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Sample records for radical reactions mechanistic

  1. Free radical scavenging reactions of sulfasalazine, 5-aminosalicylic acid and sulfapyridine: mechanistic aspects and antioxidant activity.

    PubMed

    Joshi, Ravi; Kumar, Sudheer; Unnikrishnan, M; Mukherjee, T

    2005-11-01

    Reactions of sulfasalazine (SAZ) and its metabolites, 5-aminosalicylic acid (5-ASA) and sulfapyridine (SP), with various oxidizing and reducing free radicals (hydroxyl, haloperoxyl, one-electron oxidizing, lipid peroxyl, glutathiyl, superoxide, tryptophanyl, etc.) have been studied to understand the mechanistic aspects of its action against free radicals produced during inflammation. Nanosecond pulse radiolysis technique coupled with transient spectrophotometry has been used for in situ generation of free radicals and to follow their reaction pathways. The transients produced in these reactions have been assigned and radical scavenging rate constants have been measured. In addition to scavenging of various primary and secondary free radicals by SAZ, 5-ASA and SP, 5-ASA has also been observed to efficiently scavenge radicals of biomolecules. 5-ASA has been found to be the active moiety of SAZ involved in the scavenging of oxidizing free radicals whereas reduction of SAZ produced molecular radical anion. The study suggests that free radical scavenging activity of 5-ASA may be a major path of pharmacological action of SAZ against inflammatory bowel diseases (IBD). PMID:16298742

  2. Kinetic and mechanistic studies of free-radical reactions in combustion

    SciTech Connect

    Tully, F.P.

    1993-12-01

    Combustion is driven by energy-releasing chemical reactions. Free radicals that participate in chain reactions carry the combustion process from reactants to products. Research in chemical kinetics enables us to understand the microscopic mechanisms involved in individual chemical reactions as well as to determine the rates at which they proceed. Both types of information are required for an understanding of how flames burn, why engines knock, how to minimize the production of pollutants, and many other important questions in combustion. In this program the authors emphasize accurate measurements over wide temperature ranges of the rates at which ubiquitous free radicals react with stable molecules. The authors investigate a variety of OH, CN, and CH + stable molecule reactions important to fuel conversion, emphasizing application of the extraordinarily precise technique of laser photolysis/continuous-wave laser-induced fluorescence (LP/cwLIF). This precision enables kinetic measurements to serve as mechanistic probes. Since considerable effort is required to study each individual reaction, prudent selection is critical. Two factors encourage selection of a specific reaction: (1) the rates and mechanisms of the subject reaction are required input to a combustion model; and (2) the reaction is a chemical prototype which, upon characterization, will provide fundamental insight into chemical reactivity, facilitate estimation of kinetic parameters for similar reactions, and constrain and test the computational limits of reaction-rate theory. Most studies performed in this project satisfy both conditions.

  3. Mechanistic study of the radical SAM-dependent amine dehydrogenation reactions.

    PubMed

    Ji, Xinjian; Liu, Wan-Qiu; Yuan, Shuguang; Yin, Yue; Ding, Wei; Zhang, Qi

    2016-08-18

    The radical SAM enzyme NosL catalyzes the conversion of l-Trp to 3-methyl-2-indolic acid, and this reaction is initiated by the 5'-deoxyadenosyl (dAdo) radical-mediated hydrogen abstraction from the l-Trp amino group. We demonstrate here that when d-Trp was used in the NosL reaction, hydrogen abstraction occurs promiscuously at both the amino group and Cα of d-Trp. These results inspired us to establish the detailed mechanism of l-Trp amine dehydrogenation catalyzed by a NosL mutant, and to engineer a novel radical SAM-dependent l-Tyr amine dehydrogenase from the thiamine biosynthesis enzyme ThiH. PMID:27492649

  4. Atmospheric chemical reactions of monoethanolamine initiated by OH radical: mechanistic and kinetic study.

    PubMed

    Xie, Hong-Bin; Li, Chao; He, Ning; Wang, Cheng; Zhang, Shaowen; Chen, Jingwen

    2014-01-01

    Monoethanolamine (MEA) is a benchmark and widely utilized solvent in amine-based postcombustion CO2 capture (PCCC), a leading technology for reducing CO2 emission from fossil fuel power plants. The large-scale implementation of PCCC would lead to inevitable discharges of amines to the atmosphere. Therefore, understanding the kinetics and mechanisms of the transformation of representative amine MEA in the atmosphere is of great significance for risk assessment of the amine-based PCCC. In this study, the H-abstraction reaction of MEA with ·OH, and ensuing reactions of produced MEA-radicals, including isomerization, dissociation, and bimolecular reaction MEA-radicals+O2, were investigated by quantum chemical calculation [M06-2X/aug-cc-pVTZ//M06-2X/6-311++G(d,p)] and kinetic modeling. The calculated overall rate constant [(7.27 × 10(-11)) cm(3) molecule(-1) s(-1)] for H-abstraction is in excellent agreement with the experimental value [(7.02 ± 0.46) × 10(-11) cm(3) molecule(-1) s(-1)]. The results show that the product branching ratio of NH2CH2 · CHOH (MEA-β) (43%) is higher than that of NH2 · CHCH2OH (MEA-α) (39%), clarifying that MEA-α is not an exclusive product. On the basis of the unveiled reaction mechanisms of MEA-radicals + O2, the proton transfer reaction mass spectrometry signal (m/z 60.044), not recognized in the experiment, was identified. PMID:24438015

  5. Mechanistic Enzymology of the Radical SAM Enzyme DesII

    PubMed Central

    2016-01-01

    DesII is a member of the radical SAM family of enzymes that catalyzes radical-mediated transformations of TDP-4-amino-4,6-didexoy-D-glucose as well as other sugar nucleotide diphosphates. Like nearly all radical SAM enzymes, the reactions begin with the reductive homolysis of SAM to produce a 5′-deoxyadenosyl radical which is followed by regiospecific hydrogen atom abstraction from the substrate. What happens next, however, depends on the nature of the substrate radical so produced. In the case of the biosynthetically relevant substrate, a radical-mediated deamination ensues; however, when this amino group is replaced with a hydroxyl, one instead observes dehydrogenation. The factors that govern the fate of the initially generated substrate radical as well as the mechanistic details underlying these transformations have been a key focus of research into the chemistry of DesII. This review will discuss recent discoveries pertaining to the enzymology of DesII, how it may relate to understanding other radical-mediated lyases and dehydrogenases and the working hypotheses currently being investigated regarding the mechanism of DesII catalysis.

  6. Catalytic Radical Domino Reactions in Organic Synthesis

    PubMed Central

    Sebren, Leanne J.; Devery, James J.; Stephenson, Corey R.J.

    2014-01-01

    Catalytic radical-based domino reactions represent important advances in synthetic organic chemistry. Their development benefits synthesis by providing atom- and step-economical methods to complex molecules. Intricate combinations of radical, cationic, anionic, oxidative/reductive, and transition metal mechanistic steps result in cyclizations, additions, fragmentations, ring-expansions, and rearrangements. This Perspective summarizes recent developments in the field of catalytic domino processes. PMID:24587964

  7. Free Radical Reactions in Food.

    ERIC Educational Resources Information Center

    Taub, Irwin A.

    1984-01-01

    Discusses reactions of free radicals that determine the chemistry of many fresh, processed, and stored foods. Focuses on reactions involving ascorbic acid, myoglobin, and palmitate radicals as representative radicals derived from a vitamin, metallo-protein, and saturated lipid. Basic concepts related to free radical structure, formation, and…

  8. Spectroscopic, steady-state kinetic, and mechanistic characterization of the radical SAM enzyme QueE, which catalyzes a complex cyclization reaction in the biosynthesis of 7-deazapurines

    PubMed Central

    McCarty, Reid M.; Krebs, Carsten; Bandarian, Vahe

    2013-01-01

    7-Carboxy-7-deazaguanine (CDG) synthase (QueE) catalyzes the complex heterocyclic radical-mediated conversion of 6-carboxy-5,6,7,8-tetrahydropterin (CPH4) to CDG in the third step of the biosynthetic pathway to all 7-deazapurines. Here we present a detailed characterization of QueE from Bacillus subtilis to delineate the mechanism of conversion of CPH4 to CDG. QueE is a member of the radical S-adenosyl-L-methionine (SAM) superfamily, all of which use a bound [4Fe-4S]+ cluster to catalyze the reductive cleavage of SAM cofactor to generate methionine and a 5′-deoxyadenosyl radical (5′-dAdo•), which initiates enzymatic transformations requiring H-atom abstraction. The UV-visible, EPR, and Mössbauer spectroscopic features of the homodimeric QueE point to the presence of a single [4Fe-4S] cluster per monomer. Steady-state kinetic experiments indicate a Km of 20 ± 7 μM for CPH4 and kcat of 5.4 ± 1.2 min-1 for the overall transformation. The kinetically determined Kapp for SAM is 45 ± 1 μM. QueE is also magnesium-dependent and exhibits a Kapp for the divalent metal ion of 0.21 ± 0.03 mM. The SAM cofactor supports multiple turnovers, indicating that it is regenerated at the end of each catalytic cycle. The mechanism of rearrangement of QueE was probed with CPH4 isotopologs containing deuterium at C-6 or the two prochiral positions at C-7. These studies implicate 5′-dAdo• as initiating the ring contraction reaction catalyzed by QueE by abstraction of the H-atom from C-6 of CPH4. PMID:23194065

  9. Reaction Coordinates and Mechanistic Hypothesis Tests.

    PubMed

    Peters, Baron

    2016-05-27

    Reaction coordinates are integral to several classic rate theories that can (a) predict kinetic trends across conditions and homologous reactions, (b) extract activation parameters with a clear physical interpretation from experimental rates, and (c) enable efficient calculations of free energy barriers and rates. New trajectory-based rare events methods can provide rates directly from dynamical trajectories without a reaction coordinate. Trajectory-based frameworks can also generate ideal (but abstract) reaction coordinates such as committors and eigenfunctions of the master equation. However, rates and mechanistic insights obtained from trajectory-based methods and abstract coordinates are not readily generalized across simulation conditions or reaction families. We discuss methods for identifying physically meaningful reaction coordinates, including committor analysis, variational transition state theory, Kramers-Langer-Berezhkovskii-Szabo theory, and statistical inference methods that can use path sampling data to screen, mix, and optimize thousands of trial coordinates. Special focus is given to likelihood maximization and inertial likelihood maximization approaches. PMID:27090846

  10. Reaction Coordinates and Mechanistic Hypothesis Tests

    NASA Astrophysics Data System (ADS)

    Peters, Baron

    2016-05-01

    Reaction coordinates are integral to several classic rate theories that can (a) predict kinetic trends across conditions and homologous reactions, (b) extract activation parameters with a clear physical interpretation from experimental rates, and (c) enable efficient calculations of free energy barriers and rates. New trajectory-based rare events methods can provide rates directly from dynamical trajectories without a reaction coordinate. Trajectory-based frameworks can also generate ideal (but abstract) reaction coordinates such as committors and eigenfunctions of the master equation. However, rates and mechanistic insights obtained from trajectory-based methods and abstract coordinates are not readily generalized across simulation conditions or reaction families. We discuss methods for identifying physically meaningful reaction coordinates, including committor analysis, variational transition state theory, Kramers-Langer-Berezhkovskii-Szabo theory, and statistical inference methods that can use path sampling data to screen, mix, and optimize thousands of trial coordinates. Special focus is given to likelihood maximization and inertial likelihood maximization approaches.

  11. Expanding Radical SAM Chemistry by Using Radical Addition Reactions and SAM Analogues.

    PubMed

    Ji, Xinjian; Li, Yongzhen; Xie, Liqi; Lu, Haojie; Ding, Wei; Zhang, Qi

    2016-09-19

    Radical S-adenosyl-l-methionine (SAM) enzymes utilize a [4Fe-4S] cluster to bind SAM and reductively cleave its carbon-sulfur bond to produce a highly reactive 5'-deoxyadenosyl (dAdo) radical. In almost all cases, the dAdo radical abstracts a hydrogen atom from the substrates or from enzymes, thereby initiating a highly diverse array of reactions. Herein, we report a change of the dAdo radical-based chemistry from hydrogen abstraction to radical addition in the reaction of the radical SAM enzyme NosL. This change was achieved by using a substrate analogue containing an olefin moiety. We also showed that two SAM analogues containing different nucleoside functionalities initiate the radical-based reactions with high efficiencies. The radical adduct with the olefin produced in the reaction was found to undergo two divergent reactions, and the mechanistic insights into this process were investigated in detail. Our study demonstrates a promising strategy in expanding radical SAM chemistry, providing an effective way to access nucleoside-containing compounds by using radical SAM-dependent reactions. PMID:27573794

  12. The methylthiolation reaction mediated by the Radical-SAM enzymes

    PubMed Central

    Atta, Mohamed; Arragain, Simon; Fontecave, Marc; Mulliez, Etienne; Hunt, John F.; Luff, Jon D.; Forouhar, Farhad

    2014-01-01

    Over the past ten years, considerable progress has been made in our understanding of the mechanistic enzymology of the Radical-SAM enzymes. It is now clear that these enzymes appear to be involved in a remarkably wide range of chemically challenging reactions. This review article highlights mechanistic and structural aspects of the methylthiotransferases (MTTases) sub-class of the Radical-SAM enzymes. The mechanism of methylthio insertion, now observed to be performed by three different enzymes is an exciting unsolved problem. PMID:22178611

  13. Mechanistic studies of the radical SAM enzyme spore photoproduct lyase (SPL).

    PubMed

    Li, Lei

    2012-11-01

    Spore photoproduct lyase (SPL) repairs a special thymine dimer 5-thyminyl-5,6-dihydrothymine, which is commonly called spore photoproduct or SP at the bacterial early germination phase. SP is the exclusive DNA photo-damage product in bacterial endospores; its generation and swift repair by SPL are responsible for the spores' extremely high UV resistance. The early in vivo studies suggested that SPL utilizes a direct reversal strategy to repair the SP in the absence of light. The research in the past decade further established SPL as a radical SAM enzyme, which utilizes a tri-cysteine CXXXCXXC motif to harbor a [4Fe-4S] cluster. At the 1+ oxidation state, the cluster provides an electron to the S-adenosylmethionine (SAM), which binds to the cluster in a bidentate manner as the fourth and fifth ligands, to reductively cleave the CS bond associated with the sulfonium ion in SAM, generating a reactive 5'-deoxyadenosyl (5'-dA) radical. This 5'-dA radical abstracts the proR hydrogen atom from the C6 carbon of SP to initiate the repair process; the resulting SP radical subsequently fragments to generate a putative thymine methyl radical, which accepts a back-donated H atom to yield the repaired TpT. SAM is suggested to be regenerated at the end of each catalytic cycle; and only a catalytic amount of SAM is needed in the SPL reaction. The H atom source for the back donation step is suggested to be a cysteine residue (C141 in Bacillus subtilis SPL), and the H-atom transfer reaction leaves a thiyl radical behind on the protein. This thiyl radical thus must participate in the SAM regeneration process; however how the thiyl radical abstracts an H atom from the 5'-dA to regenerate SAM is unknown. This paper reviews and discusses the history and the latest progress in the mechanistic elucidation of SPL. Despite some recent breakthroughs, more questions are raised in the mechanistic understanding of this intriguing DNA repair enzyme. This article is part of a Special Issue

  14. Physiological aspects of free-radical reactions.

    PubMed Central

    Yamazaki, I; Tamura, M; Nakajima, R; Nakamura, M

    1985-01-01

    Enzymes which catalyze the formation of free radicals in vitro will catalyze similar reactions in vivo. We believe that the formation of some kinds of free radicals has definite physiological meanings in metabolism. In this sense, the enzymes forming such free radicals are concluded to be in evolutionally advanced states. Elaborated structure and function of enzymes such as horseradish peroxidase and microsomal flavoproteins support the idea. Deleterious and side reactions caused by free radicals are assumed to be minimized in vivo by localizing the reactions, but this assumption should be verified by future studies. PMID:3007098

  15. Towards mechanistic representations of SOA from BVOC + NO3 reactions

    EPA Science Inventory

    Monoterpene reaction with nitrate radicals is a significant source of organic aerosol in the southeast United States. This source of organic aerosol represents an anthropogenic control on biogenic organic aerosol since nitrate radicals result from NOx emissions and are generally ...

  16. Radical Cyclisation of α-Halo Aluminium Acetals: A Mechanistic Study.

    PubMed

    Bénéteau, Romain; Boussonnière, Anne; Rouaud, Jean-Christophe; Lebreton, Jacques; Graton, Jérôme; Jacquemin, Denis; Sebban, Muriel; Oulyadi, Hassan; Hamdoun, Ghanem; Hancock, Amber N; Schiesser, Carl H; Dénès, Fabrice

    2016-03-24

    α-Bromo aluminium acetals are suitable substrates for Ueno-Stork-like radical cyclisations affording γ-lactols and acid-sensitive methylene-γ-lactols in high yields. The mechanistic study herein sets the scope and limitation of this reaction. The influence of the halide (or chalcogenide) atom X (X=Cl, Br, I, SPh, SePh) in the precursors α-haloesters, as well as influence of the solvent and temperature was studied. The structure of the aluminium acetal intermediates resulting from the reduction of the corresponding α-haloesters has been investigated by low-temperature (13) C-INEPT diffusion-ordered NMR spectroscopy (DOSY) experiments and quantum calculations, providing new insights into the structures of these thermally labile intermediates. Oxygen-bridged dimeric structures with a planar Al2 O2 ring are proposed for the least hindered aluminium acetals, while monomeric structures seem to prevail for the most hindered species. A comparison against the radical cyclisation of aluminium acetals derived from allyl and propargyl alcohols with the parent Ueno-Stork has been made at the BHandHLYP/6-311++G(d,p) level of theory, highlighting mechanistic similarities and differences. PMID:26890896

  17. From formamide to purine: an energetically viable mechanistic reaction pathway.

    PubMed

    Wang, Jing; Gu, Jiande; Nguyen, Minh Tho; Springsteen, Greg; Leszczynski, Jerzy

    2013-02-28

    A step-by-step mechanistic pathway following the transformation of formamide to purine through a five-membered ring intermediate has been explored by density functional theory computations. The highlight of the mechanistic route detailed here is that the proposed pathway represents the simplest reaction pathway. All necessary reactants are generated from a single starting compound, formamide, through energetically viable reactions. Several important reaction steps are involved in this mechanistic route: formylation-dehydration, Leuckart reduction, five- and six-membered ring-closure, and deamination. On the basis of the study of noncatalytic pathways, catalytic water has been found to provide energetically viable step-by-step mechanistic pathways. Among these reaction steps, five-member ring-closure is the rate-determining step. The energy barrier (ca. 42 kcal/mol) of this rate-control step is somewhat lower than the rate-determining step (ca. 44 kcal/mol) for a pyrimidine-based pathway reported previously. The mechanistic pathway reported herein is less energetically demanding than for previously proposed routes to adenine. PMID:23347082

  18. (Mechanistic examination of organometallic electron transfer reactions: Annual report, 1989)

    SciTech Connect

    Not Available

    1989-01-01

    Our mechanistic examination of electron transfer reactions between organometallic complexes has required data from our stopped-flow infrared spectrophotometer that was constructed in the first year. Our research on organometallic electron transfer reaction mechanisms was recognized by an invitation to the Symposium on Organometallic Reaction Mechanisms at the National ACS meeting in Miami. We have obtained a reasonable understanding of the electron transfer reactions between metal cations and anions and between metal carbonyl anions and metal carbonyl dimers. In addition we have begun to obtain data on the outer sphere electron transfer between metal carbonyl anions and coordination complexes and on reactions involving cluster anions.

  19. [Mechanistic examination of organometallic electron transfer reactions: Annual report, 1989

    SciTech Connect

    Not Available

    1989-12-31

    Our mechanistic examination of electron transfer reactions between organometallic complexes has required data from our stopped-flow infrared spectrophotometer that was constructed in the first year. Our research on organometallic electron transfer reaction mechanisms was recognized by an invitation to the Symposium on Organometallic Reaction Mechanisms at the National ACS meeting in Miami. We have obtained a reasonable understanding of the electron transfer reactions between metal cations and anions and between metal carbonyl anions and metal carbonyl dimers. In addition we have begun to obtain data on the outer sphere electron transfer between metal carbonyl anions and coordination complexes and on reactions involving cluster anions.

  20. Unimolecular reaction dynamics of free radicals

    SciTech Connect

    Terry A. Miller

    2006-09-01

    Free radical reactions are of crucial importance in combustion and in atmospheric chemistry. Reliable theoretical models for predicting the rates and products of these reactions are required for modeling combustion and atmospheric chemistry systems. Unimolecular reactions frequently play a crucial role in determining final products. The dissociations of vinyl, CH2= CH, and methoxy, CH3O, have low barriers, about 13,000 cm-1 and 8,000 cm-1, respectively. Since barriers of this magnitude are typical of free radicals these molecules should serve as benchmarks for this important class of reactions. To achieve this goal, a detailed understanding of the vinyl and methoxy radicals is required. Results for dissociation dynamics of vinyl and selectively deuterated vinyl radical are reported. Significantly, H-atom scrambling is shown not to occur in this reaction. A large number of spectroscopic experiments for CH3O and CHD2O have been performed. Spectra recorded include laser induced fluorescence (LIF), laser excited dispersed fluorescence (LEDF), fluorescence dip infrared (FDIR) and stimulated emission pumping (SEP). Such results are critical for implementing dynamics experiments involving the dissociation of methoxy.

  1. Deuterium Substitution used as a Tool for Investigating Mechanisms of Gas-Phase Free-Radical Reactions

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Hynes, A. J.; Nicovich, J. M.

    1997-01-01

    Results are presented and discussed for a number of gas phase free radical reactions where H/D isotope effects provide valuable mechanistic insights. The cases considered are (1) the reactions of OH, NO3, and Cl with atmospheric reduced sulfur compounds, (2) the reactions of OH and OD with CH3CN and CD3CN, and (3) the reactions of alkyl radicals with HBr and DBr.

  2. Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter

    USGS Publications Warehouse

    Lindsey, M.E.; Tarr, M.A.

    2000-01-01

    Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compound molecules bound to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanism for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently firstorder in pyrene to one that was apparently secondorder in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compounds molecules bounds to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanisms for the observed inhibition is that hydroxyl radical

  3. Structural and Mechanistic Aspects of Copper Catalyzed Atom Transfer Radical Polymerization

    NASA Astrophysics Data System (ADS)

    Pintauer, Tomislav; Matyjaszewski, Krzysztof

    During the past decade, atom transfer radical polymerization (ATRP) has had a tremendous impact on the synthesis of macromolecules with well-defined compositions, architectures, and functionalities. Structural features of copper(I) and copper(II) complexes with bidentate, tridentate, tetradentate, and multidentate nitrogen-based ligands commonly utilized in ATRP are reviewed and discussed. Additionally, recent advances in mechanistic understanding of copper-mediated ATRP are outlined.

  4. Mechanistic views on aromatic substitution reactions by gaseous cations.

    PubMed

    Fornarini, S

    1996-01-01

    Recent advances in the understanding of the gas-phase reaction of aromatics with cationic electrophiles in a thermally equilibrated domain are described. The overall substitution reaction is analyzed in terms of its elementary steps. Their contribution to the overall reactivity pattern is dissected by the use of selected systems, which allowed one to highlight the kinetic role of single elementary events. Mechanistic studies have focused on the structure and reactivity of covalent and non-covalent ionic intermediates, which display a rich chemistry and provide benchmark reactivity models. Particular interest has been devoted to proton transfer reactions, which may occur in either an intra- or intermolecular fashion in arenium intermediates. A quantitative study of their rates and associated kinetic isotope effects is reported. © 1997 John Wiley & Sons, Inc. Mass Spectrom Rev 15(6), 365-389, 1997. PMID:27082944

  5. Kinetic and mechanistic investigations of progesterone reaction with ozone.

    PubMed

    Barron, Emmanuelle; Deborde, Marie; Rabouan, Sylvie; Mazellier, Patrick; Legube, Bernard

    2006-06-01

    The removal of progesterone by ozone in aqueous solution was studied in this work. The absolute rate constant was evaluated and first by-products were identified. The reaction was studied in the 2.0-8.0 pH range and was found to be a second-order reaction, first-order relative to each compound concentration. The rate constant, determined by kinetic experiments in presence of an OH radical scavenger (tert-butanol), was independent of pH. The value was evaluated to be equal to 480+/-30 M(-1)s(-1) by two kinetic methods. Mass spectrometry analyses were performed to investigate primary degradation products generated by the reaction of ozone with progesterone. Two by-products were evidenced. According to these results, a degradation pathway of progesterone reacting with ozone was proposed. PMID:16725173

  6. Formation of bromate in sulfate radical based oxidation: mechanistic aspects and suppression by dissolved organic matter.

    PubMed

    Lutze, Holger V; Bakkour, Rani; Kerlin, Nils; von Sonntag, Clemens; Schmidt, Torsten C

    2014-04-15

    Sulfate radical based oxidation is discussed being a potential alternative to hydroxyl radical based oxidation for pollutant control in water treatment. However, formation of undesired by-products, has hardly been addressed in the current literature, which is an issue in other oxidative processes such as bromate formation in ozonation of bromide containing water (US-EPA and EU drinking water standard of bromate: 10 μg L(-1)). Sulfate radicals react fast with bromide (k = 3.5 × 10(9) M(-1) s(-1)) which could also yield bromate as final product. The mechanism of bromate formation in aqueous solution in presence of sulfate radicals has been investigated in the present paper. Further experiments were performed in presence of humic acids and in surface water for investigating the relevance of bromate formation in context of pollutant control. The formation of bromate by sulfate radicals resembles the well described mechanism of the hydroxyl radical based bromate formation. In both cases hypobromous acid is a requisite intermediate. In presence of organic matter formation of bromate is effectively suppressed. That can be explained by formation of superoxide formed in the reaction of sulfate radicals plus aromatic moieties of organic matter, since superoxide reduces hypobromous acid yielding bromine atoms and bromide. Hence formation of bromate can be neglected in sulfate radical based oxidation at typical conditions of water treatment. PMID:24565691

  7. Mechanistic Insight into the Photoredox Catalysis of Anti-Markovnikov Alkene Hydrofunctionalization Reactions

    PubMed Central

    2015-01-01

    We describe our efforts to understand the key mechanistic aspects of the previously reported alkene hydrofunctionalization reactions using 9-mesityl-10-methylacridinium (Mes-Acr+) as a photoredox catalyst. Importantly, we are able to detect alkene cation radical intermediates, and confirm that phenylthiyl radical is capable of oxidizing the persistent acridinyl radical in a fast process that unites the catalytic activity of the photoredox and hydrogen atom transfer (HAT) manifolds. Additionally, we present evidence that diphenyl disulfide ((PhS)2) operates on a common catalytic cycle with thiophenol (PhSH) by way of photolytic cleaveage of the disulfide bond. Transition structure analysis of the HAT step using DFT reveals that the activation barrier for H atom donation from PhSH is significantly lower than 2-phenylmalononitrile (PMN) due to structural reorganization. In the early stages of the reaction, Mes-Acr+ is observed to engage in off-cycle adduct formation, presumably as buildup of PhS− becomes significant. The kinetic differences between PhSH and (PhS)2 as HAT catalysts indicate that the proton transfer step may have significant rate limiting influence. PMID:25390821

  8. Revisiting the Radical Initiation Mechanism of the Diamine-Promoted Transition-Metal-Free Cross-Coupling Reaction.

    PubMed

    Zhang, Li; Yang, Huan; Jiao, Lei

    2016-06-01

    Radical chain reactions leading to C-C bond formation are widely used in organic synthesis, and initiation of the radical chain process usually requires thermolabile radical initiators. Recent studies on transition-metal-free cross-coupling reactions between aryl halides and arenes have demonstrated an unprecedented initiation system for radical chain reactions, where the combination of simple organic additives and a base was used in place of conventional radical initiators. Among them, the combination of N,N'-dimethylethylenediamine (DMEDA) and t-BuOK is one of the most efficient and representative reaction systems, and the radical initiation mechanism of this system has attracted considerable research interest. In this study, through the combination of kinetic studies, deuterium labeling experiments, and DFT calculations, the radical initiation mechanism of the diamine-promoted cross-coupling reaction was carefully reinvestigated. In light of the present study, a mechanistic network of radical initiation in the DMEDA/t-BuOK system was revealed, which differs dramatically from the previously realized single radical initiation pathway. In this mechanism, the diamine acts as a hydrogen atom donor and plays a dual role as both "radical amplifier" and "radical regulator" to initiate the radical chain process as well as to control the concentration of reactive radical species. This represents a rare example of a structurally simple molecule playing such a subtle role in the radical chain reaction system. The present study sheds some light on the novel radical initiation mode in transition-metal-free cross-coupling reactions following a base-promoted homolytic aromatic substitution (BHAS) mechanism, and may also help to understand the mechanism of relevant reactions. PMID:27228484

  9. Inactivation efficiencies of radical reactions with biologically active DNA

    NASA Astrophysics Data System (ADS)

    Lafleur, M. V. M.; Retèl, J.; Loman, H.

    Dilute aqueous solutions of biologically active θX174 DNA may serve as a simplified model system of the cell. Damage to the DNA after irradiation with γ-rays, may be ascribed to reactions with .OH, .H and e -aq or secondary radicals, arising from reactions of water radicals with added scavengers. Conversion of primary (water) radicals into secondary (scavenger) radicals leads to a considerable protection of the DNA, which, however, would have been larger if these secondary radicals did not contribute to DNA inactivation. The inactivation yield due to isopropanol or formate (secondary) radicals depends on dose rate as well as DNA concentration. Furthermore the inactivation efficiencies of the reactions of both the primary and the secondary radicals with single-stranded DNA could be established.

  10. Carbonylation reactions of alkyl iodides through the interplay of carbon radicals and Pd catalysts.

    PubMed

    Sumino, Shuhei; Fusano, Akira; Fukuyama, Takahide; Ryu, Ilhyong

    2014-05-20

    Numerous methods for transition metal catalyzed carbonylation reactions have been established. Examples that start from aryl, vinyl, allyl, and benzyl halides to give the corresponding carboxylic acid derivatives have all been well documented. In contrast, the corresponding alkyl halides often encounter difficulty. This is inherent to the relatively slow oxidative addition step onto the metal center and subsequent β-hydride elimination which causes isomerization of the alkyl metal species. Radical carbonylation reactions can override such problems of reactivity; however, carbonylation coupled to iodine atom transfer (atom transfer carbonylation), though useful, often suffers from a slow iodine atom transfer step that affects the outcome of the reaction. We found that atom transfer carbonylation of primary, secondary, and tertiary alkyl iodides was efficiently accelerated by the addition of a palladium catalyst under light irradiation. Stereochemical studies support a mechanistic pathway based on the synergic interplay of radical and Pd-catalyzed reaction steps which ultimately lead to an acylpalladium species. The radical/Pd-combined reaction system has a wide range of applications, including the synthesis of carboxylic acid esters, lactones, amides, lactams, and unsymmetrical ketones such as alkyl alkynyl and alkyl aryl ketones. The design of unique multicomponent carbonylation reactions involving vicinal C-functionalization of alkenes, double and triple carbonylation reactions, in tandem with radical cyclization reactions, has also been achieved. Thus, the radical/Pd-combined strategy provides a solution to a longstanding problem of reactivity involving the carbonylation of alkyl halides. This novel methodology expands the breadth and utility of carbonylation chemistry over either the original radical carbonylation reactions or metal-catalyzed carbonylation reactions. PMID:24712759

  11. Transverse flow reactor studies of the dynamics of radical reactions

    SciTech Connect

    Macdonald, R.G.

    1993-12-01

    Radical reactions are in important in combustion chemistry; however, little state-specific information is available for these reactions. A new apparatus has been constructed to measure the dynamics of radical reactions. The unique feature of this apparatus is a transverse flow reactor in which an atom or radical of known concentration will be produced by pulsed laser photolysis of an appropriate precursor molecule. The time dependence of individual quantum states or products and/or reactants will be followed by rapid infrared laser absorption spectroscopy. The reaction H + O{sub 2} {yields} OH + O will be studied.

  12. Reactions of methyl and ethyl radicals with uranium hexafluoride

    NASA Astrophysics Data System (ADS)

    Lyman, John L.; Laguna, Glenn

    1985-01-01

    We have measured the rates of reaction of both methyl and ethyl radicals with uranium hexafluoride (UF6) in the gas phase. The method we used was to photolyze samples of UF6 in the presence of either methane or ethane. The radicals produced by reaction of fluorine atoms with these species then react with either themselves or with UF6. We inferred the rate constants from ratios of the reaction products and the published rate constants for radical recombination. The diagnostic technique was gas chromatography. The resulting rate constants for reaction with UF6 were (1.6±0.8)×10-14 cm3 molecule-1 s-1 for methyl radicals and (4±2)×10-11 cm3 molecule-1 s-1 for ethyl radicals.

  13. Mechanistic Studies of the Radical SAM Enzyme DesII with TDP-d-Fucose**

    PubMed Central

    Ko, Yeonjin; Ruszczycky, Mark W.; Choi, Sei-Hyun

    2014-01-01

    DesII is a radical SAM enzyme that catalyzes the C4-deamination of TDP-4-amino-4,6-dideoxyglucose via a C3 radical intermediate. However, if the C4 amino group is replaced with a hydroxyl (TDP-quinovose), the hydroxyl at C3 is oxidized to a ketone with no C4-dehydration. It is hypothesized that hyperconjugation between the C4 C–N/O bond and the partially filled p-orbital at C3 of the radical intermediate modulates the degree to which elimination competes with dehydrogenation. To investigate this hypothesis, the reaction of DesII with the C4-epimer of TDP-quinovose (TDP-fucose) was examined. The majority of the reaction results in the formation of TDP-6-deoxygulose and likely regeneration of TDP-fucose. The remainder of the substrate radical partitions roughly equally between C3-dehydrogenation and C4-dehydration. Thus, changing the stereochemistry at C4 permits a more balanced competition between elimination and dehydrogenation. PMID:25418063

  14. Hydrogen transfer in SAM-mediated enzymatic radical reactions.

    PubMed

    Hioe, Johnny; Zipse, Hendrik

    2012-12-14

    S-adenosylmethionine (SAM) plays an essential role in a variety of enzyme-mediated radical reactions. One-electron reduction of SAM is currently believed to generate the C5'-desoxyadenosyl radical, which subsequently abstracts a hydrogen atom from the actual substrate in a catalytic or a non-catalytic fashion. Using a combination of theoretical and experimental bond dissociation energy (BDE) data, the energetics of these radical processes have now been quantified. SAM-derived radicals are found to react with their respective substrates in an exothermic fashion in enzymes using SAM in a stoichiometric (non-catalytic) way. In contrast, the catalytic use of SAM appears to be linked to a sequence of moderately endothermic and exothermic reaction steps. The use of SAM in spore photoproduct lyase (SPL) appears to fit neither of these general categories and appears to constitute the first example of a SAM-initiated radical reaction propagated independently of the cofactor. PMID:23139189

  15. Radical-initiated reaction of methyl linoleate with dialkyl phosphites

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The addition of dialkyl phosphite (methyl, ethyl and n-butyl) to methyl linoleate (MeLin) double bonds was investigated. The reaction proved to be more challenging than the analogous reaction with methyl oleate (MeOl), due to inhibition of the radical reaction by the bis-allylic hydrogens of MeLin a...

  16. Characteristics of Radical Reactions, Spin Rules, and a Suggestion for the Consistent Use of a Dot on Radical Species

    ERIC Educational Resources Information Center

    Wojnarovits, Laszlo

    2011-01-01

    In many chemical reactions, reactive radicals have been shown to be transient intermediates. The free radical character of a chemical species is often, but not always, indicated by adding a superscript dot to the chemical formula. A consistent use of this radical symbol on all species that have radical character is suggested. Free radicals have a…

  17. Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

    SciTech Connect

    Carraher, Jack McCaslin

    2014-01-01

    Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding ‘greener’ sources of commodity chemicals and fuels.

  18. Mechanistic Diversity of Radical S-Adenosylmethionine (SAM)-dependent Methylation*

    PubMed Central

    Bauerle, Matthew R.; Schwalm, Erica L.; Booker, Squire J.

    2015-01-01

    Radical S-adenosylmethionine (SAM) enzymes use the oxidizing power of a 5′-deoxyadenosyl 5′-radical to initiate an amazing array of transformations, usually through the abstraction of a target substrate hydrogen atom. A common reaction of radical SAM (RS) enzymes is the methylation of unactivated carbon or phosphorous atoms found in numerous primary and secondary metabolites, as well as in proteins, sugars, lipids, and RNA. However, neither the chemical mechanisms by which these unactivated atoms obtain methyl groups nor the actual methyl donors are conserved. In fact, RS methylases have been grouped into three classes based on protein architecture, cofactor requirement, and predicted mechanism of catalysis. Class A methylases use two cysteine residues to methylate sp2-hybridized carbon centers. Class B methylases require a cobalamin cofactor to methylate both sp2-hybridized and sp3-hybridized carbon centers as well as phosphinate phosphorous atoms. Class C methylases share significant sequence homology with the RS enzyme, HemN, and may bind two SAM molecules simultaneously to methylate sp2-hybridized carbon centers. Lastly, we describe a new class of recently discovered RS methylases. These Class D methylases, unlike Class A, B, and C enzymes, which use SAM as the source of the donated methyl carbon, are proposed to methylate sp2-hybridized carbon centers using methylenetetrahydrofolate as the source of the appended methyl carbon. PMID:25477520

  19. Mechanistic diversity of radical S-adenosylmethionine (SAM)-dependent methylation.

    PubMed

    Bauerle, Matthew R; Schwalm, Erica L; Booker, Squire J

    2015-02-13

    Radical S-adenosylmethionine (SAM) enzymes use the oxidizing power of a 5'-deoxyadenosyl 5'-radical to initiate an amazing array of transformations, usually through the abstraction of a target substrate hydrogen atom. A common reaction of radical SAM (RS) enzymes is the methylation of unactivated carbon or phosphorous atoms found in numerous primary and secondary metabolites, as well as in proteins, sugars, lipids, and RNA. However, neither the chemical mechanisms by which these unactivated atoms obtain methyl groups nor the actual methyl donors are conserved. In fact, RS methylases have been grouped into three classes based on protein architecture, cofactor requirement, and predicted mechanism of catalysis. Class A methylases use two cysteine residues to methylate sp(2)-hybridized carbon centers. Class B methylases require a cobalamin cofactor to methylate both sp(2)-hybridized and sp(3)-hybridized carbon centers as well as phosphinate phosphorous atoms. Class C methylases share significant sequence homology with the RS enzyme, HemN, and may bind two SAM molecules simultaneously to methylate sp(2)-hybridized carbon centers. Lastly, we describe a new class of recently discovered RS methylases. These Class D methylases, unlike Class A, B, and C enzymes, which use SAM as the source of the donated methyl carbon, are proposed to methylate sp(2)-hybridized carbon centers using methylenetetrahydrofolate as the source of the appended methyl carbon. PMID:25477520

  20. Competitive reactions of organophosphorus radicals on coke surfaces.

    PubMed

    Catak, Saron; Hemelsoet, Karen; Hermosilla, Laura; Waroquier, Michel; Van Speybroeck, Veronique

    2011-10-17

    The efficacy of organophosphorus radicals as anticoking agents was subjected to a computational study in which a representative set of radicals derived from industrially relevant organophosphorus additives was used to explore competitive reaction pathways on the graphene-like coke surface formed during thermal cracking. The aim was to investigate the nature of the competing reactions of different organophosphorus radicals on coke surfaces, and elucidate their mode of attack and inhibiting effect on the forming coke layer by use of contemporary computational methods. Density functional calculations on benzene and a larger polyaromatic hydrocarbon, namely, ovalene, showed that organophosphorus radicals have a high propensity to add to the periphery of the coke surface, inhibiting methyl radical induced hydrogen abstraction, which is known to be a key step in coke growth. Low addition barriers reported for a phosphatidyl radical suggest competitive aptitude against coke formation. Moreover, organophosphorus additives bearing aromatic substituents, which were shown to interact with the coke surface through dispersive π-π stacking interactions, are suggested to play a nontrivial role in hindering further stacking among coke surfaces. This may be the underlying rationale behind experimental observation of softer coke in the presence of organophosphorus radicals. The ultimate goal is to provide information that will be useful in building single-event microkinetic models. This study presents pertinent information on potential reactions that could be taken up in these models. PMID:21956815

  1. Kinetics and mechanistic study of the gas-phase reaction of ozone with methylbutenol

    NASA Astrophysics Data System (ADS)

    Klawatsch-Carrasco, N.; Doussin, J. F.; Rea, G.; Wenger, J.; Carlier, P.

    2003-04-01

    Biogenic volatile organic compounds (BVOCs) account for around 90% of hydrocarbon emissions into the Earth's atmosphere ([1], [2]). Several thousand different BVOCs have been identified, the most well known being unsaturated hydrocarbons. However, over the last ten years an increasing number of oxygenated BVOCs, such as methylbutenol (MBO), have also been detected in field measurement campaigns and plant emission studies ([3], [4]). In order to determine the environmental impact of BVOCs, a thorough knowledge of the rates and mechanisms for their atmospheric degradation is required. The major atmospheric degradation processes for BVOCs are gas-phase reaction with hydroxyl radicals (OH), nitrate radicals (NO_3) and ozone (O_3). These reactions produce oxidised hydrocarbons, ozone and secondary organic aerosol and, as a result, exert a strong influence on the chemical composition of the atmosphere. Very few studies are available concerning the reactivity of MBO. To extend the available database on the atmospheric chemistry of biogenic compounds, the reaction of O_3 with MBO at 296(±2) K has been investigated in atmospheric simulation chambers at LISA in Créteil (France) and CRAC in Cork (Ireland), using complementary techniques such as FTIR spectroscopy, PFBHA derivatization with GC-MS detection and a particle sizer and counter. The rate constant for the reaction was determined using an absolute rate technique, yielding a value of (8.3±0.9)× 10-18 cm^3 molecule-1s-1. Mechanistic studies of the reaction lead to the following observations: a primary formation of only three carbonyl compounds, formaldehyde (yield=0.40±0.03), acetone (yield=0.27±0.02) and 2-methyl-2-hydroxy-propanal. In addition, there is a noticeable formation of aerosols at the very beginning of the reaction that seemed to depend on the relative humidity. References: [1] Wayne, R. P. (2000). 3rd edition. Oxford university press inc. Edition. [2] Finlayson-Pitts, B. and Pitts Jr, J. N. ( 2000

  2. Tropospheric reactions of the haloalkyl radicals formed from hydroxyl radical reaction with a series of alternative fluorocarbons

    NASA Technical Reports Server (NTRS)

    Atkinson, Roger

    1990-01-01

    In the present assessment, the hydrogen containing halocarbons being considered as alternatives to the the presently used chlorofluorocarbons are the hydrochlorofluorocarbons (HCFCs) 123 (CF3CHCl2), 141b (CFCl2CH3), 142b (CF2ClCH3), 22 (CHF2Cl) and 124 (CF3CHFCl) and the hydrofluorocarbons (HFCs) 134a (CF3CH2F), 152a (CHF2CH3) and 125 (CF3CHF2). All of these HCFCs and HFCs will react with the hydroxyl (OH) radical in the troposphere, giving rise to haloalkyl radicals which then undergo a complex series of reactions in the troposphere. These reactions of the haloalkyl radicals formed from the initial OH radical reactions with the HCFCs and HFCs under tropospheric conditions are the focus here.

