Chemistry Commons^™

Nitrous Oxide In The Atmosphere: First Measurements Of A Lower Thermospheric Source, Patrick E. Sheese, Kaley A. Walker, Chris D. Boone, Peter F. Bernath, Bernd Funke

Chemistry & Biochemistry Faculty Publications

Nitrous oxide (N₂O) is an important anthropogenic greenhouse gas, as well as one of the most significant anthropogenic ozone-depleting substances in the stratosphere. The satellite-based instrument Atmospheric Chemistry Experiment-Fourier Transform Spectrometer has been observing the Earth's limb since 2004 and derives profiles of N₂O volume mixing ratios in the upper troposphere to the lower thermosphere. The resulting climatology shows that N₂O is continuously produced in the lower thermosphere via energetic particle precipitation and enhanced N₂O is present at all latitudes, during all seasons. The results are consistent with an N₂O …

Study Of Infrared Emission Spectroscopy For The B 1Δg- A 1Πu And B ′1Σg +- A 1Πu Systems Of C2, Wang Chen, Kentarou Kawaguchi, Peter F. Bernath, Jian Tang

Chemistry & Biochemistry Faculty Publications

Thirteen bands for the B¹Δ_g-A¹Π_u system and eleven bands for the B′¹Σ_g ⁺-A¹Πu system of C₂ were identified in the Fourier transform infrared emission spectra of hydrocarbon discharges. The B′¹Σ_g ⁺ v = 4 and the B¹Δ_g v = 6, 7, and 8 vibrational levels involved in nine bands were studied for the first time. A direct global analysis with Dunham parameters was carried out satisfactorily for the B¹Δ_g-A¹Π_u system except for a …

A Novel Copper (Ii) Complex Identified As A Potent Drug Against Colorectal And Breast Cancer Cells And As A Poison Inhibitor For Human Topoisomerase Iiᶐ, Shayna Sandhaus, Rosella Taylor, Tiffany Edwards, Alexis Huddleston, Stephen J. Beebe, Alvin A. Holder

Bioelectrics Publications

A novel complex, [Cu(acetylethTSC)Cl]Cl · 0.25C₂H₅OH 1 (where acetylethTSC = (E)-N-ethyl-2-[1-(thiazol-2-yl)ethylidene]hydrazinecarbothioamide), was shown to have anti-proliferative activity against various colon and aggressive breast cancer cell lines. In vitro studies showed that complex 1 acted as a poison inhibitor of human topoisomerase IIᶐ which may account for the observed anti-cancer effects.

An In Vitro Study On The Effect Of Synthesized Tin (Iv) Complexes On Glioblastoma, Colorectal, And Skin Cancer Cell Lines, Jennie L. Williams, Lesley C. Lewis-Alleyne, Melinda Solomon, Long Nguyen, Robert Johnson, Jennifer Vital, Ping Ji, John Durant, Camille Cooper, Patrice Cagle, Patrick Martin, Don Vanderveer, William L. Jarrett, Alvin A. Holder

Chemistry & Biochemistry Faculty Publications

((E)-2-(2-hydroxybenzylideneamino)phenolato-2,2-diphenyl-6-aza-1,3-dioxa-2-stanna-[d,h]dibenzocyclononene, [Sn(Ph₂SB)] (compound 1, where Ph₂SB=(E)-2-(2-hydroxybenzylideneamino)phenolato Schiff base) and two novel compounds, [[SnPh2(F-azoSB)] (compound 2, where F-azoSB=4-((E)-(4-fluorophenyl)diazenyl)-2-((E)-(2-hydroxyphenylimino)methyl)phenolato Schiff base), [[SnPh2(sulf-azoSB)]0.125CHCl₃ (compound 3, where sulfamerazineazosalSB=4-((E)-(4-hydroxy-3-((E)-(2-hydroxyphenylimino)methyl)phenyl)diazenyl)-N-(4-methylpyrimidin-2-yl) benzenesulfonamide Schiff base), and the control compound, cisplatin (compound 4) were analysed to comparatively determine their effect on cancer cell growth. Anti-cancer properties of compounds 1-4 were examined using glioblastoma (U-1242 MG), colorectal (HT-29 and HCT-116), and skin (A431) human cancer cell lines. With regards to human glioblastoma cells, compounds 1 and 3 demonstrated anti-proliferative capacity in the cell line tested. Specifically, compounds 1 and 3 inhibited cell proliferation by 50% at …

