Strength of interactions between immobilized dye molecules and sol-gel matrices

In this paper we present a new theory to re-examine the immobilization technique of dye doped sol-gel films, define the strength and types of possible bonds between the immobilized molecule and sol-gel glass, and show that the immobilized molecule is not free inside the pores as was previously thought. Immobilizing three different pH sensitive dyes with different size and functional groups inside the same sol-gel films revealed important information about the nature of the interaction between the doped molecule and the sol-gel matrix. The samples were characterized by means of ultraviolet-visible spectrophotometer (UV-VIS), thermal gravimetric analysis (TGA), mercury porosimetry (MP), nuclear magnetic resonance spectroscopy ((29)Si NMR) and field-emission environmental scanning electron microscopy (ESEM-FEG). It was found that the doped molecule itself has a great effect on the strength and types of the bonds. A number of factors were identified, such as number and types of the functional groups, overall charge, size, pK(a) and number of the silanol groups which surround the immobilized molecule. These results were confirmed by the successful immobilization of bromocresol green (BCG) after a completely polymerized sol-gel was made. The sol-gel consisted of 50% tetraethoxysilane (TEOS) and 50% methyltriethoxysilane (MTEOS) (w/w). Moreover, the effect of the immobilized molecule on the structure of the sol-gel was studied by means of a leaky waveguide (LW) mode for doped films made before and after polymerization of the sol-gel.     

Theoretical investigation into competing unimolecular reactions encountered in the pyrolysis of acetamide

Motivated by the necessity to understand the pyrolysis of alkylated amines, unimolecular decomposition of acetamide is investigated herein as a model compound. Standard heats of formation, entropies, and heat capacities, are calculated for all products and transition structures using several accurate theoretical levels. The potential energy surface is mapped out for all possible channels encountered in the pyrolysis of acetamide. The formation of acetamedic acid and 1-aminoethenol and their subsequent decomposition pathways are found to afford the two most energetically favored pathways. However, RRKM analysis shows that the fate of acetamedic acid and 1-aminoethenol at all temperatures and pressures is to reisomerize to the parent acetamide. 1-Aminoethenol, in particular, is predicted to be a long-lived species enabling its participation in bimolecular reactions that lead to the formation of the major experimental products. Results presented herein reflect the importance of bimolecular reactions involving acetamide and 1-aminoethenol in building a robust model for the pyrolysis of N-alkylated amides.     

Asymptotic formulae for eigenvalues and eigenfunctions of q‐Sturm‐Liouville problems

We investigate the asymptotic behavior of the eigenvalues and the eigenfunctions of q‐Sturm‐Liouville eigenvalue problems. For this aim we study the asymptotic behavior of q‐trigonometric functions as well as fundamental sets of solutions of the associated second order q‐difference equation. As in classical Sturm‐Liouville theory, the eigenvalues behave like zeros of q‐trigonometric functions and the eigenfunctions behave like q‐trigonometric functions. © 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Multilinear gradient elution optimization in reversed-phase liquid chromatography based on logarithmic retention models: application to separation of a set of purines, pyrimidines and nucleosides

The analytical solutions of the fundamental equation of the multilinear gradient elution are derived in two cases, when the dependence of the logarithm of the solute retention (lnk) upon the volume fraction of organic modifier (φ) is a three-parameter logarithmic expression, and when a simple linear relationship between lnk and lnφ is adopted. The derived theoretical expressions for retention times under multilinear gradient conditions are embodied to simple algorithms for fitting gradient data and especially for resolution optimization. Their performance was examined by using a mixture of 16 model compounds chosen among purines, pyrimidine and nucleosides in eluting systems modified by acetonitrile. It was found that the accuracy of the predicted gradient retention times is very satisfactory even if the simple logarithmic expression for the retention behavior of solutes, i.e. the linear dependence of lnk upon lnφ, is used.     

In vitro cytotoxic evaluation of some new heterocyclic sulfonamide derivatives

Sulfonamide‐bearing compounds posses many types of biological activities and have been recently reported to show substantial antitumor activity in vitro and/or in vivo. There are a variety of mechanisms for the anticancer activity, and the most prominent mechanism is the inhibition of carbonic anhydrase isozymes. This work reports the synthesis of some new quinoline, pyrimido[4,5‐b]quinoline and 3,1‐oxazinoquinoline derivatives bearing a sulfonamide moiety. All the newly synthesized compounds were evaluated for their in vitro anticancer activity against Ehrlich ascites carcinoma cells. Compounds 10 , 13 , and 26 were the most active compounds with IC₅₀ values of 6.1 μM, 6.8 μM, and 6.4 μM, respectively, and exhibited better activities than the reference drug doxorubicin (IC₅₀ = 68.1 μM). J. Heterocyclic Chem., 2011.     

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.     

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.