Chemistry Commons^™

The Nature, Origin And Preservation Of Amide Organic Nitrogen In Organic Matter, Georgina Anne Mckee

Chemistry & Biochemistry Theses & Dissertations

Past studies have found much of nonliving sedimentary/aqueous nitrogen-containing organic matter (NCOM) is composed of amides, assumed to be peptides/proteins. Their lability calls into question their survival, and several hypotheses have been suggested to explain this. Using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and nuclear magnetic resonance (NMR) spectroscopy I investigated the molecular amide composition in sedimentary/aqueous systems while reassessing their preservation and formation routes.

Development of a suitable methodology is essential for successful NCOM study due to electrospray ionisation source requirements: sediment samples need to be rendered into solution. Based on NMR and FT-ICR-MS analysis, I determined …

Insights Into Chemical Structure Changes Of Kerogen From Bituminous Coal In Response To Dike Intrusions Investigated By Advanced Solid-State 13C Nmr, Yuan Li

Chemistry & Biochemistry Theses & Dissertations

Variations in the chemical structures of kerogens From highly volatile bituminous coal located near two igneous dike intrusions in the Illinois Basin were examined in detail by advanced solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Spectral-editing techniques were used to identify specific functional groups. Direct polarization was used to quantify different functional groups. ¹H-¹³C two- dimensional heteronuclear NMR was used to examine connectivities and proximities, and ¹H-¹³C long-range recoupled dipolar dephasing was used to estimate aromatic cluster sizes. With decreasing distance to dike contacts and increasing thermal maturity (vitrinite reflectance R₀ from …

Section Abstracts: Chemistry

Virginia Journal of Science

Abstracts of the Chemistry Section for the 89th Annual Meeting of the Virginia Academy of Science, May 25-27, 2011, University of Richmond, Richmond VA.

Computational Investigation Of The Bioactive Selenium Compounds Ebselen And Selenious Acid, Sonia Antony

Chemistry & Biochemistry Theses & Dissertations

Selenium, a toxic element, is required in trace quantities for the proper functioning of biological systems. The experimental mechanistic study of the reactions of ebselen and selenious acid is difficult due to complexity of the reaction mixtures and the presence of short-lived intermediates. Computational modeling of the reactivity of these species can give us an insight into their mechanisms, but the process is complicated by proton exchanges associated with the mechanistic steps. In gas phase modeling, this may be corrected to a certain level using the solvent assisted proton exchange (SAPE) method. SAPE is a modeling technique that mimics solvent …

Bioinformatics, Thermodynamics And Kinetics Analysis Of An All Alpha Helical Protein With A Gree-Key Topology, Hai Li

Chemistry & Biochemistry Theses & Dissertations

Computational and experimental studies focusing on the role of conserved residues for folding and stability is an active and promising area of research. To further expand our understanding we present the results of a bioinformatics analysis of the death domain superfamily. The death domain superfamily fold consists of six α-helices arranged in a Greek-key topology, which is shared by the all β-sheet immunoglobulin and mixed α/β-plait superfamilies. Our sequence and structural studies have identified a group of conserved hydrophobic residues and corresponding long-range interactions, which we propose are important in the formation and stabilization of the hydrophobic core and native …

A Three Dimensional Green's Function Solution Technique For The Transport Of Heavy Ions In Laboratory And Space, Candice Rockell Gerstner

Mathematics & Statistics Theses & Dissertations

In the future, astronauts will be sent into space for longer durations of time compared to previous missions. The increased risk of exposure to ionizing radiation, such as Galactic Cosmic Rays and Solar Particle Events, is of great concern. Consequently, steps must be taken to ensure astronaut safety by providing adequate shielding. The shielding and exposure of space travelers is controlled by the transport properties of the radiation through the spacecraft, its onboard systems and the bodies of the individuals themselves. Meeting the challenge of future space programs will therefore require accurate and efficient methods for performing radiation transport calculations …

A Mini-Electrodialysis System For Desalting Small Volume Saline Samples For Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, Hongmei Chen, Aron Stubbins, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

An affordable, commercially available mini-electrodialysis (mini-ED) system has been evaluated for the efficient desalting of small volume samples of seawater before analysis by electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). Mini-ED FT-ICR mass spectra were compared with spectra for samples that were treated by C₁₈ solid phase extraction, a commonly used method for rapid sample preparation for this type of analysis. In this comparison, it is clear that mini-ED provides more representative molecular information, compared with C₁₈ isolation, and recovers the overwhelming majority of peaks from salt-free samples, indicating that it adequately represents the …

Fourier Transform Mass Spectrometry For The Molecular Level Characterization Of Natural Organic Matter: Instrument Capabilities, Applications, And Limitations, Rachel L. Sleighter, Patrick G. Hatcher, Goran Nikolić (Ed.)

Chemistry & Biochemistry Faculty Publications

No abstract provided.