  3. Crossed-beam studies of the dynamics of radical reactions

    SciTech Connect

    Liu, K.

    1993-12-01

    The objective of this program is to characterize the detailed dynamics of elementary radical reactions and to provide a better understanding of radical reactivity in general. The radical beam is typically generated by a laser photolysis method. After colliding with the reacting molecule in a crossed-beam apparatus, the reaction product state distribution is interrogated by laser spectroscopic techniques. Several radicals of combustion significance, such as O, CH, OH, CN and NCO have been successfully generated and their collisional behavior at the state-to-state integral cross section level of detail has been studied in this manner. During the past year, the detection system has been converted from LIF to REMPI schemes, and the emphasis of this program shifted to investigate the product angular distributions. Both inelastic and reactive processes have been studied.

  4. Pressure effects on the radical-radical recombination reaction of photochromic bridged imidazole dimers.

    PubMed

    Mutoh, Katsuya; Abe, Jiro

    2014-09-01

    The bridged imidazole dimers are some of the attractive fast photochromic compounds which have potential applications to the ophthalmic lenses, real-time hologram and molecular machines. The strategy for expanding their photochromic properties such as the colour variation and tuning the decolouration rates has been vigorously investigated, but the insight into the structural changes along the photochromic reactions has not been demonstrated in detail. Here, we demonstrated the pressure dependence of the radical-radical recombination reaction of the bridged imidazole dimers. The radical-radical interaction can be controlled by applying high pressure. Our results give fundamental information about the molecular dynamics of the bridged imidazole dimers, leading to the development of new functional photochromic machines and pressure-sensitive photochromic materials. PMID:25025786

  5. Reaction kinetics of resveratrol with tert-butoxyl radicals

    NASA Astrophysics Data System (ADS)

    Džeba, Iva; Pedzinski, Tomasz; Mihaljević, Branka

    2012-09-01

    The rate constant for the reaction of t-butoxyl radicals with resveratrol was studied under pseudo-first order conditions. The rate constant was determined by measuring the phenoxyl radical formation rate at 390 nm as function of resveratrol concentration in acetonitrile. The rate constant was determined to be 6.5×108 M-1s-1. This high value indicates the high reactivity consistent with the strong antioxidant activity of resveratrol.

  6. Roaming dynamics in radical addition-elimination reactions

    NASA Astrophysics Data System (ADS)

    Joalland, Baptiste; Shi, Yuanyuan; Kamasah, Alexander; Suits, Arthur G.; Mebel, Alexander M.

    2014-06-01

    Radical addition-elimination reactions are a major pathway for transformation of unsaturated hydrocarbons. In the gas phase, these reactions involve formation of a transient strongly bound intermediate. However, the detailed mechanism and dynamics for these reactions remain unclear. Here we show, for reaction of chlorine atoms with butenes, that the Cl addition-HCl elimination pathway occurs from an abstraction-like Cl-H-C geometry rather than a conventional three-centre or four-centre transition state. Furthermore, access to this geometry is attained by roaming excursions of the Cl atom from the initially formed adduct. In effect, the alkene π cloud serves to capture the Cl atom and hold it, allowing many subsequent opportunities for the energized intermediate to find a suitable approach to the abstraction geometry. These bimolecular roaming reactions are closely related to the roaming radical dynamics recently discovered to play an important role in unimolecular reactions.

  7. Detection of hydroxyl radical in plasma reaction on toluene removal.

    PubMed

    Guo, Yufang; Liao, Xiaobin; Ye, Daiqi

    2008-01-01

    A new method was introduced to detect the concentration of OH radical in dielectric barrier discharge (DBD) reaction. A film, which was impregnated with salicylic acid, was used to detect OH radical in plasma reaction at room temperature and atmospheric pressure. Salicylic acid reacts with OH radical and produces 2,5-dihydroxybenzoic acid (2,5-DHBA). Then, a high performance liquid chromatography (HPLC) was carried out to detect the concentration of 2,5-DHBA. Therefore, OH radical in nonthermal plasma reaction could be calculated. In this plasma reaction, the applied voltage was controlled at 10 kV, the initial concentration of toluene was 400 mg/m3, and the gas flow rate was 300 ml/min. It was observed that when the film was placed away from the plasma area, 2,5-DHBA could not be detected by HPLC, although the sampling time lasted for 48 h. On the other hand, when the film was placed in the plasma area and the sampling time being too long (> 4 h), the concentration of 2,5-DHBA was also below detection limit, and it could not be detected by HPLC. However, when the film was placed in the plasma reaction field with the sampling time being 3 h, the concentration of OH radical was calculated to be 10.54 x 10(12) cm(-3). In addition, concentration of OH radical was investigated under different humidity, such as 0.2%, 0.4%, 0.6%, 0.8%, and 1.0%. The results showed that the amount of OH radical stayed at order of magnitude of 10(12) cm(-3) and increased with the increase of humidity. PMID:19209627

  8. REACTIONS OF OXY RADICALS IN THE ATMOSPHERE

    EPA Science Inventory

    Results are presented of a research program concerned with the study of selected reactions of importance in atmospheric chemistry. The decomposition of peroxyacetyl nitrate (PAN) was studied over the temperature range 25-39C. The rate constant was determined to be log k = 16.29 -...

  9. Insights into gas-phase reaction mechanisms of small carbon radicals using isomer-resolved product detection.

    PubMed

    Trevitt, Adam J; Goulay, Fabien

    2016-02-17

    For reactive gas-phase environments, including combustion, extraterrestrials atmospheres and our Earth's atmosphere, the availability of quality chemical data is essential for predictive chemical models. These data include reaction rate coefficients and product branching fractions. This perspective overviews recent isomer-resolved production detection experiments for reactions of two of the most reactive gas phase radicals, the CN and CH radicals, with a suite of small hydrocarbons. A particular focus is given to flow-tube experiments using synchrotron photoionization mass spectrometry. Coupled with computational studies and other experiment techniques, flow tube isomer-resolved product detection have provided significant mechanistic details of these radical + neutral reactions with some general patterns emerging. PMID:26841339

  10. Vibrationally Driven Hydrogen Abstraction Reaction by Bromine Radical in Solution

    NASA Astrophysics Data System (ADS)

    Shin, Jae Yoon; Shalowski, Michael A.; Crim, F. Fleming

    2013-06-01

    Previously, we have shown that preparing reactants in specific vibrational states can affect the product state distribution and branching ratios in gas phase reactions. In the solution phase, however, no vibrational mediation study has been reported to date. In this work, we present our first attempt of vibrationally mediated bimolecular reaction in solution. Hydrogen abstraction from a solvent by a bromine radical can be a good candidate to test the effect of vibrational excitation on reaction dynamics because this reaction is highly endothermic and thus we can suppress any thermally initiated reaction in our experiment. Br radical quickly forms CT (charge transfer) complex with solvent molecule once it is generated from photolysis of a bromine source. The CT complex strongly absorbs visible light, which allows us to use electronic transient absorption for tracking Br radical population. For this experiment, we photolyze bromoform solution in dimethyl sulfoxide (DMSO) solvent with 267 nm to generate Br radical and excite the C-H stretch overtone of DMSO with 1700 nm a few hundred femtoseconds after the photolysis. Then, we monitor the population of Br-DMSO complex with 400 nm as a function of delay time between two pump beams and probe beam. As a preliminary result, we observed the enhancement of loss of Br-DMSO complex population due to the vibrational excitation. We think that increased loss of Br-DMSO complex is attributed to more loss of Br radical that abstracts hydrogen from DMSO and it is the vibrational excitation that promotes the reaction. To make a clear conclusion, we will next utilize infrared probing to directly detect HBr product formation.

  11. How Well Can New-Generation Density Functionals Describe the Energetics of Bond-Dissociation Reactions Producing Radicals?

    SciTech Connect

    Zhao, Yan; Truhlar, Donald G.

    2008-02-14

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The performance of various density functionals has been tested for three sets of reaction energies involving radicals. It is shown that two recently designed functionals, M05-2X and M06-2X, provide the best performance. These functionals provide useful and affordable methods for future mechanistic studies involving organic radicals.

  12. Mechanistic insights into light-driven graphene-induced peroxide decomposition: radical generation and disproportionation.

    PubMed

    Chu, Ya-Lan; Chen, Yen-An; Li, Wei-Chin; Chu, Jean-Ho; Chen, Chun-Hu; Chiang, Chao-Ming

    2016-07-28

    Interaction between adsorbed t-butyl peroxybenzoate and photoexcited graphene rendered trapped phenyl and t-butoxy radicals. Post-irradiation thermal desorption showed benzene, t-butanol, and isobutylene oxide as the end products. The required hydrogen atoms were obtained via the radical disproportionation. Graphene enabled radical species to be captured and their on-surface chemistry to be revealed. PMID:27366795

  13. Modeling of the Reaction Mechanism of Enzymatic Radical C-C Coupling by Benzylsuccinate Synthase.

    PubMed

    Szaleniec, Maciej; Heider, Johann

    2016-01-01

    Molecular modeling techniques and density functional theory calculations were performed to study the mechanism of enzymatic radical C-C coupling catalyzed by benzylsuccinate synthase (BSS). BSS has been identified as a glycyl radical enzyme that catalyzes the enantiospecific fumarate addition to toluene initiating its anaerobic metabolism in the denitrifying bacterium Thauera aromatica, and this reaction represents the general mechanism of toluene degradation in all known anaerobic degraders. In this work docking calculations, classical molecular dynamics (MD) simulations, and DFT+D2 cluster modeling was employed to address the following questions: (i) What mechanistic details of the BSS reaction yield the most probable molecular model? (ii) What is the molecular basis of enantiospecificity of BSS? (iii) Is the proposed mechanism consistent with experimental observations, such as an inversion of the stereochemistry of the benzylic protons, syn addition of toluene to fumarate, exclusive production of (R)-benzylsuccinate as a product and a kinetic isotope effect (KIE) ranging between 2 and 4? The quantum mechanics (QM) modeling confirms that the previously proposed hypothetical mechanism is the most probable among several variants considered, although C-H activation and not C-C coupling turns out to be the rate limiting step. The enantiospecificity of the enzyme seems to be enforced by a thermodynamic preference for binding of fumarate in the pro(R) orientation and reverse preference of benzyl radical attack on fumarate in pro(S) pathway which results with prohibitively high energy barrier of the radical quenching. Finally, the proposed mechanism agrees with most of the experimental observations, although the calculated intrinsic KIE from the model (6.5) is still higher than the experimentally observed values (4.0) which suggests that both C-H activation and radical quenching may jointly be involved in the kinetic control of the reaction. PMID:27070573

  14. Modeling of the Reaction Mechanism of Enzymatic Radical C–C Coupling by Benzylsuccinate Synthase

    PubMed Central

    Szaleniec, Maciej; Heider, Johann

    2016-01-01

    Molecular modeling techniques and density functional theory calculations were performed to study the mechanism of enzymatic radical C–C coupling catalyzed by benzylsuccinate synthase (BSS). BSS has been identified as a glycyl radical enzyme that catalyzes the enantiospecific fumarate addition to toluene initiating its anaerobic metabolism in the denitrifying bacterium Thauera aromatica, and this reaction represents the general mechanism of toluene degradation in all known anaerobic degraders. In this work docking calculations, classical molecular dynamics (MD) simulations, and DFT+D2 cluster modeling was employed to address the following questions: (i) What mechanistic details of the BSS reaction yield the most probable molecular model? (ii) What is the molecular basis of enantiospecificity of BSS? (iii) Is the proposed mechanism consistent with experimental observations, such as an inversion of the stereochemistry of the benzylic protons, syn addition of toluene to fumarate, exclusive production of (R)-benzylsuccinate as a product and a kinetic isotope effect (KIE) ranging between 2 and 4? The quantum mechanics (QM) modeling confirms that the previously proposed hypothetical mechanism is the most probable among several variants considered, although C–H activation and not C–C coupling turns out to be the rate limiting step. The enantiospecificity of the enzyme seems to be enforced by a thermodynamic preference for binding of fumarate in the pro(R) orientation and reverse preference of benzyl radical attack on fumarate in pro(S) pathway which results with prohibitively high energy barrier of the radical quenching. Finally, the proposed mechanism agrees with most of the experimental observations, although the calculated intrinsic KIE from the model (6.5) is still higher than the experimentally observed values (4.0) which suggests that both C–H activation and radical quenching may jointly be involved in the kinetic control of the reaction. PMID:27070573

  15. Phosphite radicals and their reactions. Examples of redox, substitution, and addition reactions. [Gamma rays and electrons

    SciTech Connect

    Schaefer, K.; Asmus, K.D.

    1980-08-21

    Phosphite radicals HPO/sub 3/- and PO/sub 3//sup 2/-, which exist in an acid-base equilibrium with pK = 5.75, are shown to take part in various types of reactions. In the absence of scavengers, they disappear mainly by second-order disproportionation and combination; a first-order contribution to the decay is also indicated. HPO/sub 3/- and PO/sub 3//sup 2/- are good reductants toward electron acceptors such as tetranitromethane. In this reaction phosphate and C(NO/sub 2/)/sub 3/- are formed. Phosphite radicals can, however, also act as good oxidants, e.g., toward thiols and thiolate ions. These reactions lead to the formation of RS. radicals which were identified either directly, as in the case of penicillamine, through the optical absorption of PenS. or more indirectly through equilibration of RS. with RS- to the optically absorbing RSSR-. disulfide radical anion. A homolytic substitution reaction (S/sub H/2) occurs in the reaction of the phosphite radicals with aliphatic disulfides, yielding RS. radicals and phosphate thioester RSPO/sub 3//sup 2/-. Lipoic acid, as an example of a cyclic disulfide, is reduced to the corresponding RSSR-. radical anion and also undergoes the S/sub H/2 reaction with about equal probability. An addition reaction is observed between phosphite radicals and molecular oxygen. The resulting peroxo phosphate radicals establish an acid-base equilibrium HPO/sub 5//sup -/. reversible PO/sub 5//sup 2 -/. + H+ with a pK = 3.4. Absolute rate constants were determined for all reactions discussed.

  16. Reaction of hydroxyl radical with B- and Z-DNA

    SciTech Connect

    Michalik, V.; Tartier, L.; Spotheim-Maurizot, M.; Charlier, M.

    1995-12-31

    Up to now the mechanisms of formation of DNA damages by the {center_dot}OH radical attack are only poorly understood. For example, it is not clear if {center_dot}OH radical attack depends on the DNA polymeric structure, if it is sequence specific and to what extent the {center_dot}OH induced base radicals contribute to the formation of frank strand breaks (FSB), mainly due to attack of sugars. It is accepted now that depending on sequence, topological constraints and environmental factors DNA can adopt different forms such as A, B, C, Z double helices, triple and quadruple helices. Since there are large structural differences between the DNA in B- and Z-forms one may expect differences in the {center_dot}OH radical reaction with the two forms as well as differences in the processes subsequent to {center_dot}OH radical attack which lead to strand breakage. The authors have performed a modeling of {center_dot}OH radical attack on DNA in the B- and Z-form and compared the theoretical results with the experimental patterns of strand breakage in B- and Z-DNA. The calculated probabilities of {center_dot}OH radical attack on sugars and bases in DNA of a given sequence and form were compared to the experimental yields of FSB, i.e. revealed in a neutral pH, and alkali revealed breaks (ARB) in B- and Z-DNA irradiated in dilute aqueous solution. The possible mechanism underlying the pathways from {center_dot}OH radical attack to strand breakage are discussed.

  17. In Situ Catalyst Modification in Atom Transfer Radical Reactions with Ruthenium Benzylidene Complexes.

    PubMed

    Lee, Juneyoung; Grandner, Jessica M; Engle, Keary M; Houk, K N; Grubbs, Robert H

    2016-06-01

    Ruthenium benzylidene complexes are well-known as olefin metathesis catalysts. Several reports have demonstrated the ability of these catalysts to also facilitate atom transfer radical (ATR) reactions, such as atom transfer radical addition (ATRA) and atom transfer radical polymerization (ATRP). However, while the mechanism of olefin metathesis with ruthenium benzylidenes has been well-studied, the mechanism by which ruthenium benzylidenes promote ATR reactions remains unknown. To probe this question, we have analyzed seven different ruthenium benzylidene complexes for ATR reactivity. Kinetic studies by (1)H NMR revealed that ruthenium benzylidene complexes are rapidly converted into new ATRA-active, metathesis-inactive species under typical ATRA conditions. When ruthenium benzylidene complexes were activated prior to substrate addition, the resulting activated species exhibited enhanced kinetic reactivity in ATRA with no significant difference in overall product yield compared to the original complexes. Even at low temperature, where the original intact complexes did not catalyze the reaction, preactivated catalysts successfully reacted. Only the ruthenium benzylidene complexes that could be rapidly transformed into ATRA-active species could successfully catalyze ATRP, whereas other complexes preferred redox-initiated free radical polymerization. Kinetic measurements along with additional mechanistic and computational studies show that a metathesis-inactive ruthenium species, generated in situ from the ruthenium benzylidene complexes, is the active catalyst in ATR reactions. Based on data from (1) H, (13)C, and (31)P NMR spectroscopy and X-ray crystallography, we suspect that this ATRA-active species is a RuxCly(PCy3)z complex. PMID:27186790

  18. Reactive radical facilitated reaction-diffusion modeling for holographic photopolymerization

    SciTech Connect

    Liu Jianhua; Pu Haihui; Gao Bin; Gao Hongyue; Yin Dejin; Dai Haitao

    2010-02-08

    A phenomenological concentration of reactive radical is proposed to take the role of curing light intensity in explicit proportion to the reaction rate for the conventional reaction-diffusion model. This revision rationally eliminates the theoretical defect of null reaction rate in modeling of the postcuring process, and facilitates the applicability of the model in the whole process of holographic photopolymerizations in photocurable monomer and nematic liquid crystal blend system. Excellent consistencies are obtained in both curing and postcuring processes between simulated and experimentally measured evolutions of the first order diffraction efficiency of the formed composite Bragg gratings.

  19. Heterogeneous oxidation of folpet and dimethomorph by OH radicals: A kinetic and mechanistic study

    NASA Astrophysics Data System (ADS)

    Al Rashidi, M.; Chakir, A.; Roth, E.

    2014-01-01

    This study investigates the heterogeneous OH oxidation of folpet and dimethomorph, two fungicides identified in the atmosphere of the Champagne-Ardenne region. Kinetic experiments were conducted in the relative mode, using terbuthylazine as a reference compound. The experimental method employed makes use of a simulation chamber coupled to a GC/MS analytical system. Meanwhile, the identification of (4-chlorophenyl)(3,4-dimethoxyphenyl)methanone (CPMPM), a degradation product of the OH oxidation of dimethomorph, is achieved using SPME/GC/MS. Moreover, a degradation mechanism of dimethomorph is proposed, and the heterogeneous OH reactivity of CPMPM is evaluated. The obtained OH reaction rate constants (cm3 molecule-1 s-1) are: kZ-dimethomorph = (2.0 ± 1.2) 10-14, kE-dimethomorph = (1.7 ± 1.2) 10-14, kFolpet = (1.6 ± 0.9) 10-13 and kCPMPM = (1.9 ± 1.0) 10-12. The implicated tropospheric life-times are up to 2 months, which shows that the investigated pesticides are relatively persistent towards oxidation removal processes. CPMPM, the identified product of OH oxidation of dimethomorph, is less persistent with a life time of only 6 days relative to heterogeneous oxidation by OH radicals.

  20. MICROWAVE EFFECTS IN ORGANIC SYNTHESIS: MECHANISTIC AND REACTION MEDIUM CONSIDERATIONS

    EPA Science Inventory

    The scope of applications of microwave irradiation relates to a wide spectrum of organic syntheses with numerous benefits (reduction in reaction times, improved purity of products and better yields) encompassing advantages of both thermal and (or) specific non-purely thermal effe...

  1. An improved semiclassical theory of radical pair recombination reactions.

    PubMed

    Manolopoulos, D E; Hore, P J

    2013-09-28

    We present a practical semiclassical method for computing the electron spin dynamics of a radical in which the electron spin is hyperfine coupled to a large number of nuclear spins. This can be used to calculate the singlet and triplet survival probabilities and quantum yields of radical recombination reactions in the presence of magnetic fields. Our method differs from the early semiclassical theory of Schulten and Wolynes [J. Chem. Phys. 68, 3292 (1978)] in allowing each individual nuclear spin to precess around the electron spin, rather than assuming that the hyperfine coupling-weighted sum of nuclear spin vectors is fixed in space. The downside of removing this assumption is that one can no longer obtain a simple closed-form expression for the electron spin correlation tensor: our method requires a numerical calculation. However, the computational effort increases only linearly with the number of nuclear spins, rather than exponentially as in an exact quantum mechanical calculation. The method is therefore applicable to arbitrarily large radicals. Moreover, it approaches quantitative agreement with quantum mechanics as the number of nuclear spins increases and the environment of the electron spin becomes more complex, owing to the rapid quantum decoherence in complex systems. Unlike the Schulten-Wolynes theory, the present semiclassical theory predicts the correct long-time behaviour of the electron spin correlation tensor, and it therefore correctly captures the low magnetic field effect in the singlet yield of a radical recombination reaction with a slow recombination rate. PMID:24089749

  2. Binuclear metallohydrolases: complex mechanistic strategies for a simple chemical reaction.

    PubMed

    Schenk, Gerhard; Mitić, Nataša; Gahan, Lawrence R; Ollis, David L; McGeary, Ross P; Guddat, Luke W

    2012-09-18

    Binuclear metallohydrolases are a large family of enzymes that require two closely spaced transition metal ions to carry out a plethora of hydrolytic reactions. Representatives include purple acid phosphatases (PAPs), enzymes that play a role in bone metabolism and are the only member of this family with a heterovalent binuclear center in the active form (Fe(3+)-M(2+), M = Fe, Zn, Mn). Other members of this family are urease, which contains a di-Ni(2+) center and catalyzes the breakdown of urea, arginase, which contains a di-Mn(2+) center and catalyzes the final step in the urea cycle, and the metallo-β-lactamases, which contain a di-Zn(2+) center and are virulence factors contributing to the spread of antibiotic-resistant pathogens. Binuclear metallohydrolases catalyze numerous vital reactions and are potential targets of drugs against a wide variety of human disorders including osteoporosis, various cancers, antibiotic resistance, and erectile dysfunctions. These enzymes also tend to catalyze more than one reaction. An example is an organophosphate (OP)-degrading enzyme from Enterobacter aerogenes (GpdQ). Although GpdQ is part of a pathway that is used by bacteria to degrade glycerolphosphoesters, it hydrolyzes a variety of other phosphodiesters and displays low levels of activity against phosphomono- and triesters. Such a promiscuous nature may have assisted the apparent recent evolution of some binuclear metallohydrolases to deal with situations created by human intervention such as OP pesticides in the environment. OP pesticides were first used approximately 70 years ago, and therefore the enzymes that bacteria use to degrade them must have evolved very quickly on the evolutionary time scale. The promiscuous nature of enzymes such as GpdQ makes them ideal candidates for the application of directed evolution to produce new enzymes that can be used in bioremediation and against chemical warfare. In this Account, we review the mechanisms employed by binuclear

  3. Kinetics of the Self Reaction of Cyclopentadienyl Radicals.

    PubMed

    Knyazev, Vadim D; Popov, Konstantin V

    2015-07-16

    The kinetics of the self-reaction of cyclopentadienyl radicals (c-C5H5) was studied by laser photolysis/photoionization mass spectroscopy. Overall rate constants were obtained in direct real-time experiments in the temperature region 304-600 K and at bath gas densities of (3.00-12.0) × 10(16) molecules cm(-3). The room-temperature value of the rate constant, (3.98 ± 0.41) × 10(-10) cm(3) molecule(-1) s(-1), is significantly higher than the rate constants for most hydrocarbon radical-radical reactions and coincides with the estimated collision rate. The observed overall c-C5H5 + c-C5H5 rate constant demonstrates an unprecedented strong negative temperature dependence: k1 = 2.9 × 10(-12) exp(+1489 K/T) cm(3) molecule(-1) s(-1), with estimated uncertainty increasing with temperature, from 13% at 304 to 32% at 600 K. Formation of C10H10 as the primary product of cyclopentadienyl self-reaction was observed. In additional experiments performed at the temperature of 800 K, formation of C10H10, C10H9, and C10H8 was observed. Final product analysis by gas chromatography/mass spectrometry detected two isomers of C10H8 at 800 K: naphthalene (major) and azulene (minor). PMID:25760686

  4. Kinetics of hydroperoxy radical reactions with acetone/HO2 adduct and with acetonylperoxy radical

    NASA Astrophysics Data System (ADS)

    Grieman, F. J.; VanDerGeest, K.; Newenhouse, E.; Watkins, K.; Noell, A. C.; Hui, A.; Sander, S. P.; Okumura, M.

    2013-12-01

    Reactions of hydroperoxy radical, HO2, with acetone and with acetonylperoxy radical, CH3C(O)CH2OO, may play an important role in the oxidation chemistry of the troposphere. Using a temperature-controlled slow-flow tube cell and laser flash photolysis of Cl2 to produce HO2 and CH3C(O)CH2OO from methanol and acetone, respectively, we studied the chemical kinetics involved over the temperature range of 215 to 298 K at 100 Torr. Rates of chemical reactions were determined by monitoring the HO2 concentration as a function of time by near-IR diode laser wavelength modulation spectroscopy. (See Fig.1.) The primary reactions are rapid (<100 μsec) reactions to form the adducts HO2-CH3OH and HO2-CH3C(O)CH3 followed by HO2 reactions with itself, the adducts (chaperone mechanisms), and acetonylperoxy radical. The equilibrium constants for adduct formation were determined in previous work.1,2 In this work, rate coefficients were determined for the acetone chaperone mechanism over the entire temperature range. (E.g., see Fig. 2.) The rate coefficients and energies obtained are very similar to those found for the methanol case.1 Rate coefficients for the CH3C(O)CH2OO/HO2 reaction were also determined over a smaller temperature range, extending the measured value beyond room temperature, and yielding an activation energy. 1. Christensen et al. J. Phys. Chem. A 2006, 110, 6948-6959. 2. Grieman et al. J. Phys. Chem. A 2011, 115, 10527-10538. Fig.1. HO2 decay for HO2/Acetone chemistry at T = 298 K. Fig.2. Determining rate coefficient (k") for HO2/acetone chaperone effect at T = 222.5 K.

  5. Kinetic and mechanistic study of the reaction of OH radicals with methylated benzenes: 1,4-dimethyl-, 1,3,5-trimethyl-, 1,2,4,5-, 1,2,3,5- and 1,2,3,4-tetramethyl-, pentamethyl-, and hexamethylbenzene.

    PubMed

    Alarcón, P; Bohn, B; Zetzsch, C

    2015-05-21

    The reaction of OH radicals with a series of methylated benzenes was studied in a temperature range 300-350 K using a flash-photolysis resonance fluorescence technique. Reversible OH additions led to complex OH decays dependent on the number of distinguishable adducts. Except for hexamethylbenzene, triexponential OH decay curves were obtained, consistent with formation of at least two adduct species. For three compounds that can strictly form two adduct isomers for symmetry reasons (1,4-dimethyl-, 1,3,5-trimethyl-, and 1,2,4,5-tetramethylbenzene) with OH bound ortho or ipso with respect to the methyl groups, OH decay curves were analysed in terms of a reaction mechanism in which the two adducts can be formed directly by OH addition or indirectly by isomerization. In all cases one adduct (add1) is dominating the decomposition back to OH. The other (add2) is more elusive and only detectable at elevated temperatures, similar to the single OH adduct of hexamethylbenzene. Two limiting cases of the general reaction mechanism could be examined quantitatively: reversible formation of add2 exclusively in the OH reaction or by isomerization of add1. Total OH rate constants, adduct loss rate constants and products of forward and reverse rate constants of reversible reactions were determined. From these quantities, adduct yields, equilibrium constants, as well as reaction enthalpies and entropies were derived for the three aromatics. Adduct yields strongly depend on the selected reaction model but generally formation of add1 predominates. For both models equilibrium constants of OH reactions lie between those of OH + benzene from the literature and those obtained for OH + hexamethylbenzene. The corresponding reaction enthalpies of add1 and add2 formations are in a range -87 ± 20 kJ mol(-1), less exothermic than for hexamethylbenzene (-101 kJ mol(-1)). Reaction enthalpies of possible add1 → add2 isomerizations are comparatively small. Because results for 1

  6. Parameterization of phosphine ligands reveals mechanistic pathways and predicts reaction outcomes

    NASA Astrophysics Data System (ADS)

    Niemeyer, Zachary L.; Milo, Anat; Hickey, David P.; Sigman, Matthew S.

    2016-06-01

    The mechanistic foundation behind the identity of a phosphine ligand that best promotes a desired reaction outcome is often non-intuitive, and thus has been addressed in numerous experimental and theoretical studies. In this work, multivariate correlations of reaction outcomes using 38 different phosphine ligands were combined with classic potentiometric analyses to study a Suzuki reaction, for which the site selectivity of oxidative addition is highly dependent on the nature of the phosphine. These studies shed light on the generality of hypotheses regarding the structural influence of different classes of phosphine ligands on the reaction mechanism(s), and deliver a methodology that should prove useful in future studies of phosphine ligands.

  7. Mechanistic examination of aerobic Pt oxidation: insertion of molecular oxygen into Pt-H bonds through a radical chain mechanism.

    PubMed

    Keith, Jason M; Ye, Yixin; Wei, Haochuan; Buck, Matthew R

    2016-07-19

    DFT calculations were performed in an effort to evaluate the mechanism of O2 insertion into the Pt-H bond of Tp(Me2)Pt(IV)Me2H catalyzed by AIBN or light. Results are consistent with a radical chain mechanism involving H˙ loss to form a Pt(III)˙ species followed by addition of O2 to form Pt(III)OO˙. Subsequent radical propagation involving this Pt(III)OO˙ species and an additional equivalent of the Pt(IV) starting material result in the formation of the observed Pt(IV)OOH and regeneration of the Pt(III)˙. In addition examination of the reaction between AIBN and the Pt(IV) hydroperoxo product demonstrates that radical initiation reactions involving the product occur with a lower barrier than with the initial starting material supporting the idea of autoacceleration in this reaction. Other possible mechanisms were examined in an effort to understand the limited reactivity reported in the absence of light or radical initiators. TDDFT calculations were performed in an effort to understand the reported parallel photo-induced reaction. These calculations found the reactant to be transparent in the relevant light range. An experimental UV-Vis spectrum was obtained and is in agreement with the calculations. PMID:27364984

  8. Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals.

    PubMed

    Xu, Fei; Shi, Xiangli; Zhang, Qingzhu; Wang, Wenxing

    2015-01-01

    The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600-1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH. PMID:26270566

  9. Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals

    PubMed Central

    Xu, Fei; Shi, Xiangli; Zhang, Qingzhu; Wang, Wenxing

    2015-01-01

    The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600–1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH. PMID:26270566

  10. Ion-molecule reactions with CF3 radical

    NASA Astrophysics Data System (ADS)

    Miller, Thomas M.; Shuman, Nicholas S.; Wiens, Justin P.; Sawyer, Jordan C.; Martinez, Oscar, Jr.; Ard, Shaun G.; Viggiano, Albert A.

    2015-09-01

    The first measurements of reaction rate coefficients and products are reported for reactions of the radical CF3 with Ar+, Xe+, O2+,NO+, CO2+,and C2F5+,at 300 K. The work was carried out in a fast flow of typically 1.5 Torr helium buffer gas (4% argon) using the variable electron and neutral density attachment mass spectrometry (VENDAMS) technique. CF3 was produced via dissociative electron attachment to CF3I, resulting in CF3 concentrations that were well-quantified because the plasma diffusion rate, the electron concentration, and the rate coefficient for attachment to CF3I were separately measured in the experiment. The Ar+ + CF3 reaction was found to proceed at nearly the calculated collisional rate coefficient, yielding 90% CF2+along with CF3+.Reaction of CF3 with C2F5+is slower and yields 75% C2F4+along with CF3+.CF3 undergoes charge transfer reaction with Xe+, O2+,NO+, and CO2+,yielding CF3+.Arguments will be made regarding reaction mechanisms, including the role of spin conservation. Comparisons with Ar+ and O2+reaction with CH3 will be made. Supported by Air Force Office of Scientific Research, AFOSR-2303EP.

  11. Surface Modification of Polymers by Reaction of Alkyl Radicals.

    PubMed

    Hetemi, Dardan; Médard, Jérôme; Kanoufi, Frédéric; Combellas, Catherine; Pinson, Jean; Podvorica, Fetah I

    2016-01-19

    The surfaces of poly(methyl methacrylate) and polyethylene are modified either (i) by a two-step process including the thermal reaction of alkyl radicals derived from bromohexanoic acid in a mixture of 2,6-dimethylbenzene diazonium salt and neat isopentyl nitrite at 60 °C, followed by reaction with p-nitroaniline, anthraquinone, neutral red, and polyethylene glycol moieties, or (ii) by reaction of a previously anthraquinone-modified bromohexanoic acid. The modified surfaces are characterized by IR, XPS, UV, and water contact angles. A mechanism is proposed to rationalize the results. This approach is an efficient way to modify and pattern polymer surfaces with different organic groups and chemical functionalities under mild conditions. PMID:26653398

  12. Influence of restricted diffusion on retrogressive free-radical reactions

    SciTech Connect

    Buchanan, A.C.; Britt, P.F. III; Thomas, K.B.

    1993-07-01

    The effects of restricted mass transport on retrogressive reaction pathways can be probed through the study of model compounds immobilized on silica surfaces. Silica-immobilized bibenzyl undergoes a free radical chain rearrangement reaction that converts the thermally labile bibenzylic linkage into a more refractory diphenylmethane-type linkage. The efficiency of this process was found to be quite sensitive to the structure of neighboring molecules on the surface. Co-immobilized naphthalene was more effective that co-immobilized tetralin (a hydrogen donor) in inhibiting the process, apparently by retarding the key hydrogen atom transfer step. The effect of the co-attached molecules on the retrogressive cyclization-dehydrogenation path as well as other reaction pathways for this complex system remain under investigation.

  13. Oxygen-18 tracer studies of enzyme reactions with radical/cation diagnostic probes

    SciTech Connect

    Moe, Luke A.; Fox, Brian G. . E-mail: bgfox@biochem.wisc.edu

    2005-12-09

    This review considers reactions of enzymes with the cyclopropanoid radical/cation diagnostic probes norcarane, 1,1-dimethylcyclopropane, and 1,1-diethylcyclopropane as elaborated by the use of {sup 18}O{sub 2} and {sup 18}OH{sub 2} to trace the origin of O-atoms incorporated during catalysis. The reactions of soluble and integral membrane diiron enzymes are summarized and compared to results obtained from cytochrome P450 studies. Norcarane proved to be an excellent substrate for the diiron enzyme toluene 4-monooxygenase and its engineered isoforms, with k {sub cat} and coupling between NADH utilization and total hydroxylated products comparable to that determined for toluene, the natural substrate. Results obtained with toluene 4-monooxygenase show that the un-rearranged and radical-rearranged alcohol products have a high percentage of O-atom incorporation (>80-95%) from O{sub 2}, while the cation-derived ring-expansion products have O-atom incorporation primarily derived from solvent water. Mechanistic possibilities accounting for this difference are discussed.

  14. New mechanistic insights in the NH3-SCR reactions at low temperature

    DOE PAGESBeta

    Ruggeri, Maria Pia; Selleri, Tomasso; Nova, Isabella; Tronconi, Enrico; Pihl, Josh A.; Toops, Todd J.; Partridge, Jr., William P.

    2016-05-06

    The present study is focused on the investigation of the low temperature Standard SCR reaction mechanism over Fe- and Cu-promoted zeolites. Different techniques are employed, including in situ DRIFTS, transient reaction analysis and chemical trapping techniques. The results present strong evidence of nitrite formation in the oxidative activation of NO and of their role in SCR reactions. These elements lead to a deeper understanding of the standard SCR chemistry at low temperature and can potentially improve the consistency of mechanistic mathematical models. Furthermore, comprehension of the mechanism on a fundamental level can contribute to the development of improved SCR catalysts.

  15. Peroxyl radical reactions with carotenoids in microemulsions: Influence of microemulsion composition and the nature of peroxyl radical precursor.

    PubMed

    El-Agamey, Ali; McGarvey, David J

    2016-01-01

    The reactions of acetylperoxyl radicals with different carotenoids (7,7'-dihydro-β-carotene and ζ-carotene) in SDS and CTAC microemulsions of different compositions were investigated using laser flash photolysis (LFP) coupled with kinetic absorption spectroscopy. The primary objective of this study was to explore the influence of microemulsion composition and the type of surfactant used on the yields and kinetics of various transients formed from the reaction of acetylperoxyl radicals with carotenoids. Also, the influence of the site (hydrocarbon phases or aqueous phase) of generation of the peroxyl radical precursor was examined by using 4-acetyl-4-phenylpiperidine hydrochloride (APPHCl) and 1,1-diphenylacetone (11DPA) as water-soluble and lipid-soluble peroxyl radical precursors, respectively. LFP of peroxyl radical precursors with 7,7'-dihydro-β-carotene (77DH) in different microemulsions gives rise to the formation of three distinct transients namely addition radical (λmax=460 nm), near infrared transient1 (NIR, λmax=700 nm) and 7,7'-dihydro-β-carotene radical cation (77DH(•+), λmax=770 nm). In addition, for ζ-carotene (ZETA) two transients (near infrared transient1 (NIR1, λmax=660 nm) and ζ-carotene radical cation (ZETA(•+), λmax=730-740 nm)) are generated following LFP of peroxyl radical precursors in the presence of ζ-carotene (ZETA) in different microemulsions. The results show that the composition of the microemulsion strongly influences the observed yield and kinetics of the transients formed from the reactions of peroxyl radicals (acetylperoxyl radicals) with carotenoids (77DH and ZETA). Also, the type of surfactant used in the microemulsions influences the yield of the transients formed. The dependence of the transient yields and kinetics on microemulsion composition (or the type of surfactant used in the microemulsion) can be attributed to the change of the polarity of the microenvironment of the carotenoid. Furthermore, the nature of

  16. Spin-selective recombination reactions of radical pairs: Experimental test of validity of reaction operators

    SciTech Connect

    Maeda, Kiminori; Liddell, Paul; Gust, Devens; Hore, P. J.

    2013-12-21

    Spin-selective reactions of radical pairs are conventionally modelled using an approach that dates back to the 1970s [R. Haberkorn, Mol. Phys. 32, 1491 (1976)]. An alternative approach based on the theory of quantum measurements has recently been suggested [J. A. Jones and P. J. Hore, Chem. Phys. Lett. 488, 90 (2010)]. We present here the first experimental attempt to discriminate between the two models. Pulsed electron paramagnetic resonance spectroscopy has been used to investigate intramolecular electron transfer in the radical pair form of a carotenoid-porphyrin-fullerene molecular triad. The rate of spin-spin relaxation of the fullerene radical in the triad was found to be inconsistent with the quantum measurement description of the spin-selective kinetics, and in accord with the conventional model when combined with spin-dephasing caused by rotational modulation of the anisotropic g-tensor of the fullerene radical.

  17. Mechanistic Insights from Reaction of α-Oxiranyl-Aldehydes with Cyanobacterial Aldehyde Deformylating Oxygenase

    PubMed Central

    Das, Debasis; Ellington, Benjamin; Paul, Bishwajit; Marsh, E. Neil G.

    2014-01-01

    The biosynthesis of long-chain aliphatic hydrocarbons, which are derived from fatty acids, is widespread in Nature. The last step in this pathway involves the decarbonylation of fatty aldehydes to the corresponding alkanes or alkenes. In cyanobacteria this is catalyzed by an aldehyde deformylating oxygenase. We have investigated the mechanism of this enzyme using substrates bearing an oxirane ring adjacent to the aldehyde carbon. The enzyme catalyzed the deformylation of these substrates to produce the corresponding oxiranes. Performing the reaction in D2O allowed the facial selectivity of proton addition to be examined by 1H-NMR spectroscopy. The proton is delivered with equal probability to either face of the oxirane ring, indicating the formation of an oxiranyl radical intermediate that is free to rotate during the reaction. Unexpectedly, the enzyme also catalyzes a side reaction in which oxiranyl-aldehydes undergo tandem deformylation to furnish alkanes two carbons shorter. We present evidence that this involves the rearrangement of the intermediate oxiranyl radical formed in the first step, resulting an aldehyde that is further deformylated in a second step. These observations provide support for a radical mechanism for deformylation and, furthermore, allow the lifetime of the radical intermediate to be estimated based on prior measurements of rate constants for the rearrangement of oxiranyl radicals. PMID:24313866

  18. Pressure Effects on Product Channels of Hydrocarbon Radical-Radical Reactions; Implications for Modelling of Planetary Atmospheres

    NASA Astrophysics Data System (ADS)

    Fahr, A.; Halpern, J.; N'doumi, M.

    2011-10-01

    Previously we had studied the kinetics and product channels of small unsaturated hydrocarbon radical (C2 and C3s) reactions relevant to planetary atmospheric modelling. Reactions of C2 radicals (such as vinyl, H2CCH and ethynyl C2H) and C3 radicals (such as propargyl, HCCCH2 and allyl, H2CCCH3) can affect the abundances of a large number of stable observable C3, C4, C5, C6 and larger molecules, including linear, aromatic and even poly aromatic molecules. We have experimentally determined pressuredependent product yields for self- and cross-radical reactions performed at 298 K and at selected pressures between ~4 Torr (0.5 kPa) and 760 Torr (101 kPa). Final products were determined by gas chromatograph with mass spectrometry/flame ionization detection (GC/MS/FID). In some cases complementary computational studies extended the pressure and temperature range of the observations and provided valuable information on complex reaction mechanisms. These studies provide a systematic framework so that important energetic and structural parameters for radical-radical reactions can be assessed. Here we report a compilation of our earlier results relevant to planetary atmospheres in addition to recent ones for allyl radical (H2CCCH3) reactions.

