Cross-linking mechanisms of arginine and lysine with α,β-dicarbonyl compounds in aqueous solution

Cross-linking in proteins by α,β-dicarbonyl compounds is one of the most damaging consequences of reactive carbonyl species in vivo and in foodstuffs. In this article we investigate computationally the cross-linking of glyoxal and methylglyoxal with lysine and arginine residues using density functional theory and the wB97XD dispersion-corrected functional. Five pathways, A-E, have been characterized. In pathways A and B, the reaction proceeds via formation of the Schiff base, aldimine, followed by addition of arginine. In contrast, in pathways C-E, direct addition of arginine to the dicarbonyl compounds occurs first, leading to a dihydroxyimidazolidine intermediate, which then reacts with lysine after dehydration and proton transfer reactions. The results reveal that pathways A, C, and E are competitive whereas reactions via pathways B and D are much less favorable. Inclusion of up to five explicit water molecules in the proton transfer and dehydration steps is found to lower the energy barriers in the feasible pathways by about 5-20 kcal/mol. Comparison of the mechanisms of methylglyoxal-derived imidazolium cross-linking (MODIC) and glyoxal-derived imidazolium cross-linking (GODIC) shows that the activation barriers are lower for GODIC than MODIC, in agreement with experimental observations.     

Virtual improvement of ice cream properties by computational homogenization of microstructures

Optimal shape design of microstructured materials has recently attracted a great deal of attention in materials science. The shape and the topology of the microstructure have a significant impact on the macroscopic properties. This paper presents different computational models of random microstructures, to virtually improve the physical properties of ice cream. Several sensory properties of this heterogeneous material issued from food industry are directly controlled by the elastic and thermal conducting ones. The material effective elastic and thermal conducting properties are obtained through direct large scale numerical simulations. The different formulations address the problem of finding the shape of the representative microstructural element for random heterogeneous media that increase the elastic moduli and thermal conductivity compared to existing products. The computational models are established using finite element method and images of virtual microstructures. In this paper we propose a new model of microstructures. This model is constructed with hexagonal prismatic rods and plates with volume fractions around 0.7 for the hard phase represented by hexagons of ice. A comparison between three two-phase elastic heterogeneous microstructures models is drawn. This illustrates the concept of design of microstructures using computational homogenization tools.     

The Problems of the Turbulent Burning Velocity

The paper reviews the practical problems in measuring a turbulent burning velocity that gives the mass rate of burning. These largely centre on identifying an appropriate flame surface to associate with the turbulent burning velocity, u _t , and the density of the unburned mixture. Such a flame surface has been identified, in terms of the mean reaction progress variable, $\bar {c}$ , for explosive flame propagation in a fan-stirred bomb. Measurement of $\bar {c}$ makes possible an estimation of the flame surface density, ??, from the relationship ${\it \Sigma} =k\bar {c}\left( {1-\bar {c}} \right)$ . It is shown that in such explosions, mass rates of burning derived from the measured total flame surface area agreed well with those found from the measured turbulent burning velocity. Flamelet considerations identify appropriate dimensionless correlating parameters for u _t . As a result, correlations of turbulent burning velocity divided by the effective rms turbulent velocity, are plotted against the turbulent Karlovitz stretch factor, K, for different values of the Markstein number for flame strain rate, Ma_sr. These plots cover a wide range of variables, including pressure and fuels, and are indicative of different regimes of turbulent combustion. At the lower values of K, there is some evidence of increases in u _t and k due to high-frequency flame surface wrinkling arising from flame instabilities. These increase as Ma_sr becomes more negative. It is found from the developed value of the mean flame surface density throughout the flame brush that, to a first approximation, an increase in u _t for a given mixture is accompanied by a proportional increase in the volume of the brush. The analysis shows that the volume fraction of the turbulent flame brush that is reacting is quite small.     

Adjoint polynomials of bridge–path and bridge–cycle graphs and Chebyshev polynomials

The chromatic polynomial of a simple graph G with n>0 vertices is a polynomial of degree n, where α_k(G) is the number of k-independent partitions of G for all k. The adjoint polynomial of G is defined to be , where is the complement of G. We find explicit formulas for the adjoint polynomials of the bridge–path and bridge–cycle graphs. Consequence, we find the zeros of the adjoint polynomials of several families of graphs.     

The commutation relation <Emphasis Type="Italic">xy</Emphasis>=<Emphasis Type="Italic">qyx</Emphasis>+<Emphasis Type="Italic">hf</Emphasis>(<Emphasis Type="Italic">y</Emphasis>) and Newton’s binomial formula

Let x and y be two variables satisfying the commutation relation xy=qyx+hf(y), where f(y) is a polynomial. In this paper, using Young diagrams and generating functions techniques, we study the binomial formula (x+y) ⁿ and we present an identity for x ^m y. The connection to Operator Calculus is discussed and several special cases are treated explicitly.     