Fourier Transform Emission Spectroscopy Of Yh And Yd: Observation Of New A¹Δ And B¹Π Electronic States, R. S. Ram, G. Li, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

The emission spectra of YH and YD molecules have been investigated in the 3600–12 000 cm⁻¹ region using a Fourier transform spectrometer. Molecules were formed in an yttrium hollow cathode lamp operated with a continuous flow of a mixture of Ne and Ar gases, and YH and YD were observed together in the same spectra. A group of bands observed near 1 μm have been identified as 0-0 and 1-1 bands of the A¹Δ-X¹Σ⁺ and B¹Π-X¹Σ⁺ transitions of YH and the 0-0 bands of the same two transitions …

Fossil And Contemporary Aerosol Particulate Organic Carbon In The Eastern United States: Implications For Deposition And Inputs To Watersheds, Andrew S. Wozniak, James E. Bauer, Rebecca M. Dickhut

Chemistry & Biochemistry Faculty Publications

Atmospheric particulate matter samples were collected from mid-Atlantic and northeastern U. S. (Virginia and New York, respectively) sites to assess the fossil versus contemporary sources contributing to aerosol organic carbon (OC) and the implications for its deposition to watersheds. Mean particulate matter total OC (TOC) deposition rates (wet + dry deposition) were calculated to be 1.6 and 2.4 mg C m^-2 d^-1 for the Virginia and New York sites, respectively. Wet deposition of particulate TOC was determined to be the dominant depositional mode, accounting for >65% (Virginia) and >80% (New York) of total aerosol TOC deposition. Isotopic mass …

Characterization Of Heterogeneities And Domains In Aquatic And Sedimentary Organic Matter By 1 H Spin Diffusion: Potential For Elucidating The Formation Mechanisms, Jingdong Mao, Xiaoyan Cao

Chemistry & Biochemistry Faculty Publications

Although the information on domains and heterogeneities of natural organic matter (NOM) can provide insights into its formation mechanisms, the appropriate solid-state NMR technique for measuring them is still lacking. The traditional technique requires mobility differences in NOM whereas NOM components are primarily rigid. We introduced a new ¹H spin diffusion technique, ¹H-¹³C two-dimensional heteronuclear correlation (2D HETCOR) NMR with ¹H spin diffusion, for characterization of domains and heterogeneities in aquatic and sedimentary organic matter. It was achieved by collecting a series of 2D HETCOR spectra with a variable mixing time, t_m', and …

Ace-Fts Measurements Of Trace Species In The Characterization Of Biomass Burning Plumes, K. A. Tereszchuk, G. González Abad, C. Clerbaux, D. Hurtmans, P.-F. Coheur, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

To further our understanding of the effects of biomass burning emissions on atmospheric composition, we report measurements of trace species in biomass burning plumes made by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) instrument on the SCISAT-1 satellite. An extensive set of 15 molecules, C₂H₂, C₂H₆, CH₃OH, CH₄, CO, H₂CO, HCN, HCOOH, HNO₃, NO, NO₂, N₂O₅, O-3, OCS and SF₆ are used in our analysis. Even though most biomass burning smoke is typically confined to the …

Nonuniformity In Lattice Contraction Of Bismuth Nanoclusters Heated Near Its Melting Point, A. Esmail, M. Abdel-Fattah, Hani E. Elsayed-Ali

Electrical & Computer Engineering Faculty Publications

The structural properties of bismuth nanoclusters were investigated with transmission high-energy electron diffraction from room temperature up to 525 ± 6 K. The Bi nanoclusters were fabricated by thermal evaporation at room temperature on transmission electron microscope grids coated with an ultrathin carbon film, followed by thermal and femtosecond laser annealing. The annealed sample had an average cluster size of ∼14 nm along the minor axis and ∼16 nm along the major axis. The Debye temperature of the annealed nanoclusters was found to be 53 ± 6 K along the [012] direction and 86 ± 9 K along the [110] …

Precise Control Of Highly Ordered Arrays Of Nested Semiconductor/Metal Nanotubes, Diefeng Gu, Helmut Baumgart, Kandabara Tapily, Pragya Shrestha, Gon Namkoong, Xianyu Ao, Frank Müller

Electrical & Computer Engineering Faculty Publications

Lithographically defined microporous templates in conjunction with the atomic layer deposition (ALD) technique enable remarkable control of complex novel nested nanotube structures. So far three-dimensional control of physical process parameters has not been fully realized with high precision resolution, and requires optimization in order to achieve a wider range of potential applications. Furthermore, the combination of composite insulating oxide layers alternating with semiconducting layers and metals can provide various types of novel applications and eventually provide unique and advanced levels of multifunctional nanoscale devices. Semiconducting TiO₂ nanotubes have potential applications in photovoltaic devices. The combination of nanostructured semiconducting materials …

Localized Surface Plasmon Resonance Of Single Silver Nanoparticles Studied By Dark-Field Optical Microscopy And Spectroscopy, Wei Cao, Tao Huang, Xiao-Hong Nancy Xu, Hani E. Elsayed-Ali

Electrical & Computer Engineering Faculty Publications

Localized surface plasmon resonance (LSPR) of Ag nanoparticles (NPs) with different shapes and disk-shaped Ag NP pairs with varying interparticle distance is studied using dark-field optical microscopy and spectroscopy (DFOMS). Disk-, square-, and triangular-shaped Ag NPs were fabricated on indium tin oxide-coated glass substrates by electron beam lithography. The LSPR spectra collected from single Ag NPs within 5×5 arrays using DFOMS exhibited pronounced redshifts as the NP shape changed from disk to square and to triangular. The shape-dependent experimental LSPR spectra are in good agreement with simulations using the discrete dipole approximation model, although there are small deviations in the …