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Articles 61 - 77 of 77
Full-Text Articles in Organic Chemistry
Long-Term Litter Decomposition Controlled By Manganese Redox Cycling, Marco Keiluweit, Peter Nico, Mark E. Harmon, Jingdong Mao, Jennifer Pett-Ridge, Markus Kleber
Long-Term Litter Decomposition Controlled By Manganese Redox Cycling, Marco Keiluweit, Peter Nico, Mark E. Harmon, Jingdong Mao, Jennifer Pett-Ridge, Markus Kleber
Chemistry & Biochemistry Faculty Publications
Litter decomposition is a keystone ecosystem process impacting nutrient cycling and productivity, soil properties, and the terrestrial carbon (C) balance, but the factors regulating decomposition rate are still poorly understood. Traditional models assume that the rate is controlled by litter quality, relying on parameters such as lignin content as predictors. However, a strong correlation has been observed between the manganese (Mn) content of litter and decomposition rates across a variety of forest ecosystems. Here, we show that long-term litter decomposition in forest ecosystems is tightly coupled to Mn redox cycling. Over 7 years of litter decomposition, microbial transformation of litter …
Effect Of Methoxy Substituents On The Activation Barriers Of The Glutathione Peroxidase-Like Mechanism Of An Aromatic Cyclic Seleninate, Craig A. Bayse, Ashley L. Shoaf
Effect Of Methoxy Substituents On The Activation Barriers Of The Glutathione Peroxidase-Like Mechanism Of An Aromatic Cyclic Seleninate, Craig A. Bayse, Ashley L. Shoaf
Chemistry & Biochemistry Faculty Publications
Density functional theory (DFT) models including explicit water molecules have been used to model the redox scavenging mechanism of aromatic cyclic seleninates. Experimental studies have shown that methoxy substitutions affect the rate of scavenging of reactive oxygen species differently depending upon the position. Activities are enhanced in the para position, unaffected in the meta, and decreased in the ortho. DFT calculations show that the activation barrier for the oxidation of the selenenyl sulfide, a proposed key intermediate, is higher for the ortho methoxy derivative than for other positions, consistent with the low experimental conversion rate.
Proton-Electrostatic Localization: Explaining The Bioenergetic Conundrum In Alkalophilic Bacteria, James Weifu Lee
Proton-Electrostatic Localization: Explaining The Bioenergetic Conundrum In Alkalophilic Bacteria, James Weifu Lee
Chemistry & Biochemistry Faculty Publications
The decades-longstanding energetic conundrum of alkalophilic bacteria as to how they are able to synthesize ATP has now, for the first time, been clearly solved using the proton-electrostatics localization hypothesis. This is a major breakthrough advance in understanding proton-coupling bioenergetics over the Nobel-prize work of Peter Mitchell’s chemiosmotic theory. The widespread textbook Mitchellian proton motive force (pmf) equation has now been significantly revised. Use of the newly derived equation results in an overall pmf value (215~233 mV) that is more than 4 times larger than that (44.3 mV) calculated from the Mitchellian equation for the alkalophilic bacteria growing at pH …
Experimental Demonstration Of Localized Excess Protons At A Water-Membrane Interface, Haitham A. Saeed, James W. Lee
Experimental Demonstration Of Localized Excess Protons At A Water-Membrane Interface, Haitham A. Saeed, James W. Lee
Chemistry & Biochemistry Faculty Publications
The widespread Mitchellian proton motive force equation has recently been revised with the proton-electrostatics localization hypothesis, which, for the first time, successfully elucidates the 30-year longstanding energetic conundrum of ATP synthesis in alkalophilic bacteria. To demonstrate the fundamental behavior of localized protons in a pure water-membrane-water system in relation to the newly derived pmf equation, excess protons and excess hydroxyl anions were generated by utilizing an "open-circuit" water-electrolysis system and their distributions were tested using a proton-sensing aluminum membrane. The proton-sensing film placed at the membrane-water interface displayed dramatic localized proton activity while that placed into the bulk water phase …
