Amine-Templated Aluminoborates Exhibiting Graphite and Diamond Nets

A solvothermal reaction of Al2O3, H3BO3, pyridine, and H2O at 180 degrees C/7 days in the presence of organic amine molecules gave rise to four new aluminoborates, [(C6H18N2)(AlB6O13H3)], I; [(C5H16N2) (AlB5O10)]center dot 2H(2)O, II; [(C5H16N2)-(AlB5O10)], III; and [(C5H17N3)(AlB5O10)] center dot H2O, IV, with two- and three-dimensional structures. All the structures have been formed by the connectivity involving Al3+ ions and [B5O10] cyclic pentaborate units. In 1, the 3-connected trigonal nodes form a layer that resembles a graphite structure has been observed. The compounds II, III, and IV, have 4-connected nodes that forms a diamond related three-dimensional structure. The formation of solvatomorphs in II and III is noteworthy and has been observed first time in a family of amine template aluminoborates. A comparison of the various aluminoborate structures reveals subtle relationships between the organic amines (length of the amines) and the final framework structures. The compounds have been characterized using a variety of techniques including IR, second-order optical behavior, and MAS NMR studies.

Network flow-control using asynchronous stochastic approximation

We propose several stochastic approximation implementations for related algorithms in flow-control of communication networks. First, a discrete-time implementation of Kelly's primal flow-control algorithm is proposed. Convergence with probability 1 is shown, even in the presence of communication delays and stochastic effects seen in link congestion indications. This ensues from an analysis of the flow-control algorithm using the asynchronous stochastic approximation (ASA) framework. Two relevant enhancements are then pursued: a) an implementation of the primal algorithm using second-order information, and b) an implementation where edge-routers rectify misbehaving flows. Next, discretetime implementations of Kelly's dual algorithm and primaldual algorithm are proposed. Simulation results a) verifying the proposed algorithms and, b) comparing the stability properties are presented.

Quantum spin nematics, dimerization, and deconfined criticality in Quasi-1D spin-one magnets

We study theoretically the destruction of spin nematic order due to quantum fluctuations in quasi-one-dimensional spin-1 magnets. If the nematic ordering is disordered by condensing disclinations, then quantum Berry phase effects induce dimerization in the resulting paramagnet. We develop a theory for a Landau-forbidden second order transition between the spin nematic and dimerized states found in recent numerical calculations. Numerical tests of the theory are suggested.

Phases and transitions in the spin-1 Bose-Hubbard model: Systematics of a mean-field theory

We generalize the mean-field theory for the spinless Bose-Hubbard model to account for the different types of superfluid phases that can arise in the spin-1 case. In particular, our mean-field theory can distinguish polar and ferromagnetic superfluids, Mott insulator, that arise at integer fillings at zero temperature, and normal Bose liquids into which the Mott insulators evolve at finite temperatures. We find, in contrast to the spinless case, that several of the superfluid-Mott insulator transitions are of first order at finite temperatures. Our systematic study yields rich phase diagrams that include first-order and second-order transitions and a variety of tricritical points. We discuss the possibility of realizing such phase diagrams in experimental systems.