  19. Studies on the interaction of isocyanides with imines: reaction scope and mechanistic variations.

    PubMed

    Ghashghaei, Ouldouz; Manna, Consiglia Annamaria; Vicente-García, Esther; Revés, Marc; Lavilla, Rodolfo

    2014-01-01

    The interaction of imines with isocyanides has been studied. The main product results from a sequential process involving the attack of two units of isocyanide, under Lewis acid catalysis, upon the carbon-nitrogen double bond of the imine to form the 4-membered ring system. The scope of the reaction regarding the imine and isocyanide ranges has been determined, and also some mechanistic variations and structural features have been described. PMID:24454559

  20. Studies on the interaction of isocyanides with imines: reaction scope and mechanistic variations

    PubMed Central

    Ghashghaei, Ouldouz; Manna, Consiglia Annamaria; Vicente-García, Esther; Revés, Marc

    2014-01-01

    Summary The interaction of imines with isocyanides has been studied. The main product results from a sequential process involving the attack of two units of isocyanide, under Lewis acid catalysis, upon the carbon–nitrogen double bond of the imine to form the 4-membered ring system. The scope of the reaction regarding the imine and isocyanide ranges has been determined, and also some mechanistic variations and structural features have been described. PMID:24454559

  1. Kinetics of the reaction of hydroxyl radicals with nitric acid

    NASA Technical Reports Server (NTRS)

    Margitan, J. J.; Watson, R. T.

    1982-01-01

    An extensive study was made of the reaction of hydroxyl radicals with nitric acid in a laser photolysis-resonance fluorescence system. A 266 nm laser was used to photolyze HNO3 in the temperature range 225-415 K at pressures of 20-300 torr. A temperature dependence was detected below room temperature, with a leveling off at 298 K and a wide spread in the rate constants. A pressure dependence was observed over the entire range and was more pronounced at lower temperatures. The results are noted to be in agreement with those of previous investigations. However, the wide range of rate constants are suggested to be a problem for stratospheric HO(x) modeling for anthropogenic effects. No explanation could be given of the varying results obtained by other investigators regarding the kinetics of the reactions.

  2. Mechanistic Investigation of Phosphate Ester Bond Cleavages of Glycylphosphoserinyltryptophan Radical Cations under Low-Energy Collision-Induced Dissociation

    NASA Astrophysics Data System (ADS)

    Quan, Quan; Hao, Qiang; Song, Tao; Siu, Chi-Kit; Chu, Ivan K.

    2013-04-01

    Under the conditions of low-energy collision-induced dissociation (CID), the canonical glycylphosphoserinyltryptophan radical cation having its radical located on the side chain of the tryptophan residue ([G p SW]•+) fragments differently from its tautomer with the radical initially generated on the α-carbon atom of the glycine residue ([G• p SW]+). The dissociation of [G• p SW]+ is dominated by the neutral loss of H3PO4 (98 Da), with backbone cleavage forming the [b2 - H]•+/y1 + pair as the minor products. In contrast, for [G p SW]•+, competitive cleavages along the peptide backbone, such as the formation of [G p SW - CO2]•+ and the [c2 + 2H]+/[z1 - H]•+ pair, significantly suppress the loss of neutral H3PO4. In this study, we used density functional theory (DFT) to examine the mechanisms for the tautomerizations of [G• p SW]+ and [G p SW]•+ and their dissociation pathways. Our results suggest that the dissociation reactions of these two peptide radical cations are more efficient than their tautomerizations, as supported by Rice-Ramsperger-Kassel-Marcus (RRKM) modeling. We also propose that the loss of H3PO4 from both of these two radical cationic tautomers is preferentially charge-driven, similar to the analogous dissociations of even-electron protonated peptides. The distonic radical cationic character of [G• p SW]+ results in its charge being more mobile, thereby favoring charge-driven loss of H3PO4; in contrast, radical-driven pathways are more competitive during the CID of [G p SW]•+.

  3. Kinetics of the self reaction of cyclohexyl radicals.

    PubMed

    Loginova, Ksenia A; Knyazev, Vadim D

    2011-08-11

    The kinetics of the self-reaction of cyclohexyl radicals was studied by laser photolysis/photoionization mass spectroscopy. Overall rate constants were obtained in direct real-time experiments in the temperature region 303-520 K and at bath gas (helium with up to 5% of radical precursors) densities (3.00-12.0) × 10(16) molecules cm(-3). Cyclohexyl radicals were produced by a combination of the 193 nm photolysis of oxalyl chloride ((CClO)(2)) with the subsequent fast reaction of Cl atoms with cyclohexane, and their initial concentrations were determined from real-time profiles of HCl. The observed overall c-C(6)H(11) + c-C(6)H(11) rate constants demonstrate negative temperature dependence, which can be described by the following expressions: k(1) = 4.8 × 10(-12) exp(+542 K/T) cm(3) molecule(-1) s(-1), with estimated uncertainty of 16% over the 303-520 K temperature range. The fraction of disproportionation equal to 41 ± 7% was determined at 305 K; analysis of earlier experimental determinations of the disproportionation-to-recombination branching ratio leads to recommending this room-temperature value for other temperatures. The corresponding temperature dependences of the recombination (1a, bicyclohexyl product) and the disproportionation (1b, cyclohexene and cyclohexane products) channels are k(1a) = 2.8 × 10(-12) exp(+542 K/T) and k(1b) = 2.0 × 10(-12) exp(+542 K/T) cm(3) molecule(-1) s(-1), with estimated uncertainties of 20% and 29%, respectively. PMID:21702489

  4. Steric Effects in the Reaction of Aryl Radicals on Surfaces

    SciTech Connect

    Combellas, Catherine; Jiang, Deen; Kanoufi, Frederic; Pinson, Jean; Podvorica, Fetah

    2009-01-01

    Steric effects are investigated in the reaction of aryl radicals with surfaces. The electrochemical reduction of 2-, 3-, 4-methyl, 2-methoxy, 2-ethyl, 2,6-, 2,4-, and 3,5-dimethyl, 4-tert-butyl, 3,5-bis-tert-butyl benzenediazonium, 3,5-bis(trifluoromethyl), and pentafluoro benzenediazonium tetrafluoroborates is examined in acetonitrile solutions. It leads to the formation of grafted layers only if the steric hindrance at the 2- or 2,6-position(s) is small. When the 3,5-positions are crowded with tert-butyl groups, the growth of the organic layer is limited by steric effects and a monolayer is formed. The efficiency of the grafting process is assessed by cyclic voltammetry, X-ray photoelectron spectroscopy, infrared, and ellipsometry. These experiments, together with density functional computations of bonding energies of substituted phenyl groups on a copper surface, are discussed in terms of the reactivity of aryl radicals in the electrografting reaction and in the growth of the polyaryl layer.

  5. Mechanistic studies of the radical S-adenosylmethionine enzyme DesII with TDP-D-fucose.

    PubMed

    Ko, Yeonjin; Ruszczycky, Mark W; Choi, Sei-Hyun; Liu, Hung-wen

    2015-01-12

    DesII is a radical S-adenosylmethionine (SAM) enzyme that catalyzes the C4-deamination of TDP-4-amino-4,6-dideoxyglucose through a C3 radical intermediate. However, if the C4 amino group is replaced with a hydroxy group (to give TDP-quinovose), the hydroxy group at C3 is oxidized to a ketone with no C4-dehydration. It is hypothesized that hyperconjugation between the C4 C-N/O bond and the partially filled p orbital at C3 of the radical intermediate modulates the degree to which elimination competes with dehydrogenation. To investigate this hypothesis, the reaction of DesII with the C4-epimer of TDP-quinovose (TDP-fucose) was examined. The reaction primarily results in the formation of TDP-6-deoxygulose and likely regeneration of TDP-fucose. The remainder of the substrate radical partitions roughly equally between C3-dehydrogenation and C4-dehydration. Thus, changing the stereochemistry at C4 permits a more balanced competition between elimination and dehydrogenation. PMID:25418063

  6. Reaction of Phenyl Radical with O2: Thermodynamic Properties, Important Reaction Paths and Kinetics

    SciTech Connect

    Bozzelli, J; Sebbar, N; Pitz, W; Bockhorn, H

    2001-04-12

    The Phenyl + O{sub 2} association results in a chemically activated phenyl-peroxy radical which can dissociate to phenoxy radical + O, undergo intramolecular addition of the peroxy radical to several unsaturated carbon sites or react back to phenyl + O{sub 2}. The intramolecular addition channels further react through several paths to ring opening (unsaturated + carbonyl moieties) as well as cyclopentadieny radical + CO{sub 2}. Enthalpy ({Delta}H{sub f(298)}{sup o}), Entropy (S{sub 298}), and heat capacities Cp(T) for species in the decomposition of the ring are evaluated using density functional and ab initio calculations and by comparisons to vinyl + O{sub 2} data of Mebel et al, and phenyl + O{sub 2} data of Hadad et al. Isodesmic reaction analysis is used to estimate enthalpy values of the intermediates and well depths of the adducts. High Pressure limit kinetic parameters are obtained from the calculation results using canonical Transition State Theory. Quantum RRK analysis is utilized to obtain k(E) and modified strong collision or master equation analysis is used for evaluation of pressure fall-off in this complex bimolecular, chemical activation, reaction system. Uncertainty in key barriers is discussed, resulting variations in important reaction product ratios are illustrated, and changes in these branching ratios are evaluated with a detailed reaction mechanism.

  7. Mechanisms of free-radical reactions. XX. Reactivity in the free-radical halogenation reactions of arylfluoroalkanes

    SciTech Connect

    Dneprovskii, A.S.; Eliseenkov, E.V.

    1987-09-20

    The free-radical chlorination and bromination of meta- and para-substituted benzyl fluorides and 1,1-difluoro-2-phenylethane and also the chlorination of 1-fluoro-2-arylethanes by phenylchloroiodonium chloride and the bromination of meta- and para-substituted benzyl bromides were studied by the method of competing reactions. In all cases a good correlation is observed between log k/sub rel/ and the Brown sigma/sup +/ constants. In cases where change in the reactivity in the transition from one reaction series to another is due mainly to the polar effect of the substituent while the selectivity is measured in relation to the polar effect direct relationships are observed between the reactivity and the selectivity.

  8. New aspects in the reaction mechanism of phenol with peroxynitrite: the role of phenoxy radicals.

    PubMed

    Daiber, A; Mehl, M; Ullrich, V

    1998-01-01

    The decomposition of peroxynitrite (PON) in aqueous solutions was investigated by monitoring the release of dioxygen as a function of pH together with the various reaction products generated from phenol. This substrate was used as a mechanistic model for tyrosine nitration in prostacyclin synthase for which we have reported a highly efficient nitration and inhibition by PON (Zou, M., Martin, C., and Ullrich, V. (1997) Biol Chem. 378, 707-713). Nitrite as a contaminant and product of PON generated 4-nitrosophenol and some nitrophenols in the acidic pH range. In the alkaline range high amounts of 4-nitrosophenol originated from the disproportionation of PON yielding dioxygen and NOx species. The hydroxylation of phenol occurred between pH 3 and 8 with a maximum at 4.5. The nitration by PON also required a pH between 4 and 8 but had a second maximum between 10 and 12, suggesting that in this pH range phenolate was the reacting species. All isomeric biphenols were found as dimerization products as well as 4-phenoxyphenol (4-hydroxydiphenyl ether), indicating phenoxy radicals as intermediates. Since anisol when incubated under the same conditions yielded only hydroxylation but virtually no nitration products, it was concluded that nitration of phenolic compounds requires a one-electron oxidation as a primary step, followed by addition of the nitrogen dioxide radical. PMID:9851367

  9. Structural and Mechanistic Analysis through Electronic Spectra: Aqueous Hyponitrite Radical (N2O2-) and Nitrosyl Hyponitrite Anion (N3O3-)

    SciTech Connect

    Valiev, Marat; Lymar, Sergei V.

    2011-11-03

    Aqueous hyponitrite radical (N{sub 2}O{sub 2}{sup -}) and nitrosyl hyponitrite anion (N{sub 3}O{sub 3}{sup -}) species are important intermediates in the reductive chemistry of NO. The structures and absorption spectra of various hydrated isomers of these compounds were investigated in this work using high-level quantum mechanical calculations combined with the explicit classical description of the aqueous environment. For N{sub 2}O{sub 2}{sup -}, comparison of the calculated spectra and energetics with the experimental data reveals that: (1) upon the one-electron oxidation of trans-hyponitrite (ON=NO{sub 2}{sup -}), the trans configuration of the resulting ON=NO{sup -} radical is preserved; (2) although cis- and trans-ON=NO{sup -} are energetically nearly equivalent, the barrier for the trans-cis isomerization is prohibitively high due to the partial double character of the NN bond; (3) the UV spectrum of ON=NO{sup -} was misinterpreted in the earlier pulse radiolysis work and its more recent revision has been justified. For the N{sub 3}O{sub 3}{sup -} ion, the symmetric isomer is the dominant observable species, and the asymmetric isomer contributes little to the experimental spectrum. Coherent analysis of the calculated and experimental data suggests a re-interpretation of the N{sub 2}O{sub 2}{sup -} + NO reaction mechanism, according to which the reaction evenly bifurcates to yield both the symmetric and asymmetric isomers of N{sub 3}O{sub 3}{sup -}. While the latter isomer rapidly decomposes to the final NO{sub 2}{sup -} + N{sub 2}O products, the former isomer is stable toward this decomposition but its formation is reversible with the homolysis equilibrium constant Khom = 2.2 - 10{sup -7} M. Collectively, these results demonstrate that advanced theoretical modeling can be of significant benefit in structural and mechanistic analysis of UV spectra.

  10. Parameterization of phosphine ligands reveals mechanistic pathways and predicts reaction outcomes.

    PubMed

    Niemeyer, Zachary L; Milo, Anat; Hickey, David P; Sigman, Matthew S

    2016-06-01

    The mechanistic foundation behind the identity of a phosphine ligand that best promotes a desired reaction outcome is often non-intuitive, and thus has been addressed in numerous experimental and theoretical studies. In this work, multivariate correlations of reaction outcomes using 38 different phosphine ligands were combined with classic potentiometric analyses to study a Suzuki reaction, for which the site selectivity of oxidative addition is highly dependent on the nature of the phosphine. These studies shed light on the generality of hypotheses regarding the structural influence of different classes of phosphine ligands on the reaction mechanism(s), and deliver a methodology that should prove useful in future studies of phosphine ligands. PMID:27219707

  11. The kinetics and mechanism of an aqueous phase isoprene reaction with hydroxy radical

    NASA Astrophysics Data System (ADS)

    Huang, D.; Zhang, X.; Chen, Z. M.; Zhao, Y.; Shen, X. L.

    2011-03-01

    Aqueous phase chemical processes of organic compounds in the atmosphere have received increasing attention, partly due to their potential contribution to the formation of secondary organic aerosol (SOA). Here, we analyzed the aqueous oxidation of isoprene in clouds and its reaction products, including carbonyl compounds and organic acids. We also performed a laboratory simulation to improve our understanding of the kinetics and mechanisms for the products of aqueous isoprene oxidation that are significant precursors of SOA; these included methacrolein (MACR), methyl vinyl ketone (MVK), methyl glyoxal (MG), and glyoxal (GL). We used a novel chemical titration method to monitor the concentration of isoprene in the aqueous phase. We used a box model to interpret the mechanistic differences between aqueous- and gas-phase OH radical-initiated isoprene oxidations. Our results were the first demonstration of the rate constant for the reaction between isoprene and OH radical in water, 3.50 (± 0.98) × 109 M-1 s-1 at 283 K. Molar yields were determined based on consumed isoprene. Of note, the ratio of the yields of MVK (18.9 ± 0.8%) to MACR (9.0 ± 1.1%) in the aqueous phase isoprene oxidation was approximately double that observed for the corresponding gas phase reaction. We hypothesized that this might be explained by a water-induced enhancement in the self-reaction of a hydroxy isoprene peroxyl radical (HOCH2C(CH3)(O2)CH = CH2) produced in the aqueous reaction. The observed yields for MG and GL were 11.4 ± 0.3% and 3.8 ± 0.1%, respectively. Model simulations indicated that several potential pathways may contribute to the formation of MG and GL. Finally, oxalic acid increased steadily throughout the course of the study, even after isoprene was consumed completely. The observed yield of oxalic acid was 26.2 ± 0.8% at 6 h. The observed carbon balance accounted for ~50% of the consumed isoprene. The presence of high-molecular-weight compounds may have accounted for a

  12. The kinetics and mechanism of an aqueous phase isoprene reaction with hydroxyl radical

    NASA Astrophysics Data System (ADS)

    Huang, D.; Zhang, X.; Chen, Z. M.; Zhao, Y.; Shen, X. L.

    2011-08-01

    Aqueous phase chemical processes of organic compounds in the atmosphere have received increasing attention, partly due to their potential contribution to the formation of secondary organic aerosol (SOA). Here, we analyzed the aqueous OH-initiated oxidation of isoprene and its reaction products including carbonyl compounds and organic acids, regarding the acidity and temperature as in-cloudy conditions. We also performed a laboratory simulation to improve our understanding of the kinetics and mechanisms for the products of aqueous isoprene oxidation that are significant precursors of SOA; these included methacrolein (MACR), methyl vinyl ketone (MVK), methyl glyoxal (MG), and glyoxal (GL). We used a novel chemical titration method to monitor the concentration of isoprene in the aqueous phase. We used a box model to interpret the mechanistic differences between aqueous and gas phase OH radical-initiated isoprene oxidations. Our results were the first demonstration of the rate constant for the reaction between isoprene and OH radical in water, 1.2 ± 0.4) × 1010 M-1 s-1 at 283 K. Molar yields were determined based on consumed isoprene. Of note, the ratio of the yields of MVK (24.1 ± 0.8 %) to MACR (10.9 ± 1.1%) in the aqueous phase isoprene oxidation was approximately double that observed for the corresponding gas phase reaction. We hypothesized that this might be explained by a water-induced enhancement in the self-reaction of a hydroxy isoprene peroxyl radical (HOCH2C(CH3)(O2)CH = CH2) produced in the aqueous reaction. The observed yields for MG and GL were 11.4 ± 0.3 % and 3.8 ± 0.1 %, respectively. Model simulations indicated that several potential pathways may contribute to the formation of MG and GL. Finally, oxalic acid increased steadily throughout the course of the study, even after isoprene was consumed completely. The observed yield of oxalic acid was 26.2 ± 0.8 % at 6 h. The observed carbon balance accounted for ~50 % of the consumed isoprene. The

  13. OH Production from Reactions of Organic Peroxy Radicals with HO2 : Recent Studies on Ether-Derived Peroxy Radicals

    NASA Astrophysics Data System (ADS)

    Orlando, J. J.; Tyndall, G. S.; Kegley Owen, C. S.; Reynoldson, N.

    2013-12-01

    There is now ample evidence supporting significant formation of OH radicals in the reaction of HO2 with certain organic peroxy radicals (RO2). These reaction channels serve to promote radical propagation, and thus have the potential to alter HOx budgets and partitioning and hence tropospheric oxidative capacity. While much focus has been placed on OH production from reactions involving carbonyl-containing RO2 species, it is also the case that other oxygen- substituted peroxy species (e.g., CH3OCH2OO, HOCH2OO) likely generate OH in their reactions with HO2 (see ref. 1 and refs therein). In this work, the Cl-atom-initiated oxidation of two ethers, diethyl and diisopropyl ether, is investigated over ranges of conditions in an environmental chamber, using both FTIR and GC-FID methods for product quantification. Preliminary analysis suggests that significant OH production is occurring in the reaction of HO2 with CH3CH2OCH(OO)CH3, and also provides evidence for a rapid unimolecular reaction of diisopropyl ether-derived peroxy radicals. Details of these and other results will be described. 1. Orlando, J. J., and G. S. Tyndall, 2012: Laboratory studies of organic peroxy radical chemistry: an overview with emphasis on recent issues of atmospheric significance, Chemical Society Reviews, 41, 6294-6317, doi: 10.1039/C2CS35166H.

  14. Synthetic and Mechanistic Studies of Strained Heterocycle Opening Reactions Mediated by Zirconium(IV) Imido Complexes

    PubMed Central

    Blum, Suzanne A.; Rivera, Vicki A.; Ruck, Rebecca T.; Michael, Forrest E.; Bergman, Robert G.

    2005-01-01

    The reactions of the bis(cyclopentadienyl)(tert-butylimido)zirconium complex (Cp2Zr=N-t-Bu)(THF) (1) with epoxides, aziridines, and episulfides were investigated. Heterocycles without accessible β-hydrogens undergo insertion/protonation of the C–X bond to produce 1,2-amino alcohols (X = O) and 1,2-diamines (X = NR), whereas heterocycles with accessible β-hydrogens undergo elimination/protonation to produce allylic alcohols (X = O) and allylic sulfides (X = S). Mechanistic investigations support a stepwise pathway with zwitterionic intermediates for the first reaction class and a concerted pathway for the second reaction class. Additionally, the feasibility of chirality transfer from the planar-chiral ebthi (ebthi = ethylenebis(tetrahydroindenyl)) ligand was demonstrated with a chiral analogue, (ebthi)-Zr=NAr(THF) (Ar = 2,6-dimethylphenyl), 2, through the diastereoselective ring opening of meso epoxides. PMID:16508693

  15. Kinetic studies of the hydroxyl radical reaction with PAHs

    NASA Astrophysics Data System (ADS)

    Ananthula, Rajeshwar

    An existing quartz optical reactor heating system was designed to permit higher temperature kinetic measurements more closely associated with post-combuston conditions (up to 1200 K). A pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique was then applied with this modified reactor to study the OH radical kinetics with polycyclic aromatic hydrocarbons (PAHs). The kinetics of the reaction of a surrogate three-ring PAH, anthracene (and its deuterated form) with hydroxyl (OH) radicals was investigated over the temperature range of 373 to 1200 K. This study represents the first examination of the OH kinetics for this class of reactions at elevated temperatures (>470 K). The results indicate a complex temperature dependence similar to that observed for simpler aromatic compounds, e.g., benzene. At low temperatures (373-498 K), the rate measurements exhibited Arrhenius behavior (1.82 x 10-11 exp(542.35/T) in units of cm3 molecule -1 s-1) and kinetic isotope effect (KIE) measurements were consistent with an OH addition mechanism. The low temperature results are extrapolated to atmospheric temperatures and compared with previous measurements. Rate measurements between 673 and 923 K exhibited a sharp decrease in the magnitude of the rate coefficients (a factor of 9). KIE measurements under these conditions were still consistent with an OH addition mechanism. The following modified Arrhenius equation is the best fit to our anthracene measurements between 373 and 923 K, 8.17 x 1014 T-8.3 exp(-3171.71/T) (in units of cm3 molecule-1 s-1). For a limited temperature range between 1000 and 1200 K, the rate measurements exhibited an apparent positive temperature dependence with the following Arrhenius equation the best fit to the data, 2.18 x 10-11*exp(-1734.11/T) (in units of cm3molecule-1s -1). KIE measurements above 999 K were slightly larger than unity, but inclusive regarding the mechanism of the reaction. Theoretical calculations of the KIE indicate

  16. Reactions of flavosemiquinone radicals in the presence of metal ions

    NASA Astrophysics Data System (ADS)

    Porkhun, V. I.; Sivko, A. N.; Porkhun, E. V.; Rakhimov, A. I.

    2014-06-01

    The rate constants of disproportionation of flavosemiquinone radicals were obtained by pulsed spectroscopy. The yield of the flavosemiquinone radical increased when Mohr's salt was introduced in the aqueous solutions of riboflavin. The spectral kinetic characteristics of complexes of flavosemiquinone radical anions with Zn2+ and Cd2+ ions were determined.

  17. Medium effects on reactions of the carbonate radical with thiocyanate, iodide, and ferrocyanide ions

    NASA Astrophysics Data System (ADS)

    Lymar, Sergei V.; Schwarz, Harold A.; Czapski, Gidon

    2000-10-01

    Results are presented which show that there is no pH dependence of the carbonate radical reactivity toward SCN -, I -, and Fe(CN) 64- above pH 8.5. It is demonstrated that observations in the literature on these reactions which have been interpreted to show a p Ka of 9.5 for the carbonate radical, in disagreement with other reports that the radical is not protonated in this pH region, can be explained by the medium effects. It is also shown that previous studies of the reaction between carbonate radical and thiocyanate are in error, and the mechanism of this reaction is elucidated.

  18. Electron Spin Resonance Spectroscopic Studies of Radical Cation Reactions.

    NASA Astrophysics Data System (ADS)

    Dai, Sheng

    1990-01-01

    A spin Hamiltonian suitable for theoretical analyses of ESR spectra in this work is derived by using the general effective Hamiltonian theory in the usual Schrodinger representation. The Permutation Indices method is extended to obtain the dynamic exchange equations used in ESR lineshape simulation. The correlation between beta-hydrogen coupling constants and their geometric orientations is derived through the use of a perturbation method. The three electron bond model is extended to rationalize unimolecular rearrangements of radical cations. The ring-closed radical cations of 9,10-octalin oxide and syn-sesquinorbornene oxide have been characterized by ESR spectroscopy in the CFCl_3 matrix at low temperature. The ESR spectra of the former radical cation exhibit a novel alternating linewidth effect arising from an internal relation between the coupling constants for the four equivalent pairs of hydrogens. The self-electron-transfer rate constants between the methyl viologen dication and cation have been determined by dynamic ESR lineshape simulations at room temperature in allyl alcohol, water, methanol and propargyl alcohol solvents. The radical cation formed by the radiolytic oxidation of allylamine in Freon matrices at 77 K is shown to be the 3-iminiopropyl distonic species(3-iminium-1-propyl radical) resulting from a symmetry-allowed 1,2-hydrogen shift in the parent radical cation. The nucleophilic endocyclization of the but-3-en-1-ol radical cation to the protonated tetrahydrofuran -3-yl radical was observed in the radiolytic oxidation of but-3-en-1-ol in Freon matrices. ESR studies of the radiolytic oxidation of 1,5-hexadiyne have resulted in the first spectroscopic characterization of the radical cation Cope rearrangement, the 1,5-hexadiyne radical cation isomerizing to the 1,2,4,5 -hexatetraene radical cation. ESR studies show that the symmetric(C_{rm 2v}) bicyclo (3.3.0) -octa-2,6-diene-4,8-diyl(a bridged 1,4 -bishomobenzene species) radical cation is

  19. Reaction of oleic acid particles with NO3 radicals: Products, mechanism, and implications for radical-initiated organic aerosol oxidation.

    PubMed

    Docherty, Kenneth S; Ziemann, Paul J

    2006-03-16

    The heterogeneous reaction of liquid oleic acid aerosol particles with NO3 radicals in the presence of NO2, N2O5, and O2 was investigated in an environmental chamber using a combination of on-line and off-line mass spectrometric techniques. The results indicate that the major reaction products, which are all carboxylic acids, consist of hydroxy nitrates, carbonyl nitrates, dinitrates, hydroxydinitrates, and possibly more highly nitrated products. The key intermediate in the reaction is the nitrooxyalkylperoxy radical, which is formed by the addition of NO3 to the carbon-carbon double bond and subsequent addition of O2. The nitrooxyalkylperoxy radicals undergo self-reactions to form hydroxy nitrates and carbonyl nitrates, and may also react with NO2 to form nitrooxy peroxynitrates. The latter compounds are unstable and decompose to carbonyl nitrates and dinitrates. It is noteworthy that in this reaction nitrooxyalkoxy radicals appear not to be formed, as indicated by the absence of the expected products of decomposition or isomerization of these species. This is different from gas-phase alkene-NO3 reactions, in which a large fraction of the products are formed through these pathways. The results may indicate that, for liquid organic aerosol particles in low NOx environments, the major products of the radical-initiated oxidation (including by OH radicals) of unsaturated and saturated organic compounds will be substituted forms of the parent compound rather than smaller decomposition products. These compounds will remain in the particle and can potentially enhance particle hygroscopicity and the ability of particles to act as cloud condensation nuclei. PMID:16526637

  20. Mechanistic studies of an unprecedented enzyme-catalyzed 1,2-phosphono migration reaction

    PubMed Central

    Chang, Wei-chen; Dey, Mishtu; Liu, Pinghua; Mansoorabadi, Steven O.; Moon, Sung-Ju; Zhao, Zongbao K.; Drennan, Catherine L.; Liu, Hung-wen

    2013-01-01

    (S)-2-Hydroxypropylphosphonate ((S)-2-HPP) epoxidase (HppE) is a mononuclear non-heme iron-dependent enzyme1,2,3 responsible for the last step in the biosynthesis of the clinically useful antibiotic fosfomycin4. Enzymes of this class typically catalyze oxygenation reactions that proceed via the formation of substrate radical intermediates. In contrast, HppE catalyzes an unusual dehydrogenation reaction while converting the secondary alcohol of (S)-2-HPP to the epoxide ring of fosfomycin1,5. HppE is shown here to also catalyze a biologically unprecedented 1,2-phosphono migration with the alternative substrate (R)-1-HPP. This transformation likely involves an intermediary carbocation based on observations with additional substrate analogues, such as (1R)-1-hydroxy-2-aminopropylphosphonate, and model reactions for both radical- and carbocation-mediated migration. The ability of HppE to catalyze distinct reactions depending on the regio- and stereochemical properties of the substrate is given a structural basis using X-ray crystallography. These results provide compelling evidence for the formation of a substrate-derived cation intermediate in the catalytic cycle of a mononuclear non-heme iron-dependent enzyme. The underlying chemistry of this unusual phosphono migration may represent a new paradigm for the in vivo construction of phosphonate-containing natural products that can be exploited for the preparation of novel phosphonate derivatives. PMID:23552950

  1. Selective Radical-Radical Cross-Couplings: Design of a Formal β-Mannich Reaction.

    PubMed

    Jeffrey, Jenna L; Petronijević, Filip R; MacMillan, David W C

    2015-07-01

    A direct β-coupling of cyclic ketones with imines has been accomplished via the synergistic combination of photoredox catalysis and organocatalysis. Transient β-enaminyl radicals derived from ketones via enamine and oxidative photoredox catalysis readily combine with persistent α-amino radicals in a highly selective hetero radical-radical coupling. This novel pathway to γ-aminoketones is predicated upon the use of DABCO as both a base and an electron transfer agent. This protocol also formally allows for the direct synthesis of β-Mannich products via a chemoselective three-component coupling of aryl aldehydes, amines, and ketones. PMID:26075347

  2. Isomerization and decomposition reactions in the pyrolysis of branched hydrocarbons: 4-methyl-1-pentyl radical.

    PubMed

    McGivern, W Sean; Awan, Iftikhar A; Tsang, Wing; Manion, Jeffrey A

    2008-07-31

    The kinetics of the decomposition of 4-methyl-1-pentyl radicals have been studied from 927-1068 K at pressures of 1.78-2.44 bar using a single pulse shock tube with product analysis. The reactant radicals were formed from the thermal C-I bond fission of 1-iodo-4-methylpentane, and a radical inhibitor was used to prevent interference from bimolecular reactions. 4-Methyl-1-pentyl radicals undergo competing decomposition and isomerization reactions via beta-bond scission and 1, x-hydrogen migrations (x = 4, 5), respectively, to form short-chain radicals and alkenes. Major alkene products, in decreasing order of concentration, were propene, ethene, isobutene, and 1-pentene. The observed products are used to validate a RRKM/master equation (ME) chemical kinetics model of the pyrolysis. The presence of the branched methyl moiety has a significant impact on the observed reaction rates relative to analogous reaction rates in straight-chain radical systems. Systems that result in the formation of substituted radical or alkene products are found to be faster than reactions that form primary radical and alkene species. Pressure-dependent reaction rate constants from the RRKM/ME analysis are provided for all four H-transfer isomers at 500-1900 K and 0.1-1000 bar pressure for all of the decomposition and isomerization reactions in this system. PMID:18613654

  3. Detection of free radicals produced from the reaction of cytochrome P-450 with linoleic acid hydroperoxide.

    PubMed Central

    Rota, C; Barr, D P; Martin, M V; Guengerich, F P; Tomasi, A; Mason, R P

    1997-01-01

    The ESR spin-trapping technique was employed to investigate the reaction of rabbit cytochrome P-450 1A2 (P450) with linoleic acid hydroperoxide. This system was compared with chemical systems where FeSO4 or FeCl3 was used in place of P450. The spin trap 5, 5'-dimethyl-1-pyrroline N-oxide (DMPO) was employed to detect and identify radical species. The DMPO adducts of hydroxyl, O2-., peroxyl, methyl and acyl radicals were detected in the P450 system. The reaction did not require NADPH-cytochrome P-450 reductase or NADPH. The same DMPO-radical adducts were detected in the FeSO4 system. Only DMPO-.OH radical adduct and carbon-centred radical adducts were detected in the FeCl3 system. Peroxyl radical production was completely O2-dependent. We propose that polyunsaturated fatty acids are initially reduced to form alkoxyl radicals, which then undergo intramolecular rearrangement to form epoxyalkyl radicals. Each epoxyalkyl radical reacts with O2, forming a peroxyl radical. Subsequent unimolecular decomposition of this peroxyl radical eliminates O2-. radical. PMID:9371716

  4. Reactions of Hydroxyalkyl Radicals with Cysteinyl Peptides in a NanoESI Plume

    NASA Astrophysics Data System (ADS)

    Stinson, Craig A.; Xia, Yu

    2014-07-01

    In biological systems, carbon-centered small molecule radicals are primarily formed via external radiation or internal radical reactions. These radical species can react with a variety of biomolecules, most notably nucleic acids, the consequence of which has possible links to gene mutation and cancer. Sulfur-containing peptides and proteins are reactive toward a variety of radical species and many of them behave as radical scavengers. In this study, the reactions between alkyl alcohol carbon-centered radicals (e.g., •CH2OH for methanol) and cysteinyl peptides within a nanoelectrospray ionization (nanoESI) plume were explored. The reaction system involved ultraviolet (UV) irradiation of a nanoESI plume using a low pressure mercury lamp consisting of 185 and 254 nm emission bands. The alkyl alcohol was added as solvent into the nanoESI solution and served as the precursor of hydroxyalkyl radicals upon UV irradiation. The hydroxyalkyl radicals subsequently reacted with cysteinyl peptides either containing a disulfide linkage or free thiol, which led to the formation of peptide- S-hydroxyalkyl product. This radical reaction coupled with subsequent MS/MS was shown to have analytical potential by cleaving intrachain disulfide linked peptides prior to CID to enhance sequence information. Tandem mass spectrometry via collision-induced dissociation (CID), stable isotope labeling, and accurate mass measurement were employed to verify the identities of the reaction products.

  5. Palladium(0)/NHC-Catalyzed Reductive Heck Reaction of Enones: A Detailed Mechanistic Study.

    PubMed

    Raoufmoghaddam, Saeed; Mannathan, Subramaniyan; Minnaard, Adriaan J; de Vries, Johannes G; Reek, Joost N H

    2015-12-14

    We have studied the mechanism of the palladium-catalyzed reductive Heck reaction of para-substituted enones with 4-iodoanisole by using N,N-diisopropylethylamine (DIPEA) as the reductant. Kinetic studies and in situ spectroscopic analysis have provided a detailed insight into the reaction. Progress kinetic analysis demonstrated that neither catalyst decomposition nor product inhibition occurred during the catalysis. The reaction is first order in the palladium and aryl iodide, and zero order in the activated alkene, N-heterocyclic carbene (NHC) ligand, and DIPEA. The experiments with deuterated solvent ([D7]DMF) and deuterated base ([D15]Et3N) supported the role of the amine as a reductant in the reaction. The palladium complex [Pd(0)(NHC)(1)] has been identified as the resting state. The kinetic experiments by stopped-flow UV/Vis also revealed that the presence of the second substrate, benzylideneacetone 1, slows down the oxidative addition of 4-iodoanisole through its competing coordination to the palladium center. The kinetic and mechanistic studies indicated that the oxidative addition of the aryl iodide is the rate-determining step. Various scenarios for the oxidative addition step have been analyzed by using DFT calculations (bp86/def2-TZVP) that supported the inhibiting effect of substrate 1 by formation of resting state [Pd(0)(NHC)(1)] species at the cost of further increase in the energy barrier of the oxidative addition step. PMID:26561034

  6. Structural and Mechanistic Analysis through Electronic Spectra: Aqueous Hyponitrite Radical (N(2)O(2)(-)) and Nitrosyl Hyponitrite Anion (N(3)O(3)(-))

    SciTech Connect

    Lymar S. V.; Valiev M.

    2011-11-03

    Aqueous hyponitrite radical (N{sub 2}O{sub 2}{sup -}) and nitrosyl hyponitrite anion (N{sub 3}O{sub 3}{sup -}) are important intermediates in the reductive chemistry of NO. The structures and absorption spectra of various hydrated isomers of these compounds were investigated in this work using high-level quantum mechanical calculations combined with the explicit classical description of the aqueous environment. For N{sub 2}O{sub 2}{sup -}, comparison of the calculated spectra and energetics with the experimental data reveals that (1) upon the one-electron oxidation of trans-hyponitrite (ON{double_bond}NO{sup 2-}), the trans configuration of the resulting ON{double_bond}NO{sup -} radical is preserved; (2) although cis- and trans-ON{double_bond}NO{sup -} are energetically nearly equivalent, the barrier for the trans-cis isomerization is prohibitively high because of the partial double character of the NN bond; (3) the calculations confirm that the UV spectrum of ONNO{sup -} was misinterpreted in the earlier pulse radiolysis work, and its more recent revision has been justified. For the N{sub 3}O{sub 3}{sup -} ion, the symmetric isomer the dominant observable species, and the asymmetric isomer contributes insignificantly to the experimental spectrum. Coherent analysis of the calculated and experimental data suggests a reinterpretation of the N{sub 2}O{sub 2}{sup -} + NO reaction mechanism according to which the reaction evenly bifurcates to yield both the symmetric and asymmetric isomers of N{sub 3}O{sub 3}{sup -}. While the latter isomer rapidly decomposes to the final NO{sub 2}{sup -} + N{sub 2}O products, the former isomer is stable toward this decomposition, but its formation is reversible with the homolysis equilibrium constant K{sub hom} = 2.2 x 10{sup -7} M. Collectively, these results demonstrate that advanced theoretical modeling can be of significant benefit in structural and mechanistic analysis on the basis of the electronic spectra of aqueous transients.

  7. Laboratory studies of the kinetics of tropospheric and stratospheric atom and radical reactions

    NASA Technical Reports Server (NTRS)

    Golde, Michael F.

    1987-01-01

    Direct measurements of reaction rate constants and branching fractions for elementary reactions necessary in the modeling of the troposphere or stratosphere are provided. Details of reaction mechanisms are elucidated by studying pressure and temperature dependences of reactions, as well as by use of isotopic labels. Measurement techniques are improved for radical species in the laboratory. Progress and results in each area are given.

  8. Quantum trajectory tests of radical-pair quantum dynamics in CIDNP measurements of photosynthetic reaction centers

    NASA Astrophysics Data System (ADS)

    Tsampourakis, K.; Kominis, I. K.

    2015-11-01

    Chemically induced dynamic nuclear polarization is a ubiquitous phenomenon in photosynthetic reaction centers. The relevant nuclear spin observables are a direct manifestation of the radical-pair mechanism. We here use quantum trajectories to describe the time evolution of radical-pairs, and compare their prediction of nuclear spin observables to the one derived from the radical-pair master equation. While our approach provides a consistent description, we unravel a major inconsistency within the conventional theory, thus challenging the theoretical interpretation of numerous CIDNP experiments sensitive to radical-pair reaction kinetics.

  9. Radical-based destruction of nitramines in water: kinetics and efficiencies of hydroxyl radical and hydrated electron reactions.

    PubMed

    Mezyk, Stephen P; Razavi, Behnaz; Swancutt, Katy L; Cox, Casandra R; Kiddle, James J

    2012-08-01

    In support of the potential use of advanced oxidation and reduction process technologies for the removal of carcinogenic nitro-containing compounds in water reaction rate constants for the hydroxyl radical and hydrated electron with a series of low molecular weight nitramines (R(1)R(2)-NNO(2)) have been determined using a combination of electron pulse radiolysis and transient absorption spectroscopy. The hydroxyl radical reaction rate constant was fast, ranging from 0.54-4.35 × 10(9) M(-1) s(-1), and seen to increase with increasing complexity of the nitramine alkyl substituents suggesting that oxidation primarily occurs by hydrogen atom abstraction from the alkyl chains. In contrast, the rate constant for hydrated electron reaction was effectively independent of compound structure, (k(av) = (1.87 ± 0.25) × 10(10) M(-1) s(-1)) indicating that the reduction predominately occurred at the common nitramine moiety. Concomitant steady-state irradiation and product measurements under aerated conditions also showed a radical reaction efficiency dependence on compound structure, with the overall radical-based degradation becoming constant for nitramines containing more than four methylene groups. The quantitative evaluation of these efficiency data suggest that some (~40%) hydrated electron reduction also results in quantitative nitramine destruction, in contrast to previously reported electron paramagnetic measurements on these compounds that proposed that this reduction only produced a transient anion adduct that would transfer its excess electron to regenerate the parent molecule. PMID:22788844

  10. Helical-Peptide-Catalyzed Enantioselective Michael Addition Reactions and Their Mechanistic Insights.

    PubMed

    Ueda, Atsushi; Umeno, Tomohiro; Doi, Mitsunobu; Akagawa, Kengo; Kudo, Kazuaki; Tanaka, Masakazu

    2016-08-01

    Helical peptide foldamer catalyzed Michael addition reactions of nitroalkane or dialkyl malonate to α,β-unsaturated ketones are reported along with the mechanistic considerations of the enantio-induction. A wide variety of α,β-unsaturated ketones, including β-aryl, β-alkyl enones, and cyclic enones, were found to be catalyzed by the helical peptide to give Michael adducts with high enantioselectivities (up to 99%). On the basis of X-ray crystallographic analysis and depsipeptide study, the amide protons, N(2)-H and N(3)-H, at the N terminus in the α-helical peptide catalyst were crucial for activating Michael donors, while the N-terminal primary amine activated Michael acceptors through the formation of iminium ion intermediates. PMID:27384597

  11. Reactions of Co(III)-nitrosyl complexes with superoxide and their mechanistic insights.

    PubMed

    Kumar, Pankaj; Lee, Yong-Min; Park, Young Jun; Siegler, Maxime A; Karlin, Kenneth D; Nam, Wonwoo

    2015-04-01

    New Co(III)-nitrosyl complexes bearing N-tetramethylated cyclam (TMC) ligands, [(12-TMC)Co(III)(NO)](2+) (1) and [(13-TMC)Co(III)(NO)](2+) (2), were synthesized via [(TMC)Co(II)(CH3CN)](2+) + NO(g) reactions. Spectroscopic and structural characterization showed that these compounds bind the nitrosyl moiety in a bent end-on fashion. Complexes 1 and 2 reacted with KO2/2.2.2-cryptand to produce [(12-TMC)Co(II)(NO2)](+) (3) and [(13-TMC)Co(II)(NO2)](+) (4), respectively; these possess O,O'-chelated nitrito ligands. Mechanistic studies using (18)O-labeled superoxide ((18)O2(•-)) showed that one O atom in the nitrito ligand is derived from superoxide and the O2 produced comes from the other superoxide O atom. Evidence supporting the formation of a Co-peroxynitrite intermediate is also presented. PMID:25793706

  12. Free radicals. XXIII. Reaction of triphenylimidazolyl with CH acids

    SciTech Connect

    Tanaseichuk, B.S.; Belozerov, A.I.; Sanaeva, E.P.; Butin, K.P.