Vanadium Toxicological Potential Versus Its Pharmacological Activity: New Developments And Research, Agnieszka Ścibior, Juan Llopis, Alvin A. Holder, Mario Altamirano-Lozano

Chemistry & Biochemistry Faculty Publications

Scibior, A., Llopis, J., Holder, A. A., & Altamirano-Lozano, M. (2016). Vanadium toxicological potential versus its pharmacological activity: New developments and research. Oxidative Medicine and Cellular Longevity, 2016, 1-2. doi: 10.1155/2016/7612347

Intercomparison And Evaluation Of Satellite Peroxyacetyl Nitrate Observations In The Upper Troposphere-Lower Stratosphere, Richard J. Pope, Nigel A. D. Richards, Martyn P. Chipperfield, David P. Moore, Sarah A. Monks, Stephen R. Arnold, Norbert Glatthor, Michael Kiefer, Tom J. Breider, Jeremy J. Harrison, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Peroxyacetyl nitrate (PAN) is an important chemical species in the troposphere as it aids the long-range transport of NO_x and subsequent formation of O₃ in relatively clean remote regions. Over the past few decades observations from aircraft campaigns and surface sites have been used to better understand the regional distribution of PAN. However, recent measurements made by satellites allow for a global assessment of PAN in the upper troposphere-lower stratosphere (UTLS). In this study, we investigate global PAN distributions from two independent retrieval methodologies, based on measurements from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument, on …

Uv Light-Induced Aggregation Of Titania Submicron Particles, Can Zhou, Yashar Bashirzadeh, Timothy A. Bernadowsky Jr., Xiaoyu Zhang

Mechanical & Aerospace Engineering Faculty Publications

In this study, aggregation of TiO₂ (rutile and anatase) submicron particles in deionized (DI) water under ultra-violet (UV) light irradiation was investigated. While no aggregation was observed in the dark, rutile and anatase submicron particles started aggregating upon application of UV light and ceased aggregation in about 2 and 8.4 h, respectively. It has been demonstrated that UV light directly mitigated the particle mobility of TiO₂, resulting in a neutralization effect of the Zeta potential. It was also observed that rutile particles aggregated much faster than anatase particles under UV radiation, indicating that the Zeta potential of …

Studies On Hydroxyl Radical Formation And Correlated Photoflocculation Process Using Degraded Wood Leachate As A Cdom Source, Luni Sun, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

In this study, we examined hydroxyl radical (•OH) formation with respect to photoreactivity of colored dissolved organic matter (CDOM), the Fenton reaction, and photoflocculation using leachate from decaying wood. The relationship between •OH photoproduction rate and leachate optical properties (UV-visible absorption and fluorescence excitation-emission matrices (EEMS)) was studied during irradiation using a UV solar simulator. The results showed that the •OH photochemical formation rate is strongly related to humic-like fluorescence as characterized by parallel factor analysis (PARAFAC), and that these fluorescence components are more photolabile than most of the other CDOM components. Fourier transform infrared spectroscopy (FT-IR) indicated the photodegradation …

Plutonium Immobilization And Mobilization By Soil Organic Matter, Peter H. Santschi, Kathleen A. Schwehr, Chen Xu, Matthew Athon, Yi-Fang Ho, Patrick G. Hatcher, Nicole Didonato, Daniel I. Kaplan

