Quantification Of Lignin Hydroxyl Containing Functional Groups Via 31p{1h} Nmr Spectroscopy And Synthesis Of Lignin Degradation Standards

The focus of this thesis is on the structural characterization of lignin, a complex phenol-based heteropolymer. In the first part of the study, functionalization of lignin and its known degradation products by 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP) and analysis by 31P NMR spectroscopy was investigated. Chemical shifts of derivatized alcohols, phenols, and carboxylic acids were determined that allowed for qualitative characterization of lignin. This approach was further applied for the quantitative analysis of OH-containing groups present in lignin employing the internal standard. Lignin samples, fractionated by gel permeation chromatography (GPC) based on molecular weights, were derivatized by TMDP and characterized by 31P NMR spectroscopy. It was determined that the number of hydroxyl-containing functional groups quantified in lignin samples increased by 366% after GPC. In the second part of the study, six possible lignin degradation products were synthesized. It was confirmed that one of them, (E)-4,4’-(ethane-1,2-diyl)bis(2-methoxyphenol), was present in lignin degradation samples

Multistationary and Oscillatory Modes of Free Radicals Generation by the Mitochondrial Respiratory Chain Revealed by a Bifurcation Analysis

The mitochondrial electron transport chain transforms energy satisfying cellular demand and generates reactive oxygen species (ROS) that act as metabolic signals or destructive factors. Therefore, knowledge of the possible modes and bifurcations of electron transport that affect ROS signaling provides insight into the interrelationship of mitochondrial respiration with cellular metabolism. Here, a bifurcation analysis of a sequence of the electron transport chain models of increasing complexity was used to analyze the contribution of individual components to the modes of respiratory chain behavior. Our algorithm constructed models as large systems of ordinary differential equations describing the time evolution of the distribution of redox states of the respiratory complexes. The most complete model of the respiratory chain and linked metabolic reactions predicted that condensed mitochondria produce more ROS at low succinate concentration and less ROS at high succinate levels than swelled mitochondria. This prediction was validated by measuring ROS production under various swelling conditions. A numerical bifurcation analysis revealed qualitatively different types of multistationary behavior and sustained oscillations in the parameter space near a region that was previously found to describe the behavior of isolated mitochondria. The oscillations in transmembrane potential and ROS generation, observed in living cells were reproduced in the model that includes interaction of respiratory complexes with the reactions of TCA cycle. Whereas multistationarity is an internal characteristic of the respiratory chain, the functional link of respiration with central metabolism creates oscillations, which can be understood as a means of auto-regulation of cell metabolism. © 2012 Selivanov et al

Discovery of Fast X-ray Oscillations During the 1998 Giant Flare from SGR 1900+14

We report the discovery of complex high frequency variability during the August 27, 1998 giant flare from SGR 1900+14 using the Rossi X-ray Timing Explorer (RXTE). We detect an 84 Hz oscillation (QPO) during a 1 s interval beginning approximately 1 min after the initial hard spike. The modulation amplitude is energy dependent, reaching a maximum of 26% (rms) for photons above 30 keV, and is not detected below 11 keV, with a 90% confidence upper limit of 14% (rms). Remarkably, additional QPOs are detected in the average power spectrum of data segments centered on the rotational phase at which the 84 Hz signal was detected. Two signals, at 53.5 and 155.1 Hz, are strongly detected, while a third feature at 28 Hz is found with lower significance. These QPOs are not detected at other rotational phases. The phenomenology seen in the SGR 1900+14 flare is similar to that of QPOs recently reported by Israel et al. from the December 27, 2004 flare from SGR 1806-20, suggesting they may have a common origin, perhaps torsional vibrations of the neutron star crust. Indeed, an association of the four frequencies (in increasing order) found in SGR 1900+14 with l = 2, 4, 7, and 13 toroidal modes appears plausible. We discuss our findings in the context of this model and show that if the stars have similar masses then the magnetic field in SGR 1806-20 must be about twice as large as in SGR 1900+14, broadly consistent with magnetic field estimates from pulse timing.Comment: 13 Pages, 5 figures, AASTeX, accepted for publication in the Astrophysical Journal Letter