    1986-01-10

    The triphenylimidazolyl radical is capable of dehydrogenating ..beta..-dicarbonyl compounds which are characterized by a high content of the enolic form. The dehydrogenation rate increases with increase in the pK/sub a/ value of the enol. The formation of short-lived radicals during the dehydrogenation of CH acids by triphenylimidazolyl was confirmed by their capture by a spin trap (2,4,6-tribromo-nitrosobenzene). The diphenylaminyl radical also dehydrogenates nonenolizing CH acids with a sufficiently acid CH bond.

  13. An electron spin resonance study of the reactions of lipid peroxyl radicals with antioxidants

    SciTech Connect

    Zhu, J.; Johnson, W.J.; Sevilla, C.L.; Herrington, J.W.; Sevilla, M.D. )

    1990-09-06

    The reactions of lipid carbon-centered radicals and their corresponding peroxyl radicals (RO{sub 2}{sup {sm bullet}}, LO{sub 2}{sup {sm bullet}}) with five phenolic antioxidants (BHT, BHA, PG, TBHQ, and vitamin E) in frozen saturated and unsaturated lipids at low temperatures have been elucidated through electron spin resonance spectroscopy. The lipid radicals are formed after the {gamma} or UV irradiation of the lipid matrices in the absence or presence of oxygen at 77 K. Upon warming oxygenated samples to 135 K, molecular oxygen adds to the carbon radicals forming peroxyl radicals. At 170 K peroxyl radicals in tributyrin react with added antioxidants (AH) to form antioxidant radicals (A{sup {sm bullet}}). The relative rates of reactions of these five antioxidants with the peroxyl radical of tributyrin decrease in the order BHT > TBHQ > E {>=} PG > BHA. For the reactions with triolein and trilinolein peroxyl radicals, the order of reactivity is BHT > E > BHA > TBHQ. This difference in reaction order of antioxidants in tributyrin and unsaturated lipids is explained by a dispersion model of antioxidants in lipid matrices.

  14. Dynamic Kinetic Resolution Enabled by Intramolecular Benzoin Reaction: Synthetic Applications and Mechanistic Insights.

    PubMed

    Zhang, Guoxiang; Yang, Shuang; Zhang, Xiaoyan; Lin, Qiqiao; Das, Deb K; Liu, Jian; Fang, Xinqiang

    2016-06-29

    The highly enantio-, diastereo-, and regioselective dynamic kinetic resolution of β-ketoesters and 1,3-diketones was achieved via a chiral N-heterocyclic carbene catalyzed intramolecular cross-benzoin reaction. A variety of tetralone derivatives bearing two contiguous stereocenters and multiple functionalities were liberated in moderate to excellent yields and with high levels of stereoselectivity (>95% ee and >20:1 dr in most cases). In addition, the excellent regioselectivity control for aryl/alkyl 1,3-diketones, and the superior electronic differentiation of 1,3-diarylketones were highlighted. Moreover, a set of new mechanistic rationale that differs with the currently widely accepted understanding of intramolecular benzoin reactions was established to demonstrate the superior preference of benzoin over aldol transformation: (1) A coexistence of competitive aldol and benzoin reactions was detected, but a retro-aldol-irreversible benzoin process performs a vital role in the generation of predominant benzoin products. (2) The most essential role of an N-electron-withdrawing substituent in triazolium catalysts was revealed to be accelerating the rate of the benzoin transformation, rather than suppressing the aldol process through reducing the inherent basicity of the catalyst. PMID:27270409

  15. Vibrational Excitation of Both Products of the Reaction of CN Radicals with Acetone in Solution

    PubMed Central

    2015-01-01

    Transient electronic and vibrational absorption spectroscopy unravel the mechanisms and dynamics of bimolecular reactions of CN radicals with acetone in deuterated chloroform solutions. The CN radicals are produced by ultrafast ultraviolet photolysis of dissolved ICN. Two reactive forms of CN radicals are distinguished by their electronic absorption bands: “free” (uncomplexed) CN radicals, and “solvated” CN radicals that are complexed with solvent molecules. The lifetimes of the free CN radicals are limited to a few picoseconds following their photolytic production because of geminate recombination to ICN and INC, complexation with CDCl3 molecules, and reaction with acetone. The acetone reaction occurs with a rate coefficient of (8.0 ± 0.5) × 1010 M–1 s–1 and transient vibrational spectra in the C=N and C=O stretching regions reveal that both the nascent HCN and 2-oxopropyl (CH3C(O)CH2) radical products are vibrationally excited. The rate coefficient for the reaction of solvated CN with acetone is 40 times slower than for free CN, with a rate coefficient of (2.0 ± 0.9) × 109 M–1 s–1 obtained from the rise in the HCN product v1(C=N stretch) IR absorption band. Evidence is also presented for CN complexes with acetone that are more strongly bound than the CN–CDCl3 complexes because of CN interactions with the carbonyl group. The rates of reactions of these more strongly associated radicals are slower still. PMID:26192334

  16. Vibrational Excitation of Both Products of the Reaction of CN Radicals with Acetone in Solution.

    PubMed

    Dunning, Greg T; Preston, Thomas J; Greaves, Stuart J; Greetham, Gregory M; Clark, Ian P; Orr-Ewing, Andrew J

    2015-12-17

    Transient electronic and vibrational absorption spectroscopy unravel the mechanisms and dynamics of bimolecular reactions of CN radicals with acetone in deuterated chloroform solutions. The CN radicals are produced by ultrafast ultraviolet photolysis of dissolved ICN. Two reactive forms of CN radicals are distinguished by their electronic absorption bands: "free" (uncomplexed) CN radicals, and "solvated" CN radicals that are complexed with solvent molecules. The lifetimes of the free CN radicals are limited to a few picoseconds following their photolytic production because of geminate recombination to ICN and INC, complexation with CDCl3 molecules, and reaction with acetone. The acetone reaction occurs with a rate coefficient of (8.0 ± 0.5) × 10(10) M(-1) s(-1) and transient vibrational spectra in the C═N and C═O stretching regions reveal that both the nascent HCN and 2-oxopropyl (CH3C(O)CH2) radical products are vibrationally excited. The rate coefficient for the reaction of solvated CN with acetone is 40 times slower than for free CN, with a rate coefficient of (2.0 ± 0.9) × 10(9) M(-1) s(-1) obtained from the rise in the HCN product v1(C═N stretch) IR absorption band. Evidence is also presented for CN complexes with acetone that are more strongly bound than the CN-CDCl3 complexes because of CN interactions with the carbonyl group. The rates of reactions of these more strongly associated radicals are slower still. PMID:26192334

  17. Time-resolved FTIR emission studies of laser photofragmentation and radical reactions

    SciTech Connect

    Leone, S.R.

    1993-12-01

    Recent studies have focused specifically on collision processes, such as single collision energy transfer, reaction dynamics, and radical reactions. The authors employ novel FTIR techniques in the study of single collision energy transfer processes using translationally fast H atom, as well as radical-radical reactions, e.g. CH{sub 3} + O, CF{sub 3} + H(D), and Cl + C{sub 2}H{sub 5}. The fast atoms permit unique high energy regions of certain transition states of combustion species to be probed for the first time.

  18. Exploiting time-resolved magnetic field effects for determining radical ion reaction rates

    NASA Astrophysics Data System (ADS)

    Bessmertnykh, A. O.; Borovkov, V. I.; Bagryansky, V. A.; Molin, Yu N.

    2016-07-01

    The capabilities of the method of time-resolved magnetic field effect in determining the rates of charge transfer reactions between radical ions and molecules on a nanosecond time scale have been investigated. The approach relies on the electron spin coherence in radical pair's partners generated by ionizing radiation. The spin evolution of the pair is sensitive to the reaction since the latter results in changing magnetic interactions of the unpaired electron. This process can be monitored by magnetic-field-sensitive fluorescence from an irradiated sample that is illustrated using reactions involving alkane radical cations. The accuracy and limitations of the approach are discussed.

  19. Comparing the gas-phase fragmentation reactions of protonated and radical cations of the tripeptides GXR

    NASA Astrophysics Data System (ADS)

    Wee, Sheena; O'Hair, Richard A. J.; McFadyen, W. David

    2004-05-01

    Electrospray ionization (ESI) mass spectrometry of methanolic solutions of mixtures of the copper salt (2,2':6',2''-terpyridine)copper(II) nitrate monohydrate ([Cu(II)(tpy)(NO3)2].H2O) and a tripeptide GXR (where X = 1 of the 20 naturally occurring amino acids) yielded [Cu(II)(tpy)(GXR)][radical sign]2+ ions, which were then subjected to collision induced dissociation (CID). In all but one case (GRR), these [Cu(II)(tpy)(GXR)][radical sign]2+ ions fragment to form odd electron GXR[radical sign]+ radical cations with sufficient abundance to examine their gas-phase fragmentation reactions. The GXR[radical sign]+ radical cations undergo a diverse range of fragmentation reactions which depend on the nature of the side chain of X. Many of these reactions can be rationalized as arising from the intermediacy of isomeric distonic ions in which the charge (i.e. proton) is sequestered by the highly basic arginine side chain and the radical site is located at various positions on the tripeptide including the peptide back bone and side chains. The radical sites in these distonic ions often direct the fragmentation reactions via the expulsion of small radicals (to yield even electron ions) or small neutrals (to form radical cations). Both classes of reaction can yield useful structural information, allowing for example, distinction between leucine and isoleucine residues. The gas-phase fragmentation reactions of the GXR[radical sign]+ radical cations are also compared to their even electron [GXR+H]+ and [GXR+2H]2+ counterparts. The [GXR+H]+ ions give fewer sequence ions and more small molecule losses while the [GXR+2H]2+ ions yield more sequence information, consistent with the [`]mobile proton model' described in previous studies. In general, all three classes of ions give complementary structural information, but the GXR[radical sign]+ radical cations exhibit a more diverse loss of small species (radicals and neutrals). Finally, links between these gas-phase results and key

  20. Kinetic analysis of free-radical reactions in the low-temperature autoxidation of triglycerides

    SciTech Connect

    Zhu, Jingmin; Sevilla, M.D. )

    1990-02-22

    The kinetics of the low-temperature autoxidation of triglycerides has been investigated by electron spin resonance spectroscopy. After initial radical production, four reaction stages are found in the overall autoxidation of unsaturated lipids: (1) formation of peroxyl radicals by addition of molecular oxygen to the initial carbon radicals, (2) consumption of oxygen in the autoxidation cycle, (3) decay of the lipid peroxyl radical into allylic and pentadienyl radicals, and (4) recombination of the carbon-centered radicals. Peroxyl radical decay in saturated lipids follows second-order kinetics with an apparent activation energy of ca. 50 kJ/mol. The authors find that, for polyunsaturated lipids, even at quite low temperatures (120 K), the autoxidation process occurs readily and must be considered in the storage of biological samples.

  1. Reactions of methyl radicals with silica supported silver nanoparticles in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Zidki, Tomer; Hänel, Andreas; Bar-Ziv, Ronen

    2016-07-01

    Silica supported silver nanoparticles (Ag°-SiO2-NCs, NCs=nanocomposites) suspended in aqueous solutions are efficient catalysts for the dimerization of methyl radicals to produce ethane, while bare silica is quite inert towards the interaction with methyl radicals. In the presence of small amounts of ethanol adsorbed on the SiO2 surface, the reaction path with methyl radicals is changed and methane is formed as the major product.

  2. Radical cascade reaction of alkynes with N-fluoroarylsulfonimides and alcohols.

    PubMed

    Zheng, Guangfan; Li, Yan; Han, Jingjie; Xiong, Tao; Zhang, Qian

    2015-01-01

    Cascade reactions initiated by radical addition to alkynes are synthetically very attractive because they enable access to highly complex molecular skeletons in only few synthetic steps under usually mild conditions. Here we report a general radical cascade reaction of alkynes, N-fluoroarylsulfonimides and alcohols, enabling the efficient synthesis of important α-amino-α-aryl ketones from readily available starting materials via a single operation. During this process, the highly regioselective nitrogen-centred radical addition to internal and terminal alkynes generating vinyl radicals and the next explicit migration of aryl group from the nitrogen source lead the following efficient desulfonylation, oxygenation, and semi-pinacol rearrangement. In addition, the semi-pinacol rearrangement precursors, α-alkyloxyl-α,α-diaryl imines, could also be efficiently obtained under milder conditions. This methodology might open a new entry for designing intermolecular radical cascade reaction of alkynes. PMID:25901840

  3. Coherent chemical kinetics as quantum walks. I. Reaction operators for radical pairs

    NASA Astrophysics Data System (ADS)

    Chia, A.; Tan, K. C.; Pawela, Ł.; Kurzyński, P.; Paterek, T.; Kaszlikowski, D.

    2016-03-01

    Classical chemical kinetics uses rate-equation models to describe how a reaction proceeds in time. Such models are sufficient for describing state transitions in a reaction where coherences between different states do not arise, in other words, a reaction that contains only incoherent transitions. A prominent example of a reaction containing coherent transitions is the radical-pair model. The kinetics of such reactions is defined by the so-called reaction operator that determines the radical-pair state as a function of intermediate transition rates. We argue that the well-known concept of quantum walks from quantum information theory is a natural and apt framework for describing multisite chemical reactions. By composing Kraus maps that act only on two sites at a time, we show how the quantum-walk formalism can be applied to derive a reaction operator for the standard avian radical-pair reaction. Our reaction operator predicts the same recombination dephasing rate as the conventional Haberkorn model, which is consistent with recent experiments [K. Maeda et al., J. Chem. Phys. 139, 234309 (2013), 10.1063/1.4844355], in contrast to previous work by Jones and Hore [J. A. Jones and P. J. Hore, Chem. Phys. Lett. 488, 90 (2010), 10.1016/j.cplett.2010.01.063]. The standard radical-pair reaction has conventionally been described by either a normalized density operator incorporating both the radical pair and reaction products or a trace-decreasing density operator that considers only the radical pair. We demonstrate a density operator that is both normalized and refers only to radical-pair states. Generalizations to include additional dephasing processes and an arbitrary number of sites are also discussed.

  4. EFFECTS OF RING STRAIN ON GAS-PHASE RATE CONSTANTS. 2. OH RADICAL REACTIONS WITH CYCLOALKENES

    EPA Science Inventory

    Relative rate constants for the gas phase reactions of OH radicals with a series of cycloalkenes have been determined at 298 + or - 2 K, using methyl nitrite photolysis in air as a source of OH radicals. The data show that the rate constants for the nonconjugated cycloalkenes stu...

  5. Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins.

    PubMed

    Crossley, Steven W M; Obradors, Carla; Martinez, Ruben M; Shenvi, Ryan A

    2016-08-10

    Cofactor-mimetic aerobic oxidation has conceptually merged with catalysis of syngas reactions to form a wide range of Markovnikov-selective olefin radical hydrofunctionalizations. We cover the development of the field and review contributions to reaction invention, mechanism, and application to complex molecule synthesis. We also provide a mechanistic framework for understanding this compendium of radical reactions. PMID:27461578

  6. Restricted mass transport effects on free radical reactions

    NASA Astrophysics Data System (ADS)

    Buchanan, A. C., III; Britt, P. F.; Thomas, K. B.

    Coal possesses a complex chemical and physical structure. The cross-linked, network structure can lead to alterations in normal thermally-induced, free-radical decay pathways as a consequence of restrictions on mass transport. Moreover, in coal liquefaction, access of an external hydrogen donor to a reactive radical site can be hindered by the substantial domains of microporosity present in coals. However, previous work indicates that diffusion effects do not appear to be playing an important role in this coal conversion chemistry. Several possible explanations for this phenomenon were advanced including the potential involvement of a hydrogen hopping/radical relay mechanism recently discovered model systems in the authors' laboratories. The authors have employed silica-anchored compounds to explore the effects of restricted mass transport on the pyrolysis mechanisms of coal model compounds. In studies of two-component systems, cases have been discovered where radical centers can be rapidly relocated in the diffusionally constrained environment as a consequence of rapid serial hydrogen atom transfers. This chemistry can have substantial effects on thermal decomposition rates and on product selectivities. In this study, the authors examine additional surfaces to systematically investigate the impact of molecular structure on the hydrogen atom transfer promoted radical relay mechanism. Silica-attached 1,3-diphenylpropane (approximately Ph(CH2)3Ph, or approximately DPP) was chosen as the thermally reactive component, since it can be considered prototypical of linkages in coal that do not contain weak bonds easily cleaved at coal liquefaction temperatures (ca. 4000 C), but which crack at reasonable rates if benzylic radicals can be generated by hydrogen abstraction. The rate of such hydrogen transfers under restricted diffusion will be highly dependent on the structure and proximity of neighboring molecules.

  7. Radical Coupling Reactions in Lignin Synthesis: A Density Functional Theory Study

    SciTech Connect

    Sangha, A. K.; Parks, J. M.; Standaert, R. F.; Ziebell, A.; Davis, M.; Smith, J. C.

    2012-04-26

    Lignin is a complex, heterogeneous polymer in plant cell walls that provides mechanical strength to the plant stem and confers resistance to degrading microbes, enzymes, and chemicals. Lignin synthesis initiates through oxidative radical-radical coupling of monolignols, the most common of which are p-coumaryl, coniferyl, and sinapyl alcohols. Here, we use density functional theory to characterize radical-radical coupling reactions involved in monolignol dimerization. We compute reaction enthalpies for the initial self- and cross-coupling reactions of these monolignol radicals to form dimeric intermediates via six major linkages observed in natural lignin. The 8-O-4, 8-8, and 8-5 coupling are computed to be the most favorable, whereas the 5-O-4, 5-5, and 8-1 linkages are less favorable. Overall, p-coumaryl self- and cross-coupling reactions are calculated to be the most favorable. For cross-coupling reactions, in which each radical can couple via either of the two sites involved in dimer formation, the more reactive of the two radicals is found to undergo coupling at its site with the highest spin density.

  8. Reaction mechanisms of secondary and tertiary amines with OH and NO3 radicals

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Emissions of aliphatic amines are common near agricultural facilities such as animal feed lots. Determining the reactions of these amines with common atmospheric radicals is important to understanding both daytime and nighttime atmospheric chemistry. Several smog chamber experiments were conducted ...

  9. Structure and reactions of cation-radicals of esters in freon matrices

    SciTech Connect

    Belevskii, V.N.; Belopushkin, S.I.; Fel'dman, V.I.

    1987-11-01

    In CFCl/sub 3/ matrices the cation-radicals of methyl and ethyl formates, formed in ..gamma..-irradiated solutions, at 77 K efficiently undergo intramolecular H atom transfer to form the secondary cation-radicals HC(OH)OCH/sub 2/CH/sub 2/ and DC(OH)OCD/sub 2/CH/sub 2/. This process does not occur in the deuteroformate cation-radical DCOOCH/sub 2/CD/sub 3//sup +./, which is observed in the ESR spectra in different conformations, depending on the temperature. Ion-molecule reactions involving cation-radicals are indicated

  10. Free radical reactions and antioxidant activities of sesamol: pulse radiolytic and biochemical studies.

    PubMed

    Joshi, Ravi; Kumar, M Sudheer; Satyamoorthy, K; Unnikrisnan, M K; Mukherjee, Tulsi

    2005-04-01

    Sesamol (from Sesamum indicum) is a dietary compound, which is soluble in aqueous as well as lipid phases. Free radical scavenging reactions of sesamol, 5-hydroxy-1,3-benzodioxole, have been studied using a nanosecond pulse radiolysis technique. Sesamol efficiently scavenges hydroxyl, one-electron oxidizing, organo-haloperoxyl, lipid peroxyl, and tryptophanyl radicals. Its antioxidant activity has also been evaluated with cyclic voltammetry. In biochemical studies, it has been found to inhibit lipid peroxidation, hydroxyl radical-induced deoxyribose degradation, and DNA cleavage. These antioxidant and free radical scavenging activities of sesamol have been reported in the paper. PMID:15796613

  11. Organic radicals for the enhancement of oxygen reduction reaction in Li-O2 batteries.

    PubMed

    Tesio, A Y; Blasi, D; Olivares-Marín, M; Ratera, I; Tonti, D; Veciana, J

    2015-12-25

    We examine for the first time the ability of inert carbon free-radicals as soluble redox mediators to catalyze and enhance the oxygen reduction reaction in a (TEGDME)-based electrolyte. We demonstrate that the tris(2,4,6-trichlorophenyl)methyl (TTM) radical is capable of chemically favoring the oxygen reduction reaction improving significantly the Li-O2 battery performance. PMID:26488114

  12. Cascade Reaction of Donor-Acceptor Cyclopropanes: Mechanistic Studies on Cycloadditions with Nitrosoarenes and cis-Diazenes.

    PubMed

    Chidley, Tristan; Vemula, Naresh; Carson, Cheryl A; Kerr, Michael A; Pagenkopf, Brian L

    2016-06-17

    Tandem ring opening, elimination, and cycloaddition of donor-acceptor cyclopropanes were observed in Yb(OTf)3-catalyzed cycloaddition with nitrosoarenes. The reaction results in formation of tetrahydro-1,2-oxazine instead of the normal cycloadduct isoxazolidine via in situ nitrone formation. A similar cascade sequence was observed with cis-diazines. Mechanistic studies on this unique transformation offer an entirely new approach for reaction design with donor-acceptor cyclopropanes. PMID:27267360

  13. PRODUCTS OF THE GAS-PHASE REACTIONS OF THE OH RADICAL WITH N-BUTYL METHYL ETHER AND 2-ISOPROPOXYETHANOL: REACTIONS OF ROC(O)< RADICALS. (R825252)

    EPA Science Inventory

    The products of the gas-phase reactions of the OH radical with n-butyl methyl ether and 2-isopropoxyethanol in the presence of NO have been investigated at 298 ? 2 K and 740 Torr total pressure of air by gas chromatography and in situ atmospheric pressure ionization...

  14. Reaction of diethyl maleate and diethyl fumarate with hydrated electrons and hydroxyl radicals

    NASA Astrophysics Data System (ADS)

    Bíró, Á.; Wojnárovits, L.

    1996-03-01

    In dilute aqueous solution diethyl maleate (DEM) and diethyl fumarate (DEF) scavenge hydrated electrons with a rate constant of 2.2·10 10 mol -1 dm 3 s -1. DEM - reversibly protonates with pK a = 5.2. The pK a of DEF - is below 4. The electron adducts decay in second order reactions. The OH radicals add to the double bonds with 5.9·10 9 mol -1 dm 3 s -1. In the reaction α-carboxyalkyl radicals are produced. In disproportionation of radicals oxalacetic acid ethylester forms that in alkaline solution leads to strong permanent absorbency in the UV.

  15. Effects of electron acceptors and radical scavengers on nonchain radical nucleophilic substitution reactions

    SciTech Connect

    Xianman Zhang; Dilun Yang; Youcheng Liu )

    1993-01-01

    The yields of reaction products from thermal nucleophilic substitution reactions in dimethyl sulfoxide (DMSO) of six o- and p-nitrohalobenzenes with the sodium salt of ethyl [alpha]-cyanoacetate carbanion [Na[sup +][sup [minus

  16. Thermochemistry and reaction paths in the oxidation reaction of benzoyl radical: C6H5C•(═O).

    PubMed

    Sebbar, Nadia; Bozzelli, Joseph W; Bockhorn, Henning

    2011-10-27

    Alkyl substituted aromatics are present in fuels and in the environment because they are major intermediates in the oxidation or combustion of gasoline, jet, and other engine fuels. The major reaction pathways for oxidation of this class of molecules is through loss of a benzyl hydrogen atom on the alkyl group via abstraction reactions. One of the major intermediates in the combustion and atmospheric oxidation of the benzyl radicals is benzaldehyde, which rapidly loses the weakly bound aldehydic hydrogen to form a resonance stabilized benzoyl radical (C6H5C(•)═O). A detailed study of the thermochemistry of intermediates and the oxidation reaction paths of the benzoyl radical with dioxygen is presented in this study. Structures and enthalpies of formation for important stable species, intermediate radicals, and transition state structures resulting from the benzoyl radical +O2 association reaction are reported along with reaction paths and barriers. Enthalpies, ΔfH298(0), are calculated using ab initio (G3MP2B3) and density functional (DFT at B3LYP/6-311G(d,p)) calculations, group additivity (GA), and literature data. Bond energies on the benzoyl and benzoyl-peroxy systems are also reported and compared to hydrocarbon systems. The reaction of benzoyl with O2 has a number of low energy reaction channels that are not currently considered in either atmospheric chemistry or combustion models. The reaction paths include exothermic, chain branching reactions to a number of unsaturated oxygenated hydrocarbon intermediates along with formation of CO2. The initial reaction of the C6H5C(•)═O radical with O2 forms a chemically activated benzoyl peroxy radical with 37 kcal mol(-1) internal energy; this is significantly more energy than the 21 kcal mol(-1) involved in the benzyl or allyl + O2 systems. This deeper well results in a number of chemical activation reaction paths, leading to highly exothermic reactions to phenoxy radical + CO2 products. PMID:21942384

  17. Time-resolved infrared absorption studies of the dynamics of radical reactions.

    SciTech Connect

    Macdonald, R. G.

    2008-01-01

    There is very little information available about the dynamics of radical+radical interactions. These processes are important in combustion being chain termination steps as well as generating new molecular species. To study these processes, a new experimental apparatus has been constructed to investigate radical-radical dynamics. The first radical or atomic species is produced with a known concentration in a microwave discharge flow system. The second is produced by pulsed laser photolysis of a suitable photolyte. The time dependence of individual rovibrational states of the product is followed by absorption of a continuous infrared laser. This approach will allow the reaction of interest to be differentiated from other radical reactions occurring simultaneously. The experimental approach is highly versatile, being able to detect a number of molecular species of particular interest to combustion processes such as water, methane, acetylene etc. at the state specific level. State specific infrared absorption coefficients of radicals can be measured in situ allowing for the determination of the absolute concentrations and hence branching ratios for reactions having multiple reaction pathways.

  18. Thermochemistry and Kinetic Analysis of the Unimolecular Oxiranyl Radical Dissociation Reaction: A Theoretical Study.

    PubMed

    Wang, Heng; Bozzelli, Joseph W

    2016-07-01

    Oxirane structures are important in organic synthesis, and they are important initial products in the oxidation reactions of alkyl radicals. The thermochemical properties (enthalpy of formation, entropy, and heat capacity) for the reaction steps of the unimolecular oxiranyl radical dissociation reaction are determined and compared with the available literature. The overall ring opening and subsequent steps involve four types of reactions: β-scission ring opening, intramolecular hydrogen transfer, β-scission hydrogen elimination, and β-scission methyl radical elimination. The enthalpies of formation of the transition states are determined and evaluated using six popular Density Functional Theory (DFT) calculation methods (B3LYP, B2PLYP, M06, M06-2X, ωB97X, ωB97XD), each combined with three different basis sets. The DFT enthalpy values are compared with five composite calculation methods (G3, G4, CBS-QB3, CBS-APNO, W1U), and by CCSD(T)/aug-cc-pVTZ. Kinetic parameters are determined versus pressure and temperature for the unimolecular dissociation pathways of an oxiranyl radical, which include the chemical activation reactions of the ring-opened oxiranyl radical relative to the ring-opening barrier. Multifrequency quantum Rice Ramsperger Kassel (QRRK) analysis is used to determine k(E) with master equation analysis for falloff. The major overall reaction pathway at lower combustion temperatures is oxiranyl radical dissociation to a methyl radical and carbon monoxide. Oxiranyl radical dissociation to a ketene and hydrogen atom is the key reaction path above 700 K. PMID:26990491

  19. Mechanistic study of copper-catalyzed aerobic oxidative coupling of arylboronic esters and methanol: insights into an organometallic oxidase reaction.

    PubMed

    King, Amanda E; Brunold, Thomas C; Stahl, Shannon S

    2009-04-15

    Copper-catalyzed aerobic oxidative coupling of arylboronic acid derivatives and heteroatom nucleophiles is a highly useful method for the formation of aryl-heteroatom bonds. Mechanistic studies reveal that this reaction proceeds via an "oxidase"-style mechanism. Kinetic and spectroscopic studies establish that transmetalation of the aryl group from boron to Cu(II) is the turnover-limiting step and reoxidation of the reduced catalyst by O(2) is rapid. Further mechanistic analysis implicates the involvement of an aryl-copper(III) intermediate that undergoes facile C-O bond formation. PMID:19309072

  20. Free Radical Reactions in Aqueous Solutions: Examples from Advanced Oxidation Processes for Wastewater from the Chemistry in Airborne Water Droplets

    NASA Astrophysics Data System (ADS)

    Baird, N. Colin

    1997-07-01

    Inorganic chemistry involving free radicals in aqueous solutions can be important in environmental processes. A common free radical reaction in aqueous solution is electron transfer, especially to the hydroxyl radical and to ozone. Hydrogen peroxide and free radicals related to it act as weak acids, so both their neutral and deprotonated forms must be considered in reactions. In Advanced Oxidation Processes, the hydroxyl radical concentration in water is greatly increased by reactions involving ozone and/or ultraviolet light. Irradiation of solid titanium dioxide can also be used to generate the radicals. The hydroxyl radicals are used in the Processes to initiate the oxidation of dissolved organic pollutants. Free radical reactions also play an important role in the chemistry of water droplets suspended in air in clouds and fogs. The radicals arise indirectly from the photoionization of dissolved organic compounds such as aldehydes and from the iron-catalyzed decomposition of dissolved hydrogen peroxide. They oxidize dissolved sulfur dioxide and certain organic compounds.

  1. Desaturase reactions complicate the use of norcarane as a mechanistic probe. Unraveling the mixture of twenty-plus products formed in enzyme-catalyzed oxidations of norcarane.

    PubMed

    Newcomb, Martin; Chandrasena, R Esala P; Lansakara-P, Dharmika S P; Kim, Hye-Yeong; Lippard, Stephen J; Beauvais, Laurance G; Murray, Leslie J; Izzo, Viviana; Hollenberg, Paul F; Coon, Minor J

    2007-02-16

    Norcarane, bicyclo[4.1.0]heptane, has been widely used as a mechanistic probe in studies of oxidations catalyzed by several iron-containing enzymes. We report here that, in addition to oxygenated products, norcarane is also oxidized by iron-containing enzymes in desaturase reactions that give 2-norcarene and 3-norcarene. Furthermore, secondary products from further oxidation reactions of the norcarenes are produced in yields that are comparable to those of the minor products from oxidation of the norcarane. We studied oxidations catalyzed by a representative spectrum of iron-containing enzymes including four cytochrome P450 enzymes, CYP2B1, CYPDelta2B4, CYPDelta2E1, and CYPDelta2E1 T303A, and three diiron enzymes, soluble methane monooxygenase (sMMO) from Methylococcus capsulatus (Bath), toluene monooxygenase (ToMO) from Pseudomonas stutzeri OX1, and phenol hydroxylase (PH) from Pseudomonas stutzeri OX1. 2-Norcarene and 3-norcarene and their oxidation products were found in all reaction mixtures, accounting for up to half of the oxidation products in some cases. In total, more than 20 oxidation products were identified from the enzyme-catalyzed reactions of norcarane. The putative radical-derived product from the oxidation of norcarane, 3-hydroxymethylcyclohexene (21), and the putative cation-derived product from the oxidation of norcarane, cyclohept-3-enol (22), coelute with other oxidation products on low-polarity GC columns. The yields of product 21 found in this study are smaller than those previously reported for the same or similar enzymes in studies where the products from norcarene oxidations were ignored, and therefore, the limiting values for lifetimes of radical intermediates produced in the enzyme-catalyzed oxidation reactions are shorter than those previously reported. PMID:17288366

  2. Radical-neutral chemical reactions studied at low temperature with VUV synchrotron photoionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Soorkia, Satchin; Leone, Stephen R.; Wilson, Kevin R.

    2012-11-01

    A pulsed Laval nozzle apparatus employing tunable VUV synchrotron photoionization and quadrupole mass spectrometry for the study of radical-neutral chemical reactions of importance for modeling the atmosphere of Titan and the outer planets is described. The apparatus enables the study of low-temperature kinetics and isomer-resolved product branching of highly reactive radicals with unsaturated hydrocarbons reactions. The low-temperature branching ratio for the reaction of the ethynyl radical (C2H) with allene (C3H4) has been measured for the first time at 79 K. This reaction is found to yield 1,4-pentadiyne as the major reaction product (50+10%), followed by ethynylallene (28+10%) and methyldiacetylene (22+10%) via H-atom elimination from the initially formed C5H5 adduct. The derived branching ratios can be directly used to predict the chemical evolution of Titan's atmosphere.

  3. Kinetic and Mechanistic Studies of Carbon-to-Metal Hydrogen Atom Transfer Involving Os-Centered Radicals: Evidence for Tunneling

    SciTech Connect

    Lewandowska-Androlojc, Anna; Grills, David C.; Zhang, Jie; Bullock, R. Morris; Miyazawa, Akira; Kawanishi, Yuji; Fujita, Etsuko

    2014-03-05

    We have investigated the kinetics of novel carbon-to-metal hydrogen atom transfer reactions, in which homolytic cleavage of a C-H bond is accomplished by a single metal-centered radical. Studies by means of time-resolved IR spectroscopic measurements revealed efficient hydrogen atom transfer from xanthene, 9,10-dihydroanthracene and 1,4-cyclohexadiene to Cp(CO)2Os• and (n5-iPr4C5H)(CO)2Os• radicals, formed by photoinduced homolysis of the corresponding osmium dimers. The rate constants for hydrogen abstraction from these hydrocarbons were found to be in the range 1.54 × 105 M 1 s 1 -1.73 × 107 M 1 s-1 at 25 °C. For the first time, kinetic isotope effects for carbon-to-metal hydrogen atom transfer were determined. Large primary kinetic isotope effects of 13.4 ± 1.0 and 16.6 ± 1.4 were observed for the hydrogen abstraction from xanthene to form Cp(CO)2OsH and (n5-iPr4C5H)(CO)2OsH, respectively, at 25 °C. Temperature-dependent measurements of the kinetic isotope effects over a 60 -C temperature range were carried out to obtain the difference in activation energies and the pre-exponential factor ratio. For hydrogen atom transfer from xanthene to (n5-iPr4C5H)(CO)2Os•, the (ED - EH) = 3.25 ± 0.20 kcal/mol and AH/AD = 0.056 ± 0.018 values are greater than the semi-classical limits and thus suggest a quantum mechanical tunneling mechanism. The work at BNL was carried out under contract DE-AC02-98CH10886 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Geosciences & Biosciences, Office of Basic Energy Sciences. RMB also thanks the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences for support. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  4. Reactions of a persistent phosphinyl radical/diphosphine with heteroallenes.

    PubMed

    Giffin, Nick A; Hendsbee, Arthur D; Masuda, Jason D

    2016-08-01

    The persistent phosphinyl radical, (H2C)2(NDipp)2P˙, formed upon dissolution from the homolytic cleavage of the P-P bond in the diphosphane [(H2C)2(NDipp)2P]2, was reacted with carbon disulfide, phenyl isocyanate, and phenyl isothiocyanate. The phosphinyl fragments add across the C[double bond, length as m-dash]S or C[double bond, length as m-dash]O double bond to give neutral, diamagnetic species. PMID:27443569

  5. Electron transfer reactions within zeolites: Radical cation from benzonorbornadiene

    SciTech Connect

    Pitchumani, K.; Ramamurthy, V.; Corbin, D.R.

    1996-08-28

    Zeolites are being used as solid acid catalysts in a number of commercial processes. Occasionally zeolites are also reported to perform as electron transfer agents. Recently, we observed that radical cations of certain olefins and thiophene oligomers can be generated spontaneously within ZSM-5 zeolites. We noticed that these radical cations generated from diphenyl polyenes and thiophene oligomers were remarkably stable (at room temperature) within ZSM-5 and can be characterized spectroscopically at leisure. We have initiated a program on electron transfer processes within large pore zeolites. The basis of this approach is that once a cation radical is generated within a large pore zeolite, it will have sufficient room to undergo a molecular transformation. Our aim is to identify a condition under which electron transfer can be routinely and reliably carried out within large pore zeolites such as faujasites. To our great surprise, when benzonorbornadiene A and a number of olefins were included in divalent cation exchanged faujasites. they were transformed into products very quickly (<15 min). This observation allowed us to explore the use of zeolites as oxidants. Results of our studies on benzonorbornadiene are presented in this communication. 16 refs., 1 fig.

  6. Novel reactions of one-electron oxidized radicals of selenomethionine in comparison with methionine.

    PubMed

    Mishra, B; Sharma, A; Naumov, S; Priyadarsini, K I

    2009-05-28

    Pulse radiolysis studies on hydroxyl (*OH) radical reactions of selenomethionine (SeM), a selenium analogue of methionine, were carried out, and the resultant transient radical cations and their subsequent reactions have been reported. At pH<3, the >Se*-OH radical adducts produced on reaction of SeM with *OH radical were converted to selenium centered radical cations (Se*+M), which react with another molecule of SeM to form dimer radical cation M(Se therefore Se)M+. At pH 7, the >Se*-OH radical adducts were converted to a monomer radical of the type (Se therefore N)M+ that acquires intramolecular stability through interaction with the lone pair of the N atom and this radical is denoted as SeM*+. SeM*+ decayed by first order kinetics, and the reduction potential of the couple SeM*+/SeM was determined to be 1.21+/-0.05 V vs NHE at pH 7. SeM*+ oxidized ABTS2- and TMPD with rate constants of (2.5+/-0.1)x10(8) and (6.1+/-0.2)x10(8) M(-1) s(-1), respectively, and reacted with hydroxide ion with a rate constant of (3.8+/-0.9)x10(5) M(-1) s(-1). SeM*+ reacts with molecular oxygen, and the rate constant for this reaction was determined to be (4.3+/-0.2)x10(8) M(-1) s(-1); similar reaction with methionine could not be observed experimentally. Like methionine radical cations, SeM*+ undergoes decarboxylation, although with lesser yield, to produce reducing 3-methyl-selenopropyl amino radicals (referred as alpha-amino radicals). The formation of these radicals was confirmed both by the estimation of the liberated CO2 and by one-electron reduction of MV2+, thionine, and PNAP. These results have been supported by quantum chemical calculations. Implications of these results in the biological role of SeM have also been briefly discussed. PMID:19408939

  7. Carbon–sulfur bond-forming reaction catalysed by the radical SAM enzyme HydE

    NASA Astrophysics Data System (ADS)

    Rohac, Roman; Amara, Patricia; Benjdia, Alhosna; Martin, Lydie; Ruffié, Pauline; Favier, Adrien; Berteau, Olivier; Mouesca, Jean-Marie; Fontecilla-Camps, Juan C.; Nicolet, Yvain

    2016-05-01

    Carbon–sulfur bond formation at aliphatic positions is a challenging reaction that is performed efficiently by radical S-adenosyl-L-methionine (SAM) enzymes. Here we report that 1,3-thiazolidines can act as ligands and substrates for the radical SAM enzyme HydE, which is involved in the assembly of the active site of [FeFe]-hydrogenase. Using X-ray crystallography, in vitro assays and NMR spectroscopy we identified a radical-based reaction mechanism that is best described as the formation of a C-centred radical that concomitantly attacks the sulfur atom of a thioether. To the best of our knowledge, this is the first example of a radical SAM enzyme that reacts directly on a sulfur atom instead of abstracting a hydrogen atom. Using theoretical calculations based on our high-resolution structures we followed the evolution of the electronic structure from SAM through to the formation of S-adenosyl-L-cysteine. Our results suggest that, at least in this case, the widely proposed and highly reactive 5‧-deoxyadenosyl radical species that triggers the reaction in radical SAM enzymes is not an isolable intermediate.

  8. Carbon-sulfur bond-forming reaction catalysed by the radical SAM enzyme HydE.

    PubMed

    Rohac, Roman; Amara, Patricia; Benjdia, Alhosna; Martin, Lydie; Ruffié, Pauline; Favier, Adrien; Berteau, Olivier; Mouesca, Jean-Marie; Fontecilla-Camps, Juan C; Nicolet, Yvain

    2016-05-01

    Carbon-sulfur bond formation at aliphatic positions is a challenging reaction that is performed efficiently by radical S-adenosyl-L-methionine (SAM) enzymes. Here we report that 1,3-thiazolidines can act as ligands and substrates for the radical SAM enzyme HydE, which is involved in the assembly of the active site of [FeFe]-hydrogenase. Using X-ray crystallography, in vitro assays and NMR spectroscopy we identified a radical-based reaction mechanism that is best described as the formation of a C-centred radical that concomitantly attacks the sulfur atom of a thioether. To the best of our knowledge, this is the first example of a radical SAM enzyme that reacts directly on a sulfur atom instead of abstracting a hydrogen atom. Using theoretical calculations based on our high-resolution structures we followed the evolution of the electronic structure from SAM through to the formation of S-adenosyl-L-cysteine. Our results suggest that, at least in this case, the widely proposed and highly reactive 5'-deoxyadenosyl radical species that triggers the reaction in radical SAM enzymes is not an isolable intermediate. PMID:27102684

  9. Formation of radical-anions and radicals in the reaction of sodium sulfide with aromatic halogen compounds

    SciTech Connect

    Annenkova, V.Z.; Antonik, L.M.; Vakul'skaya, T.I.; Voronkov, M.G.

    1986-03-20

    The ESR and UV spectroscopic methods were used to establish the mechanism of the substitution of a chlorine atom by sulfide sulfur in the reactions of 2,5-dichloro-nitrobenzene (i) and p-dichlorobenzene (II) with sodium sulfide in N-methyl-2-pyrrolidone. The S/sub 2//sup -./ and S/sub 3//sup -./ radical-anions were detected and identified. The former corresponds to a narrow singlet with a g factor of 2.005 (lambdamax 440 nm), while the latter corresponds to a broad ESR signal with a g value of 2.028 (lambdamax 618 nm) (1-3). The formation of the radical-anion of the reagent gave grounds for supposing that the reaction of (I) and (II) with sodium sulfide takes place through a one-electron transfer stage. Thus, a stable radical-anion characterized by hyperfine structure (hfs) (3/sub N/ x 2/sub H/ x 3/sub H/ x 3/sub H/ with constants of 11.6, 3.7, 3.5, and 0.7 Oe respectively) is formed in the nitrobenzene-sodium sulfide system.

  10. Reaction of chlorine radical with tetrahydrofuran: a theoretical investigation on mechanism and reactivity in gas phase.