Numerical approaches to new particle formation and growth in the atmosphere

Aerosols impact the planet and our daily lives through various effects, perhaps most notably those related to their climatic and health-related consequences. While there are several primary particle sources, secondary new particle formation from precursor vapors is also known to be a frequent, global phenomenon. Nevertheless, the formation mechanism of new particles, as well as the vapors participating in the process, remain a mystery. This thesis consists of studies on new particle formation specifically from the point of view of numerical modeling. A dependence of formation rate of 3 nm particles on the sulphuric acid concentration to the power of 1-2 has been observed. This suggests nucleation mechanism to be of first or second order with respect to the sulphuric acid concentration, in other words the mechanisms based on activation or kinetic collision of clusters. However, model studies have had difficulties in replicating the small exponents observed in nature. The work done in this thesis indicates that the exponents may be lowered by the participation of a co-condensing (and potentially nucleating) low-volatility organic vapor, or by increasing the assumed size of the critical clusters. On the other hand, the presented new and more accurate method for determining the exponent indicates high diurnal variability. Additionally, these studies included several semi-empirical nucleation rate parameterizations as well as a detailed investigation of the analysis used to determine the apparent particle formation rate. Due to their high proportion of the earth's surface area, oceans could potentially prove to be climatically significant sources of secondary particles. In the lack of marine observation data, new particle formation events in a coastal region were parameterized and studied. Since the formation mechanism is believed to be similar, the new parameterization was applied in a marine scenario. The work showed that marine CCN production is feasible in the presence of additional vapors contributing to particle growth. Finally, a new method to estimate concentrations of condensing organics was developed. The algorithm utilizes a Markov chain Monte Carlo method to determine the required combination of vapor concentrations by comparing a measured particle size distribution with one from an aerosol dynamics process model. The evaluation indicated excellent agreement against model data, and initial results with field data appear sound as well.

Non-Gaussian Cosmological Perturbations from Hybrid Inflation and Preheating

This thesis consists of four research papers and an introduction providing some background. The structure in the universe is generally considered to originate from quantum fluctuations in the very early universe. The standard lore of cosmology states that the primordial perturbations are almost scale-invariant, adiabatic, and Gaussian. A snapshot of the structure from the time when the universe became transparent can be seen in the cosmic microwave background (CMB). For a long time mainly the power spectrum of the CMB temperature fluctuations has been used to obtain observational constraints, especially on deviations from scale-invariance and pure adiabacity. Non-Gaussian perturbations provide a novel and very promising way to test theoretical predictions. They probe beyond the power spectrum, or two point correlator, since non-Gaussianity involves higher order statistics. The thesis concentrates on the non-Gaussian perturbations arising in several situations involving two scalar fields, namely, hybrid inflation and various forms of preheating. First we go through some basic concepts -- such as the cosmological inflation, reheating and preheating, and the role of scalar fields during inflation -- which are necessary for the understanding of the research papers. We also review the standard linear cosmological perturbation theory. The second order perturbation theory formalism for two scalar fields is developed. We explain what is meant by non-Gaussian perturbations, and discuss some difficulties in parametrisation and observation. In particular, we concentrate on the nonlinearity parameter. The prospects of observing non-Gaussianity are briefly discussed. We apply the formalism and calculate the evolution of the second order curvature perturbation during hybrid inflation. We estimate the amount of non-Gaussianity in the model and find that there is a possibility for an observational effect. The non-Gaussianity arising in preheating is also studied. We find that the level produced by the simplest model of instant preheating is insignificant, whereas standard preheating with parametric resonance as well as tachyonic preheating are prone to easily saturate and even exceed the observational limits. We also mention other approaches to the study of primordial non-Gaussianities, which differ from the perturbation theory method chosen in the thesis work.

The effect of halogen atom on the molecular quadratic nonlinearity of half sandwich complexes in the presence of an acceptor

Half sandwich complexes of the type [CpM(CO)(n)X] {X=Cl, Br, I; If, M=Fe, Ru; n=2 and if M=Mo; n=3} and [CpNiPPh3X] {X=Cl, Br, I} have been synthesized and their second order molecular nonlinearity (beta) measured at 1064 nm in CHCl3 by the hyper-Rayleigh scattering technique. Iron complexes consistently display larger beta values than ruthenium complexes while nickel complexes have marginally larger beta values than iron complexes. In the presence of an acceptor ligand such as CO or PPh3, the role of the halogen atom is that of a pi donor. The better overlap of Cl orbitals with Fe and Ni metal centres make Cl a better pi donor than Br or I in the respective complexes. Consequently, M-pi interaction is stronger in Fe/Ni-Cl complexes. The value of beta decreases as one goes down the halogen group. For the complexes of 4d metal ions where the metal-ligand distance is larger, the influence of pi orbital overlap appears to be less important, resulting in moderate changes in beta as a function of halogen substitution. (C) 2006 Elsevier B.V. All rights reserved.