Chemistry & Biochemistry Faculty Publications

The human and environmental risks associated with Pu disposal, remediation, and nuclear accidents scenarios stems mainly from the very long half-lives of several of its isotopes. The SRS, holding one-third of the nation’s Pu inventory, has a long-term stewardship commitment to investigation of Pu behavior in the groundwater and downgradient vast wetlands. Pu is believed to be essentially immobile due to its low solubility and high particle reactivity to mineral phase or natural organic matter (NOM). For example, in sediments collected from a region of SRS, close to a wetland and a groundwater plume, 239,240Pu concentrations suggest immobilization by NOM …

Satellite Observations Of Stratospheric Hydrogen Flouride And Comparisons With Slimcat Calculations, Jeremy J. Harrison, Martyn P. Chipperfield, Christopher D. Boone, Sandip S. Dhomse, Peter F. Bernath, Lucien Froidevaux

Chemistry & Biochemistry Faculty Publications

The vast majority of emissions of fluorine-containing molecules are anthropogenic in nature, e.g. chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Many of these fluorine-containing species deplete stratospheric ozone and are regulated by the Montreal Protocol. Once in the atmosphere they slowly degrade, ultimately leading to the formation of hydrogen fluoride (HF), the dominant reservoir of stratospheric fluorine due to its extreme stability. Monitoring the growth of stratospheric HF is therefore an important marker for the success of the Montreal Protocol. We report the comparison of global distributions and trends of HF measured in the Earth's atmosphere by the satellite remote-sensing …

Single Nanoparticle Plasmonic Spectroscopy For Study Of The Efflux Function Of Multidrug Abc Membrance Transporters Of Single Live Cells, Lauren M. Browning, Kerry J. Lee, Pavan K. Cherukuri, Prakash D. Nallathamby, Seth Warren, Jean-Michel Jault, Xiao-Hong Nancy Xu

Chemistry & Biochemistry Faculty Publications

ATP-binding cassette (ABC) membrane transporters exist in all living organisms and play key roles in a wide range of cellular and physiological functions. The ABC transporters can selectively extrude a wide variety of structurally and functionally unrelated substrates, leading to multidrug resistance. Despite extensive study, their efflux molecular mechanisms remain elusive. In this study, we synthesized and characterized purified silver nanoparticles (Ag NPs) (97 ± 13 nm in diameter), and used them as photostable optical imaging probes to study efflux kinetics of ABC membrane transporters (BmrA) of single live cells (B. subtilis). The NPs with concentrations up to …

The Role Of Microbial Exopolymers In Determining The Fate Of Oil And Chemical Dispersants In The Ocean, Antonietta Quigg, Uta Passow, Wei-Chun Chin, Chen Xu, Shawn Doyle, Laura Bretherton, Manoj Kamalanathan, Alicia K. Williams, Jason B. Sylvan, Zoe V. Finkel, Anthony H. Knap, Kathleen A. Schwehr, Saijin Zhang, Luni Sun, Terry L. Wade, Wassim Obeid, Patrick G. Hatcher, Peter H. Santschi

Chemistry & Biochemistry Faculty Publications

The production of extracellular polymeric substances (EPS) by planktonic microbes can influence the fate of oil and chemical dispersants in the ocean through emulsification, degradation, dispersion, aggregation, and/or sedimentation. In turn, microbial community structure and function, including the production and character of EPS, is influenced by the concentration and chemical composition of oil and chemical dispersants. For example, the production of marine oil snow and its sedimentation and flocculent accumulation to the seafloor were observed on an expansive scale after the Deepwater Horizon oil spill in the Northern Gulf of Mexico in 2010, but little is known about the underlying …