Ft-Raman Study of Three Synthetic Solid Solutions Formed by Orthorhombic Sulfates: Celestite-Barytes,Barytes-Anglesite and Celestite-Anglesite

Abstract

In the present work, three different solid solutions whose end-members are the orthorhombic sulfates celestite (SrSO₄), barytes (BaSO₄) and anglesite (PbSO₄) are studied using FT-Raman spectroscopy. Sulfate anion symmetric internal modes have been examined in detail by means of band-shape analysis and component fitting procedures. the symmetric stretching mode v₁(A₁) changes its wavenumber position linearly with the cationic composition of the samples which further confirms the ideal character of the solid solutions studied. the corresponding full-width at half-height is strongly increased in the central components of the different solid solutions which can be understood as an effect of the positional disorder induced by random cationic substitution. Similar results are observed in the symmetric bending mode, v² (E). the study of the low frequency spectral region permits one to differentiate translational modes of the sulfate anion, which changes its wavenumber position when the alkali-earth metal ion changes from rotational modes. This permits the tentative band assignment of the anglesite rotational Raman bands at 134 and 152 cm^?1, which were previously not assigned.     

Solid‐particle erosion in the tube end of the tube sheet of a shell‐and‐tube heat exchanger

Erosion is one of the major problems in many industrial processes, and in particular, in heat exchangers. The effects of flow velocity and sand particle size on the rate of erosion in a typical shell‐and‐tube heat exchanger were investigated numerically using the Lagrangian particle‐tracking method. Erosion and penetration rates were obtained for sand particles of diameters ranging from 10 to 500 µm and for inlet flow velocities ranging from 0.197 to 2.95 m/s. A flow visualization experiment was conducted with the objective of verifying the accuracy of the continuous phase calculation procedure. Comparison with available experimental data of penetration rates was also conducted. These comparisons resulted in a good agreement. The results show that the location and number of eroded tubes depend mainly on the particle size and velocity magnitude at the header inlet. The rate of erosion depends exponentially on the velocity. The particle size shows negligible effect on the erosion rate at high velocity values and the large‐size particles show less erosion rates compared to the small‐size particles at low values of inlet flow velocities. The results indicated that the erosion and penetration rates are insignificant at the lower end of the velocity range. However, these rates were found to increase continuously with the increase of the inlet flow velocity for all particle sizes. The particle size creating the highest erosion rate was found to depend on the flow velocity range. Copyright © 2005 John Wiley & Sons, Ltd.     

On the zeros of basic finite Hankel transforms

In this article we prove that the basic finite Hankel transform whose kernel is the third-type Jackson q-Bessel function has only infinitely many real and simple zeros, provided that q satisfies a condition additional to the standard one. We also study the asymptotic behavior of the zeros. The obtained results are applied to investigate the zeros of q-Bessel functions as well as the zeros of q-trigonometric functions. A basic analog of a theorem of G. Pólya (1918) on the zeros of sine and cosine transformations is also given.     

Kinetic spectrophotometric method for the determination of trace amounts of oxalate by an activation effect.

A new, simple and inexpensive kinetic catalytic spectrophotometric method for the determination of oxalate is described. The method is based on an activation effect of oxalate on a catalytic effect of iron(II) on the oxidation of iodide by bromate. The reaction is monitored by measuring the absorbance of triiodide ion at lambda max = 352 nm. A calibration graph was obtained from 0.10 - 7.0 microg cm(-3) of oxalate with a detection limit of 0.080 microg cm(-3). The standard deviations for ten replicate determinations of 0.50, 1.0 and 5.0 microg cm(-3) of oxalate were 4.0, 2.6 and 1.8%, respectively. The applicability of the method was demonstrated by the determination of oxalate ion in real samples.     

The stabilization mechanism and structure of turbulent hydrocarbon lifted flames

The structure and stabilization mechanism of turbulent lifted non-premixed hydrocarbon flames have been investigated using combined laser imaging techniques. The techniques include Rayleigh scattering, laser induced predissociation fluorescence of OH, LIF of PAH, LIF of CH₂O, and planar imaging velocimetry. The geometrical structure of multi-reaction zones and flow field at the stabilization region have been simultaneously measured in 16 hydrocarbon flames. The data reveal the existence of triple flame structure at the stabilization region of turbulent lifted flames. Increasing the jet velocity leads to an increase of the lift-off height and to a broadening of the lift-off region. Further analysis of the stabilization criterion at the lift-off height based on the premixed nature of triple-flame propagation and flow field data has been presented and discussed.