Spectral and kinetic characterization of 7,8-diaminopelargonic acid synthase from Mycobacterium tuberculosis

The indispensability of biotin for crucial processes like lipid biosynthesis coupled to the absence of the biotin biosynthesis pathway in humans make the enzymes of this pathway, attractive targets for development of novel drugs against numerous pathogens including M. tuberculosis. We report the spectral and kinetic characterization of the Mycobacterium tuberculosis 7,8-Diamino-pelargonic acid (DAPA) synthase, the second enzyme of the biotin biosynthesis pathway. In contrast to the E. coli enzyme, no quinonoid intermediate was detected during the steady state reaction between the enzyme and S-adenosyl-L-methionine (SAM). The second order rate constant for this half of the reaction was determined to be 1.75 +/- 0.11 M-1 s(-1). The K-m values for 7-keto-8-aminopelargonic acid (KAPA) and SAM are 2.83 mu M and 308.28 mu M, respectively whereas the V-max and k(cat) values for the enzyme are 0.02074 mu moles/min/ml and 0.003 s(-1), respectively. Our initial studies pave the way for further detailed mechanistic and kinetic characterization of the enzyme.

Thermodynamic and kinetic studies on the mechanism of binding of methylumbelliferyl glycosides to jacalin

The binding of Artocarpus integrifolia lectin (jacalin) to 4-methylumbelliferyl (Meumb)-glycosides, Gal alpha Meumb, Gal beta Meumb, GalNAc alpha Meumb, GalNAc beta-Meumb, and Gal beta 3GalNAc beta Meumb was examined by extrinsic fluorescence quenching titration and stopped flow spectrofluorimetry. The binding was characterized by 100% quenching of fluorescence of Meumb-glycosides. Their association constants range from 2.0 x 10(4) to 1.58 x 10(6) M-1 at 15 degrees C. Entropic contribution is the major stabilizing force for avid binding of Meumb-glycosides indicating the existence of a hydrophobic site that is complementary to their methylumbelliferyl group. The second order association rate constants for interaction of these sugars with lectin at 15 degrees C vary from 8.8 x 10(5) to 3.24 x 10(6) M-1 S-1, at pH 7.2. The first order dissociation rate constants range from 2.30 to 43.0 S-1 at 15 degrees C. Despite the differences in their association rate constants, the overall values of association constants for these saccharides are determined by their dissociation rate constants. The second order rate constant for the association of Meumb-glycosides follows a pattern consistent with the magnitude of the activation energies involved therin. Activation parameters for association of all ligands illustrate that the origin of the barrier between binding of jacalin to Meumb-glycosides is entropic, and the enthalpic contribution is small. A correlation between these parameters and the structure of the ligands on the association rates underscores the importance of steric factors in determining protein saccharide recognitions.

On an asymptotic method of Krylov-Bogoliubov for overdamped nonlinear systems

A general asymptotic method based on the work of Krylov-Bogoliubov is developed to obtain the response of nonlinear over damped systems. A second-order system with both roots real is treated first and the method is then extended to higher-order systems. Two illustrative examples show good agreement with results obtained by numerical integration.

Theory of laminar flame propagation with non-normal diffusion.

A study has been made of the problem of steady, one-dimensional, laminar flame propagation in premixed gases, with the Lewis number differing from (and equal to) unity. Analytical solutions, using the method of matched asymptotic expansions, have been obtained for large activation energies. Numerical solutions have been obtained for a wide range of the reduced activation temperature parameter (n {geometrically equal to} E/RTb), and the Lewis number δ. The studies reveal that the flame speed eigenvalue is linear in Lewis number for first order and quadratic in Lewis number for second order reactions. For a quick determination of flame speeds, with reasonable accuracy, a simple rule, expressing the flame speed eigenvalue as a function of the Lewis number and the centroid of the reaction rate function, is proposed. Comparisons have been made with some of the earlier works, for both first and second order reactions.

Hydrochlorination of methanol to methyl chloride in fixed catalyst beds

The vapor phase hydrochlorination of methanol to methyl chloride in fixed beds with silica gel-alumina (88 to 12) and γ-alumina catalysts was studied in a glass tubular reactor in the temperature range of 300° to 390°C. Of the two catalysts studied, γ-alumina gave nearly equilibrium conversions under the experimental conditions. The data are expressed in the form of second-order irreversible rate equations for both the catalysts studied.

Raman spectra of alkali halides

In this article, we present a comparative study of the Raman spectra of alkali halides in relation to the lattice dynamics ofBorn andRaman. It is shown that the experimentally observed limit of the second-order spectra in almost all the cases can be explained well by the Lyddane-Sachs-Teller relation. It is also seen, while, an explanation of the second-order Raman spectrum of a crystal of diamond or zinc blende structure requires the frequencies from the critical points,W, Gamma, X andL inBorn's analysis, the frequencies fromGamma, X andL alone are sufficient and necessary for an interpretation of the same onRaman's model. Some similarities in the determination of the long wave properties of crystals like elastic constants and limiting frequencies of the lattice vibrations in the symmetry directions in both the models are pointed out.

Ultrasonic wave characteristics of nanorods via nonlocal strain gradient models

This paper studies an ultrasonic wave dispersion characteristics of a nanorod. Nonlocal strain gradient models (both second and fourth order) are introduced to analyze the ultrasonic wave behavior in nanorod. Explicit expressions are derived for wave numbers and the wave speeds of the nanorod. The analysis shows that the fourth order strain gradient model gives approximate results over the second order strain gradient model for dynamic analysis. The second order strain gradient model gives a critical wave number at certain wave frequency, where the wave speeds are zero. A relation among the number of waves along the nanorod, the nonlocal scaling parameter (e(0)a), and the length of the nanorod is obtained from the nonlocal second order strain gradient model. The ultrasonic wave characteristics of the nanorod obtained from the nonlocal strain gradient models are compared with the classical continuum model. The dynamic response behavior of nanorods is explained from both the strain gradient models. The effect of e(0)a on the ultrasonic wave behavior of the nanorods is also observed. (C) 2010 American Institute of Physics.