    PubMed

    Begum, Samiyara; Subramanian, Ranga

    2014-06-01

    Reaction of chlorine (Cl) radical with heterocyclic saturated ether, tetrahydrofuran has been studied. The detailed reactivity and mechanism of this reaction is analyzed using hybrid density functional theory (DFT), B3LYP and BB1K methods, and aug-cc-pVTZ basis set. To explore the mechanism of the reaction of tetrahydrofuran with Cl radical, four possible sites of hydrogen atom (H) abstraction pathways in tetrahydrofuran were analyzed. The barrier height and rate constants are calculated for the four H-abstraction channels. The BB1K calculated rate constant for α-axial H-abstraction is comparable with the experimentally determined rate constant. It reflects that α-axial H-abstraction is the main degradation pathway of tetrahydrofuran with Cl radical. DFT-based reactivity descriptors are also calculated and these values describe α-axial H-abstraction as the main reaction channel. PMID:24867438

  11. Theoretical study on the mechanism and kinetics of acetaldehyde and hydroperoxyl radical: An important atmospheric reaction

    NASA Astrophysics Data System (ADS)

    Farnia, Solaleh; Vahedpour, Morteza; Abedi, Mostafa; Farrokhpour, Hossein

    2013-09-01

    A systematic theoretical study was performed on the mechanism and kinetics of the atmospheric reaction of acetaldehyde (CH3CHO) and hydroperoxyl radical (HO2) in the gas phase. The DFT-B3LYP/6-311++G(3df,3pd) and CCSD(T)/6-311++G(d,p) methods were employed for calculations. Based on the calculations, this reaction leads to four different products through radical addition and hydrogen abstraction mechanisms which are very important in atmospheric and combustion chemistry. The favorable reaction paths begin with α-hydroxyethylperoxy radical, CH3CH(OO)OH, in a exothermic process and finally leads to the product P1 (CH3COOH + OH). The overall rate constants for favorite reaction paths have been calculated at different temperatures (200-2500 K).

  12. Formation of environmentally persistent free radicals from the heterogeneous reaction of ozone and polycyclic aromatic compounds.

    PubMed

    Borrowman, Cuyler K; Zhou, Shouming; Burrow, Timothy E; Abbatt, Jonathan P D

    2016-01-01

    In the 1980s long-lived radical species were identified in cigarette tar. Since then, environmentally persistent free radicals (EPFRs) have been observed in ambient particulate matter, and have been generated in particulate matter generated from internal combustion engines. For the first time, we measure in situ the formation and decay of EPFRs through the heterogeneous reaction of ozone and several polycyclic aromatic compounds (PAC). Solid anthracene (ANT), pyrene (PY), benzo[a]pyrene (BAP), benzo[ghi]perylene (BGHIP), 1,4-naphthoquinone (1,4NQ), and 9,10-anthraquinone (AQ) were reacted with gas-phase ozone in a flow system placed in the active cavity of an electron paramagnetic resonance (EPR) spectrometer, and the formation of radicals was measured on the timescale of tens of minutes at ambient levels of ozone down to 30 ppb. For most substrates the net radical production is initially rapid, slows at intermediate times, and is followed by a slow decay. For oxidized solid BAP, radical signal persists for many days in the absence of ozone. To evaluate the effect of substrate phase, the solid PAHs were also dissolved in squalane, an organic oil inert to ozone, which yielded a much higher maximum radical concentration and faster radical decay when exposed to ozone. With higher mobility, reactants were apparently able to more easily diffuse and react with each other, yielding the higher radical concentrations. The EPR spectra exhibit three radicals types, two of which have been assigned to semiquinone species and one to a PAH-derived, carbon-centered radical. Although our system uses levels of PAC not typically found in the environment it is worth noting that the amounts of radical formed, on the order of 10(18) radicals per g, are comparable to those observed in ambient particulate matter. PMID:26603953

  13. Direct Observation of Sulfur Radicals as Reaction Media in lithium Sulfur Batteries

    SciTech Connect

    Wang, Qiang; Zheng, Jianming; Walter, Eric D.; Pan, Huilin; Lu, Dongping; Zuo, Pengjian; Chen, Honghao; Deng, Zhiqun; Liaw, Bor Yann; Yu, Xiqian; Yang, Xiaoning; Zhang, Jiguang; Liu, Jun; Xiao, Jie

    2014-12-09

    Lithium sulfur (Li-S) battery has been regaining tremendous interest in recent years because of its attractive attributes such as high gravimetric energy, low cost and environmental benignity. However, it is still not conclusively known how polysulfide ring/chain participates in the whole cycling and whether the discharge and charge process follow the same pathway. Herein, we demonstrate the direct observation of sulfur radicals by using in situ electron paramagnetic resonance (EPR) technique. Based on the concentration changes of sulfur radicals at different potentials, it is revealed that the chemical and electrochemical reactions in Li-S cell are driven each other to proceed through sulfur radicals, leading to two completely different reaction pathways during discharge and charge. The proposed radical mechanism may provide new insights to investigate the interactions between sulfur species and the electrolyte, inspiring novel strategies to develop Li-S battery technology.

  14. Direct Observation of Sulfur Radicals as Reaction Media in Lithium Sulfur Batteries

    DOE PAGESBeta

    Wang, Qiang; Zheng, Jianming; Walter, Eric; Pan, Huilin; Lv, Dongping; Zuo, Pengjian; Chen, Honghao; Deng, Z. D.; Liaw, Bor Y.; Yu, Xiqian; et al

    2015-01-09

    Lithium sulfur (Li-S) battery has been regaining tremendous interest in recent years because of its attractive attributes such as high gravimetric energy, low cost and environmental benignity. However, it is still not conclusively known how polysulfide ring/chain participates in the whole cycling and whether the discharge and charge processes follow the same pathway. Herein, we demonstrate the direct observation of sulfur radicals by using in situ electron paramagnetic resonance (EPR) technique. Based on the concentration changes of sulfur radicals at different potentials and the electrochemical characteristics of the cell, it is revealed that the chemical and electrochemical reactions in Li-Smore » cell are driving each other to proceed through sulfur radicals, leading to two completely different reaction pathways during discharge and charge. The proposed radical mechanism may provide new perspectives to investigate the interactions between sulfur species and the electrolyte, inspiring novel strategies to develop Li-S battery technology.« less

  15. Rate constants for the reactions of free radicals with oxygen in solution

    SciTech Connect

    Maillard, B.; Ingold, K.U.; Scaiano, J.C.

    1983-07-27

    The kinetics of the rections of several free radicals with oxygen have been examined in solution at 300 K using laser flash photolysis techniques. The reactions of resonance-stabilized radicals are only slightly slower than those of nonstabilized radicals: for example, for tert-butyl (in cyclohexane), 4.93 x 10/sup 9/; benzyl, 2.36 x 10/sup 9/ (in cyclohexane); cyclohexadienyl (in benzene), 1.64 x 10/sup 9/ M/sup -1/ s/sup -1/. The reaction of butyl-tin (n-Bu/sub 3/Sn.) radicals is unusually fast (7.5 x 10/sup 9/ M/sup -1/ s/sup -1/), a fact that has been tentatively attributed to a relaxation of spin selection rules due to heavy atom effects. 1 table.

  16. Direct Observation of Sulfur Radicals as Reaction Media in Lithium Sulfur Batteries

    SciTech Connect

    Wang, Qiang; Zheng, Jianming; Walter, Eric; Pan, Huilin; Lv, Dongping; Zuo, Pengjian; Chen, Honghao; Deng, Z. D.; Liaw, Bor Y.; Yu, Xiqian; Yang, Xiao-Qing; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

    2015-01-09

    Lithium sulfur (Li-S) battery has been regaining tremendous interest in recent years because of its attractive attributes such as high gravimetric energy, low cost and environmental benignity. However, it is still not conclusively known how polysulfide ring/chain participates in the whole cycling and whether the discharge and charge processes follow the same pathway. Herein, we demonstrate the direct observation of sulfur radicals by using in situ electron paramagnetic resonance (EPR) technique. Based on the concentration changes of sulfur radicals at different potentials and the electrochemical characteristics of the cell, it is revealed that the chemical and electrochemical reactions in Li-S cell are driving each other to proceed through sulfur radicals, leading to two completely different reaction pathways during discharge and charge. The proposed radical mechanism may provide new perspectives to investigate the interactions between sulfur species and the electrolyte, inspiring novel strategies to develop Li-S battery technology.

  17. Branching ratios between the abstraction and addition channels in the reactions of OH radicals with monoterpenes

    NASA Astrophysics Data System (ADS)

    Rio, C.; Loison, J. C.; Caralp, F.; Flaud, P. M.; Villenave, E.

    2009-04-01

    Secondary Organic Aerosol (SOA) formation in the atmosphere is described as a mass transfer of volatile organic compound oxidation products with low vapour pressures in particular phases. Among the different aerosol components, the SOA represent an important fraction, but, the fundamental processes governing their physics and chemistry in the atmosphere are poorly understood. So it is important to characterize and understand the mechanisms of their formation. It is well-known that atmospheric oxidation of monoterpenes is an important process in tropospheric SOA formation. Consequently, the identification and quantification of reaction products from the oxidation of monoterpenes in the gas phase have been receiving great attention over the past years. However, the atmospheric degradation leads to the formation of a plethora of reaction products and proceeds through a very complex mechanism that is still not fully characterised. In our study, we have focused on SOA formation from OH + monoterpene reactions and more precisely on the primary oxidation steps of γ-terpinene and d-limonene by OH radicals. Indeed, the primary reaction of monoterpenes with hydroxyl radicals can in principle occur by two reaction pathways: OH-addition and H-abstraction. In this work, we have determined branching ratios of these reactions. Although there seems to be a consensus in the literature that OH-monoterpene reactions proceed almost exclusively by addition, several measurements have shown that in some case H-abstraction can represent up to 30% of the total reaction rate constant. Therefore it is necessary to determine this branching ratio in order to know, in particular, the main peroxy radicals formed and propose a mechanism for the gas phase oxidation of terpene by hydroxyl radicals. (γ-terpinene + OH) and (d-limonene + OH) reactions have been studied i) at atmospheric pressure, using laser photolysis coupled with UV absorption radical detection, and ii) at low pressure, using

  18. Reactions and structural investigation of chlorpromazine radical cation

    NASA Astrophysics Data System (ADS)

    Joshi, Ravi; Ghanty, Tapan K.; Mukherjee, T.

    2008-10-01

    Experimental and theoretical studies have been carried out to understand pro-oxidant behaviour of chlorpromazine radical cation (CPZ rad + ). Pulse radiolysis studies have shown that CPZ rad + oxidizes physiological antioxidants (uric acid and bilirubin), and biomolecules like, tyrosine and proteins (bovine serum albumin and casein), thereby acting as a pro-oxidant. Ab-initio quantum chemical calculations suggest structural and electronic changes on oxidation of CPZ. The calculations with Hartree-Fock and density functional methods show that ring nitrogen atom is the site of electron removal from CPZ and sulfur atom is the site of maximum spin in CPZ rad + . The calculations also suggest that oxidation of CPZ leads to increase in planarity of the tricyclic ring as well as tilting of alkyl side chain towards chlorine containing ring. The structural changes on oxidation of CPZ and spin delocalization in CPZ rad + fairly explain the pro-oxidant activity of CPZ.

  19. Spectroscopy and reaction dynamics of collision complexes containing hydroxyl radicals

    SciTech Connect

    Lester, M.I.

    1993-12-01

    The DOE supported work in this laboratory has focused on the spectroscopic characterization of the interaction potential between an argon atom and a hydroxyl radical in the ground X{sup 2}II and excited A {sup 2}{summation}{sup +} electronic states. The OH-Ar system has proven to be a test case for examining the interaction potential in an open-shell system since it is amenable to experimental investigation and theoretically tractable from first principles. Experimental identification of the bound states supported by the Ar + OH (X {sup 2}II) and Ar + OH(A {sup 2}{summation}{sup +}) potentials makes it feasible to derive realistic potential energy surfaces for these systems. The experimentally derived intermolecular potentials provide a rigorous test of ab initio theory and a basis for understanding the dramatically different collision dynamics taking place on the ground and excited electronic state surfaces.

  20. Mapping Nanomagnetic Fields Using a Radical Pair Reaction

    NASA Astrophysics Data System (ADS)

    Lee, Hohjai; Yang, Nan; Cohen, Adam

    2012-02-01

    We visualized the magnetic field around ferromagnetic nanostructures using a combination of a standard epifluorescence microscope and a fluorescence chemical indicator of magnetic field (H. Lee et al., Nano Lett. DOI: 10.1021/nl202950h). The indicator was a chain-linked electron donor-acceptor molecule, phenanthrene-(CH2)12-O-(CH2)2-dimethylaniline, that forms spin-correlated radical pairs upon photoexcitation. The magnetic field altered the coherence spin dynamics, yielding an 80% increase in exciplex fluorescence in a 0.1 T magnetic field. The magnetic field distributions were quantified to precision of 1.8 x 10-4 T by image analysis and agreed with finite-element nonmagnetic simulations.

  1. Metal-Catalyzed β-Functionalization of Michael Acceptors through Reductive Radical Addition Reactions.

    PubMed

    Streuff, Jan; Gansäuer, Andreas

    2015-11-23

    Transition-metal-catalyzed radical reactions are becoming increasingly important in modern organic chemistry. They offer fascinating and unconventional ways for connecting molecular fragments that are often complementary to traditional methods. In particular, reductive radical additions to α,β-unsaturated compounds have recently gained substantial attention as a result of their broad applicability in organic synthesis. This Minireview critically discusses the recent landmark achievements in this field in context with earlier reports that laid the foundation for today's developments. PMID:26471460

  2. Determination of the upper and lower limits of the mechanistic stoichiometry of incompletely coupled fluxes. Stoichiometry of incompletely coupled reactions.

    PubMed

    Beavis, A D; Lehninger, A L

    1986-07-15

    A rationale is formulated for the design of experiments to determine the upper and lower limits of the mechanistic stoichiometry of any two incompletely coupled fluxes J1 and J2. Incomplete coupling results when there is a branch at some point in the sequence of reactions or processes coupling the two fluxes. The upper limit of the mechanistic stoichiometry is given by the minimum value of dJ2/dJ1 obtained when the fluxes are systematically varied by changes in steps after the branch point. The lower limit is given by the maximum value of dJ2/dJ1 obtained when the fluxes are varied by changes in steps prior to the branch point. The rationale for determining these limits is developed from both a simple kinetic model and from a linear nonequilibrium thermodynamic treatment of coupled fluxes, using the mechanistic approach [Westerhoff, H. V. & van Dam, K. (1979) Curr. Top. Bioenerg. 9, 1-62]. The phenomenological stoichiometry, the flux ratio at level flow and the affinity ratio at static head of incompletely coupled fluxes are defined in terms of mechanistic conductances and their relationship to the mechanistic stoichiometry is discussed. From the rationale developed, experimental approaches to determine the mechanistic stoichiometry of mitochondrial oxidative phosphorylation are outlined. The principles employed do not require knowledge of the pathway or the rate of transmembrane leaks or slippage and may also be applied to analysis of the stoichiometry of other incompletely coupled systems, including vectorial H+/O and K+/O translocation coupled to mitochondrial electron transport. PMID:3015612

  3. Structure reactivity relationship in the reaction of DNA guanyl radicals with hydroxybenzoates

    NASA Astrophysics Data System (ADS)

    Do, Trinh T.; Tang, Vicky J.; Aguilera, Joseph A.; Milligan, Jamie R.

    2010-11-01

    In DNA, guanine bases are the sites from which electrons are most easily removed. As a result of hole migration to this stable location on guanine, guanyl radicals are major intermediates in DNA damage produced by the direct effect of ionizing radiation (ionization of the DNA itself and not through the intermediacy of water radicals). We have modeled this process by employing gamma irradiation in the presence of thiocyanate ions, a method which also produces single electron oxidized guanyl radicals in plasmid DNA in aqueous solution. The stable products formed in DNA from these radicals are detected as strand breaks after incubation with the FPG protein. When a phenolic compound is present in the solution during gamma irradiation, the formation of guanyl radical species is decreased by electron donation from the phenol to the guanyl radical. We have quantified the rate of this reaction for four different phenolic compounds bearing carboxylate substituents as proton acceptors. A comparison of the rates of these reactions with the redox strengths of the phenolic compounds reveals that salicylate reacts ca. 10-fold faster than its structural analogs. This observation is consistent with a reaction mechanism involving a proton coupled electron transfer, because intra-molecular transfer of a proton from the phenolic hydroxyl group to the carboxylate group is possible only in salicylate, and is favored by the strong 6-membered ring intra-molecular hydrogen bond in this compound.

  4. Catalytic N-radical cascade reaction of hydrazones by oxidative deprotonation electron transfer and TEMPO mediation.

    PubMed

    Hu, Xiao-Qiang; Qi, Xiaotian; Chen, Jia-Rong; Zhao, Quan-Qing; Wei, Qiang; Lan, Yu; Xiao, Wen-Jing

    2016-01-01

    Compared with the popularity of various C-centred radicals, the N-centred radicals remain largely unexplored in catalytic radical cascade reactions because of a lack of convenient methods for their generation. Known methods for their generation typically require the use of N-functionalized precursors or various toxic, potentially explosive or unstable radical initiators. Recently, visible-light photocatalysis has emerged as an attractive tool for the catalytic formation of N-centred radicals, but the pre-incorporation of a photolabile groups at the nitrogen atom largely limited the reaction scope. Here, we present a visible-light photocatalytic oxidative deprotonation electron transfer/2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediation strategy for catalytic N-radical cascade reaction of unsaturated hydrazones. This mild protocol provides a broadly applicable synthesis of 1,6-dihydropyradazines with complete regioselectivity and good yields. The 1,6-dihydropyradazines can be easily transformed into diazinium salts that showed promising in vitro antifungal activities against fungal pathogens. DFT calculations are conducted to explain the mechanism. PMID:27048886

  5. Catalytic N-radical cascade reaction of hydrazones by oxidative deprotonation electron transfer and TEMPO mediation

    PubMed Central

    Hu, Xiao-Qiang; Qi, Xiaotian; Chen, Jia-Rong; Zhao, Quan-Qing; Wei, Qiang; Lan, Yu; Xiao, Wen-Jing

    2016-01-01

    Compared with the popularity of various C-centred radicals, the N-centred radicals remain largely unexplored in catalytic radical cascade reactions because of a lack of convenient methods for their generation. Known methods for their generation typically require the use of N-functionalized precursors or various toxic, potentially explosive or unstable radical initiators. Recently, visible-light photocatalysis has emerged as an attractive tool for the catalytic formation of N-centred radicals, but the pre-incorporation of a photolabile groups at the nitrogen atom largely limited the reaction scope. Here, we present a visible-light photocatalytic oxidative deprotonation electron transfer/2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediation strategy for catalytic N-radical cascade reaction of unsaturated hydrazones. This mild protocol provides a broadly applicable synthesis of 1,6-dihydropyradazines with complete regioselectivity and good yields. The 1,6-dihydropyradazines can be easily transformed into diazinium salts that showed promising in vitro antifungal activities against fungal pathogens. DFT calculations are conducted to explain the mechanism. PMID:27048886

  6. Reaction kinetics of the CN radical with methyl bromide

    NASA Astrophysics Data System (ADS)

    Hodny, Michael; Hershberger, John F.

    2016-02-01

    The kinetics of the CN + CH3Br reaction were studied using transient infrared laser absorption spectroscopy to detect CN reactants and HCN products. This reaction has a rate constant of k = (2.20 ± 0.6) × 10-12 exp (453 ± 98/T) cm3 molecule-1 s-1 over the range 298-523 K. Hydrogen abstraction to produce HCN + CH2Br is only a minor reaction product, with a branching fraction of 0.12 ± 0.02. Other product channels, including BrCN + CH3, CH2CN + HBr, CH3CN + Br are likely. An upper limit of 0.01 was established for the HBr yield. These results are in qualitative agreement with recent ab initio calculations.

  7. Reaction dynamics of phenyl radicals in extreme environments: a crossed molecular beam study.

    PubMed

    Gu, Xibin; Kaiser, Ralf I

    2009-02-17

    Polycyclic aromatic hydrocarbons (PAHs)organic compounds that consist of fused benzene ringsand their hydrogen-deficient precursors have attracted extensive interest from combustion scientists, organic chemists, astronomers, and planetary scientists. On Earth, PAHs are toxic combustion products and a source of air pollution. In the interstellar medium, research suggests that PAHs play a role in unidentified infrared emission bands, diffuse interstellar bands, and the synthesis of precursor molecules to life. To build clean combustion devices and to understand the astrochemical evolution of the interstellar medium, it will be critical to understand the elementary reaction mechanisms under single collision conditions by which these molecules form in the gas phase. Until recently, this work had been hampered by the difficulty in preparing a large concentration of phenyl radicals, but the phenyl radical represents one of the most important radical species to trigger PAH formation in high-temperature environments. However, we have developed a method for producing these radical species and have undertaken a systematic experimental investigation. In this Account, we report on the chemical dynamics of the phenyl radical (C(6)H(5)) reactions with the unsaturated hydrocarbons acetylene (C(2)H(2)), ethylene (C(2)H(4)), methylacetylene (CH(3)CCH), allene (H(2)CCCH(2)), propylene (CH(3)CHCH(2)), and benzene (C(6)H(6)) utilizing the crossed molecular beams approach. For nonsymmetric reactants such as methylacetylene and propylene, steric effects and the larger cones of acceptance drive the addition of the phenyl radical to the nonsubstituted carbon atom of the hydrocarbon reactant. Reaction intermediates decomposed via atomic hydrogen loss pathways. In the phenyl-propylene system, the longer lifetime of the reaction intermediate yielded a more efficient energy randomization compared with the phenyl-methylacetylene system. Therefore, two reaction channels were open: hydrogen

  8. [Riboflavin-radical formation by mechanochemical solid-state reaction using stainless steel vessel].

    PubMed

    Kondo, Shin-ichi; Furuta, Youji; Okita, Shintarou; Sasai, Yasushi; Aramaki, Hideki; Kuzuya, Masayuki

    2004-03-01

    The mechanochemical reaction of free riboflavin (FR) due to vibratory ball milling was carried out in a stainless steel vessel at room temperature under anaerobic conditions. The ESR of the fractured sample showed a broad single-line spectrum. It is suggested that the solid-state single-electron transfer (SSET) reaction from the surface of the stainless steel vessel to FR proceeded during the vibratory milling, resulting in the formation of the corresponding anion radicals. When the mechanochemical reaction of FR in the presence of calcium pantothenate (PC) was carried out, the radical concentration increased with the increasing PC content. It was shown that the anion radical in the metal complex was stable for a lengthy period of time even in highly humid air. PMID:15049132

  9. Gas Phase Degradation of Polybrominated Diphenylethers: Photolysis vs. Reaction with OH Radical

    NASA Astrophysics Data System (ADS)

    Raff, J. D.; Hites, R. A.

    2005-12-01

    Polybrominated diphenylethers (PBDEs) are a class of flame-retardants produced in large quantities (70,000 metric tons in 2003) and added to polymers used to fabricate materials for electronics, textiles, construction, and other applications. Their volatility and persistence make them susceptible to atmospheric transport and their structural resemblance to polychlorinated diphenyls (PCBs) and dibenzo-p-dioxins (PCDDs) has raised concern about their possible toxicity. The dominant atmospheric loss processes for PBDEs are by direct photolysis and reaction with OH radical. Data on OH radical rate constants of selected PBDE congeners determined by a relative rate technique utilizing a small volume reaction chamber and mass spectrometric detection will be presented. Estimated photolysis rate constants have also been derived for PBDEs and will be discussed in terms of the relative importance of photolysis vs. reaction with OH radical as loss processes for PBDEs in the troposphere.

  10. Study on the NO{sub 3} radical reactivity: Reactions with cyclic alkenes

    SciTech Connect

    Martinez, E.; Cabanas, B.; Aranda, A.; Martin, P.; Notario, A.; Salgado, S.

    1999-07-08

    Much effort has been expended in studies of NO{sub 3} radical chemistry. The emphasis has been placed on investigating reaction rates and products of various organic and inorganic compounds to understand the behavior of this reactive radical in the atmosphere. The rate constants of the reactions of NO{sub 3} with cyclopentene, cyclohexene, cycloheptene, 1-methylcyclohexene, and methylenecyclohexane have been measured as a function of temperature at low pressure in a fast flow system with LiF detection of NO{sub 3}. The measured room temperature (298 K) rate constants for these reactions are given. The proposed Arrhenius expressions for the studied reactions are also given. The influence of substitution in the double bond and the ring size effect in unsubstituted cyclic monoalkenes has been investigated for the reactivity of the NO{sub 3} radical reactions. The rate coefficients and the activation energies for the reaction of the nitrate radical with methylenecyclohexane and 1-methylcyclohexene have also been compared with the corresponding values of some selected terpenes with similar structure to these compounds.

  11. Photoinduced reactions of 1-(dimethylethyl)-2,2-dimethylpropyl and cyclohexyl radicals in low-temperature solids

    NASA Astrophysics Data System (ADS)

    Koizumi, Hitoshi; Takada, Tomoya; Ichikawa, Tsuneki; Lund, Anders

    2001-06-01

    Photoinduced reactions of 1-(dimethylethyl)-2,2-dimethylpropyl and cyclohexyl radicals in 77 K solids were studied by the ESR method. 1-(Dimethylethyl)-2,2-dimethylpropyl is converted to 2,2,4,4-tetramethylpentyl radical with photoirradiation of 254 nm light. A hydrogen atom of methyl groups can hence directly transfer to the radical site at a carbon atom other than an adjacent one in the photoinduced reactions of alkyl radicals. Cyclohexyl radical is converted to cyclopentylmethyl radical with irradiation of 254 nm light. The photolysis of cyclohexyl radical causes C-C bond scission, and results in the formation of 5-hexenyl radical. It is then converted to cyclopentylmethyl radical through intramolecular rearrangement.

  12. Growth of polyaromatic molecules via ion-molecule reactions: An experimental and theoretical mechanistic study

    SciTech Connect

    Ascenzi, Daniela; Aysina, Julia; Tosi, Paolo; Maranzana, Andrea; Tonachini, Glauco

    2010-11-14

    The reactivity of naphthyl cations with benzene is investigated in a joint experimental and theoretical approach. Experiments are performed by using guided ion beam tandem mass spectrometers equipped with electron impact or atmospheric pressure chemical ion sources to generate C{sub 10}H{sub 7}{sup +} with different amounts of internal excitation. Under single collision conditions, C-C coupling reactions leading to hydrocarbon growth are observed. The most abundant ionic products are C{sub 16}H{sub 13}{sup +}, C{sub 16}H{sub n}{sup +} (with n=10-12), and C{sub 15}H{sub 10}{sup +}. From pressure-dependent measurements, absolute cross sections of 1.0{+-}0.3 and 2{+-}0.6 A{sup 2} (at a collision energy of about 0.2 eV in the center of mass frame) are derived for channels leading to the formation of C{sub 16}H{sub 12}{sup +} and C{sub 15}H{sub 10}{sup +} ions, respectively. From cross section values a phenomenological total rate constant k=(5.8{+-}1.9)x10{sup -11} cm{sup 3} s{sup -1} at an average collision energy of about 0.27 eV can be estimated for the process C{sub 10}H{sub 7}{sup +}+C{sub 6}H{sub 6}{yields} all products. The energy behavior of the reactive cross sections, as well as further experiments performed using partial isotopic labeling of reagents, support the idea that the reaction proceeds via a long lived association product, presumably the covalently bound protonated phenylnaphthalene, from which lighter species are generated by elimination of neutral fragments (H, H{sub 2}, CH{sub 3}). A major signal relevant to the fragmentation of the initial adduct C{sub 16}H{sub 13}{sup +} belongs to C{sub 15}H{sub 10}{sup +}. Since it is not obvious how CH{sub 3} loss from C{sub 16}H{sub 13}{sup +} can take place to form the C{sub 15}H{sub 10}{sup +} radical cation, a theoretical investigation focuses on possible unimolecular transformations apt to produce it. Naphthylium can act as an electrophile and add to the {pi} system of benzene, leading to a barrierless

  13. Characterization of the peroxidase mechanism upon reaction of prostacyclin synthase with peracetic acid. Identification of a tyrosyl radical intermediate.

    PubMed

    Yeh, Hui-Chun; Gerfen, Gary J; Wang, Jinn-Shyan; Tsai, Ah-Lim; Wang, Lee-Ho

    2009-02-10

    Prostacyclin synthase (PGIS) is a membrane-bound class III cytochrome P450 that catalyzes an isomerization of prostaglandin H(2), an endoperoxide, to prostacyclin. We report here the characterization of the PGIS intermediates in reactions with other peroxides, peracetic acid (PA), and iodosylbenzene. Rapid-scan stopped-flow experiments revealed an intermediate with an absorption spectrum similar to that of compound ES (Cpd ES), which is an oxo-ferryl (Fe(IV)O) plus a protein-derived radical. Cpd ES, formed upon reaction with PA, has an X-band (9 GHz) EPR signal of g = 2.0047 and a half-saturation power, P(1/2), of 0.73 mW. High-field (130 GHz) EPR reveals the presence of two species of tyrosyl radicals in Cpd ES with their g-tensor components (g(x), g(y), g(z)) of 2.00970, 2.00433, 2.00211 and 2.00700, 2.00433, 2.00211 at a 1:2 ratio, indicating that one is involved in hydrogen bonding and the other is not. The line width of the g = 2 signal becomes narrower, while its P(1/2) value becomes smaller as the reaction proceeds, indicating migration of the unpaired electron to an alternative site. The rate of electron migration ( approximately 0.2 s(-1)) is similar to that of heme bleaching, suggesting the migration is associated with the enzymatic inactivation. Moreover, a g = 6 signal that is presumably a high-spin ferric species emerges after the appearance of the amino acid radical and subsequently decays at a rate comparable to that of enzymatic inactivation. This loss of the g = 6 species thus likely indicates another pathway leading to enzymatic inactivation. The inactivation, however, was prevented by the exogenous reductant guaiacol. The studies of PGIS with PA described herein provide a mechanistic model of a peroxidase reaction catalyzed by the class III cytochromes P450. PMID:19187034

  14. EPR Spin Trapping of an Oxalate-Derived Free Radical in the Oxalate Decarboxylase Reaction

    PubMed Central

    Imaram, Witcha; Saylor, Benjamin T.; Centonze, Christopher P.; Richards, Nigel G. J.; Angerhofer, Alexander

    2011-01-01

    EPR spin trapping experiments on bacterial oxalate decarboxylase from Bacillus subtilis under turn-over conditions are described. The use of doubly 13C-labeled oxalate leads to a characteristic splitting of the observed radical adducts using the spin trap N-tert-butyl-α-phenylnitrone linking them directly to the substrate. The radical was identified as the carbon dioxide radical anion which is a key intermediate in the hypothetical reaction mechanism of both decarboxylase and oxidase activities. X-ray crystallography had identified a flexible loop, SENS161-4, which acts as a lid to the putative active site. Site directed mutagenesis of the hinge amino acids, S161 and T165 was explored and showed increased radical trapping yields compared to the wild type. In particular, T165V shows approximately ten times higher radical yields while at the same time its decarboxylase activity was reduced by about a factor of ten. This mutant lacks a critical H-bond between T165 and R92 resulting in compromised control over its radical chemistry allowing the radical intermediate to leak into the surrounding solution. PMID:21277974

  15. Trajectory calculations of OH radical- and Cl atom-initiated reaction of glyoxal: atmospheric chemistry of the HC(O)CO radical.

    PubMed

    Setokuchi, Osamu

    2011-04-01

    On-the-fly quasi-classical trajectory calculations using the density functional method were carried out to investigate the dynamics of the HC(O)CO radical, formed by OH radical- and Cl atom-initiated reactions of glyoxal at 298 K. The energy difference between the A' HC(O)CO radical, formed immediately after H atom abstraction, and the most stable A″ HC(O)CO radical is estimated to be 6.0 kcal mol(-1). The surplus energy followed by relaxation from A' HC(O)CO to A″ HC(O)CO goes to internal energy of the nascent HC(O)CO radicals and causes prompt decomposition into HCO + CO. The average internal energy partitioned into the HC(O)CO radical is higher in the OH reaction than in the Cl reaction, in accordance with exothermicity of the reactions. A fraction of the nascent HC(O)CO radicals (91% for the OH reaction and 47% for the Cl reaction) promptly decomposes into HCO and CO within 2.5 ps. The remaining HC(O)CO radicals, which do not undergo prompt decomposition, decompose thermally or add with O(2) in the presence of O(2). I re-evaluated the previous two experiment results of the product yield ratio [CO]/[CO(2)] vs. [O(2)](-1) in the Cl atom-initiated reaction, in light of the reaction mechanism involving prompt decomposition. The two results give 9.5 × 10(6) s(-1) and 1.08 × 10(7) s(-1) for the thermal decomposition rate and 47% and 41% for the fraction of prompt decomposition in the Cl atom-initiated reaction, in good agreement with the present trajectory calculation. PMID:21359367

  16. Gas-phase reactions of aryl radicals with 2-butyne: experimental and theoretical investigation employing the N-methyl-pyridinium-4-yl radical cation.

    PubMed

    Lam, A K Y; Li, C; Khairallah, G; Kirk, B B; Blanksby, S J; Trevitt, A J; Wille, U; O'Hair, R A J; da Silva, G

    2012-02-21

    Aromatic radicals form in a variety of reacting gas-phase systems, where their molecular weight growth reactions with unsaturated hydrocarbons are of considerable importance. We have investigated the ion-molecule reaction of the aromatic distonic N-methyl-pyridinium-4-yl (NMP) radical cation with 2-butyne (CH(3)C≡CCH(3)) using ion trap mass spectrometry. Comparison is made to high-level ab initio energy surfaces for the reaction of NMP and for the neutral phenyl radical system. The NMP radical cation reacts rapidly with 2-butyne at ambient temperature, due to the apparent absence of any barrier. The activated vinyl radical adduct predominantly dissociates via loss of a H atom, with lesser amounts of CH(3) loss. High-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry allows us to identify small quantities of the collisionally deactivated reaction adduct. Statistical reaction rate theory calculations (master equation/RRKM theory) on the NMP+2-butyne system support our experimental findings, and indicate a mechanism that predominantly involves an allylic resonance-stabilized radical formed via H atom shuttling between the aromatic ring and the C(4) side-chain, followed by cyclization and/or low-energy H atom β-scission reactions. A similar mechanism is demonstrated for the neutral phenyl radical (Ph˙)+2-butyne reaction, forming products that include 3-methylindene. The collisionally deactivated reaction adduct is predicted to be quenched in the form of a resonance-stabilized methylphenylallyl radical. Experiments using a 2,5-dichloro substituted methyl-pyridiniumyl radical cation revealed that in this case CH(3) loss from the 2-butyne adduct is favoured over H atom loss, verifying the key role of ortho H atoms, and the shuttling mechanism, in the reactions of aromatic radicals with alkynes. As well as being useful phenyl radical analogues, pyridiniumyl radical cations may form in the ionosphere of Titan, where they could undergo rapid

  17. Formation of TEMPOL-hydroxylamine during reaction between TEMPOL and hydroxyl radical: HPLC/ECD study.

    PubMed

    Kudo, Wataru; Yamato, Mayumi; Yamada, Ken-Ichi; Kinoshita, Yuichi; Shiba, Takeshi; Watanabe, Toshiaki; Utsumi, Hideo

    2008-05-01

    Nitroxyl radicals are important antioxidants that have been used to protect animal tissues from oxidative damage. Their reaction with hydroxyl radical ((*)OH) is generally accepted to be the mechanism of antioxidant function. However, the direct interaction of nitroxyl radicals with (*)OH does not always provide a satisfactory explanation in various pH, because the concentration of hydrogen ion may affect the generation of secondary (*)OH-derived radicals. In the present study, it was confirmed that the reaction between 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPOL) and (*)OH generated TEMPOL-hydroxylamine, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPON) and TEMPON-hydroxylamine using HPLC coupled with electrochemical detection. In the absence of NADH, TEMPOL-H may be generated by the reaction with secondary (*)OH-derived radicals in acidic condition. In the presence of NADH, a large proportion of the non-paramagnetic products was TEMPOL-H. Finally, it was clarified that TEMPOL-H was generated during dopamine metabolism, which is believed to be one of the (*)OH sources in pathological processes such as Parkinson's disease. PMID:18484414

  18. Polycyclic aromatic hydrocarbon (PAH) formation from benzyl radicals: a reaction kinetics study.

    PubMed

    Sinha, Sourab; Raj, Abhijeet

    2016-03-01

    The role of resonantly stabilized radicals such as propargyl, cyclopentadienyl and benzyl in the formation of aromatic hydrocarbons such as benzene and naphthalene in the high temperature environments has been long known. In this work, the possibility of benzyl recombination to form three-ring aromatics, phenanthrene and anthracene, is explored. A reaction mechanism for it is developed, where reaction energetics are calculated using density functional theory (B3LYP functional with 6-311++G(d,p) basis set) and CBS-QB3, while temperature-dependent reaction kinetics are evaluated using transition state theory. The mechanism begins with barrierless formation of bibenzyl from two benzyl radicals with the release of 283.2 kJ mol(-1) of reaction energy. The further reactions involve H-abstraction by a H atom, H-desorption, H-migration, and ring closure to gain aromaticity. Through mechanism and rate of production analyses, the important reactions leading to phenanthrene and anthracene formation are determined. Phenanthrene is found to be the major product at high temperatures. Premixed laminar flame simulations are carried out by including the proposed reactions for phenanthrene formation from benzyl radicals and compared to experimentally observed species profiles to understand their effects on species concentrations. PMID:26923612

  19. Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

    NASA Astrophysics Data System (ADS)

    Carraher, Jack McCaslin

    Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding 'greener' sources of commodity chemicals and fuels. High-valent Chromium from Hydroperoxido-Chromium(III). The decomposition of pentaaquahydroperoxido chromium(III) ion (hereafter Cr aqOOH2+) in acidic aqueous solutions is kinetically complex and generates mixtures of products (Craq3+, HCrO 4-, H2O2, and O2). The yield of high-valent chromium products (known carcinogens) increased from a few percent at pH 1 to 70 % at pH 5.5 (near biological pH). Yields of H 2O2 increased with acid concentration. The reproducibility of the kinetic data was poor, but became simplified in the presence of H2O2 or 2,2‧-azinobis(3-ethylbenzothiazoline-6-sulfonate) dianion (ABTS2-). Both are capable of scavenging strongly oxidizing intermediates). The observed rate constants (pH 1, [O2] ≤ 0.03 mM) in the presence of these scavengers are independent of [scavenger] and within the error are the same (k,ABTS2- = (4.9 +/- 0.2) x 10-4 s-1 and kH2O2 = (5.3 +/- 0.7) x 10-4 s-1); indicating involvement of the scavengers in post-rate determining steps. In the presence of either scavenger, decomposition of CrOOH2+ obeyed a two-term rate law, k obs / s-1 = (6.7 +/- 0.7) x 10-4 + (7.6 +/- 1.1) x 10-4 [H+]. Effect of [H+] on the kinetics and the product distribution, cleaner kinetics in the presence of scavengers, and independence of kobs on [scavenger] suggest a dual-pathway mechanism for the decay of Craq OOH2+. The H+-catalyzed path

  20. Atmospheric Reactions of a Series of Hexenols with OH Radical and Ozone

    NASA Astrophysics Data System (ADS)

    Gai, Yanbo; Lin, Xiaoxiao; Ma, Qiao; Yang, Chengqiang; Zhao, Weixiong; Zhang, Weijun

    2016-04-01

    C6 hexenols are one of the most significant groups of biogenic volatile organic compounds (BVOCs). Because of their antibacterial properties, C6 hexenols can be emitted by a wide number of plants in response to changes in the ambient environment. The oxidation of these compounds in the atmosphere is involved in the formation of tropospheric ozone and secondary organic aerosols (SOA), thus causing significant effects on atmospheric chemistry and the climate. The lack of corresponding kinetic parameters and product information of their oxidation reactions will result in incomplete atmospheric chemical mechanisms and models. In this paper, we will overview our recent research progress on the study of the atmospheric reactions of a series of C6 hexenols with OH radicals and ozone. A series of studies were conducted using both experimental and theoretical methods. Corresponding rate constants were obtained, and reaction mechanisms were also analyzed. It could be concluded that both the nature of the substituent and its position play a fundamental role in the reactivity of the C6 hexenols toward OH radicals and O3. An activating effect of the -OH group in OH radical reactions was found, thus making the H-abstraction channel non-negligible in reactions of these unsaturated alcohols with OH radicals. The removal of these C6 hexenols by ozone also showed great importance and could be competitive with the major recognized sinks by OH radicals. These studies are of great significance for understanding the mechanism of atmospheric chemical reactions of hexenols and improving the atmospheric chemistry model. Experimental detail and corresponding results will be presented. Acknowledgements. This work was supported by the National Natural Science Foundation of China (21307137, 41575125 and 91544228), and the Natural Science Foundation of Anhui Province (1508085J03).

  1. Synthesis of Tetrahydronaphthyridines from Aldehydes and HARP Reagents via Radical Pictet-Spengler Reactions.

    PubMed

    Jackl, Moritz K; Kreituss, Imants; Bode, Jeffrey W

    2016-04-15

    The combination of aldehydes with newly designed HARP (halogen amine radical protocol) reagents gives access to α-substituted tetrahydronaphthyridines. By using different HARP reagents, various regioisomeric structures can be prepared in a single operation. These products, which are of high value in medicinal chemistry, are formed in a predictable manner via a formal Pictet-Spengler reaction of electron-poor pyridines that would not participate in the corresponding polar reactions. PMID:27026179

  2. Radical formation in the [MeReO3]-catalyzed aqueous peroxidative oxidation of alkanes: a theoretical mechanistic study.