Redox Active Motifs In Selenoproteins, Fei Li, Yuliya Pepelyayeva, Elias S. J. Arner, Craig A. Bayse, Sharon Rozovsky
Redox Active Motifs In Selenoproteins, Fei Li, Yuliya Pepelyayeva, Elias S. J. Arner, Craig A. Bayse, Sharon Rozovsky
Chemistry & Biochemistry Faculty Publications
Selenoproteins use the rare amino acid selenocysteine (Sec) to act as the first line of defense against oxidants, which are linked to aging, cancer, and neurodegenerative diseases. Many selenoproteins are oxidoreductases in which the reactive Sec is connected to a neighboring Cys and able to form a ring. These Sec-containing redox motifs govern much of the reactivity of selenoproteins. To study their fundamental properties, we have used Se-77 NMR spectroscopy in concert with theoretical calculations to determine the conformational preferences and mobility of representative motifs. This use of Se-77 as a probe enables the direct recording of the properties of …
Role Of Extractable And Residual Organic Matter Fractions On Sorption Of Phenanthrene In Sediments, Yulong Zhang, Yong Ran, Jingdong Mao
Role Of Extractable And Residual Organic Matter Fractions On Sorption Of Phenanthrene In Sediments, Yulong Zhang, Yong Ran, Jingdong Mao
Chemistry & Biochemistry Faculty Publications
Two sediments were demineralized and sequentially fractionated into extracted fractions [free lipid (FL), bound lipid (BL) and lignin (LG)] and residual fractions [free lipid free (FLF), bound lipid free (BLF) and lignin free (LGF)]. The sorption isotherms of phenanthrene (Phen) were examined to evaluate the importance of various fractions on sorption. A lignin extraction procedure was for the first time applied to separate the lignin or degraded lignin fraction from sediment organic matter (SOM). The extracted LG was similar to model lignin in terms of elemental ratios and sorption behavior. FL and LG fractions were quite important, as their contents …
Interaction Mechanism Of Benzene And Phenanthrene In Condensed Organic Matter: Importance Of Adsorption (Nanopore-Filling), Ke Sun, Yong Ran, Yu Yang, Baoshan Xing, Jingdong Mao
Interaction Mechanism Of Benzene And Phenanthrene In Condensed Organic Matter: Importance Of Adsorption (Nanopore-Filling), Ke Sun, Yong Ran, Yu Yang, Baoshan Xing, Jingdong Mao
Chemistry & Biochemistry Faculty Publications
Although microporosity and surface area of natural organic matter (NOM) are crucial to mechanistic evaluation of the sorption process for nonpolar organic contaminants (NOCs), they have wrongly been estimated by the N2 adsorption technique. Nuclear magnetic resonance spectroscopy (13C NMR), and benzene, carbon dioxide, and nitrogen adsorption techniques were used to characterize structural and surface properties for different condensed NOM samples, which were related to the sorption behavior of phenanthrene (Phen). It was found that the revised Freundlich model by taking the chemical activity into account can well describe the isotherms for benzene and Phen. The benzene …
Silver Nanoparticles Induce Developmental Stage-Specific Embryonic Phenotypes In Zebrafish, Kerry J. Lee, Lauren M. Browning, Prakash D. Nallathamby, Christopher J. Osgood, Xiao-Hong Nancy Xu
Silver Nanoparticles Induce Developmental Stage-Specific Embryonic Phenotypes In Zebrafish, Kerry J. Lee, Lauren M. Browning, Prakash D. Nallathamby, Christopher J. Osgood, Xiao-Hong Nancy Xu
Chemistry & Biochemistry Faculty Publications
Much is anticipated from the development and deployment of nanomaterials in biological organisms, but concerns remain regarding their biocompatibility and target specificity. Here we report our study of the transport, biocompatibility and toxicity of purified and stable silver nanoparticles (Ag NPs, 13.1 ± 2.5 nm in diameter) upon the specific developmental stages of zebrafish embryos using single NP plasmonic spectroscopy. We find that single Ag NPs passively diffuse into five different developmental stages of embryos (cleavage, early-gastrula, early-segmentation, late-segmentation, and hatching stages), showing stage-independent diffusion modes and diffusion coefficients. Notably, the Ag NPs induce distinctive stage and dose-dependent phenotypes and …