Formation of structure in dark energy cosmologies

Acceleration of the universe has been established but not explained. During the past few years precise cosmological experiments have confirmed the standard big bang scenario of a flat universe undergoing an inflationary expansion in its earliest stages, where the perturbations are generated that eventually form into galaxies and other structure in matter, most of which is non-baryonic dark matter. Curiously, the universe has presently entered into another period of acceleration. Such a result is inferred from observations of extra-galactic supernovae and is independently supported by the cosmic microwave background radiation and large scale structure data. It seems there is a positive cosmological constant speeding up the universal expansion of space. Then the vacuum energy density the constant describes should be about a dozen times the present energy density in visible matter, but particle physics scales are enormously larger than that. This is the cosmological constant problem, perhaps the greatest mystery of contemporary cosmology. In this thesis we will explore alternative agents of the acceleration. Generically, such are called dark energy. If some symmetry turns off vacuum energy, its value is not a problem but one needs some dark energy. Such could be a scalar field dynamically evolving in its potential, or some other exotic constituent exhibiting negative pressure. Another option is to assume that gravity at cosmological scales is not well described by general relativity. In a modified theory of gravity one might find the expansion rate increasing in a universe filled by just dark matter and baryons. Such possibilities are taken here under investigation. The main goal is to uncover observational consequences of different models of dark energy, the emphasis being on their implications for the formation of large-scale structure of the universe. Possible properties of dark energy are investigated using phenomenological paramaterizations, but several specific models are also considered in detail. Difficulties in unifying dark matter and dark energy into a single concept are pointed out. Considerable attention is on modifications of gravity resulting in second order field equations. It is shown that in a general class of such models the viable ones represent effectively the cosmological constant, while from another class one might find interesting modifications of the standard cosmological scenario yet allowed by observations. The thesis consists of seven research papers preceded by an introductory discussion.

On Guo and Nixon's Criterion for Feature Subset Selection: Assumptions, Implications,and Alternative Options

Guo and Nixon proposed a feature selection method based on maximizing I(x; Y),the multidimensional mutual information between feature vector x and class variable Y. Because computing I(x; Y) can be difficult in practice, Guo and Nixon proposed an approximation of I(x; Y) as the criterion for feature selection. We show that Guo and Nixon's criterion originates from approximating the joint probability distributions in I(x; Y) by second-order product distributions. We remark on the limitations of the approximation and discuss computationally attractive alternatives to compute I(x; Y).

Adsorption of anionic dyes on chitosan grafted poly(alkyl methacrylate)s

Chitosan grafted poly(alkyl methacrylate)s (namely chitosan grafted poly(methyl methacrylate) (ChgPMMA), chitosan grafted poly(ethyl methacrylate)(ChgPEMA), chitosan grafted poly(butyl methacrylate) (ChgPBMA) and chitosan grafted poly(hexyl methacrylate) (ChgPHMA)) were synthesized and characterized by using FT-IR and C-13 NMR techniques. The adsorption batch experiments on these grafted copolymers were conducted by using an anionic sulfonated dye. Orange-G. A pseudo-second-order kinetic model was used to determine the kinetics of adsorption. The effect of grafting, effect of process variables and the effect of different sulfonated anionic dyes (Orange-C, Congo Red, Remazol Brill Blue R and Methyl Blue) on the adsorption kinetics was determined. The Langmuir and Freundlich models were used to fit the adsorption isotherms and from the values of correlation coefficients (R-2), it was observed that the experimental data fits very well to the Langmuir model. The values of the maximum adsorption capacity of the adsorbents follow the order: ChgPMMA > ChgPEMA > ChgPBMA > ChgPHMA > chitosan. (C) 2010 Elsevier B.V. All rights reserved.

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.