Probing the Oxidation Chemistry of Dimethoxymethane, a Model OME Fuel

The threat posed by anthropogenic global warming, along with attached mitigation policies, drives the search for alternative fuels or additives; this search requires understanding the combustion chemistry of possible biofuel candidates. The low-temperature oxidation of a potential diesel fuel substitute, dimethoxymethane (DMM, m/z 76), is herein investigated at 500K, 600K, and 700K using synchrotron radiation coupled with multiplexed photoionization mass spectrometry at the Advanced Light Source within the Lawrence Berkeley National Laboratory. The experimental data is resolved in 3 dimensions: time, mass, and photon energy; this allows for identification, characterization, and quantification of primary products. Energetics calculations are carried out at the CBS-QB3 level of theory for adiabatic ionization energies and proposed potential energy surfaces, while B3LYP level is utilized for simulated photoionization efficiency spectra. Methyl formate and formaldehyde are confirmed as the major primary products by matching the kinetic traces from product formation with the depletion of the DMM parent reactant and fragments (m/z 75, 45)

Characterization of the CH Addition Product from Meta- and Ortho-Xylene + CH Reaction and Direct Experimental Observation of the Tetrabromine Cluster Br4 using Synchrotron Photoionization Mass Spectrometry

This thesis is centered on the use of a unique gas-phase spectroscopy technique to characterize products and elucidate reaction mechanisms. Experiments were carried out at the Chemical Dynamics Beamline 9.0.2 of the Advanced Light Source located at the Lawrence Berkeley National Laboratory in Berkeley, CA. Computational work was performed on the scientific supercomputer at USF to supplement experimental findings. Chapter 1 contextualizes the work spurred in response to the deleterious interactions of anthropogenic emissions on Earth’s climate. Chapter 2 describes the theoretical manipulations foundational to the experimental design and interpretation. Chapter 3 delves into the physical details of the experimental setup and data analysis. A joint experimental and computational investigation into the addition product resulting from methylidene radical reaction with meta- and ortho-xylene is discussed in Chapter 4. Finally, Chapter 5 concludes with a novel observation and characterization of a Bromine cluster (n=4)

Recent laboratory tests of a hard x-ray solar flare polarimeter

We report on the development of a Compton scatter polarimeter for measuring the linear polarization of hard X-rays (50 - 300 keV) from solar flares. Such measurements would be useful for studying the directivity (or beaming) of the electrons that are accelerated in solar flares. We initially used a simple prototype polarimeter to successfully demonstrate the reliability of our Monte Carlo simulation code and to demonstrate our ability to generate a polarized photon source in the lab. We have recently fabricated a science model based on a modular design concept that places a self-contained polarimeter module on the front-end of a 5-inch position- sensitive PMT (PSPMT). The PSPMT is used to determine the Compton interaction location within an annular array of small plastic scintillator elements. Some of the photons that scatter within the plastic scintillator array are subsequently absorbed by a small centrally-located array of CsI(Tl) crystals that is read out by an independent multi-anode PMT. The independence of the two PMT readout schemes provides appropriate timing information for event triggering. We are currently testing this new polarimeter design in the laboratory to evaluate the performance characteristics of this design. Here we present the initial results from these laboratory tests. The modular nature of this design lends itself toward its accommodation on a balloon or spacecraft platform. A small array of such modules can provide a minimum detectable polarization (MDP) of less than 1% in the integrated 50 - 300 keV energy range for X-class solar flares

Controlling for Confounding Via Propensity Score Methods Can Result in Biased Estimation of the Conditional AUC: A Simulation Study

In the medical literature, there has been an increased interest in evaluating association between exposure and outcomes using nonrandomized observational studies. However, because assignments to exposure are not random in observational studies, comparisons of outcomes between exposed and nonexposed subjects must account for the effect of confounders. Propensity score methods have been widely used to control for confounding, when estimating exposure effect. Previous studies have shown that conditioning on the propensity score results in biased estimation of conditional odds ratio and hazard ratio. However, research is lacking on the performance of propensity score methods for covariate adjustment when estimating the area under the ROC curve (AUC). In this paper, AUC is proposed as measure of effect when outcomes are continuous. The AUC is interpreted as the probability that a randomly selected nonexposed subject has a better response than a randomly selected exposed subject. A series of simulations has been conducted to examine the performance of propensity score methods when association between exposure and outcomes is quantified by AUC; this includes determining the optimal choice of variables for the propensity score models. Additionally, the propensity score approach is compared with that of the conventional regression approach to adjust for covariates with the AUC. The choice of the best estimator depends on bias, relative bias, and root mean squared error. Finally, an example looking at the relationship of depression/anxiety and pain intensity in people with sickle cell disease is used to illustrate the estimation of the adjusted AUC using the proposed approaches

Development of a hard X-ray polarimeter for astrophysics

We have been developing a Compton scatter polarimeter for measuring the linear polarization of hard X-rays (100-300 keV) from astrophysical sources. A laboratory prototype polarimeter has been used to successfully demonstrate the reliability of our Monte Carlo simulation code and to demonstrate our ability to generate a polarized photon source in the lab. Our design concept places a self-containedpolarimeter module on the front-end of a a 5-inch position sensitive PMT (PSPMT). We are currently working on the fabrication of a science model based on this PSPMT concept. Although the emphasis of our development effort is towards measuring hard X-rays from solar flares, our design has the advantage that it is sensitive over a rather large field-of-view (\u3e1 steradian), a feature that makes it especially attractive for γ-ray burst studies