pKa values of peptides in aqueous and aqueous-organic media. Prediction of chromatographic and electrophoretic behaviour

In the present work, models describing the effect of the pH on the chromatographic and electrophoretic behaviour for polyprotic peptides were compared. The proposed models can be simultaneously used for determination of dissociation constants and selection of the optimum pH for the separation of peptides, in water and acetonitrile-water mixtures widely used in liquid chromatography and in capillary electrophoresis. The models use the pH value measured in the acetonitrile-water mixture instead of the pH value in water and take into account the effect of the activity coefficients. They permit the determination of the acidity constants in the aqueous and hydro-organic mobile phase from chromatographic retention and electrophoretic migration measurements, respectively. The values obtained by both proposed techniques agree with the potentiometric values previously determined. The suitability of the proposed models for predicting chromatographic and electrophoretic behaviour of compounds studied from a limited number of experimental data was also compared. The separation between solutes by both techniques in a complex mixture can be easily predicted, making simple and rapid pH selection to achieve optimum separation.     

Nuclear-related analytical techniques: Literature retrieval from the INIS database

The applicability of the INIS database for literature retrieval on nuclear-related analytical techniques [e.g. neutron activation analysis (NAA), X-ray fluorescence (XRF), particle-induced X-ray emission (PIXE)] has been studied. There exist about 9700 documents on NAA and other forms of activation analysis, about 3500 documents on XRF and about 1200 documents on PIXE in the database collected from 1976 until July 1988. They cover a variety of elements and matrices in the fields of biology, geochemistry and the physical sciences. Some technical notes and comments on the practical use of this database are also included.     

Roe‐type Riemann solvers for general hyperbolic systems

We present a Roe‐type weak formulation Riemann solver where the average coefficient matrix is computed numerically. The novelty of this approach is that it is general enough that can be applied to any hyperbolic system while retaining the accuracy of the original Roe solver. We show applications to the compressible Euler equations with general equation of state. An alternative version of the method uses directly the eigenvectors in the averaging process, simplifying the algorithm. These new solvers are applied in conservative and path‐conservative schemes with high‐order accuracy and on unstructured meshes. Copyright © 2014 John Wiley & Sons, Ltd.     

Influence of surface heterogeneity in electroosmotic flows—Implications in chromatography, fluid mixing, and chemical reactions in microdevices

We analyze the influence of surface heterogeneity, inducing a random ζ-potential at the walls in electroosmotic incompressible flows. Specifically, we focus on how surface heterogeneity modifies the physico-chemical processes (transport, chemical reaction, mixing) occurring in microchannel and microreactors. While the macroscopic short-time features associated with solute transport (e.g. chromatographic patterns) do not depend significantly on ζ-potential heterogeneity, spatial randomness in the surface ζ-potential modifies the spectral properties of the advection-diffusion operator, determining different long-term properties of transport/reaction phenomena compared to the homogeneous case. Examples of physical relevance (chromatography, infinitely fast reactions) are addressed.     

Asymmetry of velocity distributions in peripheral reactions with heavy ions at Fermi energies

The asymmetry of velocity distributions of projectile-like fragments produced in heavy ion collisions is considered. The calculations performed in the transport model approach (Vlasov kinetic equation with the collision term) are compared with the experimental data for the ²²Ne (40MeV/nucleon) + ⁹Be and ¹⁸O (35 MeV/nucleon) + ⁹Be(¹⁸¹Ta) reactions. It is found that the velocity distributions contain two components: a direct component centered at the beam velocity and a dissipative component at lower energies, leading to asymmetry of velocity distributions. The direct component is interpreted empirically within the Goldhaber model, and the centroids and widths σ₀ of the distributions for each fragment are extracted. It is found that value of σ₀ derived from experimental data is smaller by a factor of 2 than the theoretical one. The dissipative (also called deep inelastic) component is described well by the transport calculations. It is shown that the ratio of yields of direct and dissipative components, which determines the asymmetry of velocity distributions, depends on shape of the deflection function. Original Russian Text ? T.I. Mikhailova, B. Erdemchimeg, G. Kaminski, A.G. Artyukh, M. Colonna, M. Di Toro, I.N. Mikhailov, Yu.M. Sereda, H.H. Wolter, 2009, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2009, Vol. 73, No. 6, pp. 898–903.     

Pre-equilibrium dipole strength in charge asymmetric peripheral heavy-ion reactions

We report on the results obtained from the study of the ³²S + ⁶⁴Ni and ³²S + ⁵⁸Ni peripheral reactions at incident energies E _lab = 288 MeV and E _lab = 320 MeV, respectively. High-energy γ-rays were detected in an array of 8 seven-pack BaF₂ clusters. Coincidence with complex fragments detected in 12 three-stage telescopes ensured the selection of peripheral reaction events. All of the relevant reaction parameters were kept constant with the exception of the different initial dipole moment caused by the different entrance channel charge asymmetry. While for quasi-elastic events no N/Z effect was observed in the differential γ-ray multiplicities of the two reactions, for deep-inelastic events a larger dipole γ-ray emission occurs during the more N/Z asymmetric reaction. A theoretical interpretation based on a collective Bremsstrahlung analysis of the reaction dynamics is presented. Received: 26 September 2002 / Accepted: 13 November 2002 / Published online: 6 March 2003 RID="a" ID="a"e-mail: pierroutsakou@na.infn.it RID="b" ID="b"Present address: INFN, Laboratori Nazionali di Legnaro, Padova, Italy. Communicated by C. Signorini     

Interferometry based on Lau effect with a grating registered in a photorefractive crystal

The use of a grating in the form of modulation of birefringence in a BSO crystal in a novel Lau interferometer set-up is proposed. The system behaves as a conventional Lau interferometer implemented by using two amplitude gratings. Moreover, it permits control of the visibility and provides a contrast inversion of the interferometric fringes by rotating a polarizer. Two alternative experimental arrangements with similar performance are presented. A theoretical approach is outlined and the predicted behavior is confirmed by results obtained under different experimental conditions.