Sensitivity and parameter-estimation precision for alternate LISA configurations

We describe a simple framework to assess the LISA scientific performance (more specifically, its sensitivity and expected parameter-estimation precision for prescribed gravitational-wave signals) under the assumption of failure of one or two inter-spacecraft laser measurements (links) and of one to four intra-spacecraft laser measurements. We apply the framework to the simple case of measuring the LISA sensitivity to monochromatic circular binaries, and the LISA parameter-estimation precision for the gravitational-wave polarization angle of these systems. Compared to the six-link baseline configuration, the five-link case is characterized by a small loss in signal-to-noise ratio (SNR) in the high-frequency section of the LISA band; the four-link case shows a reduction by a factor of sqrt(2) at low frequencies, and by up to ~2 at high frequencies. The uncertainty in the estimate of polarization, as computed in the Fisher-matrix formalism, also worsens when moving from six to five, and then to four links: this can be explained by the reduced SNR available in those configurations (except for observations shorter than three months, where five and six links do better than four even with the same SNR). In addition, we prove (for generic signals) that the SNR and Fisher matrix are invariant with respect to the choice of a basis of TDI observables; rather, they depend only on which inter-spacecraft and intra-spacecraft measurements are available.Comment: 17 pages, 4 EPS figures, IOP style, corrected CQG versio

The Influence of Quadrature Errors on Isogeometric Mortar Methods

Mortar methods have recently been shown to be well suited for isogeometric analysis. We review the recent mathematical analysis and then investigate the variational crime introduced by quadrature formulas for the coupling integrals. Motivated by finite element observations, we consider a quadrature rule purely based on the slave mesh as well as a method using quadrature rules based on the slave mesh and on the master mesh, resulting in a non-symmetric saddle point problem. While in the first case reduced convergence rates can be observed, in the second case the influence of the variational crime is less significant

Nuclei in Strongly Magnetised Neutron Star Crusts

We discuss the ground state properties of matter in outer and inner crusts of neutron stars under the influence of strong magnetic fields. In particular, we demonstrate the effects of Landau quantization of electrons on compositions of neutron star crusts. First we revisit the sequence of nuclei and the equation of state of the outer crust adopting the Baym, Pethick and Sutherland (BPS) model in the presence of strong magnetic fields and most recent versions of the theoretical and experimental nuclear mass tables. Next we deal with nuclei in the inner crust. Nuclei which are arranged in a lattice, are immersed in a nucleonic gas as well as a uniform background of electrons in the inner crust. The Wigner-Seitz approximation is adopted in this calculation and each lattice volume is replaced by a spherical cell. The coexistence of two phases of nuclear matter - liquid and gas, is considered in this case. We obtain the equilibrium nucleus corresponding to each baryon density by minimizing the free energy of the cell. We perform this calculation using Skyrme nucleon-nucleon interaction with different parameter sets. We find nuclei with larger mass and charge numbers in the inner crust in the presence of strong magnetic fields than those of the zero field case for all nucleon-nucleon interactions considered here. However, SLy4 interaction has dramatic effects on the proton fraction as well as masses and charges of nuclei. This may be attributed to the behaviour of symmetry energy with density in the sub-saturation density regime. Further we discuss the implications of our results to shear mode oscillations of magnetars.Comment: presented in "Exciting Physics Symposium" held in Makutsi, South Africa in November, 2011 and to be published in a book by Springer Verla

Two Mode Quantum Systems: Invariant Classification of Squeezing Transformations and Squeezed States

