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Full-Text Articles in Physical Sciences and Mathematics

Potentially Massive And Global Non-Pyrogenic Production Of Condensed "Black" Carbon Through Biomass Oxidation, Aleksandar I. Goranov, Hongmei Chen, Jianshu Duan, Satish C. B. Myneni, Patrick G. Hatcher Jan 2024

Potentially Massive And Global Non-Pyrogenic Production Of Condensed "Black" Carbon Through Biomass Oxidation, Aleksandar I. Goranov, Hongmei Chen, Jianshu Duan, Satish C. B. Myneni, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

With the increased occurrences of wildfires worldwide, there has been an increase in scientific interest surrounding the chemistry of fire-derived "black" carbon (BC). Traditionally, wildfire research has assumed that condensed aromatic carbon (ConAC) is exclusively produced via combustion, and thus, ConAC is equated to BC. However, the lack of correlations between ConAC in soils or rivers and wildfire history suggests that ConAC may be produced non-pyrogenically. Here, we show quantitative evidence that this occurs during the oxidation of biomass with environmentally ubiquitous hydroxyl radicals. Pine wood boards exposed to iron nails and natural weather conditions for 12 years yielded a …


Advanced Raman Spectroscopy Detection Of Oxidative Damage In Nucleic Acid Bases: Probing Chemical Changes And Intermolecular Interactions In Guanosine At Ultralow Concentration, Francesca Ripanti, Claudia Fasolato, Flavia Mazzarda, Simonetta Palleschi, Marina Ceccarini, Chunchun Li, Margherita Bignami, Enrico Bodo, Steven E.J. Bell, Filomena Mazzei, Paolo Postorino Jan 2021

Advanced Raman Spectroscopy Detection Of Oxidative Damage In Nucleic Acid Bases: Probing Chemical Changes And Intermolecular Interactions In Guanosine At Ultralow Concentration, Francesca Ripanti, Claudia Fasolato, Flavia Mazzarda, Simonetta Palleschi, Marina Ceccarini, Chunchun Li, Margherita Bignami, Enrico Bodo, Steven E.J. Bell, Filomena Mazzei, Paolo Postorino

Bioelectrics Publications

DNA/RNA synthesis precursors are especially vulnerable to damage induced by reactive oxygen species occurring following oxidative stress. Guanosine triphosphates are the prevalent oxidized nucleotides, which can be misincorporated during replication, leading to mutations and cell death. Here, we present a novel method based on micro-Raman spectroscopy, combined with ab initio calculations, for the identification, detection, and quantification of oxidized nucleotides at low concentration. We also show that the Raman signature in the terahertz spectral range (<100 >cm(-1)) contains information on the intermolecular assembly of guanine in tetrads, which allows us to further boost the oxidative damage detection limit. Eventually, we …


Synthesis, Characterization, And Kinetics Studies Of New Cobalt Complexes For The Production Of H2 In Acidic Media, Michael John Celestine Dec 2020

Synthesis, Characterization, And Kinetics Studies Of New Cobalt Complexes For The Production Of H2 In Acidic Media, Michael John Celestine

Chemistry & Biochemistry Theses & Dissertations

The kinetics and mechanism of the oxidation of [Co(dmgBF2)2(OH2)2] (where dmgBF2 = difluoroboryldimethylglyoximato) by sodium hypochlorite (NaOCl), sodium bromate (NaBrO3), and bromine (Br2) was investigated by stopped-flow spectrophotometry at 450 nm over a wide temperature range. The pKa1 value for [Co(dmgBF2)2(OH2)2] was calculated as 5.27 ± 0.14 at I = 0.60 (NaCl). From the variation in pH studies, the activation parameters were derived from the proposed mechanisms for NaOCl, ΔH1*, ΔH2*, ΔS1*, and …


Measurement Of Antioxidant Activity Toward Superoxide In Natural Waters, D. Whitney King, Emma Berger, Zachary Helm, Eleanor Irish, Kenneth Mopper Jan 2016

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 …


Studies On Hydroxyl Radical Formation And Correlated Photoflocculation Process Using Degraded Wood Leachate As A Cdom Source, Luni Sun, Kenneth Mopper Jan 2016

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 …


Molecular Characterization Of The Soluble Fraction Of Atmospheric Particulate Matter Obtained By Chemical Oxidation With Nitric Acid, Amanda Susan Priest Apr 2010

Molecular Characterization Of The Soluble Fraction Of Atmospheric Particulate Matter Obtained By Chemical Oxidation With Nitric Acid, Amanda Susan Priest

Chemistry & Biochemistry Theses & Dissertations

The availability of information regarding the composition of ambient atmospheric particulate matter and the transformations that these compounds may undergo upon atmospheric transit is surprisingly absent. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry is used in this study to rapidly evaluate the composition of the water-soluble organic fraction of standard and collected atmospheric particulate matter samples, and the changes that these mixtures undergo upon oxidation with nitric acid. The standard samples include representative particulate matter collected over the course of a year in Washington, D.C. and particulate matter from the exhaust of a diesel-powered engine. The collected sample …


A Diffuse Reflectance Infrared Fourier Transform Spectroscopic Investigation Of The Oxidation Of Co On Platinum/Tin(Iv) Oxide-Based Catalysts, Julie Christi Stiltner Patrick Jul 1994

A Diffuse Reflectance Infrared Fourier Transform Spectroscopic Investigation Of The Oxidation Of Co On Platinum/Tin(Iv) Oxide-Based Catalysts, Julie Christi Stiltner Patrick

Chemistry & Biochemistry Theses & Dissertations

Platinum/tin(IV) oxide-based catalysts have been developed for the oxidation of carbon monoxide at 55 °C and 1 atmosphere pressure. A diffuse reflectance infrared fourier transform spectroscopic (DRIFTS) investigation of this oxidation has been performed. Four catalyst samples have been subjected to a 5% carbon monoxide pretreatment at 125 °C, helium exposure at 55 °C, bottled air (20% oxygen) exposure at 55 °c, and exposure to a 2:1 stoichiometric mixture of carbon monoxide and oxygen at 55 °C. During the course of these exposures, evidence for the development of two different surface carbon monoxide configurations has been found: one that is …