Measurement Of Antioxidant Activity Toward Superoxide In Natural Waters, D. Whitney King, Emma Berger, Zachary Helm, Eleanor Irish, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Antioxidants are a class of molecules that provide a protective function against reactive oxygen species (ROS) in biological systems by out competing physiologically important molecules for ROS oxidation. In natural waters, the reactivity of antioxidants gives an estimate of oxidative stress, and may determine the reactivity and distribution of reactive oxidants. We present an analytical method to measure antioxidant activity in natural waters through the competition between ascorbic acid, an antioxidant, and MCLA, a chemiluminescent probe for superoxide. A numerical kinetic model of the analytical method has been developed to optimize analytical performance. Measurements of antioxidant concentrations in pure and …

Anticancer, Biophysical And Computational Investigations Of Half-Sandwich Ruthenium(Ii) Thiosemicarbazone Complexes: The Effect Of Arene Versus Thiacrown Face-Cap, Floyd A. Beckford, Alyssa Stott, P. Canisius Mbarushimana, Marc-Andre Leblanc, Kinsey Hall, Samantha Smith, Jimmie L. Bullock, Dennis J. Houghton, Alvin A. Holder, Nikolay Gerasimchuk, Antonio Gonzalez-Sarrías

Chemistry & Biochemistry Faculty Publications

A series of half-sandwich ruthenium complexes, two containing an arene face-cap and the other a thiacrown ether face-cap were synthesized to investigate the necessity of the arene for anticancer activity in this class of compounds. The complexes are formulated as [(h⁶-p-cymene)Ru(dmabTSC)Cl]PF₆, [(h⁶-benzene)Ru(dmabTSC)Cl]PF₆ (arene complexes), and [([9]aneS₃(dmabTSC)Cl]PF₆ (dmabTSC = dimethylaminobenzaldehye thiosemicarbazone). It was observed that none of the complexes showed good anticancer activity in vitro against HCT-116 and Caco-2 (colon adenocarcinoma) cells. All three complexes can bind strongly to calf-thymus DNA with binding constants on the order of 10 …

Characterization Of Biochars Produced From Peanut Hulls And Pine Wood With Different Pyrolysis Conditions, James W. Lee, Bob Hawkins, Michelle K. Kidder, Barbara R. Evans, A. C. Buchanan, Danny Day

Chemistry & Biochemistry Faculty Publications

Background

Application of modern biomass pyrolysis methods for production of biofuels and biochar is potentially a significant approach to enable global carbon capture and sequestration. To realize this potential, it is essential to develop methods that produce biochar with the characteristics needed for effective soil amendment.

Methods

Biochar materials were produced from peanut hulls and pine wood with different pyrolysis conditions, then characterized by cation exchange (CEC) capacity assays, nitrogen adsorption–desorption isotherm measurements, micro/nanostructural imaging, infrared spectra and elemental analyses.

Results

Under a standard assay condition of pH 8.5, the CEC values of the peanut hull-derived biochar materials, ranging from …

Water Vapour Variability In The High-Latitude Upper Troposphere- Part 2: Impact Of Volcanic Eruptions, Christopher E. Sioris, Jason Zou, C. Thomas Mcelroy, Chris D. Boone, Patrick E. Sheese, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

The impact of volcanic eruptions on water vapour in the high-latitude upper troposphere is studied using deseasonalized time series based on observations by the Atmospheric Chemistry Experiment (ACE) water vapour sensors, namely MAESTRO (Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) and the Fourier Transform Spectrometer (ACE-FTS). The two eruptions with the greatest impact on the high-latitude upper troposphere during the time frame of this satellitebased remote sensing mission are chosen. The Puyehue-Cordón Caulle volcanic eruption in June 2011 was the most explosive in the past 24 years and is shown to be able to account …

Global Stratospheric Measurements Of The Isotopologues Of Methane From The Atmospheric Chemistry Experiment Fourier Transform Spectrometer, Eric M. Buzan, Chris A. Beale, Chris. D. Boone, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