Isotopic Characterization Of Aerosol Organic Carbon Components Over The Eastern United States, Andrew S. Wozniak, James E. Bauer, Rebecca M. Dickhut, Xu Li, Ann P. Mcnichol
Isotopic Characterization Of Aerosol Organic Carbon Components Over The Eastern United States, Andrew S. Wozniak, James E. Bauer, Rebecca M. Dickhut, Xu Li, Ann P. Mcnichol
Chemistry & Biochemistry Faculty Publications
Carbon isotopic signatures (δ13C, Δ14C) of aerosol particulate matter total organic carbon (TOC) and operationally defined organic carbon (OC) components were measured in samples from two background sites in the eastern U.S. TOC and water-soluble OC (WSOC)δ13C values (−27 to −24‰) indicated predominantly terrestrial C3 plant and fossil derived sources. Total solvent extracts (TSE) and their aliphatic, aromatic, and polar OC components were depleted in δ13C (−30 to −26‰) relative to TOC and WSOC. Δ14C signatures of aerosol TOC and TSE (−476 to +25‰) suggest variable fossil contributions (∼5–50%) …
Compositional Features Of Japanese Humic Substances Society Standard Soil Humic And Fulvic Acids By Fourier Transform Ion Cyclotron Resonance Mass Spectrometry And X-Ray Diffraction Profile Analysis, Kosuke Ikeya, Rachel L. Sleighter, Patrick G. Hatcher, Akira Watanabe
Compositional Features Of Japanese Humic Substances Society Standard Soil Humic And Fulvic Acids By Fourier Transform Ion Cyclotron Resonance Mass Spectrometry And X-Ray Diffraction Profile Analysis, Kosuke Ikeya, Rachel L. Sleighter, Patrick G. Hatcher, Akira Watanabe
Chemistry & Biochemistry Faculty Publications
The composition of humic acids (HAs) and Fulvic Acids (FAs) from Inogashira (Umbric Andosol) and Dando (Dystric Cambisol) soils authorized as standard samples by the Japanese Humic Substances Society was characterized using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and X-ray diffraction (XRD) 11 band profile analysis. In FTICR-MS, the number of peaks that molecular formulas were assigned to was 2549-2913 for the FAs and 1943-2457 for the HAs. Molecular formulas with H/C and O/C ratios similar to condensed hydrocarbons were dominant in both the HAs, while those with H/C and O/C ratios similar to lignin were more abundant …
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.)
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.
Effluent Organic Nitrogen (Eon): Bioavailability And Photochemical And Salinity-Mediated Release, Deborah A. Bronk, Quinn N. Roberts, Marta P. Sanderson, Elizabeth A. Canuel, Patrick G. Hatcher, Rajaa Mesfioui, Katherine C. Filippino, Margaret R. Mulholland, Nancy G. Love
Effluent Organic Nitrogen (Eon): Bioavailability And Photochemical And Salinity-Mediated Release, Deborah A. Bronk, Quinn N. Roberts, Marta P. Sanderson, Elizabeth A. Canuel, Patrick G. Hatcher, Rajaa Mesfioui, Katherine C. Filippino, Margaret R. Mulholland, Nancy G. Love
Chemistry & Biochemistry Faculty Publications
The goal of this study was to investigate three potential ways that the soluble organic nitrogen (N) fraction of wastewater treatment plant (WWTP) effluents, termed effluent organic N (EON), could contribute to coastal eutrophication - direct biological removal, photochemical release of labile compounds, and salinity-mediated release of ammonium (NH4+). Effluents from two WWTPs were used in the experiments. For the bioassays, EON was added to water from four salinities (∼0 to 30) collected from the James River (VA) in August 2008, and then concentrations of N and phosphorus compounds were measured periodically over 48 h. Bioassay results, based …
Sequence And Structural Analysis Of The Chitinase Insertion Domain Reveals Two Conserved Motifs Involved In Chitin Binding, Hai Li, Lesley H. Greene
Sequence And Structural Analysis Of The Chitinase Insertion Domain Reveals Two Conserved Motifs Involved In Chitin Binding, Hai Li, Lesley H. Greene
Chemistry & Biochemistry Faculty Publications