    PubMed

    Kuznetsov, Maxim L; Pombeiro, Armando J L

    2009-01-01

    Plausible mechanisms of radical formation in the catalytic system [MeReO(3)]/H(2)O(2)/H(2)O-CH(3)CN for the oxidation of alkanes to alcohols and ketones, via radical pathways, are investigated extensively at the density functional theory level. The most favorable route is based on the monoperoxo complex [MeReO(2)(O(2))(H(2)O)] and includes the formation of an H(2)O(2) adduct, water-assisted H-transfer from H(2)O(2) to the peroxo ligand, and generation of HOO(*). The thus formed reduced Re(VI) complex [MeReO(2)(OOH)(H(2)O)] reacts with H(2)O(2), resulting, upon water-assisted H-transfer and O-OH bond homolysis, in the regeneration of the oxo-Re(VII) catalyst and formation of the HO(*) radical that reacts further with the alkane. Water plays a crucial role by (i) stabilizing transition states for the proton migrations and providing easy intramolecular H-transfers in the absence of any N,O-ligands and (ii) saturating the Re coordination sphere what leads to a decrease of the activation barrier for the formation of HOO(*). The activation energy of the radical formation calculated for [MeReO(3)] (17.7 kcal/mol) is compatible with that determined experimentally [Shul'pin et al. J. Chem. Soc., Perkin Trans. 2 2001, 1351 .] for oxo-V-based catalytic systems (17 +/- 2 kcal/mol), and the overall type of mechanism proposed for such V catalysts is also effective for [MeReO(3)]. PMID:19049432

  3. KINETICS AND PRODUCTS OF THE REACTIONS OF SELECTED DIOLS WITH THE OH RADICAL. (R825252)

    EPA Science Inventory

    Using a relative rate method, rate constants have been measured at 296 ? 2 K for the gas-phase reactions of OH radicals with 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, and 2-methyl-2,4-pentanediol, with rate constants (in units of 10-12 cm3 molecule

  4. A theoretical and experimental study of unimolecular and biomolecular radical hydrogen transfer reactions

    SciTech Connect

    Franz, J.A.; Autrey, T.; Gleicher, G.J.; Camaioni, D.M; Ferris, K.F.

    1991-04-01

    We have examined the intramolecular radical hydrogen transfer (RHT) reaction of the 2-(2-phenylethyl)cyclohexadienyl radical. Intramolecular hydrogen shift from the cyclohexadienyl ring to the ipso position of the phenyl ring, followed by {beta}-scission would have given benzene and ethylbenzene as products. Competing with this reaction is {beta}-scission to give benzyl radical and isotoluene, or hydrogen loss to give bibenzyl. Studies to date suggest a barrier for thermoneutral hydrogen transfer in the RHT reaction between aromatic systems of ca. 18 kcal/mole. None of the studies of RHT or equivalent mechanisms have attempted to directly observe H{sub 2}, and direct determination of Arrhenius parameters and a detailed examination of the pathway of the hydrogen transfer process remains to be carried out. To better understand the structural and energetic aspects of RHT, we have carried out a semiempirical molecular orbital study of bimolecular and intramolecular RHT reactions for a variety of aromatic systems. We also examined in detail the energetics of hydrogen transfer between ethyl radical and ethylene via RHT, an addition/metathesis/scission pathway, and a hybrid concerted'' pathway. 11 refs., 1 fig., 4 tabs.

  5. Temperature-dependent kinetics of the vinyl radical (C2H3) self-reaction.

    SciTech Connect

    Jusinski, Leonard E.; Zador, Judit; Taatjes, Craig A.; Selby, Talitha M.; Meloni, Giovanni; Knepp, Adam M.; Ismail, Huzeifa; Green, William H.; Abel, Paul R.; Fahr, Askar; Osborn, David L

    2008-10-01

    The rate coefficient for the self-reaction of vinyl radicals has been measured by two independent methods. The rate constant as a function of temperature at 20 Torr has been determined by a laser-photolysis/laser absorption technique. Vinyl iodide is photolyzed at 266 nm, and both the vinyl radical and the iodine atom photolysis products are monitored by laser absorption. The vinyl radical concentration is derived from the initial iodine atom concentration, which is determined by using the known absorption cross section of the iodine atomic transition to relate the observed absorption to concentration. The measured rate constant for the self-reaction at room temperature is approximately a factor of 2 lower than literature recommendations. The reaction displays a slightly negative temperature dependence, which can be represented by a negative activation energy, (E{sub a}/R) = -400 K. The laser absorption results are supported by independent experiments at 298 K and 4 Torr using time-resolved synchrotron-photoionization mass-spectrometric detection of the products of divinyl ketone and methyl vinyl ketone photolysis. The photoionization mass spectrometry experiments additionally show that methyl + propargyl are formed in the vinyl radical self-reaction, with an estimated branching fraction of 0.5 at 298 K and 4 Torr.

  6. Rate of reaction of superoxide radical with chloride-containing species

    SciTech Connect

    Long, C.A.; Bielski, B.H.J.

    1980-01-01

    This paper evaluates the rate constants for the reaction of superoxide radical with five common chloride-containing species (Cl/sup -/, ClO/sup -/, ClO/sub 2//sup -/, ClO/sub 3//sup -/, and ClO/sub 4//sup -/ and proposes a mechanism for those which react.

  7. Markovnikov free radical addition reactions, a sleeping beauty kissed to life.

    PubMed

    Hoffmann, Reinhard W

    2016-02-01

    This review covers free radical additions, which are initiated by the formal addition of a hydrogen atom to a C[double bond, length as m-dash]C double bond. These reactions originated in the realms of inorganic chemistry, polymer chemistry, and organic chemistry, whereby barriers between these disciplines impeded the rapid implementation of the findings. PMID:26753913

  8. Energies and kinetics of radical pairs involving bacteriochlorophyll and bacteriopheophytin in bacterial reaction centers

    PubMed Central

    Shuvalov, Vladimir A.; Parson, William W.

    1981-01-01

    Absorbance changes reflecting the formation of a transient radical-pair state, PF, were measured in reaction centers from Rhodopseudomonas sphaeroides under conditions that blocked electron transfer to a later carrier (a quinone, Q). The temperature dependence of the absorbance changes suggests that PF is an equilibrium mixture of two states, which appear to be mainly 1[P[unk]B[unk

  9. On the Outcome of the Reactions Between Hydrocarbon Radicals and O2 in Helium Nanodroplets

    NASA Astrophysics Data System (ADS)

    Morrison, A. M.; Douberly, G. E.

    2012-06-01

    Helium nanodroplet isolation and infrared laser spectroscopy are used to investigate the CH3 + O2 and C3H3 (propargyl) + O2 reactions. The hydrocarbon radicals are generated in an effusive pyrolysis source located upstream from a differentially pumped O2 gas pick-up cell. In this experimental configuration, the reaction occurs between sequentially picked-up and presumably cold fragments. The CH3 + O2 reaction leads barrierlessly to the methyl-peroxy radical, and despite having to dissipate an energy of approximately 30 kcal/mol, the infrared spectra reveal a large abundance of droplets containing the cold CH3O2 radical. Theoretical studies have predicted an approximately 2-4 kcal/mol barrier in the entrance channel of the C3H3 + O2 reaction. Therefore, we initially expected to see a weakly bound “entrance channel” C3H3--O2 van-der-Waals complex, given the rapid cooling provided by the dissipative helium environment. However, only the trans-acetylenic isomer of the propargyl-peroxy radical is observed. The dipole moment of this species is measured with infrared laser Stark spectroscopy.

  10. Unusual spin-trap chemistry for the reaction of hydroxyl radical with the carcinogen N-nitrosodimethylamine

    NASA Astrophysics Data System (ADS)

    Wink, David A.; Desrosiers, Marc F.

    The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3,5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant ( .Br -2). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive intermediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide radical. Unexpectedly, addition of DBNBS to a solution containing dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented.

  11. Cyclopentadienone Oxidation Reaction Kinetics and Thermochemistry for the Alcohols, Hydroperoxides, and Vinylic, Alkoxy, and Alkylperoxy Radicals.

    PubMed

    Yommee, Suriyakit; Bozzelli, Joseph W

    2016-01-28

    Cyclopentadienone has one carbonyl and two olefin groups resulting in 4n + 2 π-electrons in a cyclic five-membered ring structure. Thermochemical and kinetic parameters for the initial reactions of cyclopentadienone radicals with O2 and the thermochemical properties for cyclopentadienone-hydroperoxides, alcohols, and alkenyl, alkoxy, and peroxy radicals were determined by use of computational chemistry. The CBS-QB3 composite and B3LYP density functional theory methods were used to determine the enthalpies of formation (ΔfH°298) using the isodesmic reaction schemes with several work reactions for each species. Entropy and heat capacity, S°(T) and Cp°(T) (50 K ≤ T ≤ 5000 K) are determined using geometric parameters, internal rotor potentials, and frequencies from B3LYP/6-31G(d,p) calculations. Standard enthalpies of formation are reported for parent molecules as cyclopentadienone, cyclopentadienone with alcohol, hydroperoxide substituents, and the cyclopentadienone-yl vinylic, alkoxy, and peroxy radicals corresponding to loss of a hydrogen atom from the carbon and oxygen sites. Entropy and heat capacity vs temperature also are reported for the parent molecules and for radicals. The thermochemical analysis shows The R(•) + O2 well depths are deep, on the order of 50 kcal mol(-1), and the R(•) + O2 reactions to RO + O (chain branching products) for cyclopentadienone-2-yl and cyclopentadienone-3-yl have unusually low reaction (ΔHrxn) enthalpies, some 20 or so kcal/mol below the entrance channels. Chemical activation kinetics using quantum RRK analysis for k(E) and master equation for falloff are used to show that significant chain branching as a function of temperature and pressure can occur when these vinylic radicals are formed. PMID:26784854

  12. From allylic alcohols to aldols through a new nickel-mediated tandem reaction: synthetic and mechanistic studies.

    PubMed

    Cuperly, David; Petrignet, Julien; Crévisy, Christophe; Grée, René

    2006-04-12

    Nickel hydride type complexes have been successfully developed as catalysts for the tandem isomerization-aldolization reaction of allylic alcohols with aldehydes. Optimization of the reaction conditions has shown that a cocatalyst, such as MgBr2, has a very positive effect on the kinetics of the reaction and in the yields of aldols. Under such optimized conditions {[NiHCl(dppe)] + MgBr(2) at 3-5 mol %)}, this reaction affords the aldols in good to excellent yields. It is a full-atom-economy-type reaction that occurs under mild conditions. Furthermore, it has a broad scope for the allylic alcohols and it is compatible with a wide range of aldehydes, including very bulky derivatives. The reaction is completely regioselective, but it exhibits a low stereoselectivity, except for allylic alcohols with a bulky substituent at the carbinol center. The use of chiral nonracemic catalysts was not successful, affording only racemic compounds. However, it was possible to use asymmetric synthesis for the preparation of optically active aldols. Various mechanistic studies have been performed using, for instance, a deuterated alcohol or a deuterated catalyst. They gave strong support to a mechanism involving first a transition-metal-mediated isomerization of the allylic alcohol into the free enol, followed by the addition of the latter intermediate onto the aldehyde in an "hydroxyl-carbonyl-ene" type reaction. These results confirm that allylic alcohols can be considered as new and useful partners in the development of the aldol reaction. PMID:16506253

  13. A new hypothesis about the relationship between free radical reactions and hemorheological properties in vivo.

    PubMed

    Mo, J; Fan, J; Guo, Z; Hunag, C; Yan, B; Wang, F; Wang, D; Sun, S

    1993-12-01

    This paper is concerned with a hypothesis that disturbance of free radical reactions may lead to abnormality of hemorheological properties in vivo, and so the free radicals generated in vivo may damage certain tissue cells indirectly by reducing the supply of oxygen and nutrients to these cells through slowing the circulation of blood. This hypothesis is based on the following evidence: A. We have found that the whole blood viscosity at low shear rate correlates to the lipid peroxidation in the patients suffering from certain cardio- or cerebrovascular diseases, and in dogs during liver ischemia reperfusion or hemorrhagic pancreatitis. B. Reports have shown that several alterations of hemorheological properties may take place as a result of free radical reactions, such as lipid peroxidation. For instance, lipid peroxidation may lead to decrease of deformability of red cells, increase of aggregation of red cells, formation of liquid thrombin, etc. C. We have demonstrated that some alterations of hemorheological properties involve the role of free radicals in rats suffering from intestinal ischemia/reperfusion. As evidence for this conclusion, superoxide dismutase (SOD) used as a specific scavenger of superoxide anion radical (O2-) can significantly prevent the intestinal ischemia/reperfusion induced changes of lipid peroxidation, red cell aggregation, Cassion's viscosity and whole blood viscosity at low shear rate in rats. PMID:8183128

  14. Multiple re-encounter approach to radical pair reactions and the role of nonlinear master equations

    SciTech Connect

    Clausen, Jens; Tiersch, Markus; Briegel, Hans J.; Guerreschi, Gian Giacomo

    2014-08-07

    We formulate a multiple-encounter model of the radical pair mechanism that is based on a random coupling of the radical pair to a minimal model environment. These occasional pulse-like couplings correspond to the radical encounters and give rise to both dephasing and recombination. While this is in agreement with the original model of Haberkorn and its extensions that assume additional dephasing, we show how a nonlinear master equation may be constructed to describe the conditional evolution of the radical pairs prior to the detection of their recombination. We propose a nonlinear master equation for the evolution of an ensemble of independently evolving radical pairs whose nonlinearity depends on the record of the fluorescence signal. We also reformulate Haberkorn's original argument on the physicality of reaction operators using the terminology of quantum optics/open quantum systems. Our model allows one to describe multiple encounters within the exponential model and connects this with the master equation approach. We include hitherto neglected effects of the encounters, such as a separate dephasing in the triplet subspace, and predict potential new effects, such as Grover reflections of radical spins, that may be observed if the strength and time of the encounters can be experimentally controlled.

  15. Reactions of reducing and oxidizing radicals with caffeic acid:. a pulse radiolysis and theoretical study

    NASA Astrophysics Data System (ADS)

    Li, Xifeng; Cai, Zhongli; Katsumura, Yosuke; Wu, Guozhong; Muroya, Yusa

    2001-01-01

    Molecular calculations coupled with pulse radiolysis studies are performed to understand the reactions of radicals with caffeic acid. From molecular calculation, we find that e aq- and ·OH tend to form adducts with caffeic acid, while N 3rad tends to abstract H from 4-hydroxyl group in benzene ring, generating a semi-quinoid radical. Based on comparison of the heat of formation, the most favorable radical attack sites and the most stable radical structures are predicted. The calculation results suggest that the stability of the electron adducts radicals < ·OH adducts of caffeic ions, in good agreement with their experimental second-order decay rate constants (2 k=(1.1±0.2)×10 9, (6.0±0.4)×10 7 and (2.0±0.2)×10 7 M -1 s -1, respectively), determined by pulse radiolysis. Molecular calculations seem to be a powerful tool to predict the stability and structures of transient radicals.

  16. Addition reaction of alkyl radical to C60 fullerene: Density functional theory study

    NASA Astrophysics Data System (ADS)

    Tachikawa, Hiroto; Kawabata, Hiroshi

    2016-02-01

    Functionalized fullerenes are known as a high-performance molecules. In this study, the alkyl-functionalized fullerenes (denoted by R-C60) have been investigated by means of the density functional theory (DFT) method to elucidate the effects of functionalization on the electronic states of fullerene. Also, the reaction mechanism of alkyl radicals with C60 was investigated. The methyl, ethyl, propyl, and butyl radicals (denoted by n = 1-4, where n means the number of carbon atoms in the alkyl radical) were examined as alkyl radicals. The DFT calculation showed that the alkyl radical binds to the carbon atom of C60 at the on-top site, and a strong C-C single bond is formed. The binding energies of alkyl radicals to C60 were distributed in the range of 31.8-35.1 kcal mol-1 at the CAM-B3LYP/6-311G(d,p) level. It was found that the activation barrier exists before alkyl addition, the barrier heights were calculated to be 2.1-2.8 kcal mol-1. The electronic states of R-C60 complexes were discussed on the basis of the theoretical results.

  17. Laser flash photolysis studies of radical-radical reaction kinetics: The HO{sub 2} + IO reaction

    SciTech Connect

    Cronkhite, J.M.; Stickel, R.E.; Nicovich, J.M.; Wine, P.H.

    1999-04-29

    Reactive iodine as a potential tropospheric O{sub 3} sink has received considerable attention recently. Laser flash photolysis of Cl{sub 2}/CH{sub 3}OH/O{sub 2}/I{sub 2}/NO{sub 2}/SF{sub 6}N{sub 2} mixtures at 308 nm has been coupled with simultaneous time-resolved detection of HO{sub 2} (by infrared tunable diode laser absorption spectroscopy) and IO (by visible absorption spectroscopy) to investigate the kinetics of the atmospherically important reaction HO{sub 2} + IO {r_arrow} products over the temperature range 274--373 K in N{sub 2} buffer gas at pressures of 12 and 25 Torr. All experiments were performed under near pseudo-first-order conditions with HO{sub 2} in excess over IO. At 298 K, the rate coefficient was determined to be (9.7 {+-} 2.9) {times} 10{sup {minus}11} cm{sup 3} molecule{sup {minus}1}s{sup {minus}1}, with the primary source of uncertainty being knowledge of the infrared line strength(s) required to convert measured HO{sub 2} absorbances to absolute concentrations. The temperature dependence of the HO{sub 2} + IO rate coefficient was found to be adequately described by the Arrhenius expression k = 9.3 {times} 10{sup {minus}12} exp(680/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The results reported in this study are compared with other recent studies of HO{sub 2} + IO kinetics, and the potential roles of this reaction in atmospheric chemistry are discussed.

  18. Mechanistic Examination of Cβ–Cγ Bond Cleavages of Tryptophan Residues during Dissociations of Molecular Peptide Radical Cations

    SciTech Connect

    Song, Tao; Ma, Ching-Yung; Chu, Ivan K.; Siu, Chi-Kit; Laskin, Julia

    2013-02-14

    In this study, we used collision-induced dissociation (CID) to examine the gas-phase fragmentations of [GnW]•+ (n = 2-4) and [GXW]•+ (X = C, S, L, F, Y, Q) species. The Cβ–Cγ bond cleavage of a C-terminal decarboxylated tryptophan residue ([M - CO2]•+) can generate [M - CO2 - 116]+, [M - CO2 - 117]•+, and [1H-indole]•+ (m/z 117) species as possible product ions. Competition between the formation of [M - CO2 - 116]+ and [1H-indole]•+ systems implies the existence of a proton-bound dimer formed between the indole ring and peptide backbone. Formation of such a proton-bound dimer is facile via a protonation of the tryptophan γ-carbon atom as suggested by density functional theory (DFT) calculations. DFT calculations also suggested the initially formed ion 2--the decarboxylated species that is active against Cβ–Cγ bond cleavage -can efficiently isomerize to form a more-stable -radical isomer (ion 9) as supported by Rice-Ramsperger-Kassel-Marcus (RRKM) modeling. The Cβ–Cγ bond cleavage of a tryptophan residue also can occur directly from peptide radical cations containing a basic residue. CID of [WGnR]•+ (n = 1-3) radical cations consistently resulted in predominant formation of [M-116]+ product ions. It appears that the basic arginine residue tightly sequesters the proton and allows the charge-remote Cβ–Cγ bond cleavage to prevail over the charge-directed one. DFT calculations predicted the barrier for the former is 6.2 kcal mol -1 lower than that of the latter. Furthermore, the pathway involving a salt-bridge intermediate also was accessible during such a bond cleavage event.

  19. Sub-millitesla magnetic field effects on the recombination reaction of flavin and ascorbic acid radicals.

    PubMed

    Evans, Emrys W; Kattnig, Daniel R; Henbest, Kevin B; Hore, P J; Mackenzie, Stuart R; Timmel, Christiane R

    2016-08-28

    Even though the interaction of a <1 mT magnetic field with an electron spin is less than a millionth of the thermal energy at room temperature (kBT), it still can have a profound effect on the quantum yields of radical pair reactions. We present a study of the effects of sub-millitesla magnetic fields on the photoreaction of flavin mononucleotide with ascorbic acid. Direct control of the reaction pathway is achieved by varying the rate of electron transfer from ascorbic acid to the photo-excited flavin. At pH 7.0, we verify the theoretical prediction that, apart from a sign change, the form of the magnetic field effect is independent of the initial spin configuration of the radical pair. The data agree well with model calculations based on a Green's function approach that allows multinuclear spin systems to be treated including the diffusive motion of the radicals, their spin-selective recombination reactions, and the effects of the inter-radical exchange interaction. The protonation states of the radicals are uniquely determined from the form of the magnetic field-dependence. At pH 3.0, the effects of two chemically distinct radical pair complexes combine to produce a pronounced response to ∼500 μT magnetic fields. These findings are relevant to the magnetic responses of cryptochromes (flavin-containing proteins proposed as magnetoreceptors in birds) and may aid the evaluation of effects of weak magnetic fields on other biologically relevant electron transfer processes. PMID:27586950

  20. Determination of the rate constant of hydroperoxyl radical reaction with phenol

    NASA Astrophysics Data System (ADS)

    Kozmér, Zsuzsanna; Arany, Eszter; Alapi, Tünde; Takács, Erzsébet; Wojnárovits, László; Dombi, András

    2014-09-01

    The rate constant of HO2rad reaction with phenol (kHO2rad +phenol) was investigated. The primary radical set produced in water γ radiolysis (rad OH, eaq- and Hrad ) was transformed to HO2rad /O2rad - by using dissolved oxygen and formate anion (in the form of either formic acid or sodium formate). The concentration ratio of HO2rad /O2rad - was affected by the pH value of the solution: under acidic conditions (using HCOOH) almost all radicals were converted to HO2rad , while under alkaline conditions (using HCOONa) to O2rad -. The degradation rate of phenol was significantly higher using HCOOH. From the ratio of reaction rates under the two reaction conditions kHO2rad +phenol was estimated to be (2.7±1.2)×103 L mol-1 s-1.

  1. Absolute rate constants of alkoxyl radical reactions in aqueous solution. [Tert-butyl hydroperoxide

    SciTech Connect

    Erben-Russ, M.; Michel, C.; Bors, W.; Saran, M.

    1987-04-23

    The pulse radiolysis technique was used to generate the alkoxyl radical derived from tert-butyl hydroperoxide (/sup t/BuOOH) in aqueous solution. The reactions of this radical with 2,2'-azinobis(3-ethyl-6-benzothiazolinesulfonate) (ABTS) and promethazine were monitored by kinetic spectroscopy. The unimolecular decay rate constant of the tert-butoxyl radical (/sup t/BuO) was determined to be 1.4 x 10/sup 6/ s/sup -1/. On the basis of this value, the rate constants for /sup t/BuO attack on quercetin, crocin, crocetin, ascorbate, isoascorbate, trolox c, glutathione, thymidine, adenosine, guanosine, and unsaturated fatty acids were determined. In addition, the reaction of /sup t/BuO with the polyunsaturated fatty acids (PUFA) was observed by directly monitoring the formation of the fatty acid pentadienyl radicals. Interestingly, the attack of /sup t/BuO on PUFA was found to be faster by about one order of magnitude as compared to the same reaction in a nonpolar solvent.

  2. Concurrent esterification and N-acetylation of amino acids with orthoesters: A useful reaction with interesting mechanistic implications.

    PubMed

    Gibson, Sarah; Romero, Dickie; Jacobs, Hollie K; Gopalan, Aravamudan S

    2010-12-22

    The concurrent esterification and N-acetylation of amino acids has been studied with triethyl orthoacetate (TEOA) and triethyl orthoformate (TEOF). In a surprising finding, only one equivalent of TEOA in refluxing toluene was necessary to convert L-proline and L-phenylalanine to the corresponding N-acetyl ethyl esters in good yield. The same transformation using TEOF was not effective. Stereochemical outcome and stoichiometric studies as well as structural variation of the amino acids in this reaction provided unexpected mechanistic insight. PMID:21286246

  3. Concurrent esterification and N-acetylation of amino acids with orthoesters: A useful reaction with interesting mechanistic implications

    PubMed Central

    Gibson, Sarah; Romero, Dickie; Jacobs, Hollie K.; Gopalan, Aravamudan S.

    2010-01-01

    The concurrent esterification and N-acetylation of amino acids has been studied with triethyl orthoacetate (TEOA) and triethyl orthoformate (TEOF). In a surprising finding, only one equivalent of TEOA in refluxing toluene was necessary to convert L-proline and L-phenylalanine to the corresponding N-acetyl ethyl esters in good yield. The same transformation using TEOF was not effective. Stereochemical outcome and stoichiometric studies as well as structural variation of the amino acids in this reaction provided unexpected mechanistic insight. PMID:21286246

  4. Computational Chemistry in the Undergraduate Laboratory: A Mechanistic Study of the Wittig Reaction

    ERIC Educational Resources Information Center

    Albrecht, Birgit

    2014-01-01

    The Wittig reaction is one of the most useful reactions in organic chemistry. Despite its prominence early in the organic chemistry curriculum, the exact mechanism of this reaction is still under debate, and this controversy is often neglected in the classroom. Introducing a simple computational study of the Wittig reaction illustrates the…

  5. Mechanistic investigation of the uncatalyzed esterification reaction of acetic acid and acid halides with methanol: a DFT study.

    PubMed

    Lawal, Monsurat M; Govender, Thavendran; Maguire, Glenn E M; Honarparvar, Bahareh; Kruger, Hendrik G

    2016-10-01

    Implementation of catalysts to drive reactions from reactants to products remains a burden to synthetic and organic chemists. In spite of investigations into the kinetics and mechanism of catalyzed esterification reactions, less effort has been made to explore the possibility of an uncatalyzed esterification process. Therefore, a comprehensive mechanistic perspective for the uncatalyzed mechanism at the molecular level is presented. Herein, we describe the non-catalyzed esterification reaction of acetic acid and its halide derivatives (XAc, where X= OH, F, Cl, Br, I) with methanol (MeOH) through a concerted process. The reaction in vacuum and methanol was performed using the density functional theory (DFT) method at M06-2X level with def2-TZVP basis set after a careful literature survey and computations. Esterification through cyclic 4- or 6-membered transition state structures in one- or two-step concerted mechanisms were investigated. The present study outlines the possible cyclic geometry conformations that may occur during experiments at simple ratio of reactants. The free energy of activation for acetic acid and acetyl chloride are 36 kcal mol(-1) and 21 kcal mol(-1), respectively. These are in good agreement with available experimental results from the literature. The selected quantum chemical descriptors proved to be useful tools in chemical reactivity prediction for the reaction mechanism. This quantum mechanics study can serve as a necessary step towards revisiting uncatalyzed reaction mechanisms in some classical organic reactions. PMID:27604278

  6. Experimental and theoretical investigation of the self-reaction of phenyl radicals.

    SciTech Connect

    Tranter, R. S.; Klippenstein, S. J.; Harding, L. B.; Giri, B. R.; Yang, X.; Kiefer, J. H.; Chemical Sciences and Engineering Division; Univ. of Illinois at Chicago

    2010-08-19

    A combination of experiment and theory is applied to the self-reaction kinetics of phenyl radicals. The dissociation of phenyl iodide is observed with both time-of-flight mass spectrometry, TOF-MS, and laser schlieren, LS, diagnostics coupled to a diaphragmless shock tube for temperatures ranging from 1276 to 1853 K. The LS experiments were performed at pressures of 22 {+-} 2, 54 {+-} 7, and 122 {+-} 6 Torr, and the TOF-MS experiments were performed at pressures in the range 500-700 Torr. These observations are sensitive to both the dissociation of phenyl iodide and to the subsequent self-reaction of the phenyl radicals. The experimental observations indicate that both these reactions are more complicated than previously assumed. The phenyl iodide dissociation yields {approx}6% C{sub 6}H{sub 4} + HI in addition to the major and commonly assumed C{sub 6}H{sub 5} + I channel. The self-reaction of phenyl radicals does not proceed solely by recombination, but also through disproportionation to benzene + o-/m-/p-benzynes, with comparable rate coefficients for both. The various channels in the self-reaction of phenyl radicals are studied with ab initio transition state theory based master equation calculations. These calculations elucidate the complex nature of the C{sub 6}H{sub 5} self-reaction and are consistent with the experimental observations. The theoretical predictions are used as a guide in the development of a model for the phenyl iodide pyrolysis that accurately reproduces the observed laser schlieren profiles over the full range of the observations.

  7. Experimental study of the reactions of limonene with OH and OD radicals: kinetics and products.

    PubMed

    Braure, Tristan; Bedjanian, Yuri; Romanias, Manolis N; Morin, Julien; Riffault, Véronique; Tomas, Alexandre; Coddeville, Patrice

    2014-10-01

    The kinetics of the reactions of limonene with OH and OD radicals has been studied using a low-pressure flow tube reactor coupled with a quadrupole mass spectrometer: OH + C10H16 → products (1), OD + C10H16 → products (2). The rate constants of the title reactions were determined using four different approaches: either monitoring the kinetics of OH (OD) radicals or limonene consumption in excess of limonene or of the radicals, respectively (absolute method), and by the relative rate method using either the reaction OH (OD) + Br2 or OH (OD) + DMDS (dimethyl disulfide) as the reference one and following HOBr (DOBr) formation or DMDS and limonene consumption, respectively. As a result of the absolute and relative measurements, the overall rate coefficients, k1 = (3.0 ± 0.5) × 10(-11) exp((515 ± 50)/T) and k2 = (2.5 ± 0.6) × 10(-11) exp((575 ± 60)/T) cm(3) molecule(-1) s(-1), were determined at a pressure of 1 Torr of helium over the temperature ranges 220-360 and 233-353 K, respectively. k1 was found to be pressure independent over the range 0.5-5 Torr. There are two possible pathways for the reaction between OH (OD) and limonene: addition of the radical to one of the limonene double bonds (reactions 1a and 2a ) and abstraction of a hydrogen atom (reactions 1b and 2b ), resulting in the formation of H2O (HOD). Measurements of the HOD yield as a function of temperature led to the following branching ratio of the H atom abstraction channel: k2b/k2 = (0.07 ± 0.03) × exp((460 ± 140)/T) for T = (253-355) K. PMID:25211148

  8. Role of oxygen radical reactions in the browning and cross-linking of lysozyme by glucose

    SciTech Connect

    Hull, C.J.; Thorpe, S.R.; Baynes, J.W.

    1986-05-01

    Lysozyme (LZM) was used as a model protein for studies on the effects of oxygen on the Maillard reaction. During a 4 wk incubation in 0.25 M glucose (0.2 M phosphate buffer, pH 7.4, 37/sup 0/C) the kinetics of glycation of LZM were similar under air and N/sub 2/, yielding approx.2 mol Lys modified per mol LZM. Fructoselysine (FL) was the major Lys derivative formed under air and N/sub 2/, while N/sup epsilon/-carboxymethyllysine (CML) accounted for approx.30% of FL formed at 4 wk under air. A loss of 1 mol Arg per mol LZM was also observed under both air and N/sub 2/, with greater loss from LZM dimer vs. monomer, suggesting a role for Arg in the crosslinking reaction. Dimer and monomer did not differ in content of Lys, FL or CML (under air), but dimer was 4 times as fluorescent as monomer, suggesting that crosslink structures are fluorescent. Despite significant differences in kinetics of crosslinking, browning and development of fluorescence of LZM under air vs. N/sub 2/, products formed had similar absorbance and fluorescence spectra. Based on inhibition by chelators and radical scavengers, the more rapid crosslinking and development of fluorescence under air was shown to result from oxygen radical reactions. These results indicate that both radical and non-radical processes may contribute to the Maillard reaction, but that the browning, fluorescence and crosslinking of protein may proceed in the absence of oxygen and oxygen radicals.

  9. Kinetics of the reactions of SH radicals with NO2 and O2

    NASA Technical Reports Server (NTRS)

    Stachnik, R. A.; Molina, M. J.

    1987-01-01

    The SH + NO2 reaction rate constant was measured by monitoring SH concentrations with long-path optical absorption at 324 nm in a laser photolysis system. At 298 K, the rate constant was found to be (4.8 + or - 1.0) x 10 to the -11th cu cm/molecule per sec. An upper limit of 4 x 10 to the -19th cu cm/molecule per sec was inferred for the SH + O2 reaction, indicating that the atmospheric oxidation of the SH radical may occur via reaction with species such as NO2 and O3.

  10. Kinetics of CH(X 2Pi) radical reactions with cyclopropane, cyclopentane, and cyclohexane

    NASA Technical Reports Server (NTRS)

    Zabarnick, S.; Fleming, J. W.; Lin, M. C.

    1988-01-01

    Rate constants have been obtained for CH(X 2Pi) radical reactions with cyclopropane, cyclopentane, and cyclohexane in order to establish the rate of CH insertion into secondary C-H bonds in alkanes. Data indicate that there is no measurable dependence on photolysis laser energy. The reactions all exhibited rate constants that decrease with increasing temperature. It is suggested that a possible set of pathways for the cycloalkane reactions is a ring-opening process where the excited adduct decomposes to a hydrogen atom and a diene.

  11. Photoinitiated electron-transfer reactions of aromatic imides with phenylcyclopropanes. Formation of radical ion pair cycloadducts. Mechanism of the reaction

    SciTech Connect

    Somich, C.; Mazzocchi, P.H.; Edwards, M.; Morgan, T.; Ammon, H.L. )

    1990-04-27

    Few investigations have addressed the cyclization of a radical anion-radical cation pair resulting from photoinitiated electron transfer. One system taht meets the criteria necessary to observe this phenomenon is the acceptor-donor pair N-methylphthalimide (NMP) and phenylcyclopropane (PC). Irradiation of NMP or N-methyl-2,3-naphthalimide (NMN) in the presence of PC in acetonitrile gave rise to two spiro tetrahydrofuranyl lactams. The regiochemistry and relative stereochemistry of these compounds were determined by NMR techniques and X-ray crystallography. The mechanism of the reaction proceeds via electron transfer from PC to the imide followed by coupling of the radical ion pair at the 1,2-position of the carbonyl to the cyclopropane ring in a stepwise fashion. Fluorescence quenching experiments, reaction efficiency, and the free energy for electron transfer using various aromatic substituted phenylcyclopropanes provided strong evidence that electron transfer occurs. The reaction of cis-2-deutero-1-phenylcyclopropane (PC-d) with NMN established that cycloaddition is stepwise rather than concerted and that both syn and anti reactive intermediates are equally accessible.

  12. Production of sulfate radical and hydroxyl radical by reaction of ozone with peroxymonosulfate: a novel advanced oxidation process.

    PubMed

    Yang, Yi; Jiang, Jin; Lu, Xinglin; Ma, Jun; Liu, Yongze

    2015-06-16

    In this work, simultaneous generation of hydroxyl radical (•OH) and sulfate radical (SO4•−) by the reaction of ozone (O3) with peroxymonosulfate (PMS; HSO5−) has been proposed and experimentally verified. We demonstrate that the reaction between the anion of PMS (i.e.,SO52−) and O3 is primarily responsible for driving O3 consumption with a measured second order rate constant of (2.12 ± 0.03) × 10(4) M(-1) s(-1). The formation of both •OH and SO4•− from the reaction between SO52− and O3 is confirmed by chemical probes (i.e., nitrobenzene for •OH and atrazine forb oth •OH and SO4•−). The yields of •OH and SO4•− are determined to be 0.43 ± 0.1 and 0.45 ± 0.1 per mol of O3 consumption, respectively. An adduct,−O3SOO− + O3 → −O3SO5−, is assumed as the first step, which further decomposes into SO5•− and O3•−. The subsequent reaction of SO5•− with O3is proposed to generate SO4•−, while O3•− converts to •OH. A definition of R(ct,•OH) and R(ct,SO4•−) (i.e., respective ratios of •OH and SO4•− exposures to O3 exposure) is adopted to quantify relative contributions of •OH and SO4•−. Increasing pH leads to increases in both values of R(ct,•OH) and R(ct,SO4•−) but does not significantly affect the ratio of R(ct,SO4•−) to R(ct,•OH) (i.e., R(ct,SO4•−)/R(ct,•OH)), which represents the relative formation of SO4•− to •OH. The presence of bicarbonate appreciably inhibits the degradation of probes and fairly decreases the relative contribution of •OH for their degradation, which may be attributed to the conversion of both •OH and SO4•− to the more selective carbonate radical (CO3•−).Humic acid promotes O3 consumption to generate •OH and thus leads to an increase in the R(ct,•OH) value in the O3/PMS process,w hile humic acid has negligible influence on the R(ct,SO4•−) value. This discrepancy is reasonably explained by the negligible effect of humic acid on SO

  13. Oxygen radical-mediated oxidation reactions of an alanine peptide motif - density functional theory and transition state theory study

    PubMed Central

    2012-01-01

    Background Oxygen-base (O-base) oxidation in protein backbone is important in the protein backbone fragmentation due to the attack from reactive oxygen species (ROS). In this study, an alanine peptide was used model system to investigate this O-base oxidation by employing density functional theory (DFT) calculations combining with continuum solvent model. Detailed reaction steps were analyzed along with their reaction rate constants. Results Most of the O-base oxidation reactions for this alanine peptide are exothermic except for the bond-breakage of the Cα-N bond to form hydroperoxy alanine radical. Among the reactions investigated in this study, the activated energy of OH α-H abstraction is the lowest one, while the generation of alkylperoxy peptide radical must overcome the highest energy barrier. The aqueous situation facilitates the oxidation reactions to generate hydroxyl alanine peptide derivatives except for the fragmentations of alkoxyl alanine peptide radical. The Cα-Cβ bond of the alkoxyl alanine peptide radical is more labile than the peptide bond. Conclusion the rate-determining step of oxidation in protein backbone is the generation of hydroperoxy peptide radical via the reaction of alkylperoxy peptide radical with HO2. The stabilities of alkylperoxy peptide radical and complex of alkylperoxy peptide radical with HO2 are crucial in this O-base oxidation reaction. PMID:22524792

  14. O(1D) Reaction with Methane Studied by State Resolved Scattering Distribution Measurements of Methyl Radicals

    NASA Astrophysics Data System (ADS)

    Suzuki, Toshinori

    2014-06-01

    The scattering distributions of state-selected methyl radicals are measured for the O(^1D_2) reaction with methane using a crossed molecular beam ion imaging method at collision energies of 0.9 - 6.8 kcal/mol. The results are compared with the reaction with deuterated methane to examine the isotope effects. The scattering distributions exhibit contributions from both the insertion and abstraction pathways respectively on the ground and excited-state potential energy surfaces. Insertion is the main pathway, and it provides a strongly forward-enhanced angular distribution of methyl radicals. Abstraction is a minor pathway, causing backward scattering of methyl radicals with a discrete speed distribution. From the collision energy dependence of the abstraction/insertion ratio, the barrier height for the abstraction pathway is estimated for O(^1D_2) with CH_4 and CD_4, respectively. The insertion pathway of the O(^1D_2) reaction with CH_4 has a narrower angular width in the forward scattering and a larger insertion/abstraction ratio than the reaction with CD_4, which indicate that the insertion reaction with CH_4 has a larger cross section and a shorter reaction time than the reaction with CD_4. Additionally, while the insertion reaction with CD_4 exhibits strong angular dependence of the CD_3 speed distribution, CH_3 exhibits considerably smaller dependence. The result suggests that, although intramolecular vibrational redistribution (IVR) within the lifetime of the methanol intermediate is restrictive in both isotopomers, relatively more extensive IVR occurs in CD_3OD than CH_3OH, presumably due to the higher vibrational state density.

  15. Alkyl bromides as mechanistic probes of reductive dehalogenation: reactions of vicinal dibromide stereoisomers with zerovalent metals.

    PubMed

    Totten, L A; Jans, U; Roberts, A L

    2001-06-01

    Whether reductive dehalogenation proceeds via a one- or a two-electron mechanism has been suggested to affect product distributions, hence potentially influencing the success of engineered treatment systems. In this work, we explore vicinal dibromide stereoisomers as "probes" of the concertedness of electron transfer in reduction by aqueous suspensions of iron and zinc metal. Dibromides consisted of 2,3-dibromopentane (diBP) stereoisomers and (+/-)-1,2-dibromo-1,2-diphenylethane. All dibromides reacted with metals to give the same E:Z ratio of olefins observed during dehalogenation by iodide (a two-electron reductant). Reduction by Cr(II) (a one-electron reductant) yielded distinctly different proportions of E and Z olefins. Although this might be construed as evidence that metals function as two-electron reductants, high stereo-specificity was also obtained for reduction of diBPs by Fe(II) adsorbed to goethite, a presumed one-electron reductant; this can be explained by two single-electron transfers in rapid succession, facilitated by the locally elevated concentration of reducing equivalents at the oxide-water interface. The results suggest that reduction of alkyl halides by metals is not likely to produce free radicals that persist long enough to undergo radical-radical coupling or hydrogen-atom abstraction from minor dissolved constituents. Apparent free-radical coupling products are more likely to result from (possibly surface-bound) organometallic intermediates. PMID:11414030

  16. A resistive pyrolytic radical source for gas-surface reaction studies

    NASA Astrophysics Data System (ADS)

    Lee, David Y.; Jobbins, Matthew M.; Kandel, S. Alex

    2012-04-01

    We describe a thermal gas cracker designed to produce low fluxes of gas-phase radicals for use in radical-surface reaction studies. A resistively heated thin piece of highly oriented pyrolytic graphite is used as the pyrolysis filament, with the major advantage that this material remains inert at high temperatures. The instrument is built within an existing titanium sublimation pump, which simplifies construction and allows for self-pumping of the radical source. Thermal generation of Cl atoms from Cl2 was chosen to test the effectiveness of the instrument. 35Cl and 37Cl were generated with a concomitant decrease in parent 70Cl2 and 72Cl2 species, as monitored by a residual gas analyzer. The cracking fraction of Cl2 as a function of cell temperature is reported, with nearly full conversion achieved at high temperature.

  17. Coherent chemical kinetics as quantum walks. II. Radical-pair reactions in Arabidopsis thaliana

    NASA Astrophysics Data System (ADS)

    Chia, A.; Górecka, A.; Kurzyński, P.; Paterek, T.; Kaszlikowski, D.

    2016-03-01

    We apply the quantum-walk approach proposed in the preceding paper [A. Chia et al., preceding paper, Phys. Rev. E 93, 032407 (2016), 10.1103/PhysRevE.93.032407] to a radical-pair reaction where realistic estimates for the intermediate transition rates are available. The well-known average hitting time from quantum walks can be adopted as a measure of how quickly the reaction occurs and we calculate this for varying degrees of dephasing in the radical pair. The time for the radical pair to react to a product is found to be independent of the amount of dephasing introduced, even in the limit of no dephasing where the transient population dynamics exhibits strong coherent oscillations. This can be seen to arise from the existence of a rate-limiting step in the reaction and we argue that in such examples, a purely classical model based on rate equations can be used for estimating the time scale of the reaction but not necessarily its population dynamics.

  18. Reactions of CH3, CH3O, and CH3O2 radicals with O3

    NASA Technical Reports Server (NTRS)

    Simonaitis, R.; Heicklen, J.

    1975-01-01

    Ozone was photolyzed at 253.7 nm at 25 and -52 degrees in the presence of CH4 and O2 to measure the reactions of O3 with CH3, CH3O, and CH3O2. The O(1D) atoms produced in the primary photochemical act react with CH4 to give CH3 radicals which in turn can react with O2 to give CH3O2 and CH3O radicals. At very high O2 to O3 concentration ratios, the quantum yield of O3 disappearance approached 1.0, indicating that O3 reactions with CH3O2 and CH3O are slow. Upper limits to the rate coefficients at 25 degrees were computed. At lower values of the concentration ratio, chain decomposition of O3 occurred which could be explained by the reaction of O3 with CH3 radicals to produce CH2O, O2, and H atoms all the time. The two routes to these products are considered, and the preferred reaction channel is found.