Catalytic dehydrogenation of 2-propanol to acetone

Catalytic dehydrogenation of 2-propanol over Cu-SiO2 catalyst was investigated. The undesired side reaction of dehydration can be controlled by a selective catalyst and choice of proper operating conditions. The kinetics of the heterogeneous catalytic reaction can be adequately expressed by a forward first-order and reverse second-order mechanism. The rate-controlling step with chemically pure 2-propanol is single-site surface reaction, while for the technical grade alcohol the adsorption of alcohol is rate-controlling. The static bed data are compared with the fluidized bed dat

Mechanism of the addition of alcohols to substituted phenylisothiocyanates : Electrical effects of the substituents on the reaction

The addition reaction of alcohols to substituted phenylisothiocyanates is found to be a second-order reaction. The reaction is catalysed by triethylamine. First-order rate constants of the addition reaction have been determined in excess of ethanol, for a number of substituted phenylisothiocyanates and the rate data give a satisfactory linear correlation with Hammett σ constants of groups. While the energies of activation vary randomly with substitution, the entropies of activation bear a linear relationship to the energies of activation. Infra-red spectra indicate that the thiourethanes which are the products of the addition reaction exist in the thioamide form. The most prominent resonance form which can satisfactorily explain both the kinetic and infrared data, has been suggested.

A weighted mean square method of linearization in non-linear oscillations

The paper deals with a linearization technique in non-linear oscillations for systems which are governed by second-order non-linear ordinary differential equations. The method is based on approximation of the non-linear function by a linear function such that the error is least in the weighted mean square sense. The method has been applied to cubic, sine, hyperbolic sine, and odd polynomial types of non-linearities and the results obtained are more accurate than those given by existing linearization methods.

Thermal expansion of triglycine sulphate

Matthias, Miller and Remeika1 were the first to observe that triglycine sulphate becomes ferroelectric below 47°C. The dielectric properties and the specific heat of this crystal have been studied through the transition temperature by Hoshino, Mitsui, Jona and Pepinsky2. The observed variation of the dielectric properties as a function of temperature in this crystal shows that the transition is of second order. Hoshino et al. concluded that the anomaly is not of the λ-type, since their specific heat - temperature curve showed only a hump. It was decided to investigate the thermal expansion of this crystal as it might throw some light on the nature of the transition.

Equivalence conditions for classes of linear and non-linear distributed parameter systems

Equivalence of certain classes of second-order non-linear distributed parameter systems and corresponding linear third-order systems is established through a differential transformation technique. As linear systems are amenable to analysis through existing techniques, this study is expected to offer a method of tackling certain classes of non-linear problems which may otherwise prove to be formidable in nature.

A fast time-domain algorithm for the assessment of tissue blood flow in laser-Doppler flowmetry

In this study, we derive a fast, novel time-domain algorithm to compute the nth-order moment of the power spectral density of the photoelectric current as measured in laser-Doppler flowmetry (LDF). It is well established that in the LDF literature these moments are closely related to fundamental physiological parameters, i.e. concentration of moving erythrocytes and blood flow. In particular, we take advantage of the link between moments in the Fourier domain and fractional derivatives in the temporal domain. Using Parseval's theorem, we establish an exact analytical equivalence between the time-domain expression and the conventional frequency-domain counterpart. Moreover, we demonstrate the appropriateness of estimating the zeroth-, first- and second-order moments using Monte Carlo simulations. Finally, we briefly discuss the feasibility of implementing the proposed algorithm in hardware.

Asymptotic behaviour and boundedness of linear systems with time varying coefficients

Motivated by developments in spacecraft dynamics, the asymptotic behaviour and boundedness of solution of a special class of time varying systems in which each term appears as the sum of a constant and a time varying part, are analysed in this paper. It is not possible to apply standard textbook results to such systems, which are originally in second order. Some of the existing results are reformulated. Four theorems which explore the relations between the asymptotic behaviour/boundedness of the constant coefficient system, obtained by equating the time varying terms to zero, to the corresponding behaviour of the time varying system, are developed. The results show the behaviour of the two systems to be intimately related, provided the solutions of the constant coefficient system approach zero are bounded for large values of time, and the time varying terms are suitably restrained. Two problems are tackled using these theorems.

A four-timescale algorithm for constrained stochastic optimization of RED

The overall performance of random early detection (RED) routers in the Internet is determined by the settings of their associated parameters. The non-availability of a functional relationship between the RED performance and its parameters makes it difficult to implement optimization techniques directly in order to optimize the RED parameters. In this paper, we formulate a generic optimization framework using a stochastically bounded delay metric to dynamically adapt the RED parameters. The constrained optimization problem thus formulated is solved using traditional nonlinear programming techniques. Here, we implement the barrier and penalty function approaches, respectively. We adopt a second-order nonlinear optimization framework and propose a novel four-timescale stochastic approximation algorithm to estimate the gradient and Hessian of the barrier and penalty objectives and update the RED parameters. A convergence analysis of the proposed algorithm is briefly sketched. We perform simulations to evaluate the performance of our algorithm with both barrier and penalty objectives and compare these with RED and a variant of it in the literature. We observe an improvement in performance using our proposed algorithm over RED, and the above variant of it.