This paper presents an analysis of observations of methane and its two major isotopologues, CH₃D and ¹³CH₄, from the Atmospheric Chemistry Experiment (ACE) satellite between 2004 and 2013. Additionally, atmospheric methane chemistry is modeled using the Whole Atmospheric Community Climate Model (WACCM). ACE retrievals of methane extend from 6 km for all isotopologues to 75 km for ¹²CH₄, 35 km for CH₃D, and 50 km for ¹³CH₄. While total methane concentrations retrieved from ACE agree well with the model, values of δD-CH₄ and δ¹³C-CH …

Synthesis And Characterization Of Azo-Guanidine Based Alcoholic Media Naked Eye Dna Sensor, Ataf A. Altaf, Uzma Hashmat, Muhammad Yousaf, Bhajan Lal, Shafiq Ullah, Alvin A. Holder, Amin Badshah

Chemistry & Biochemistry Faculty Publications

DNA sensing always has an open meadow of curiosity for biotechnologists and other researchers. Recently, in this field, we have introduced an emerging class of molecules containing azo and guanidine functionalities. In this study, we have synthesized three new compounds (UA1, UA6 and UA7) for potential application in DNA sensing in alcoholic medium. The synthesized materials were characterized by elemental analysis, FTIR, UV-visible, ¹H NMR and ¹³C NMR spectroscopies. Their DNA sensing potential were investigated by UV-visible spectroscopy. The insight of interaction with DNA was further investigated by electrochemical (cyclic voltammetry) and hydrodynamic (viscosity) studies. …

Detailed Source-Specific Molecular Composition Of Ambient Aerosol Organic Matter Using Ultrahigh Resolution Mass Spectrometry And H Nmr, Amanda S. Willoughby, Andrew S. Wozniak, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Organic aerosols (OA) are universally regarded as an important component of the atmosphere that have far-ranging impacts on climate forcing and human health. Many of these impacts are related to OA molecular characteristics. Despite the acknowledged importance, current uncertainties related to the source apportionment of molecular properties and environmental impacts make it difficult to confidently predict the net impacts of OA. Here we evaluate the specific molecular compounds as well as bulk structural properties of total suspended particulates in ambient OA collected from key emission sources (marine, biomass burning, and urban) using ultrahigh resolution mass spectrometry (UHR-MS) and proton nuclear …

Validation Of Ace-Fts Version 3.5 Noy Species Profiles Using Correlative Satellite Measurements, Patrick E. Sheese, Kaley A. Walker, Chris D. Boone, Chris A. Mclinden, Peter F. Bernath, Adam E. Bourassa, John P. Burrows, Doug A. Degenstein, Bernd Funke, Didier Fussen

Chemistry & Biochemistry Faculty Publications

The ACE-FTS (Atmospheric Chemistry Experiment - Fourier Transform Spectrometer) instrument on the Canadian SCISAT satellite, which has been in operation for over 12 years, has the capability of deriving stratospheric profiles of many of the NOy (N + NO + NO₂ + NO₃ + 2 x N₂O₅ + HNO₃ + HNO₄ + ClONO₂ + BrONO₂) species. Version 2.2 of ACE-FTS NO, NO₂, HNO₃, N₂O₅, and ClONO₂ has previously been validated, and this study compares the most recent version (v3.5) of …

Upper Tropospheric Water Vapour Variability At High Latitudes- Part 1: Influence Of The Annular Modes, Christopher E. Sioris, Jason Zou, David A. Plummer, Chris D. Boone, C. Thomas Mcelroy, Patrick E. Sheese, Omid Moeini, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Seasonal and monthly zonal medians of water vapour in the upper troposphere and lower stratosphere (UTLS) are calculated for both Atmospheric Chemistry Experiment (ACE) instruments for the northern and southern high-latitude regions (60-90° N and 60-90°S). Chosen for the purpose of observing high-latitude processes, the ACE orbit provides sampling of both regions in 8 of 12 months of the year, with coverage in all seasons. The ACE water vapour sensors, namely MAESTRO (Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) and the Fourier Transform Spectrometer (ACE-FTS) are currently the only satellite instruments that can probe from …