  19. Electronic nonadiabatic effects in low temperature radical-radical reactions. I. C(3P) + OH(2Π).

    PubMed

    Maergoiz, A I; Nikitin, E E; Troe, J

    2014-07-28

    The formation of collision complexes, as a first step towards reaction, in collisions between two open-electronic shell radicals is treated within an adiabatic channel approach. Adiabatic channel potentials are constructed on the basis of asymptotic electrostatic, induction, dispersion, and exchange interactions, accounting for spin-orbit coupling within the multitude of electronic states arising from the separated reactants. Suitable coupling schemes (such as rotational + electronic) are designed to secure maximum adiabaticity of the channels. The reaction between C((3)P) and OH((2)Π) is treated as a representative example. The results show that the low temperature association rate coefficients in general cannot be represented by results obtained with a single (generally the lowest) potential energy surface of the adduct, asymptotically reaching the lowest fine-structure states of the reactants, and a factor accounting for the thermal population of the latter states. Instead, the influence of non-Born-Oppenheimer couplings within the multitude of electronic states arising during the encounter markedly increases the capture rates. This effect extends up to temperatures of several hundred K. PMID:25084905

  20. Radical Rearrangement Catalysis in an Enzyme at 190-207 K: Mechanistic Features Revealed by Substrate ^1H/^2H Isotope Effects

    NASA Astrophysics Data System (ADS)

    Zhu, Chen; Warncke, Kurt

    2009-11-01

    The decay kinetics of both the natural abundance and [1,1,2,2-^2H4]-aminoethanol generated Co^II-substrate radical pair catalytic intermediate in ethanolamine ammonia-lyase (EAL) from Salmonella typhimrium have been measured by using time-resolved, full-spectrum X-band continuous-wave electron paramagnetic resonance (EPR) spectroscopy in frozen aqueous solution from 190 to 207 K. The decay reaction proceeds through sequential radical covalent rearrangement and hydrogen atom transfer (HT) steps. In the temperature range from 190 to 207 K, the decay is biexponential, and the two phases correspond to distinct populations [1]. The ^1H/^2H isotope effects (IE) on the fast phase and slow phase are 1.3 and 0.8, respectively. These IE are not caused by a primary kinetic IE. Therefore, HT is rapid, relative to rearrangement. We propose that the fast phase is rate-determined by the rearrangement step, and that the slow phase is rate-determined by a step after rearrangement that is associated with protein guidance of the reactions. The results reveal microscopic features of the core reaction chemistry and protein dynamics participation in the reaction, which are not accessible at ambient temperatures.[4pt] [1] Zhu, C., Warncke, K. Biophys. J. 95, 5890 (2008). Supported by grant DK54514 from NIDDK/NIH.

  1. Concerted effects of substituents in the reaction of •OH radicals with aromatics: The hydroxybenzaldehydes

    NASA Astrophysics Data System (ADS)

    Albarran, Guadalupe; Mendoza, Edith; Schuler, Robert H.

    2016-07-01

    In the present work, we have examined the distribution of products in the radiolytic hydroxylation of 2-, 3- and 4-hydroxybenzaldehyde to obtain information on the concerted effect of the -CHO and -OH groups at the addition site of •OH radicals. The •OH radical was found to selectively add to the free positions of the aromatic ring. Furthermore, the •OH radical reacts by substitution at the ipso position followed by elimination of the substituent, producing dihydroxybenzene compounds. Additionally, the formation of carboxylic acids as an initial product has been conclusively identified by retention times and UV and mass spectra. These acids are formed as a result of the radiolytic oxidation of the initial radical formed by the addition reaction of the •OH radicals to the meso position (exocyclic carbon). The identification of the products, dihydroxybenzaldehydes, dihydroxybenzenes and hydroxybenzoic acids and calculation of their yields were achieved through HPLC. The G values of each product are given, which reflect the charge distributions in the hydroxybenzaldehydes, such that the formyl group modifies the ortho-para directing effect of the -OH substituent. The 3 and 5 positions in 2- and 4-hydroxybenzaldehyde showed increased the electronic density compared to that of phenol, indicating that the formyl group has a significant effect on the electronic structure of those hydroxybenzaldehydes. In 3-hydroxybenzaldehyde, the -OH substituent had a dominant ortho-directing effect similar to that observed for phenol.

  2. Some reactions and properties of nitro radical-anions important in biology and medicine.

    PubMed Central

    Wardman, P

    1985-01-01

    Nitroaromatic compounds, ArNO2 have widespread actual or potential use in medicine and cancer therapy. There is direct proof that free-radical metabolites are involved in many applications, and an appreciation of the conceptual basis for their therapeutic differential; however, an understanding of the detailed mechanisms involved is lacking. Redox properties control most biological responses of nitro compounds, and the characteristics of the one-electron couple: ArNO2/ArNO2- are detailed. The "futile metabolism" of nitroaryl compounds characteristic of most aerobic nitroreductase systems reflects competition between natural radical-decay pathways and a one-electron transfer reaction to yield superoxide ion, O2-. Prototropic properties control the rate of radical decay, and redox properties control the rate of electron transfer to O2 or other acceptors. There are clear parallels in the chemistry of ArNO2- and O2-. While nitro radicals have frequently been invoked as damaging species, they are very unreactive (except as simple reductants). It seems likely that reductive metabolism of nitroaryl compounds, although generally involving nitro radical-anions as obligate intermediates (and this is required for therapeutic selectivity towards anaerobes), results in biological damage via reductive metabolites of higher reduction order than the one-electron product. PMID:3830700

  3. Characterization of the reaction rate coefficient of DNA with the hydroxyl radical

    SciTech Connect

    Milligan, J.R.; Ward, J.F.; Aguilera, J.A.

    1996-11-01

    Using agarose gel electrophoresis, we have measured the yield of single-strand breaks (SSBs) induced by {sup 137}Cs {gamma} irradiation in a variety of plasmid DNA substrates ranging in size from 2.7 kb to 38 kb irradiated in aerobic aqueous solution in the presence of the hydroxyl radical scavenger dimethyl sulfoxide (DMSO). Under these conditions DNA SSBs are caused mainly by the hydroxyl radical. Using the competition between DMSO and DNA for the hydroxyl radical, we have estimated the rate coefficient for the reaction of the hydroxyl radical with DNA. The results cannot be characterized by conventional steady-state competition kinetics. However, it is possible to describe the second-order rate constant for the reaction as a function of the scavenging capacity of the solution. The second-order rate constant increases with increasing scavenging capacity, rising from about 5x10{sup 8} dm{sup 3} mol{sup -1} s{sup -1} at 10{sup 5} s{sup -1} to about 10{sup 10} dm{sup 3} mol{sup -1} s{sup -1} at 10{sup 10} s{sup -1}. This dependence of the second-order rate constant on the scavenging capacity appears to be more pronounced for larger plasmids. 17 refs., 4 figs.

  4. Gas-Phase Reactions of Methoxyphenols with NO3 Radicals: Kinetics, Products, and Mechanisms.

    PubMed

    Zhang, Haixu; Yang, Bo; Wang, Youfeng; Shu, Jinian; Zhang, Peng; Ma, Pengkun; Li, Zhen

    2016-03-01

    Methoxyphenols, a group of important tracers for wood smoke, are emitted to the atmosphere in large quantities, but their transformations are rarely studied. In this study, the kinetics and products of the gas-phase reactions of eugenol and 4-ethylguaiacol with NO3 radicals were investigated online using a vacuum ultraviolet photoionization gas time-of-flight mass spectrometer. The rate coefficients of the gaseous reactions of eugenol and 4-ethylguaiacol with NO3 radicals were (1.6 ± 0.4) × 10(-13) and (1.1 ± 0.2) × 10(-12) cm(3) molecule(-1) s(-1) (at 298 K), indicating that the atmospheric lifetimes of the NO3 radicals were 3.5 and 0.5 h, respectively. With the aid of gas-chromatography-mass-spectrometry analysis, several types of degradation products were identified with nitro derivatives as the major products. The configurations of the nitro-product isomers and their formation mechanisms were determined via theoretical calculations. On the basis of these products, degradation pathways of the methoxyphenols with NO3 radicals were proposed. This study determines the degradation rates and mechanisms of the methoxyphenols at night and implies the significant NO3 nighttime chemistry. PMID:26845070

  5. Formation of polycyclic aromatic hydrocarbons from bimolecular reactions of phenyl radicals at high temperatures.

    PubMed

    Constantinidis, P; Schmitt, H-C; Fischer, I; Yan, B; Rijs, A M

    2015-11-21

    The self-reaction of the phenyl radical is one of the key reactions in combustion chemistry. Here we study this reaction in a high-temperature flow reactor by IR/UV ion dip spectroscopy, using free electron laser radiation as mid-infrared source. We identified several major reaction products based on their infrared spectra, among them indene, 1,2-dihydronaphthalene, naphthalene, biphenyl and para-terphenyl. Due to the structural sensitivity of the method, the reaction products were identified isomer-selectively. The work shows that the formation of indene and naphthalene, which was previously considered to be evidence for the HACA (hydrogen abstraction C2H2 addition) mechanism in the formation of polycyclic aromatic hydrocarbons and soot can also be understood in a phenyl addition model. PMID:26457393

  6. Mechanistic Significance of the Si–O–Pd Bond in the Palladium-Catalyzed Cross-Coupling Reactions of Alkenylsilanolates

    PubMed Central

    2016-01-01

    Through the combination of reaction kinetics (both catalytic and stoichiometric) and solid-state characterization of arylpalladium(II) alkenylsilanolate complexes, the intermediacy of covalent adducts containing Si–O–Pd linkages in the cross-coupling reactions of organosilanolates has been unambiguously established. Two mechanistically distinct pathways have been demonstrated: (1) transmetalation via a neutral 8-Si-4 intermediate that dominates in the cross-coupling of potassium alkenylsilanolates, and (2) transmetalation via an anionic 10-Si-5 intermediate that dominates in the cross-coupling of cesium alkenylsilanolates. Arylpalladium(II) alkenylsilanolate complexes bearing various phosphine ligands (both bidentate and monodentate) have been isolated, fully characterized, and evaluated for their kinetic competence under thermal (stoichiometric) and anionic (catalytic) conditions. Comparison of the rates for thermal and anionic activation demonstrates that intermediates containing the Si–O–Pd linkage are involved in the cross-coupling process. PMID:25945390

  7. Free radicals: how do we stand them? Anaerobic and aerobic free radical (chain) reactions involved in the use of fluorogenic probes and in biological systems.

    PubMed

    Liochev, Stefan I

    2014-01-01

    Biologically significant conclusions have been based on the use of fluorogenic and luminogenic probes for the detection of reactive species. The basic mechanisms of the processes involved have not been satisfactorily elucidated. In the present work, the mechanism of the enzyme and photosensitized oxidation of NAD(P)H by resorufin is analyzed and appears to involve both aerobic and anaerobic free radical chain reactions. There are two major fallouts of this analysis. Many of the conclusions about the participation of radicals based on the use of probes such as resorufin and Amplex red need reevaluation. It is also concluded that anaerobic free radical reactions may be biologically significant, and the possible existence of enzymatic systems to eliminate certain free radicals is discussed. PMID:24356000

  8. A Metal and Base-Free Chemoselective Primary Amination of Boronic Acids Using Cyanamidyl/Arylcyanamidyl Radical as Aminating Species: Synthesis and Mechanistic Studies by Density Functional Theory.

    PubMed

    Chatterjee, Nachiketa; Arfeen, Minhajul; Bharatam, Prasad V; Goswami, Avijit

    2016-06-17

    An efficient, metal and base-free, chemoselective synthesis of aryl-, heteroaryl-, and alkyl primary amines from the corresponding boronic acids has been achieved at ambient temperature mediated by [bis(trifluoroacetoxy)iodo]benzene (PIFA) and N-bromosuccinimide (NBS) using cyanamidyl/arylcyanamidyl radicals as the aminating species. The primary amine compounds were initially obtained as their corresponding ammonium trifluoroacetate salts which, on treatment with aq NaOH, provide the free amines. Finally, the primary amines were isolated through column chromatography over silica-gel using hexane-EtOAc solvent system as the eluent. The reactions are sufficiently fast, completing within 1 h. Quantum chemical calculations in combination with experimental observations validate that the ipso amination of substituted boronic acids involves the formation of cyanamidyl/arylcyanamidyl radical, followed by regiospecific interaction of its nitrile-N center with boron atom of the boronic acids, leading to chemoselective primary amination. PMID:27182931

  9. Reaction Rates of Semi-Volatile Organic Compounds with the Hydroxyl Radical.

    NASA Astrophysics Data System (ADS)

    Anderson, Philip Neal

    1995-01-01

    The atmosphere is the primary route of global dispersion of many semi-volatile organic compounds (SOCs), including polychlorinated biphenyls, dibenzo-p-dioxins, and dibenzofurans. While the long-distance atmospheric transport of these compounds has been well established, the importance of chemical reactions that may occur while SOCs are in the atmosphere is largely unknown. For most semi-volatile organic compounds in the vapor phase, the most significant atmospheric reaction is likely to be attack by the hydroxyl radical (OH). The importance of this removal pathway, relative to other loss mechanisms from the atmosphere, is dependent on the reaction rate of a given semi-volatile organic compound with OH. A system was constructed and validated to measure the reaction rate of OH with semi-volatile organic compounds in the laboratory. The system featured a small, heated, quartz chamber with on-line detection of reactants by mass spectrometry. OH radicals were generated by the 254 nm photolysis of O _3 in the presence of H_2 O. The temperature dependent reaction rates of OH with 15 polychlorinated biphenyl congeners (PCBs), containing 0-5 chlorines, were measured. Calculated atmospheric lifetimes of PCBs due to OH-initiated reactions ranged from 2 days for biphenyl to 34 days for a pentachlorobiphenyl. Using an average of reaction rates extrapolated to atmospheric temperatures, the lifetime in the atmosphere for total PCBs due to OH reaction was calculated. A model for the vertical concentration gradient of PCBs in the troposphere was developed and used to calculate the flux (16 mug m^{-2} yr^{-1}) and total global flow (8,300 tonnes yr^{-1}) of PCBs removed from the atmosphere by OH-PCB reaction. This pathway is very large in comparison to any other known permanent PCB loss processes from the environment, such as deep ocean sediment burial (240 tonnes yr^ {-1}). The reaction of PCBs with OH may be the dominant removal mechanism of PCBs from the natural environment.

  10. A shock tube study of the reactions of the hydroxyl radical with combustion species

    SciTech Connect

    Cohen, N.; Koffend, J.B.

    1993-12-01

    To extend the semi-empirical techniques of Benson and coworkers, and to extend the database of reliable high temperature measurements of OH radicals with hydrocarbons and other fuels and their decomposition products, the authors undertook a research program with both experimental and computational tasks. The experimental goal was to design a procedure for measuring, at combustion temperatures, the reaction rate coefficients of OH radicals with fuels and other species of importance in combustion or propulsion systems. The computational effort was intended to refine the semi-empirical transition-state-theory procedures for extrapolating rate coefficients of reactions of OH with combustion species of interest, for predicting rate coefficients for species not studied in the laboratory, and to examine the ability of the theory to predict rate coefficients for different pathways in the case the reagent possessed more than one nonequivalent H atoms.

  11. A shock tube study of the reactions of the hydroxyl radical with combustion species and pollutants

    SciTech Connect

    Cohen, N.

    1992-08-01

    To extend the database of reliable high temperature measurements of OH radicals with hydrocarbons and other fuels and their decomposition products, we undertook, a research program with both experimental and computational tasks. The experimental goal was to design a procedure for measuring, at combustion temperatures, the reaction rate coefficients of OH radicals with fuels and other species of importance in combustion or propulsion systems. The computational effort was intended to refine the semi-empirical thermochemical kinetics/ transition-state-theory (TK-TST) procedures for extrapolating rate coefficients of reactions of OH with combustion species of interest, for predicting rate coefficients for species not studied in the laboratory, and to examine the ability of the theory to predict rate coefficients for different pathways in cases where the reagent possessed nonequivalent H atoms.

  12. Mechanistic investigation of oxidative Mannich reaction with tert-butyl hydroperoxide. The role of transition metal salt.

    PubMed

    Ratnikov, Maxim O; Doyle, Michael P

    2013-01-30

    A general mechanism is proposed for transition metal-catalyzed oxidative Mannich reactions of N,N-dialkylanilines with tert-butyl hydroperoxide (TBHP) as the oxidant. The mechanism consists of a rate-determining single electron transfer (SET) that is uniform from 4-methoxy- to 4-cyano-N,N-dimethylanilines. The tert-butylperoxy radical is the major oxidant in the rate-determining SET step that is followed by competing backward SET and irreversible heterolytic cleavage of the carbon-hydrogen bond at the α-position to nitrogen. A second SET completes the conversion of N,N-dimethylaniline to an iminium ion that is subsequently trapped by the nucleophilic solvent or the oxidant prior to formation of the Mannich adduct. The general role of Rh(2)(cap)(4), RuCl(2)(PPh(3))(3), CuBr, FeCl(3), and Co(OAc)(2) in N,N-dialkylaniline oxidations by T-HYDRO is to initiate the conversion of TBHP to tert-butylperoxy radicals. A second pathway, involving O(2) as the oxidant, exists for copper, iron, and cobalt salts. Results from linear free-energy relationship (LFER) analyses, kinetic and product isotope effects (KIE and PIE), and radical trap experiments of N,N-dimethylaniline oxidation by T-HYDRO in the presence of transition metal catalysts are discussed. Kinetic studies of the oxidative Mannich reaction in methanol and toluene are also reported. PMID:23298175

  13. Cationic Pd(II)-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies

    PubMed Central

    Nishikata, Takashi; Abela, Alexander R; Huang, Shenlin

    2016-01-01

    Summary Cationic palladium(II) complexes have been found to be highly reactive towards aromatic C–H activation of arylureas at room temperature. A commercially available catalyst [Pd(MeCN)4](BF4)2 or a nitrile-free cationic palladium(II) complex generated in situ from the reaction of Pd(OAc)2 and HBF4, effectively catalyzes C–H activation/cross-coupling reactions between aryl iodides, arylboronic acids and acrylates under milder conditions than those previously reported. The nature of the directing group was found to be critical for achieving room temperature conditions, with the urea moiety the most effective in promoting facile coupling reactions at an ortho C–H position. This methodology has been utilized in a streamlined and efficient synthesis of boscalid, an agent produced on the kiloton scale annually and used to control a range of plant pathogens in broadacre and horticultural crops. Mechanistic investigations led to a proposed catalytic cycle involving three steps: (1) C–H activation to generate a cationic palladacycle; (2) reaction of the cationic palladacycle with an aryl iodide, arylboronic acid or acrylate, and (3) regeneration of the active cationic palladium catalyst. The reaction between a cationic palladium(II) complex and arylurea allowed the formation and isolation of the corresponding palladacycle intermediate, characterized by X-ray analysis. Roles of various additives in the stepwise process have also been studied. PMID:27340491

  14. Vitamin E analogue Trolox C. E.s.r. and pulse-radiolysis studies of free-radical reactions.

    PubMed Central

    Davies, M J; Forni, L G; Willson, R L

    1988-01-01

    The reactions between Trolox C, a water-soluble vitamin E analogue, and several oxidizing free radicals including the hydroxyl radical and various peroxy radicals were examined by using the pulse-radiolysis technique. The results demonstrate that Trolox C may undergo rapid one-electron-transfer reactions as well as hydrogen-transfer processes; the resulting phenoxyl radical is shown to be relatively stable, in common with the phenoxyl radical derived from vitamin E. The reactions between the Trolox C phenoxyl radical and a variety of biologically relevant reducing compounds were examined by using both pulse radiolysis and e.s.r. The results demonstrate that the Trolox C phenoxyl radical is readily repaired by ascorbate (k = 8.3 x 10(6) dm3.mol-1.s-1) and certain thiols (k less than 10(5) dm3.mol-1.s-1) but not by urate, NADH or propyl gallate. Evidence from e.s.r. studies indicates that thiol-containing compounds may also enter into similar repair reactions with the alpha-tocopherol phenoxyl radical. Kinetic evidence is presented that suggests that Trolox C may 'repair' proteins that have been oxidized by free radicals. PMID:2849418

  15. New Mechanistic Insights on the Selectivity of Transition-Metal-Catalyzed Organic Reactions: The Role of Computational Chemistry.

    PubMed

    Zhang, Xinhao; Chung, Lung Wa; Wu, Yun-Dong

    2016-06-21

    With new advances in theoretical methods and increased computational power, applications of computational chemistry are becoming practical and routine in many fields of chemistry. In organic chemistry, computational chemistry plays an indispensable role in elucidating reaction mechanisms and the origins of various selectivities, such as chemo-, regio-, and stereoselectivities. Consequently, mechanistic understanding improves synthesis and assists in the rational design of new catalysts. In this Account, we present some of our recent works to illustrate how computational chemistry provides new mechanistic insights for improvement of the selectivities of several organic reactions. These examples include not only explanations for the existing experimental observations, but also predictions which were subsequently verified experimentally. This Account consists of three sections discuss three different kinds of selectivities. The first section discusses the regio- and stereoselectivities of hydrosilylations of alkynes, mainly catalyzed by [Cp*Ru(MeCN)3](+) or [CpRu(MeCN)3](+). Calculations suggest a new mechanism that involves a key ruthenacyclopropene intermediate. This mechanism not only explains the unusual Markovnikov regio-selectivity and anti-addition stereoselectivity observed by Trost and co-workers, but also motivated further experimental investigations. New intriguing experimental observations and further theoretical studies led to an extension of the reaction mechanism. The second section includes three cases of meta-selective C-H activation of aryl compounds. In the case of Cu-catalyzed selective meta-C-H activation of aniline, a new mechanism that involves a Cu(III)-Ar-mediated Heck-like transition state, in which the Ar group acts as an electrophile, was proposed. This mechanism predicted a higher reactivity for more electron-deficient Ar groups, which was supported by experiments. For two template-mediated, meta-selective C-H bond activations catalyzed by

  16. Chemistry of polycyclic aromatic hydrocarbons formation from phenyl radical pyrolysis and reaction of phenyl and acetylene.

    PubMed

    Comandini, A; Malewicki, T; Brezinsky, K

    2012-03-15

    An experimental investigation of phenyl radical pyrolysis and the phenyl radical + acetylene reaction has been performed to clarify the role of different reaction mechanisms involved in the formation and growth of polycyclic aromatic hydrocarbons (PAHs) serving as precursors for soot formation. Experiments were conducted using GC/GC-MS diagnostics coupled to the high-pressure single-pulse shock tube present at the University of Illinois at Chicago. For the first time, comprehensive speciation of the major stable products, including small hydrocarbons and large PAH intermediates, was obtained over a wide range of pressures (25-60 atm) and temperatures (900-1800 K) which encompass the typical conditions in modern combustion devices. The experimental results were used to validate a comprehensive chemical kinetic model which provides relevant information on the chemistry associated with the formation of PAH compounds. In particular, the modeling results indicate that the o-benzyne chemistry is a key factor in the formation of multi-ring intermediates in phenyl radical pyrolysis. On the other hand, the PAHs from the phenyl + acetylene reaction are formed mainly through recombination between single-ring aromatics and through the hydrogen abstraction/acetylene addition mechanism. Polymerization is the common dominant process at high temperature conditions. PMID:22339468

  17. Gas-Phase Ozonolysis of Cycloalkenes: Formation of Highly Oxidized RO2 Radicals and Their Reactions with NO, NO2, SO2, and Other RO2 Radicals.

    PubMed

    Berndt, Torsten; Richters, Stefanie; Kaethner, Ralf; Voigtländer, Jens; Stratmann, Frank; Sipilä, Mikko; Kulmala, Markku; Herrmann, Hartmut

    2015-10-15

    The gas-phase reaction of ozone with C5-C8 cycloalkenes has been investigated in a free-jet flow system at atmospheric pressure and a temperature of 297 ± 1 K. Highly oxidized RO2 radicals bearing at least 5 O atoms in the molecule and their subsequent reaction products were detected in most cases by means of nitrate-CI-APi-TOF mass spectrometry. Starting from a Criegee intermediate after splitting-off an OH-radical, the formation of these RO2 radicals can be explained via an autoxidation mechanism, meaning RO2 isomerization (ROO → QOOH) and subsequently O2 addition (QOOH + O2 → R'OO). Time-dependent RO2 radical measurements concerning the ozonolysis of cyclohexene indicate rate coefficients of the intramolecular H-shifts, ROO → QOOH, higher than 1 s(-1). The total molar yield of highly oxidized products (predominantly RO2 radicals) from C5-C8 cycloalkenes in air is 4.8-6.0% affected with a calibration uncertainty by a factor of about two. For the most abundant RO2 radical from cyclohexene ozonolysis, O,O-C6H7(OOH)2O2 ("O,O" stands for two O atoms arising from the ozone attack), the determination of the rate coefficients of the reaction with NO2, NO, and SO2 yielded (1.6 ± 0.5) × 10(-12), (3.4 ± 0.9) × 10(-11), and <10(-14) cm(3) molecule(-1) s(-1), respectively. The reaction of highly oxidized RO2 radicals with other peroxy radicals (R'O2) leads to detectable accretion products, RO2 + R'O2 → ROOR' + O2, which allows to acquire information on peroxy radicals not directly measurable with the nitrate ionization technique applied here. Additional experiments using acetate as the charger ion confirm conclusively the existence of highly oxidized RO2 radicals and closed-shell products. Other reaction products, detectable with this ionization technique, give a deeper insight in the reaction mechanism of cyclohexene ozonolysis. PMID:26392132

  18. Mechanistic insights into the dehalogenation reaction of fluoroacetate/fluoroacetic acid

    SciTech Connect

    Miranda-Rojas, Sebastián; Toro-Labbé, Alejandro

    2015-05-21

    Fluoroacetate is a toxic compound whose environmental accumulation may represent an important contamination problem, its elimination is therefore a challenging issue. Fluoroacetate dehalogenase catalyzes its degradation through a two step process initiated by an S{sub N}2 reaction in which the aspartate residue performs a nucleophilic attack on the carbon bonded to the fluorine; the second step is hydrolysis that releases the product as glycolate. In this paper, we present a study based on density functional theory calculations of the S{sub N}2 initiation reaction modeled through the interaction between the substrate and the propionate anion as the nucleophile. Results are analyzed within the framework of the reaction force and using the reaction electronic flux to identify and characterize the electronic activity that drives the reaction. Our results reveal that the selective protonation of the substrate catalyzes the reaction by decreasing the resistance of the structural and electronic reorganization needed to reach the transition state. Finally, the reaction energy is modulated by the degree of stabilization of the fluoride anion formed after the S{sub N}2 reaction. In this way, a site-induced partial protonation acts as a chemical switch in a key process that determines the output of the reaction.

  19. A temperature dependent kinetic study of the reaction of the hydroxyl radical with CH2Br

    NASA Technical Reports Server (NTRS)

    Zhang, Zhengyu; Saini, Rameshwar D.; Kurylo, Michael; Huie, Robert E.

    1992-01-01

    Rate constants have been measured for the gas phase reaction of the hydroxyl radical (OH) with CH3Br over the temperature range 250 to 400 K. The Arrhenius expression k = (5.79 x 10 exp -12) exp(-1560/T) cu cm/molecule per sec was derived from the kinetic data. From the rate constant at 277 K, the tropospheric lifetime of CH3Br with respect to reaction with OH is estimated to be 2.2 years and the overall atmospheric lifetime to be 2.1 years.

  20. Mechanistic Insights into Radical-Mediated Oxidation of Tryptophan from ab Initio Quantum Chemistry Calculations and QM/MM Molecular Dynamics Simulations.

    PubMed

    Wood, Geoffrey P F; Sreedhara, Alavattam; Moore, Jamie M; Wang, John; Trout, Bernhardt L

    2016-05-12

    An assessment of the mechanisms of (•)OH and (•)OOH radical-mediated oxidation of tryptophan was performed using density functional theory calculations and ab initio plane-wave Quantum Mechanics/Molecular Mechanics (QM/MM) molecular dynamics simulations. For the (•)OH reactions, addition to the pyrrole ring at position 2 is the most favored site with a barrierless reaction in the gas phase. The subsequent degradation of this adduct through a H atom transfer to water was intermittently observed in aqueous-phase molecular dynamics simulations. For the (•)OOH reactions, addition to the pyrrole ring at position 2 is the most favored pathway, in contrast to the situation in the model system ethylene, where concerted addition to the double bond is preferred. From the (•)OOH position 2 adduct QM/MM simulations show that formation of oxy-3-indolanaline occurs readily in an aqueous environment. The observed transformation starts from an initial rupture of the O-O bond followed by a H atom transfer with the accompanying loss of an (•)OH radical to solution. Finally, classical molecular dynamics simulations were performed to equate observed differential oxidation rates of various tryptophan residues in monoclonal antibody fragments. It was found that simple parameters derived from simulation correlate well with the experimental data. PMID:27082439

  1. Synchronous vs asynchronous diffusion-reaction processes involving geminate radical pairs

    NASA Astrophysics Data System (ADS)

    Urie, Kristopher G.; Kozak, John J.; Abad, E.

    2010-10-01

    We report lattice Monte Carlo calculations to study the efficiency of diffusion-controlled reactive processes involving geminate radical pairs. Whereas our earlier study [J.J. Kozak, C. Nicolis, G. Nicolis, N.J. Turro, J. Phys. Chem. 105 (2001) 10949] focused on factors affecting the reaction efficiency when a pair of coreactants moved synchronously on a surface modeled as a d=2 dimensional square planar lattice subject to periodic boundary conditions, we document here differences in reaction efficiency when a pair of coreactants can move synchronously or asynchronously on surfaces which are topologically different but characterized by the same number N of sites. As before, the first surface is taken to be a d=2 square planar lattice; the second surface considered is a Cartesian shell, the bounded surface of a cube. When studied as a function of system size, we find that synchronous dynamics are more efficient than asynchronous dynamics in optimizing diffusion-reaction processes; and, reactions on planar, periodic surfaces are more efficient than on cubic shells. The relevance of these conclusions to experimental studies on two radiation-induced, radical decay reactions [the one cited above and A.J. Frank, M. Grätzel, J.J. Kozak, J. Am. Chem. Soc. 98 (1976) 3317] is noted and discussed.

  2. Rate constant calculations of H-atom abstraction reactions from ethers by HȮ2 radicals.

    PubMed

    Mendes, Jorge; Zhou, Chong-Wen; Curran, Henry J

    2014-02-27

    In this work, we detail hydrogen atom abstraction reactions from six ethers by the hydroperoxyl radical, including dimethyl ether, ethyl methyl ether, propyl methyl ether, isopropyl methyl ether, butyl methyl ether, and isobutyl methyl ether, in order to test the effect of the functional group on the rate constant calculations. The Møller-Plesset (MP2) method with the 6-311G(d,p) basis set has been employed in the geometry optimizations and frequency calculations of all of the species involved in the above reaction systems. The connections between each transition state and the corresponding local minima have been determined by intrinsic reaction coordinate calculations. Energies are reported at the CCSD(T)/cc-pVTZ level of theory and include the zero-point energy corrections. As a benchmark in the electronic energy calculations, the CCSD(T)/CBS extrapolation was used for the reactions of dimethyl ether + HȮ2 radicals. A systematic calculation of the high-pressure limit rate constants has been performed using conventional transition-state theory, including asymmetric Eckart tunneling corrections, in the temperature range of 500-2000 K. The one dimensional hindrance potentials obtained at MP2/6-311G(d,p) for the reactants and transition states have been used to describe the low frequency torsional modes. Herein, we report the calculated individual, average, and total rate constants. A branching ratio analysis for every reaction site has also been performed. PMID:24483837

  3. A DFT Study Toward the Reaction Mechanisms of TNT With Hydroxyl Radicals for Advanced Oxidation Processes.

    PubMed

    He, Xi; Zeng, Qun; Zhou, Yang; Zeng, Qingxuan; Wei, Xianfeng; Zhang, Chaoyang

    2016-05-26

    The degradation pathway of environmental contaminant 2,4,6-trinitrotoluene (TNT) was investigated computationally at the SMD(Pauling)/M06-2X/6-311+G(d,p) level of theory. The dominant decomposition pathway of TNT → 4,6-dinitro-o-cresol → 4,6-dinitro-2-hydroxybenzylalcohol → 4,6-dinitro-2-hydroxybenzaldehyde was provided, and the corresponding predicted products and their distributions are in a good agreement with available experimental data on TNT degradation by Fenton reaction. It was shown that the mechanism of addition-elimination is crucial for this stage of the reaction. The reaction of H atom abstraction is a minor competing pathway. The details on transition states, intermediate radicals, and free energy surfaces for all proposed reactions are given and make up for a lack of experimental knowledge. PMID:27135259

  4. Menshutkin reaction between DABCO and benzyfluoride/fluorodiphenylmethane: a mechanistic study.

    PubMed

    Singh, Amritpal; Goel, Neetu

    2014-06-01

    The microcosmic mechanism of the Menshutkin reaction between DABCO and benzyl fluoride/fluorodiphenylmethane has been investigated in both the gas and solvent phase by performing DFT calculations at B3LYP/6-31G(d,p) level of theory. The Gibbs free energy profiles to reach the possible transition states, i.e., five-membered ring transition state and SN2 transition state show that the reaction between DABCO and benzyl fluoride proceeds through SN2 transition state in accordance with previously reported studies, while the reaction between DABCO and fluorodiphenylmethane proceeds through five-membered ring transition state contrary to earlier literature. The role of solvent has been elucidated by reoptimizing the structures using SMD model of solvation. Hydrogen bonding and steric hinderance have been identified as the key factors in guiding the reaction pathway of commercially important Menshutkin reaction. PMID:24827613

  5. Explaining the atypical reaction profiles of heme enzymes with a novel mechanistic hypothesis and kinetic treatment.

    PubMed

    Manoj, Kelath Murali; Baburaj, Arun; Ephraim, Binoy; Pappachan, Febin; Maviliparambathu, Pravitha Parapurathu; Vijayan, Umesh K; Narayanan, Sivaprasad Valiyaveettil; Periasamy, Kalaiselvi; George, Ebi Ashley; Mathew, Lazar T

    2010-01-01

    Many heme enzymes show remarkable versatility and atypical kinetics. The fungal extracellular enzyme chloroperoxidase (CPO) characterizes a variety of one and two electron redox reactions in the presence of hydroperoxides. A structural counterpart, found in mammalian microsomal cytochrome P450 (CYP), uses molecular oxygen plus NADPH for the oxidative metabolism (predominantly hydroxylation) of substrate in conjunction with a redox partner enzyme, cytochrome P450 reductase. In this study, we employ the two above-mentioned heme-thiolate proteins to probe the reaction kinetics and mechanism of heme enzymes. Hitherto, a substrate inhibition model based upon non-productive binding of substrate (two-site model) was used to account for the inhibition of reaction at higher substrate concentrations for the CYP reaction systems. Herein, the observation of substrate inhibition is shown for both peroxide and final substrate in CPO catalyzed peroxidations. Further, analogy is drawn in the "steady state kinetics" of CPO and CYP reaction systems. New experimental observations and analyses indicate that a scheme of competing reactions (involving primary product with enzyme or other reaction components/intermediates) is relevant in such complex reaction mixtures. The presence of non-selective reactive intermediate(s) affords alternate reaction routes at various substrate/product concentrations, thereby leading to a lowered detectable concentration of "the product of interest" in the reaction milieu. Occam's razor favors the new hypothesis. With the new hypothesis as foundation, a new biphasic treatment to analyze the kinetics is put forth. We also introduce a key concept of "substrate concentration at maximum observed rate". The new treatment affords a more acceptable fit for observable experimental kinetic data of heme redox enzymes. PMID:20498847

  6. Explaining the Atypical Reaction Profiles of Heme Enzymes with a Novel Mechanistic Hypothesis and Kinetic Treatment

    PubMed Central

    Manoj, Kelath Murali; Baburaj, Arun; Ephraim, Binoy; Pappachan, Febin; Maviliparambathu, Pravitha Parapurathu; Vijayan, Umesh K.; Narayanan, Sivaprasad Valiyaveettil; Periasamy, Kalaiselvi; George, Ebi Ashley; Mathew, Lazar T.

    2010-01-01

    Many heme enzymes show remarkable versatility and atypical kinetics. The fungal extracellular enzyme chloroperoxidase (CPO) characterizes a variety of one and two electron redox reactions in the presence of hydroperoxides. A structural counterpart, found in mammalian microsomal cytochrome P450 (CYP), uses molecular oxygen plus NADPH for the oxidative metabolism (predominantly hydroxylation) of substrate in conjunction with a redox partner enzyme, cytochrome P450 reductase. In this study, we employ the two above-mentioned heme-thiolate proteins to probe the reaction kinetics and mechanism of heme enzymes. Hitherto, a substrate inhibition model based upon non-productive binding of substrate (two-site model) was used to account for the inhibition of reaction at higher substrate concentrations for the CYP reaction systems. Herein, the observation of substrate inhibition is shown for both peroxide and final substrate in CPO catalyzed peroxidations. Further, analogy is drawn in the “steady state kinetics” of CPO and CYP reaction systems. New experimental observations and analyses indicate that a scheme of competing reactions (involving primary product with enzyme or other reaction components/intermediates) is relevant in such complex reaction mixtures. The presence of non-selective reactive intermediate(s) affords alternate reaction routes at various substrate/product concentrations, thereby leading to a lowered detectable concentration of “the product of interest” in the reaction milieu. Occam's razor favors the new hypothesis. With the new hypothesis as foundation, a new biphasic treatment to analyze the kinetics is put forth. We also introduce a key concept of “substrate concentration at maximum observed rate”. The new treatment affords a more acceptable fit for observable experimental kinetic data of heme redox enzymes. PMID:20498847

  7. Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface-Immobilized Copper Thioether Clip-Phen Derivative.

    PubMed

    Romo, Adolfo I B; Abreu, Dieric S; de F Paulo, Tércio; Carepo, Marta S P; Sousa, Eduardo H S; Lemus, Luis; Aliaga, Carolina; Batista, Alzir A; Nascimento, Otaciro R; Abruña, Héctor D; Diógenes, Izaura C N

    2016-07-11

    Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip-phen derivative, 1,3-bis(1,10-phenanthrolin-2-yloxy)-N-(4-(methylthio)benzylidene)propan-2-amine (2CP-Bz-SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric Cu(I) intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H2 O2 , thus pointing to a mechanism involving a Fenton-like reaction that results in the production of OH(.) . PMID:27310653

  8. Mechanistic features of the copper-free Sonogashira reaction from ESI-MS.

    PubMed

    Ahmadi, Zohrab; Yunker, Lars P E; Oliver, Allen G; McIndoe, J Scott

    2015-12-21

    The mechanism of the Sonogashira reaction in methanol was studied in detail using pressurized sample infusion electrospray ionization mass spectrometry (PSI-ESI-MS). Several key intermediates were identified and their structures were assigned by MS/MS studies. Cationic and anionic charged-tagged substrates were employed to look into the mechanism of this reaction from variety of angles. A reverse kinetic isotope effect was observed in which the reaction rate is accelerated in deuterated solvents (kH/kD = 0.6). The reaction was found to be zero order with respect to the aryl iodide and first order with respect to the phenylacetylene. A Hammett parameter of ρ = 1.4 indicates that the reaction is more favorable for aryl iodides with para EWGs. No evidence of product inhibition, dimerization of palladium catalyst, or agglomeration were observed. However, catalyst decomposition was inferred from a non-zero intercept in the plot of catalyst loading versus reaction rate. Monitoring the reaction by PSI-ESI-(-)MS on neutral and negatively charged substrates at variety of concentrations and conditions did not reveal any detectable anionic palladium complexes. Likewise no evidence of carbopalladation and relevant intermediates in the absence of a base was observed. PMID:26469767

  9. Inorganic phosphate promotes redox cycling of iron in liver microsomes: effects on free radical reactions.

    PubMed

    Reinke, L A; Moore, D R; Rau, J M; McCay, P B

    1995-02-01

    The phosphate buffer concentration used in spin trapping experiments with liver microsomes markedly influenced rates of free radical formation from ethanol and dimethylsulfoxide, but not from carbon tetrachloride. Effects of phosphate concentration on ethanol radical formation were abolished by addition of deferoxamine or bathophenanthrolene, indicating that an iron-phosphate complex might be involved. High concentrations of phosphate stimulated rates of microsomal Fe+3 reduction and facilitated the mobilization of microsomal nonheme iron, but had little effect on a variety of microsomal monooxygenase enzyme activities. Although microsomal oxygen utilization and superoxide production were relatively unaffected by phosphate, hydrogen peroxide concentrations were markedly decreased in the presence of high concentrations of phosphate. Taken together, the data suggest that a ferric-phosphate complex may be enzymatically reduced by microsomal enzymes and NADPH. Reoxidation of ferrous ion is nonenzymatically promoted by phosphate and/or H2O2 produced by the microsomes. During the process of reoxidation, one or more oxidizing intermediates may be formed which initiate secondary free radical reactions. Although the reactivity of the intermediate(s) is similar to that of the hydroxyl radical, no spin trapping evidence was obtained to support this assignment. PMID:7864631

  10. Direct Excitation of the Reaction Coordinate: Overtone-Induced Predissociation of the Hydroxymethyl Radical

    NASA Astrophysics Data System (ADS)

    Reisler, Hanna; Ryazanov, Mikhail; Rodrigo, Chirantha P.

    2011-06-01

    The overtone-induced vibrational predissociation of the hydroxymethyl radical is achieved following excitation of the radical to the third O-H stretch overtone. The excited O-H stretch is also the bond that breaks; i.e. overtone excitation is in the reaction coordinate. The production of H atoms takes place via tunneling through the barrier to the H + formaldehyde channel. H-atom photofragment yield spectra in the region of the third overtone reveal two mixed bands with contributions from the third OH overtone and a combination band comprised of two quanta of OH stretch and one quantum of CH asymmetric stretch. Using velocity map imaging, sliced images of H-atom products are obtained with kinetic energy resolution sufficient to reveal the vibrational structure in the formaldehyde co-fragment. As expected, most of the formaldehyde molecules are born without vibrational excitation but some exhibit excitation in other modes, such as wagging and CO stretch. The rotational contours of the vibrational bands are well described by temperatures in the range 100-150 K. Slice imaging allows scanning the pump laser while monitoring H fragments in selected kinetic energy ranges, and in this way it is demonstrated that all the observed vibrational levels of formaldehyde have their parentage in the hydroxymethyl radical. The barrier to isomerization to methoxy is comparable to the barrier to direct dissociation and the role of isomerization is investigated by using partially deuterated radicals.