Background: Chitinases are prevalent in life and are found in species including archaea, bacteria, fungi, plants, and animals. They break down chitin, which is the second most abundant carbohydrate in nature after cellulose. Hence, they are important for maintaining a balance between carbon and nitrogen trapped as insoluble chitin in biomass. Chitinases are classified into two families, 18 and 19 glycoside hydrolases. In addition to a catalytic domain, which is a triosephosphate isomerase barrel, many family 18 chitinases contain another module, i.e., chitinase insertion domain. While numerous studies focus on the biological role of the catalytic domain in chitinase activity, …
Theoretical Studies Of 2,3 -Sigmatropic Rearrangements Of Allylic Selenoxides And Selenimides, Craig A. Bayse, Sonia Antony
Theoretical Studies Of 2,3 -Sigmatropic Rearrangements Of Allylic Selenoxides And Selenimides, Craig A. Bayse, Sonia Antony
Chemistry & Biochemistry Faculty Publications
Density-functional theory is used to model the endo and exo transition states for [2,3]-sigmatropic rearrangement of allylic aryl-selenoxides and -selenimides. The endo transition state is generally preferred for selenoxides if there is no substitution at the 2 position of the allyl group. Based upon the relative energies of the endo and exo transition states, enantioselectivity of rearrangements is expected to be greatest for molecules with substitutions at the 1- or (E)-3- position of the allyl group. Ortho substitution of a nitro group on the ancillary selenoxide phenyl ring reduces the activation barriers, increases the difference between the endo and exo …
Lignin Degradation In Wood-Feeding Insects, Scott M. Geib, Timothy R. Filley, Patrick G. Hatcher, Kelli Hoover, John E. Carlson, Maria Del Mar Jimenez-Gasco, Akiko Nakagawa-Izumi, Rachel L. Sleighter, Ming Tien
Lignin Degradation In Wood-Feeding Insects, Scott M. Geib, Timothy R. Filley, Patrick G. Hatcher, Kelli Hoover, John E. Carlson, Maria Del Mar Jimenez-Gasco, Akiko Nakagawa-Izumi, Rachel L. Sleighter, Ming Tien
Chemistry & Biochemistry Faculty Publications
The aromatic polymer lignin protects plants from most forms of microbial attack. Despite the fact that a significant fraction of all lignocellulose degraded passes through arthropod guts, the fate of lignin in these systems is not known. Using tetramethylammonium hydroxide thermochemolysis, we show lignin degradation by two insect species, the Asian longhorned beetle (Anoplophora glabripennis) and the Pacific dampwood termite (Zootermopsis angusticollis). In both the beetle and termite, significant levels of propyl side-chain oxidation (depolymerization) and demethylation of ring methoxyl groups is detected; for the termite, ring hydroxylation is also observed. In addition, culture-independent fungal gut …
Elliptical Micro-Ring Organic Lasers, P. R. Korade, John Ballato, R, V. Gregory
Elliptical Micro-Ring Organic Lasers, P. R. Korade, John Ballato, R, V. Gregory
Chemistry & Biochemistry Faculty Publications
Multimode laser action was observed from optically excited 2,5-dioctyloxy poly(para-phenylene-vinylene), DOO-PPV, micro-rings coaxially deposited around glass optical fibres of elliptical cross-section. The laser emission was found to be dependent upon the incident angle of the excitation and exhibited linewidths of approximately 1.2 Å, quality factors (Q) exceeding 5000, and thresholds below 0.3 μJ pulse. Such elliptical organic micro-ring lasers offer increased tailorability in emission properties over more conventional analogues of circular cross-section. Also discussed is the potential for such low-threshold lasers to serve as integrated sources for fibre lasers and amplifiers.
Meso-1, 2-Bis (Methylazo)-1, 2-Diphenylethane, Craig A. Bayse, Barry K. Carpenter, Rudy L. Luck
Meso-1, 2-Bis (Methylazo)-1, 2-Diphenylethane, Craig A. Bayse, Barry K. Carpenter, Rudy L. Luck
Chemistry & Biochemistry Faculty Publications
The title compound, meso-1,2-bis(methyldiazenyl)-1,2-diphenylethane, C16H18N4, is arranged in a disordered manner around an inversion point. The N—N atom distances in the azo group of 1.192 (8) and 1.195 (8) Å, and the C—C atom distances in the ethylene moiety at 1.512 (8) and 1.503 (8) Å in the two models [refined to 51.7 (6) and 48.3 (6)% occupancies] were not significantly different.