Mipas Imk/Iaa Cfc-11 (Ccl3f) And Cfc-12 (Ccl2f2) Measurements: Accuracy, Precision And Long-Term Stability, E. Eckert, A. Laeng, S. Lossow, S. Kellmann, G. Stiller, T. Von Clarmann, N. Glatthor, M. Hopfner, M. Kiefer, H. Oelhaf, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

Profiles of CFC-11 (CCl₃F) and CFC-12 (CCl₂F₂) of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the European satellite Envisat have been retrieved from versions MIPAS/4.61 to MI-PAS/4.62 and MIPAS/5.02 to MIPAS/5.06 level-1b data using the scientific level-2 processor run by Karlsruhe Institute of Technology (KIT), Institute of Meteorology and Climate Research (IMK) and Consejo Superior de Investigaciones Cientificas (CSIC), Instituto de Astrofisica de Andalucia (IAA). These profiles have been compared to measurements taken by the balloon-borne cryosampler, Mark IV (MkIV) and MIPAS-Balloon (MIPAS-B), the airborne MIPAS-STRatospheric aircraft (MIPAS-STR), the satellite-borne Atmospheric Chemistry …

Rcd+: Fast Loop Modeling Server, José R. López-Blanco, Alejandro J. Canosa-Valis, Yaohang Li, Pablo Chacón

Computer Science Faculty Publications

Modeling loops is a critical and challenging step in protein modeling and prediction. We have developed a quick online service (http://rcd.chaconlab.org) for ab initio loop modeling combining a coarse-grained conformational search with a full-atom refinement. Our original Random Coordinate Descent (RCD) loop closure algorithm has been greatly improved to enrich the sampling distribution towards near-native conformations. These improvements include a new workflow optimization, MPI-parallelization and fast backbone angle sampling based on neighbor-dependent Ramachandran probability distributions. The server starts by efficiently searching the vast conformational space from only the loop sequence information and the environment atomic coordinates. The generated closed loop …

Validation Of The Global Distribution Of Co2 Volume Mixing Ratio In The Mesosphere And Lower Thermosphere From Saber, L. Rezac, Y. Jian, J. Yue, J. M. Russell Iii, A. Kutepov, R. Garcia, K. Walker, P. Bernath

Chemistry & Biochemistry Faculty Publications

The Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument on board the Thermosphere Ionosphere Mesosphere Energetics and Dynamics satellite has been measuring the limb radiance in 10 broadband infrared channels over the altitude range from ~ 400 km to the Earth's surface since 2002. The kinetic temperatures and CO₂ volume mixing ratios (VMRs) in the mesosphere and lower thermosphere have been simultaneously retrieved using SABER limb radiances at 15 and 4.3 μm under nonlocal thermodynamic equilibrium (non-LTE) conditions. This paper presents results of a validation study of the SABER CO₂ VMRs obtained with a two-channel, self-consistent …

Energy-Efficient Computational Chemistry: Comparison Of X86 And Arm Systems, Kristopher Keipert, Gaurav Mitra, Vaibhav Sunriyal, Sarom S. Leang, Masha Sosonkina, Alistair P. Rendell, Mark S. Gordon

Computational Modeling & Simulation Engineering Faculty Publications

The computational efficiency and energy-to-solution of several applications using the GAMESS quantum chemistry suite of codes is evaluated for 32-bit and 64-bit ARM-based computers, and compared to an x86 machine. The x86 system completes all benchmark computations more quickly than either ARM system and is the best choice to minimize time to solution. The ARM64 and ARM32 computational performances are similar to each other for Hartree-Fock and density functional theory energy calculations. However, for memory-intensive second-order perturbation theory energy and gradient computations the lower ARM32 read/write memory bandwidth results in computation times as much as 86% longer than on the …

