reactions were performed experimentally in a lab-scale fixed-bed chromatographic reactor packed with a strong acidic ion exchange resin. The chosen reactions can be considered to represent a relative fast (MF) and a relative slow (MA) reaction. The processes which take place inside the reactor were described and simulated using an isothermal equilibrium dispersive model. The essential model parameters were determined experimentally at different temperatures and flow rates. The performance of the chromatographic reactor was evaluated at several discrete constant temperature levels by quantifying product purity, productivity and yield. The work provides insight regarding the influence of temperature and flow rate on values of the model parameters and the performance criteria.     

Electronic structures, vibrational and thermochemical properties of neutral and charged niobium clusters Nb(n), n = 7-12

Geometric and electronic structures, vibrational properties, and relative stabilities of niobium clusters Nb(n), n = 7-12, are studied using both DFT (BPW91 and M06 functionals) and CCSD(T) calculations with the cc-pVnZ-PP basis set. In each cluster, various lower-lying states are very close in energy in such a way that the ground state cannot be unambiguously established by DFT computations. Nb clusters tend to prefer the lowest possible spin state as the ground state, except for Nb(12) ((3)A(g)). The optimal structure of the cluster at a certain size does not simply grow from that of the smaller one by adding an atom randomly. Instead, the Nb clusters prefer a close-packed growth behavior. Nb(10) has a spherically aromatic character, high chemical hardness and large HOMO-LUMO gap. Electron affinities, ionization energies, binding energy per atom, and the stepwise dissociation energies are evaluated. Energetic properties exhibit odd-even oscillations. Comparison with experimental values shows that both BPW91 and M06 functionals are reliable in predicting the EA and IE values, but the BPW91 is deficient in predicting the binding and dissociation energies. We re-examine in particular the experimental far IR spectra previously recorded using the IR-MPD and free electron laser spectrometric techniques and propose novel assignments for Nb(7) and Nb(9) systems. The IR spectra of the anions are also predicted.     

Local shrinkage and stress induced by thermo-oxidation in composite materials at high temperatures

The paper is concerned with the modelling, simulation and experimental characterisation of local shrinkage strains and stresses induced by thermo-oxidation phenomena in the IM7/977-2 carbon/epoxy composite material at elevated temperatures. The oxygen concentration and mechanical fields were established through a coupled model constructed from a unified multiphysical approach and the thermodynamics of irreversible processes. The model was implemented in the ABAQUS^® finite element commercial code. Simulations of thermo-oxidation-induced matrix shrinkage were run at a local scale, i.e., the scale of the elementary constituents of the composite, the fibre and the matrix. The experimental assessment was done at the same scale, and the local matrix shrinkage profiles were measured by confocal interferometric microscopy.A good agreement was found between the simulated and measured profiles, validating the unified model. The thermo-oxidation induced stress field was analysed to understand the influence of the environment on the onset of damage in composite materials at elevated temperature.     

QR methods and error analysis for computing Lyapunov and Sacker�CSell spectral intervals for linear differential-algebraic equations

In this paper, we propose and investigate numerical methods based on QR factorization for computing all or some Lyapunov or Sacker?CSell spectral intervals for linear differential-algebraic equations. Furthermore, a perturbation and error analysis for these methods is presented. We investigate how errors in the data and in the numerical integration affect the accuracy of the approximate spectral intervals. Although we need to integrate numerically some differential-algebraic systems on usually very long time-intervals, under certain assumptions, it is shown that the error of the computed spectral intervals can be controlled by the local error of numerical integration and the error in solving the algebraic constraint. Some numerical examples are presented to illustrate the theoretical results.     

Primitive symmetric designs with up to 2500 points

By this article we conclude the construction of all primitive ( v, k,λ ) symmetric designs with v < 2500 , up to a few unsolved cases. Complementary to the designs with prime power number of points published previously, here we give 55 primitive symmetric designs with v ≠ p ^m , p prime and m positive integer, together with the analysis of their full automorphism groups. The research involves programming and wide‐range computations. We make use of the software package GAP and the library of primitive groups which it contains. © 2011 Wiley Periodicals, Inc. J Combin Designs 19:463‐474, 2011     

Dynamic Picone's identity and its applications

We prove some Picone-type identities and inequalities for a class of first-order nonlinear dynamic systems and derive various weighted inequalities of Wirtinger type and Hardy type on time scales. As applications we study oscillatory and related properties of these systems including Reid's roundabout theorem on disconjugacy, Sturm's separation and comparison theorems, as well as a variational method in the oscillation theory.     

A simple spectral theory of polynomially bounded solutions and applications to differential equations

Semigroup Forum - In this paper we present a simple spectral theory of polynomially bounded functions on the half line, and then apply it to study the asymptotic behavior of solutions of fractional...     

X‐ray absorption study of the local structure at the NiO/oxide interfaces

This work reports an X‐ray absorption near‐edge structure (XANES) spectroscopy study at the Ni K‐edge in the early stages of growth of NiO on non‐ordered SiO₂, Al₂O₃ and MgO thin films substrates. Two different coverages of NiO on the substrates have been studied. The analysis of the XANES region shows that for high coverages (80 Eq‐ML) the spectra are similar to that of bulk NiO, being identical for all substrates. In contrast, for low coverages (1 Eq‐ML) the spectra differ from that of large coverages indicating that the local order around Ni is limited to the first two coordination shells. In addition, the results also suggest the formation of cross‐linking bonds Ni—O—M (M = Si, Al, Mg) at the interface.     

A strongly regularN-full graph of small order

For every positive integern we show the construction of a strongly regular graph of order at most 2 ⁿ⁺² which contains every graph of ordern as a subgraph. The estimation concerning the construction is best possible.