A general analysis of squeezing transformations for two mode systems is given based on the four dimensional real symplectic group Sp(4,\Re)\/. Within the framework of the unitary metaplectic representation of this group, a distinction between compact photon number conserving and noncompact photon number nonconserving squeezing transformations is made. We exploit the Sp(4,\Re)-SO(3,2)\/ local isomorphism and the U(2)\/ invariant squeezing criterion to divide the set of all squeezing transformations into a two parameter family of distinct equivalence classes with representative elements chosen for each class. Familiar two mode squeezing transformations in the literature are recognized in our framework and seen to form a set of measure zero. Examples of squeezed coherent and thermal states are worked out. The need to extend the heterodyne detection scheme to encompass all of U(2)\/ is emphasized, and known experimental situations where all U(2)\/ elements can be reproduced are briefly described.Comment: Revtex 37 pages, Latex figures include

Novel approach to the study of quantum effects in the early universe

We develop a theoretical frame for the study of classical and quantum gravitational waves based on the properties of a nonlinear ordinary differential equation for a function $\sigma(\eta)$ of the conformal time $\eta$, called the auxiliary field equation. At the classical level, $\sigma(\eta)$ can be expressed by means of two independent solutions of the ''master equation'' to which the perturbed Einstein equations for the gravitational waves can be reduced. At the quantum level, all the significant physical quantities can be formulated using Bogolubov transformations and the operator quadratic Hamiltonian corresponding to the classical version of a damped parametrically excited oscillator where the varying mass is replaced by the square cosmological scale factor $a^{2}(\eta)$. A quantum approach to the generation of gravitational waves is proposed on the grounds of the previous $\eta-$dependent Hamiltonian. An estimate in terms of $\sigma(\eta)$ and $a(\eta)$ of the destruction of quantum coherence due to the gravitational evolution and an exact expression for the phase of a gravitational wave corresponding to any value of $\eta$ are also obtained. We conclude by discussing a few applications to quasi-de Sitter and standard de Sitter scenarios.Comment: 20 pages, to appear on PRD. Already published background material has been either settled up in a more compact form or eliminate

Lifetimes of states in 19Ne above the 15 O + alpha breakup threshold

The 15O(alpha,gamma)19Ne reaction plays a role in the ignition of Type I x-ray bursts on accreting neutron stars. The lifetimes of states in 19Ne above the 15O + alpha threshold of 3.53 MeV are important inputs to calculations of the astrophysical reaction rate. These levels in 19Ne were populated in the 3He(20Ne,alpha)19Ne reaction at a 20Ne beam energy of 34 MeV. The lifetimes of six states above the threshold were measured with the Doppler shift attenuation method (DSAM). The present measurements agree with previous determinations of the lifetimes of these states and in some cases are considerably more precise

Advancing the State-of-the-Practice for Liquid Rocket Engine Injector Design

Current shortcomings in both the overall injector design process and its underlying combustion stability assessment methodology are rooted in the use of empirically based or low fidelity representations of complex physical phenomena and geometry details that have first order effects on performance, thermal environments and combustion stability. The result is a design and analysis capability that is often inadequate to reliably arrive at a suitable injector design in an efficient manner. Specifically, combustion instability has been particularly difficult to predict and mitigate. Large hydrocarbon-fueled booster engines have been especially problematic in this regard. Where combustion instability has been a problem, costly and time-consuming redesign efforts have often been an unfortunate consequence. This paper presents an overview of a recently completed effort at NASA Marshall Space Flight Center to advance the state-of-the-practice for liquid rocket engine injector design. Multiple perturbations of a gas-centered swirl coaxial (GCSC) element that burned gaseous oxygen and RP-1 were designed, assessed for combustion stability, and tested. Three designs, one stable, one marginally unstable and one unstable, were used to demonstrate both an enhanced overall injector design process and an improved combustion stability assessment process. High-fidelity results from state-of-the-art computational fluid dynamics CFD simulations were used to substantially augment and improve the injector design methodology. The CFD results were used to inform and guide the overall injector design process. They were also used to upgrade selected empirical or low-dimensional quantities in the ROCket Combustor Interactive Design (ROCCID) stability assessment tool. Hot fire single element injector testing was used to verify both the overall injector designs and the stability assessments. Testing was conducted at the Air Force Research Laboratory and at Purdue University. Companion papers provide details of the overall injector design process, full- and sub-scale testing, ROCCID-based stability assessments and the CFD simulations