Synthesis, Characterisation, Electrochemical, And Spectroscopic Studies Of Cobaloximes: Unique Clues Of Cobalt(I) Species In Various Solvents, Michael John Celestine

Chemistry & Biochemistry Theses & Dissertations

With the dwindling amount of fossil fuels in the world’s reserve is said to run out in the future. The use of alternative fuels such as hydrogen can be produced from renewable sources. One source is the use of first row transition metal complexes that can harness the power of the sun to reduce protons to hydrogen. In this thesis we investigated a well-known hydrogen evolution catalyst in a quest to understand the behavior of different oxidation states that occur during the catalytic cycle.

In an attempt to synthesize a binuclear ruthenium(II) complex, [{Ru(phen)2}2{µmes(1,4-phO-Izphen)3}](PF6)4, as a possible photosensitizer for the …

Source-Specific Molecular Signatures For Light-Absorbing Organic Aerosols, Amanda Susan Willoughby

Chemistry & Biochemistry Theses & Dissertations

Organic aerosols (OA) are universally regarded as an important component of the atmosphere based on quantitative significance as well as the far-reaching impact they have on global climate forcing and human health. Despite the acknowledged importance, OA amounts and impacts remain the largest uncertainties regarding radiative forcing estimates. Incomplete chemical characterization of aerosol organic matter (OM) and a lack of concrete source apportionment is a major source of this uncertainty. The primary focus of this study is to provide much needed molecular details regarding ambient OA from key emission sources, and establish links between molecular and optical properties.

Complete chemical …

Artificial Maturation Studies Of Polymethylenic Plant Biopolymers: Investigating The Chemical Alterations From Plant Material To Coal, Blaine Elizabeth Hartman

Chemistry & Biochemistry Theses & Dissertations

The thermal maturation and alternation of vascular plant material into coals and as expelled petroleum-like compounds is the main focus of this dissertation. Utilizing artificial maturation studies, like hydrothermal liquefaction, yields useful information regarding how plant material is preserved in coals and the potential certain plant biopolymers possess to generate liquid fuels is acquired. The studies within this dissertation focus on utilizing the aliphatic biopolymers, cutin, cutan, and suberan, found in the epidermis of certain plants. These biopolymers contain minimal amounts of heteroatoms and are comprised of long polymethylenic chains, which are desirable characteristics in generating bio-oils. Additionally, understanding the …

Computational Investigation Of Pernicious Compounds: Arsenic And High Energy Density Materials And Their Relevant Mechanisms, Lenora Kathleen Harper

Chemistry & Biochemistry Theses & Dissertations

The underlying mechanisms of chemical warfare agents (CWAs) and high energy density materials (HEDMs) are poorly understood, yet important to the development of chemical applications in military science and technology. The reactivity of arsenite and arsenic-based CWA lewisite with biological thiols plays an important role in toxicity of these elements. Toxic effects of arsenite are eliminated when arsenite and selenite are co-administered, due to their antagonistic relationship. The arsenic-based CWA lewisite is detoxified by the dithiol-containing British anti-lewisite (BAL). The reduction of arsenous acid by thiol, the formation of an As-Se species, and the detoxification of lewisite with BAL have …

Study Of Photochemical Formation Of Hydroxyl Radical In Natural Waters, Luni Sun

Chemistry & Biochemistry Theses & Dissertations

This dissertation mainly focuses on the sources of the hydroxyl radical (•OH) from photochemical reactions in natural waters, in particular from reactions involving dissolved organic matter (DOM). Firstly, an accurate method for estimating •OH formation rate during long-term irradiation was developed. It was observed that previous methods for measuring •OH formation rates in the natural waters, which were based upon sequentially determined cumulative concentrations of probe photoproducts, significantly underestimated actual •OH formation rates. It was found that the underestimation was mainly due to the degradation of the probe photoproducts and that only ‘instantaneous’ formation rates were appropriate for accurately estimating …