  11. Mechanistic and kinetic study on the reactions of coumaric acids with reactive oxygen species: a DFT approach.

    PubMed

    Garzón, Andrés; Bravo, Iván; Barbero, Antonio J; Albaladejo, José

    2014-10-01

    The mechanism and kinetics of reactions between coumaric acids and a series of reactive oxygen species ((•)OX) was studied through the density functional theory (DFT). H atom abstraction from -OH and -COOH groups and addition to the nonaromatic double bond were the most representative reaction pathways chosen for which free energy barriers and rate constants were calculated within the transition state theory (TST) framework. From these calculations, it was estimated that (•)OH > (•)OCH3 > (•)OOH > (•)OOCH3 is the order of reactivity of (•)OX with any coumaric acid. The highest rate constant was estimated for p-coumaric acid + (•)OH reaction, whereas the rest of the (•)OX species are more reactive with o-coumaric acid. On the basis of the calculated rate constants, H abstraction from a -OH group should be the main mechanism for the reactions involving (•)OCH3, (•)OOH, and (•)OOCH3 radicals. Nevertheless, the addition mechanism, which sometimes is not considered in theoretical studies on reactions of phenolic compounds with electrophilic species, could play a relevant role in the global mechanism of coumaric acid + (•)OH reactions. PMID:25166496

  12. Coal liquefaction model studies: free radical chain decomposition of diphenylpropane, dibenzyl ether, and phenyl ether via. beta. -scission reactions

    SciTech Connect

    Gilbert, K.E.; Gajewski, J.J.

    1982-01-01

    The thermal decompositions of 1,3-diphenylpropane (1), dibenzyl ether (2), and phenethyl phenyl ether (3) have been found to proceed by free radical chain processes. 1 gave toluene and styrene with a reaction order of 1.55, E/sub A/ = 51.4 kcal/mol, and log A = 12.5. The reaction could be initiated by benzyl phenyl ether but not by 1,2-diphenylethane. 2 gave toluene and benzaldehyde with a reaction order of 1.43, E/sub A/ = 48 kcal/mol, and log A = 12.6. The reaction could be initiated with benzyl phenyl ether. 3 gave phenol and styrene with a reaction order of 1.21, E/sub A/ = 50.3 kcal/mol, and log A = 12.3. The reaction could be initiated by benzyl phenyl ether. All of the data are consistent with free radical chain processes with the reaction order determined by the termination reaction. No evidence for concerted reactions has been found. The thermal chemistry of three-atom links is best described by free radical chain processes. The products are consistent with a free radical chain process involving a ..beta..-scission reaction, and the reaction orders range between first and three-halves order depending upon the nature of the chain termination reaction. Activation parameters are readily estimated from thermochemical kinetic data on the individual reactions with log A approx. = 12 and E/sub A/approx. = 50 kcal/mol. Unlike the one- and two-atom linkages, reactions of the three-atom linkages are promoted by free radical initiators. The potential for inhibition of free radical chains also exists and is currently being studied. 4 tables.

  13. Ruthenium Catalyzed Intramolecular C-S Coupling Reactions: Synthetic Scope and Mechanistic Insight.

    PubMed

    Sharma, Shivani; Pathare, Ramdas S; Maurya, Antim K; Gopal, Kandasamy; Roy, Tapta Kanchan; Sawant, Devesh M; Pardasani, Ram T

    2016-02-01

    A ruthenium catalyzed intramolecular C-S coupling reaction of N-arylthioureas for the synthesis of 2-aminobenzothiazoles has been developed. Kinetic, isotope labeling, and computational studies reveal the involvement of an electrophilic ruthenation pathway instead of a direct C-H activation. Stereoelectronic effect of meta-substituents on the N-arylthiourea dictates the final regioselective outcome of the reaction. PMID:26761401

  14. Peroxyl Radical Reactions in Water Solution: A Gym for Proton-Coupled Electron-Transfer Theories.

    PubMed

    Amorati, Riccardo; Baschieri, Andrea; Morroni, Gloria; Gambino, Rossana; Valgimigli, Luca

    2016-06-01

    The reactions of alkylperoxyl radicals with phenols have remained difficult to investigate in water. We describe herein a simple and reliable method based on the inhibited autoxidation of water/THF mixtures, which we calibrated against pulse radiolysis. With this method we measured the rate constants kinh for the reactions of 2-tetrahydrofuranylperoxyl radicals with reference compounds: urate, ascorbate, ferrocenes, 2,2,5,7,8-pentamethyl-6-chromanol, Trolox, 6-hydroxy-2,5,7,8-tetramethylchroman-2-acetic acid, 2,6-di-tert-butyl-4-methoxyphenol, 4-methoxyphenol, catechol and 3,5-di-tert-butylcatechol. The role of pH was investigated: the value of kinh for Trolox and 4-methoxyphenol increased 11- and 50-fold from pH 2.1 to 12, respectively, which indicate the occurrence of a SPLET-like mechanism. H(D) kinetic isotope effects combined with pH and solvent effects suggest that different types of proton-coupled electron transfer (PCET) mechanisms are involved in water: less electron-rich phenols react at low pH by concerted electron-proton transfer (EPT) to the peroxyl radical, whereas more electron-rich phenols and phenoxide anions react by multi-site EPT in which water acts as proton relay. PMID:27111024

  15. Ab initio molecular dynamics of the reaction of quercetin with superoxide radical

    NASA Astrophysics Data System (ADS)

    Lespade, Laure

    2016-08-01

    Superoxide plays an important role in biology but in unregulated concentrations it is implicated in a lot of diseases such as cancer or atherosclerosis. Antioxidants like flavonoids are abundant in plant and are good scavengers of superoxide radical. The modeling of superoxide scavenging by flavonoids from the diet still remains a challenge. In this study, ab initio molecular dynamics of the reaction of the flavonoid quercetin toward superoxide radical has been carried out using Car-Parrinello density functional theory. The study has proven different reactant solvation by modifying the number of water molecules surrounding superoxide. The reaction consists in the gift of a hydrogen atom of one of the hydroxyl groups of quercetin to the radical. When it occurs, it is relatively fast, lower than 100 fs. Calculations show that it depends largely on the environment of the hydroxyl group giving its hydrogen atom, the geometry of the first water layer and the presence of a certain number of water molecules in the second layer, indicating a great influence of the solvent on the reactivity.

  16. Surprisingly Long-Lived Ascorbyl Radicals in Acetonitrile: Concerted Proton-Electron Transfer Reactions and Thermochemistry

    PubMed Central

    Warren, Jeffrey J.; Mayer, James M.

    2008-01-01

    Proton-coupled electron transfer (PCET) reactions and thermochemistry of 5,6-isopropylidene ascorbate (iAscH−) have been examined in acetonitrile solvent.iAscH− is oxidized by 2,4,6-tBu3C6H2O• and by excess TEMPO• to give the corresponding 5,6-isopropylidene ascorbyl radical anion (iAsc•−), which persists for hours at 298 K in dry MeCN solution. The stability of iAsc•− is surprising in light of the transience of the ascorbyl radical in aqueous solutions, and is due to the lack of the protons needed for radical disproportionation. A concerted proton-electron transfer (CPET) mechanism is indicated for the reactions of iAscH−. Redox potential, pKa and equilibrium measurements define the thermochemical landscape for 5,6-isopropylidene ascorbic acid and its derivatives in MeCN. These measurements give an O–H bond dissociation free energy (BDFE) for iAscH−of 65.4 ± 1.5 kcal mol−1 in MeCN. Similar studies on underivatized ascorbate indicate a BDFE of 67.8 ± 1.2 kcal mol−1. These values are much lower than the aqueous BDFE for ascorbate of 74.0 ± 1.5 kcal mol−1 derived from reported data. PMID:18505256

  17. Surprisingly long-lived ascorbyl radicals in acetonitrile: concerted proton-electron transfer reactions and thermochemistry.

    PubMed

    Warren, Jeffrey J; Mayer, James M

    2008-06-18

    Proton-coupled electron transfer (PCET) reactions and thermochemistry of 5,6-isopropylidene ascorbate (iAscH-) have been examined in acetonitrile solvent. iAscH- is oxidized by 2,4,6-tBu3C6H2O. and by excess TEMPO. to give the corresponding 5,6-isopropylidene ascorbyl radical anion (iAsc.-), which persists for hours at 298 K in dry MeCN solution. The stability of iAsc.- is surprising in light of the transience of the ascorbyl radical in aqueous solutions and is due to the lack of the protons needed for radical disproportionation. A concerted proton-electron transfer (CPET) mechanism is indicated for the reactions of iAscH-. Redox potential, pKa and equilibrium measurements define the thermochemical landscape for 5,6-isopropylidene ascorbic acid and its derivatives in MeCN. These measurements give an O-H bond dissociation free energy (BDFE) for iAscH- of 65.4 +/- 1.5 kcal mol-1 in MeCN. Similar studies on underivatized ascorbate indicate a BDFE of 67.8 +/- 1.2 kcal mol-1. These values are much lower than the aqueous BDFE for ascorbate of 74.0 +/- 1.5 kcal mol-1 derived from reported data. PMID:18505256

  18. Products and kinetics of the heterogeneous reaction of particulate ametryn with NO3 radicals.

    PubMed

    Liu, Chang-Geng; Shu, Ji-Nian; Yang, Bo; Zhang, Peng

    2014-12-01

    As a renowned s-triazine herbicide, ametryn is worldwide emitted into the atmosphere in both gaseous and particulate phases via spray drifts from treatments and post application emissions, but its chemical degradation in the atmosphere has not been well characterized. In this study, the heterogeneous kinetics of particulate ametryn with NO3 radicals were investigated with a mixed-phase relative rate method. A vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and an atmospheric gas analysis mass spectrometer were synchronously used to online monitor the decays of particulate ametryn and gas-phase isoprene. The reactive uptake coefficient of NO3 radicals on ametryn particles was calculated to be 2.9 × 10(-2), according to the measured ametryn loss ratio and the average NO3 concentration. The effective rate constant for the heterogeneous reaction of particulate ametryn with NO3 radicals measured under experimental conditions was 8.4 × 10(-13) cm(3) molecule(-1) s(-1). In addition, atraton, ametryn sulfoxide and ametryn sulfone were identified as the reaction products by gas-chromatography-mass spectrometry (GC-MS) analysis. The experimental results might shed light on the chemical behavior of atmospheric ametryn at night-time. PMID:25301341

  19. Aluminium ion-promoted radical-scavenging reaction of methylated hydroquinone derivatives.

    PubMed

    Nakanishi, Ikuo; Ohkubo, Kei; Ogawa, Yukihiro; Matsumoto, Ken-Ichiro; Ozawa, Toshihiko; Fukuzumi, Shunichi

    2016-08-16

    The effect of the aluminium ion (Al(3+)) on the scavenging reaction of a 2,2-diphenyl-1-picrylhydrazyl radical (DPPH˙), as a reactivity model of reactive oxygen species, with hydroquinone (QH2) and its methylated derivatives (MenQH2, n = 1-4) was investigated using stopped-flow and electrochemical techniques in a hydroalcoholic medium. The second-order rate constants (k) for the DPPH˙-scavenging reaction of the hydroquinones increased with the increasing number of methyl substituents. Upon addition of Al(3+), the k values significantly increased depending on the concentration of Al(3+). Such an accelerating effect of Al(3+) on the DPPH˙-scavenging rates of the hydroquinones results from the remarkable positive shift of the one-electron reduction potential (Ered) of DPPH˙ in the presence of Al(3+). These results demonstrate that Al(3+), a strong Lewis acid, can act as a radical-scavenging promoter by stabilising the one-electron reduced species of the radical, although Al(3+) is reported not only to act as a pro-oxidant but also to strongly interact with biomolecules, showing toxicities. PMID:27492849

  20. Gas-phase reactions of organic radicals and diradicals with ions

    NASA Astrophysics Data System (ADS)

    Zhang, Xu; Bierbaum, Veronica M.; Ellison, G. Barney; Kato, Shuji

    2004-02-01

    Reactions of polyatomic organic radicals with gas phase ions have been studied at thermal energy using a flowing afterglow-selected ion flow tube (FA-SIFT) instrument. A supersonic pyrolysis nozzle produces allyl radical (CH2CHCH2) and ortho-benzyne diradical (o-C6H4) for reaction with ions. We have observed: [CH2CHCH2+H3O+→C3H6++H2O], [CH2CHCH2+HO-→no ion products], [o-C6H4+H3O+→C6H5++H2O], and [o-C6H4+HO-→C6H3-+H2O]. The proton transfer reactions with H3O+ occur at nearly every collision (kII≅10-9 cm3s-1). The exothermic proton abstraction for o-C6H4+HO- is unexpectedly slow (kII≅10-10 cm3s-1). This has been rationalized by competing associative detachment: o-C6H4+HO-→C6H5O+e-. The allyl+HO- reaction proceeds presumably via similar detachment pathways.

  1. Gas-Phase Reaction of Hydroxyl Radical with p-Cymene over an Extended Temperature Range.

    PubMed

    Bedjanian, Yuri; Morin, Julien; Romanias, Manolis N

    2015-11-12

    The kinetics of the reaction of OH radicals with p-cymene has been studied in the temperature range of 243-898 K using a flow reactor combined with a quadrupole mass spectrometer: OH + p-cymene → products. The reaction rate constant was determined as a result of absolute measurements, from OH decay kinetics in excess of p-cymene and employing the relative rate method with OH reactions with n-pentane, n-heptane,1,3-dioxane, HBr, and Br2 as the reference ones. For the rate coefficient of the H atom abstraction channel, the expression k1b = (3.70 ± 0.42) × 10(-11) exp[-(772 ± 72)/T] was obtained over the temperature range of 381-898 K. The total rate constant (addition + abstraction) determined at T = 243-320 K was k1 = (1.82 ± 0.48) × 10(-12) exp[(607 ± 70)/T] or, in a biexponential form, k1 = k1a + k1b = 3.7 × 10(-11) exp(-772/T) + 6.3 × 10(-13) exp(856/T), independent of the pressure between 1 and 5 Torr of helium. In addition, our results indicate that the reaction pathway involving alkyl radical elimination upon initial addition of OH to p-cymene is most probably unimportant. PMID:26473634

  2. Investigation of terpinolene + ozone or terpinolene + nitrate radical reaction products using denuder/filter apparatus

    NASA Astrophysics Data System (ADS)

    Harrison, Joel C.; Wells, J. R.

    2013-12-01

    Terpinolene's (1-methyl-4-(propan-2-ylidene)cyclohexene) reaction with ozone or the nitrate radical was investigated using a denuder/filter apparatus in order to characterize gas-phase and particulate reaction products. Identification of the reaction products (i.e., aldehydes, ketones, dicarbonyls and carboxylic acids) was made using two derivatization methods; O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) to derivatize the carbonyl products or 3-Ethyl-1-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDC) and 2,2,2-trifluoroethylamine hydrochloride (TFEA) to derivatize the carboxylic acid products. Proposed carbonyl products for ozonolysis of terpinolene are: 4-methylcyclohex-3-en-1-one, 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, 3-oxobutanal, and 6-oxo-3-(propan-2-ylidene)heptanal. Proposed carbonyl products for nitrate radical reaction of terpinolene are: 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, and 4-oxopentanal. No carboxylic acid products were detected with either oxidizing reactant.

  3. Investigation of terpinolene + ozone or terpinolene + nitrate radical reaction products using denuder/filter apparatus

    PubMed Central

    Harrison, Joel C.; Wells, J.R.

    2015-01-01

    Terpinolene’s (1-methyl-4-(propan-2-ylidene)cyclohexene) reaction with ozone or the nitrate radical was investigated using a denuder/filter apparatus in order to characterize gas-phase and particulate reaction products. Identification of the reaction products (i.e., aldehydes, ketones, dicarbonyls and carboxylic acids) was made using two derivatization methods; O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) to derivatize the carbonyl products or 3-Ethyl-1-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDC) and 2,2,2-trifluoroethylamine hydrochloride (TFEA) to derivatize the carboxylic acid products. Proposed carbonyl products for ozonolysis of terpinolene are: 4-methylcyclohex-3-en-1-one, 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, 3-oxobutanal, and 6-oxo-3-(propan-2-ylidene)heptanal. Proposed carbonyl products for nitrate radical reaction of terpinolene are: 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, and 4-oxopentanal. No carboxylic acid products were detected with either oxidizing reactant. PMID:26527171

  4. Aqueous Secondary Organic Aerosol (aqSOA) Formation By Radical Reactions: Model Studies Comparing the Role of OH Versus Organic Radicals

    NASA Astrophysics Data System (ADS)

    Ervens, B.; Renard, P.; Reed Harris, A.; Vaida, V.; Monod, A.

    2014-12-01

    Chemical reactions in the aqueous phase are thought to significantly contribute to ambient aerosol mass under specific conditions. Results from many laboratory studies suggest that these reactions are efficiently initiated by the OH radical and lead to high molecular weight compounds (oligomers). Recent laboratory experiments have shown that methyl vinyl ketone (MVK) can form oligomers in high yield in aqueous solutions similar to aerosol water. Additional experiments have shown that the direct photolysis of pyruvic acid can generate organic radicals that initiate similar oligomer products upon oxidation of MVK (Renard et al., submitted). Sources of the OH radical in the aerosol aqueous phase include the direct uptake from the gas phase, Fenton reactions and, to a smaller extent, direct photolyses of hydrogen peroxide and nitrate. Recent model studies imply that under many conditions, aqSOA formation might be oxidant-limited since these OH(aq) sources are not sufficient to provide a continuous OH supply. This limitation can be (partially) removed if additional radical sources in the multiphase system are considered. Exemplary, we include the direct photolysis of aqueous pyruvic acid as a proxy for possible other radical sources. Model results will be shown and consequences for aqSOA formation and processing under ambient conditions will be discussed.

  5. Cyclic Versus Linear Isomers Produced by Reaction of the Methylidyne Radical (CH) with Small Unsaturated Hydrocarbons

    SciTech Connect

    Goulay, Fabien; Trevitt, Adam J.; Meloni, Giovanni; Selby, Talitha M.; Osborn, David L.; Taatjes, Craig A.; Vereecken, Luc; Leone, Stephen R.

    2008-12-05

    The reactions of the methylidyne radical (CH) with ethylene, acetylene, allene, and methylacetylene are studied at room temperature using tunable vacuum ultraviolet (VUV) photoionization and time-resolved mass spectrometry. The CH radicals are prepared by 248 nm multiphoton photolysis of CHBr3 at 298 K and react with the selected hydrocarbon in a helium gas flow. Analysis of photoionization efficiency versus VUV photon wavelength permits isomer-specific detection of the reaction products and allows estimation of the reaction product branching ratios. The reactions proceed by either CH insertion or addition followed by H atom elimination from the intermediate adduct. In the CH + C2H4 reaction the C3H5 intermediate decays by H atom loss to yield 70(+-8)percent allene, 30(+-8)percent methylacetylene and less than 10percent cyclopropene, in agreement with previous RRKM results. In the CH + acetylene reaction, detection of mainly the cyclic C3H2 isomer is contrary to a previous RRKM calculation that predicted linear triplet propargylene to be 90percent of the total H-atom co-products. High-level CBS-APNO quantum calculations and RRKM calculation for the CH + C2H2 reaction presented in this manuscript predict a higher contribution of the cyclic C3H2 (27.0percent) versus triplet propargylene (63.5percent) than these earlier predictions. Extensive calculations on the C3H3 and C3H2D system combined with experimental isotope ratios for the CD + C2H2 reaction indicate that H-atom assisted isomerization in the present experiments is responsible for the discrepancy between the RRKM calculations and the experimental results. Cyclic isomers are also found to represent 30(+-6)percent of the detected products in the case of CH + methylacetylene, together with 33(+-6)percent 1,2,3-butatriene and 37(+-6)percent vinylacetylene. The CH + allene reaction gives 23(+-5)percent 1,2,3-butatriene and 77(+-5)percent vinylacetylene, whereas cyclic isomers are produced below the detection limit

  6. Reactions of clofibric acid with oxidative and reductive radicals-Products, mechanisms, efficiency and toxic effects

    NASA Astrophysics Data System (ADS)

    Csay, Tamás; Rácz, Gergely; Salik, Ádám; Takács, Erzsébet; Wojnárovits, László

    2014-09-01

    The degradation of clofibric acid induced by hydroxyl radical, hydrated electron and O2-•/HO2• reactive species was studied in aqueous solutions. Clofibric acid was decomposed more effectively by hydroxyl radical than by hydrated electron or O2-•/HO2•. Various hydroxylated, dechlorinated and fragmentation products have been identified and quantified. A new LC-MS method was developed based on 18O isotope labeling to follow the formation of hydroxylated derivatives of clofibric acid. Possible degradation pathways have been proposed. The overall degradation was monitored by determination of sum parameters like COD, TOC and AOX. It was found that the organic chlorine degrades very effectively prior to complete mineralization. After the treatment no toxic effect was found according to Vibrio fischeri tests. However, at early stages some of the reaction products were more harmful than clofibric acid.

  7. Relative rate constants for the reactions of atomic oxygen with HO2 anad OH radicals

    NASA Technical Reports Server (NTRS)

    Keyser, L. F.

    1983-01-01

    Relative rate constants for the reactions O + HO2 - OH + O2 (1) and O + OH - H + O2 (2) were obtained by using the discharge-flow resonance fluorescence technique at 2 torr total pressure and 299 K. HO2 radicals were generated by reacting atomic hydrogen with an excess of O2. Quasi-steady-state concentrations of OH and HO2 were established in the presence of excess atomic oxygen. Observed concentration ratios, namely the ratio of the OH concentration to the HO2 concentration, resulted in a value of 1.7 + or 0.2 for k1/k2. The error limits are twice the standard deviation obtained from the data analysis. Overall experimental error is estimated to be + or - 25 percent. This result confirms earlier direct measurements of k1 and k2 which required knowledge of absolute radical or atomic oxygen concentrations.

  8. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

    NASA Astrophysics Data System (ADS)

    Lewis, Alan M.; Manolopoulos, David E.; Hore, P. J.

    2014-07-01

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene triad containing considerably more nuclear spins which has recently been used to establish a "proof of principle" for the operation of a chemical compass [K. Maeda, K. B. Henbest, F. Cintolesi, I. Kuprov, C. T. Rodgers, P. A. Liddell, D. Gust, C. R. Timmel, and P. J. Hore, Nature (London) 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C.+PF.- radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical.

  9. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions.

    PubMed

    Lewis, Alan M; Manolopoulos, David E; Hore, P J

    2014-07-28

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene triad containing considerably more nuclear spins which has recently been used to establish a "proof of principle" for the operation of a chemical compass [K. Maeda, K. B. Henbest, F. Cintolesi, I. Kuprov, C. T. Rodgers, P. A. Liddell, D. Gust, C. R. Timmel, and P. J. Hore, Nature (London) 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C(·+)PF(·-) radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical. PMID:25084885

  10. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

    SciTech Connect

    Lewis, Alan M.; Manolopoulos, David E.; Hore, P. J.

    2014-07-28

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene triad containing considerably more nuclear spins which has recently been used to establish a “proof of principle” for the operation of a chemical compass [K. Maeda, K. B. Henbest, F. Cintolesi, I. Kuprov, C. T. Rodgers, P. A. Liddell, D. Gust, C. R. Timmel, and P. J. Hore, Nature (London) 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C{sup ·+}PF{sup ·−} radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical.

  11. Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

    PubMed Central

    Behenna, Douglas C.; Mohr, Justin T.; Sherden, Nathaniel H.; Marinescu, Smaranda C.; Harned, Andrew M.; Tani, Kousuke; Seto, Masaki; Ma, Sandy; Novák, Zoltán; Krout, Michael R.; McFadden, Ryan M.; Roizen, Jennifer L.; Enquist, John A.; White, David E.; Levine, Samantha R.; Petrova, Krastina V.; Iwashita, Akihiko; Virgil, Scott C.; Stoltz, Brian M.

    2012-01-01

    α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursors: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center. PMID:22083969

  12. Enantioselective decarboxylative alkylation reactions: catalyst development, substrate scope, and mechanistic studies.

    PubMed

    Behenna, Douglas C; Mohr, Justin T; Sherden, Nathaniel H; Marinescu, Smaranda C; Harned, Andrew M; Tani, Kousuke; Seto, Masaki; Ma, Sandy; Novák, Zoltán; Krout, Michael R; McFadden, Ryan M; Roizen, Jennifer L; Enquist, John A; White, David E; Levine, Samantha R; Petrova, Krastina V; Iwashita, Akihiko; Virgil, Scott C; Stoltz, Brian M

    2011-12-01

    α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center. PMID:22083969

  13. Mechanistic insight into the hydrazine decomposition on Rh(111): effect of reaction intermediate on catalytic activity.

    PubMed

    Deng, Zhigang; Lu, Xiaoqing; Wen, Zengqiang; Wei, Shuxian; Liu, Yunjie; Fu, Dianling; Zhao, Lianming; Guo, Wenyue

    2013-10-14

    Periodic density functional theory (DFT) calculations have been performed to systematically investigate the effect of reaction intermediate on catalytic activity for hydrazine (N2H4) decomposition on Rh(111). Reaction mechanisms via intramolecular and NH2-assisted N2H4 decompositions are comparatively analyzed, including adsorption configuration, reaction energy and barrier of elementary step, and reaction network. Our results show that the most favorable N2H4 decomposition pathway starts with the initial N-N bond scission to the NH2 intermediate, followed by stepwise H stripping from adsorbed N2Hx (x = 1-4) species, and finally forms the N2 and NH3 products. Comparatively, the stepwise intramolecular dehydrogenation via N2H4→ N2H3→ N2H2→ N2H → N2, and N2H4→ NH2→ NH → N with or without NH2 promotion effect, are unfavorable due to higher energy barriers encountered. Energy barrier analysis, reaction rate constants, and electronic structures are used to identify the crucial competitive route. The promotion effect of the NH2 intermediate is structurally reflected in the weakening of the N-H bond and strengthening of the N-N bond in N2Hx in the coadsorption system; it results intrinsically from the less structural deformation of the adsorbate, and weakening of the interaction between dehydrogenated fragment and departing H in transition state. Our results highlight the crucial effect of reaction intermediate on catalytic activity and provide a theoretical approach to analyze the effect. PMID:23990024

  14. Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide

    NASA Astrophysics Data System (ADS)

    Birdsall, A. W.; Miner, C. R.; Mael, L. E.; Elrod, M. J.

    2014-08-01

    Recently, methacrylic acid epoxide (MAE) has been proposed as a precursor to an important class of isoprene-derived compounds found in secondary organic aerosol (SOA): 2-methylglyceric acid (2-MG) and a set of oligomers, nitric acid esters and sulfuric acid esters related to 2-MG. However, the specific chemical mechanisms by which MAE could form these compounds have not been previously studied. In order to determine the relevance of these processes to atmospheric aerosol, MAE and 2-MG have been synthesized and a series of bulk solution-phase experiments aimed at studying the reactivity of MAE using nuclear magnetic resonance (NMR) spectroscopy have been performed. The present results indicate that the acid-catalyzed MAE reaction is more than 600 times slower than a similar reaction of an important isoprene-derived epoxide, but is still expected to be kinetically feasible in the atmosphere on more acidic SOA. The specific mechanism by which MAE leads to oligomers was identified, and the reactions of MAE with a number of atmospherically relevant nucleophiles were also investigated. Because the nucleophilic strengths of water, sulfate, alcohols (including 2-MG), and acids (including MAE and 2-MG) in their reactions with MAE were found to be of a similar magnitude, it is expected that a diverse variety of MAE + nucleophile product species may be formed on ambient SOA. Thus, the results indicate that epoxide chain reaction oligomerization will be limited by the presence of high concentrations of non-epoxide nucleophiles (such as water); this finding is consistent with previous environmental chamber investigations of the relative humidity-dependence of 2-MG-derived oligomerization processes and suggests that extensive oligomerization may not be likely on ambient SOA because of other competitive MAE reaction mechanisms.

  15. Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide

    NASA Astrophysics Data System (ADS)

    Birdsall, A. W.; Miner, C. R.; Mael, L. E.; Elrod, M. J.

    2014-12-01

    Recently, methacrylic acid epoxide (MAE) has been proposed as a precursor to an important class of isoprene-derived compounds found in secondary organic aerosol (SOA): 2-methylglyceric acid (2-MG) and a set of oligomers, nitric acid esters, and sulfuric acid esters related to 2-MG. However, the specific chemical mechanisms by which MAE could form these compounds have not been previously studied with experimental methods. In order to determine the relevance of these processes to atmospheric aerosol, MAE and 2-MG have been synthesized and a series of bulk solution-phase experiments aimed at studying the reactivity of MAE using nuclear magnetic resonance (NMR) spectroscopy have been performed. The present results indicate that the acid-catalyzed MAE reaction is more than 600 times slower than a similar reaction of an important isoprene-derived epoxide, but is still expected to be kinetically feasible in the atmosphere on more acidic SOA. The specific mechanism by which MAE leads to oligomers was identified, and the reactions of MAE with a number of atmospherically relevant nucleophiles were also investigated. Because the nucleophilic strengths of water, sulfate, alcohols (including 2-MG), and acids (including MAE and 2-MG) in their reactions with MAE were found to be of similar magnitudes, it is expected that a diverse variety of MAE + nucleophile product species may be formed on ambient SOA. Thus, the results indicate that epoxide chain reaction oligomerization will be limited by the presence of high concentrations of non-epoxide nucleophiles (such as water); this finding is consistent with previous environmental chamber investigations of the relative humidity dependence of 2-MG-derived oligomerization processes and suggests that extensive oligomerization may not be likely on ambient SOA because of other competitive MAE reaction mechanisms.

  16. CN radical reactions with hydrogen cyanide and cyanogen - Comparison of theory and experiment

    NASA Technical Reports Server (NTRS)

    Yang, D. L.; Yu, T.; Lin, M. C.; Melius, C. F.

    1992-01-01

    The method of laser photolysis/laser-induced fluorescence is used to obtain absolute rate constants for CN radical reactions with HCN and C2N2. The rate constants were found to be temperature-dependent in the range 300-740 K and pressure independent in the range 100-600 Torr. Rice-Remsperger-Kassel-Marcus theory for both reactions employing the transition state parameters obtained by the BAC-MP4 method are made. These calculations yielded reasonable results for the CN + HCN reaction, predicting both the temperature dependence and pressure independence. No pressure effect was observed in the pressure range 100-1000 Torr at temperatures below 900 K, confirming the experimental results.

  17. Theoretical study on the gas phase reaction of allyl chloride with hydroxyl radical.

    PubMed

    Zhang, Yunju; Chao, Kai; Sun, Jingyu; Zhang, Wanqiao; Shi, Haijie; Yao, Cen; Su, Zhongmin; Pan, Xiumei; Zhang, Jingping; Wang, Rongshun

    2014-02-28

    The reaction of allyl chloride with the hydroxyl radical has been investigated on a sound theoretical basis. This is the first time to gain a conclusive insight into the reaction mechanism and kinetics for important pathways in detail. The reaction mechanism confirms that OH addition to the C=C double bond forms the chemically activated adducts, IM1 (CH2CHOHCH2Cl) and IM2 (CH2OHCHCH2Cl) via low barriers, and direct H-abstraction paths may also occur. Variational transition state model and multichannel RRKM theory are employed to calculate the temperature-, pressure-dependent rate constants. The calculated rate constants are in good agreement with the experimental data. At 100 Torr with He as bath gas, IM6 formed by collisional stabilization is the major products in the temperature range 200-600 K; the production of CH2CHCHCl via hydrogen abstractions becomes dominant at high temperatures (600-3000 K). PMID:24588171

  18. Fundamental kinetics and mechanistic pathways for oxidation reactions in supercritical water

    NASA Technical Reports Server (NTRS)

    Webley, Paul A.; Tester, Jefferson W.

    1988-01-01

    Oxidation of the products of human metabolism in supercritical water has been shown to be an efficient way to accomplish the on-board water/waste recycling in future long-term space flights. Studies of the oxidation kinetics of methane to carbon dioxide in supercritical water are presented in this paper in order to enhance the fundamental understanding of the oxidation of human waste compounds in supercritical water. It is concluded that, although the elementary reaction models remain the best hope for simulating oxidation in supercritical water, several modifications to existing mechanisms need to be made to account for the role of water in the reaction mechanism.

  19. Elusive Reaction Intermediates in Solution Explored by ESI-MS: Reverse Periscope for Mechanistic Investigations.

    PubMed

    Iacobucci, Claudio; Reale, Samantha; De Angelis, Francesco

    2016-02-24

    Just as periscopes allow a submarine to visually search for objects above the surface of the sea, in a reversed periscope fashion electrospray mass spectrometry (ESI-MS) can analyze the compounds at the gas phase/liquid phase interface for chemical entities which may exist in solution. The challenge is the identification and structural characterization of key elusive reaction intermediates in chemical transformations, intermediates which are able to explain how chemical processes occur. This Minireview summarizes recent selected publications on the use of ESI-MS techniques for studying solution intermediates of homogeneous chemical reactions. PMID:26799781

  20. Low-temperature Kinetic Studies of OH Radical Reactions Relevant to Planetary Atmospheres

    NASA Astrophysics Data System (ADS)

    Townsend, T. M.; Antiñolo, M.; Ballesteros, B.; Jimenez, E.; Canosa, A.

    2011-05-01

    In the solar system, the temperature (T) of the atmosphere of giant planets or their satellites is only several tens of Kelvin (K). The temperature of the tropopause of Titan (satellite of Saturn) and the surface of Mars is 70 K and 210 K, respectively. In the Earth's atmosphere, T decreases from 298 K (surface) to 210 K close to the T-inversion region (tropopause). The principal oxidants in the Earth's lower atmosphere are ozone, the hydroxyl (OH) radical and hydrogen peroxide. A number of critical atmospheric chemical problems depend on the Earth's oxidising capacity, which is essentially the global burden of these oxidants. In the interstellar clouds and circumstellar envelopes, OH radicals have also been detected. As the chemistry of atmospheres is highly influenced by temperature, the knowledge of the T-dependence of the rate coefficients for OH-reactions (k) is the key to understanding the underlying molecular mechanisms. In general, these reactions take place on a short temporal scale. Therefore, a detection technique with high temporal resolution is required. Measurements of k at low temperatures can be achieved by maintaining a thermalised environment using either cryogenic cooling (T>200 K) or supersonic gas expansion with a Laval nozzle (several tens of K). The pulsed laser photolysis technique coupled with laser induced fluorescence detection has been widely used in our laboratory to determine the rate coefficients of OH-reactions with different volatile organic compounds, such as alcohols (1), saturated and unsaturated aliphatic aldehydes (2), linear ketones (3), as a function of temperature (260 350 K). An experimental system based on the CRESU (Cinetique de Reaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique is currently under construction. This technique will allow the performance of kinetic studies of OH-reactions of astrophysical interest at temperatures lower than 200 K.

  1. Kinetic and mechanistic study of the atmospheric reaction of MBO331 with Cl atoms

    NASA Astrophysics Data System (ADS)

    Rodríguez, Diana; Rodríguez, Ana; Garzón, Andrés; Granadino-Roldán, José M.; Soto, Amparo; Aranda, Alfonso; Notario, Alberto

    2012-12-01

    The present work deals with the reaction of 3-methyl-3-buten-1-ol (MBO331) with Cl atoms, which has been investigated by gas chromatography with flame ionization detection (GC-FID) at atmospheric pressure in N2 or air, using the relative rate technique. The rate constant reaction at 298 ± 1 K was found to be (5.01 ± 0.70) × 10-10 cm3 molecule-1 s-1, using cyclohexane, octane and 1-butene as a reference compounds. The temperature dependence for the reaction was studied within the 298-333 K range. Additionally, a product identification under atmospheric conditions has been performed for the first time by GC-MS, with 3-methyl-3-butenal, methacrolein and chloroacetone being observed as degradation products. A theoretical study on the reaction at the QCISD(T)/6-311G**//MP2/6-311G** level was also carried out to obtain more information on the mechanism. From the theoretical study it can be predicted that Cl addition to the double bond proceeds through lower energy barriers than H-abstraction pathways and therefore is energetically favoured. Finally, atmospheric implications of the results obtained are discussed.

  2. INTERACTIONS OF LIGHT AND CHEMICAL REACTIONS IN THE AQUATIC ENVIRONMENT: KINETIC AND MECHANISTIC ASPECTS

    EPA Science Inventory

    Changes in the ozone layer over the past two decades have resulted in increases in solar ultraviolet (UV) radiation that reaches the surface of aquatic environments. Recent studies have demonstrated that these UV increases cause changes in photochemical reactions that affect the...

  3. Kinetic and mechanistic study of reaction between sulfide and sulfite in aqueous solution

    SciTech Connect

    Siu, T.; Jia, C.Q.

    1999-10-01

    The reaction between sulfide and sulfite in neutral to weak alkaline aqueous solutions was studied by following thiosulfate and sulfite concentrations using ion chromatography. The thiosulfate formation rate from the reaction 2HS{sup {minus}} + 4HSO{sub 3}{sup {minus}} {yields} 3S{sub 2}O{sub 3}{sup 2{minus}} + 3H{sub 2}O at pH 8 to 9 was found to be d[S{sub 2}O{sub 3}{sup 2{minus}}]/dt = k{sub A}[HS{sup {minus}}][HSO{sub 3}{sup {minus}}]{sup 2}, where k{sub A} = 1.1 x 10{sup 12} exp({minus}48000/RT) M{sup {minus}2} s{sup {minus}1}. A mechanism for this reaction has been proposed with disulfite (S{sub 2}O{sub 5}{sup 2{minus}}) and HSO{sub 2}{sup {minus}} intermediates. The measured rate of sulfite disappearance was higher than that calculated from the stoichiometry of the above reaction. This phenomenon is attributed to other reactions, that consume sulfite and form other sulfur compounds such as polythionates, polysulfides, and elemental sulfur. These reactions were treated as a single reaction, whose rate was found to be ({minus}d[HSO{sub 3}{sup {minus}}]/dt){sub B} = k{sub B}[H{sup +}]{sup {minus}0.6}[HS{sup {minus}}]{sup 0.7}[HSO{sub 3}{sup {minus}}]{sup 1.5}, where k{sub B} = 5 x 10{sup {minus}5} M{sup {minus}0.6} s{sup {minus}1} at 20 C. A kinetic model was established on the basis of the kinetic data obtained in this and a previous work. The experimental data at pH 7 agreed with the model prediction in a satisfactory manner. The biphasic behavior of thiosulfate is considered to be critical in developing a new sulfur-producing flue gas desulfurization (SP-FGD) process based on sulfur dioxide absorption using sodium sulfide solution.

  4. On the time behaviour of the concentration of pyrazinium radical cations in the early stage of the Maillard reaction

    NASA Astrophysics Data System (ADS)

    Stoesser, Reinhard; Klein, Jeannette; Peschke, Simone; Zehl, Andrea; Cämmerer, Bettina; Kroh, Lothar W.

    2007-08-01

    During the early stage of the Maillard reaction pyrazinium radical cations were detected by ESR within the reaction system D-glucose/glycine. The spectra were characterized by completely resolved hyperfine structure. The partial pressure of oxygen and the radical concentrations were measured directly in the reaction mixture by ESR using solutions of the spin probe TEMPOL and of DPPH, respectively. There are quantitative and qualitative relations of the actual concentration of the radical ions to the partial pressure of oxygen, the temperature-time regime and the mechanical mixing of the reaction system. These macroscopic parameters significantly affect both the induction period and the velocity of the time-dependent formation of free radicals. From in situ variations of p(O 2) and p(Ar) including the connected mixing effects caused by the passing the gases through the reaction mixture, steric and chemical effects of the stabilization of the radical ions were established. The determination of suitable and relevant conditions for stabilization and subsequent radical reactions contributes to the elucidation of the macroscopically known antioxidant activity of Maillard products.

  5. Laser Flash Photolysis Studies of Radical-Radical Reaction Kinetics: The O((sup 3)P(sub J)) + BrO Reaction

    NASA Technical Reports Server (NTRS)

    Thorn, R. P.; Cronkhite, J. M.; Nicovich, J. M.; Wine, P. H.

    1997-01-01

    A novel dual laser flash photolysis-long path absorption-resonance fluorescence technique has been employed to study the kinetics of the important stratospheric reaction 0((sup 3)P(sub j)) + Br yields(k1) BrO((sup 2)P(sub J)) + O2 as a function of temperature (231-328 K) and pressure (25-150 Torr) in N2 buffer gas. The experimental approach preserves the principal advantages of the flash photolysis method, i.e., complete absence of surface reactions and a wide range of accessible pressures, but also employs techniques which are characteristic of the discharge flow method, namely chemical titration as a means for deducing the absolute concentration of a radical reactant and use of multiple detection axes. We find that k1 is independent of pressure, and that the temperature dependence of k1 is adequately described by the Arrhenius expression k1(T) = 1.91 x 10(exp -11)(230/J) cu cm/ molecule.s; the absolute accuracy of measured values for k1 is estimated to vary from +/- 20 percent at at T approximately 230 K to +/- 30 percent at T approximately 330 K. Our results demonstrate that the O((sup 3)P(sub j)) + BrO rate coefficient is significantly faster than previously 'guesstimated,' and suggest that the catalytic cycle with the O((sup 3)P(sub j)) + BrO reaction as its rate-limiting step is the dominant stratospheric BrO(x), odd-oxygen destruction cycle at altitudes above 24 km.

  6. Products of the OH radical-initiated reactions of 2- and 3-hexyl nitrate

    NASA Astrophysics Data System (ADS)

    Aschmann, Sara M.; Arey, Janet; Atkinson, Roger

    2012-01-01

    Products of the gas-phase reaction of OH radicals with 2-hexyl nitrate (containing 13% 3-hexyl nitrate) have been investigated by gas chromatography with mass spectral and flame ionization detection, and by direct air sampling atmospheric pressure ionization tandem mass spectrometry. The products identified and quantified from 2-hexyl nitrate were: 2-hexanone (8.6 ± 1.3%), propanal (3.4 ± 0.8%), butanal (2.3 ± 0.6%) and 5-hydroxy-2-hexanone (25%), where the molar yields are given in parentheses. 3-Hexanone was observed from the 3-hexyl nitrate reaction, with a molar formation yield of 9.5 ± 2.1%. Organic nitrates of molecular weight 133, 161, 177 and 208 were also observed, and these are attributed to C 4-carbonyl nitrate(s), C 6-carbonyl-nitrates, C 6-hydroxycarbonyl-nitrates and C 6-dinitrates, respectively, and are expected to account for all or most of the non-quantified reaction products from OH + 2- and 3-hexyl nitrate. 5-Hydroxy-2-hexanone formation indicates that the CH 3CH(ONO 2)CH 2CH 2CH(O rad )CH 3 alkoxy radical dominantly reacts by isomerization.

  7. Kinetic Reaction Mechanism of Sinapic Acid Scavenging NO2 and OH Radicals: A Theoretical Study.

    PubMed

    Lu, Yang; Wang, AiHua; Shi, Peng; Zhang, Hui; Li, ZeSheng

    2016-01-01

    The mechanism and kinetics underlying reactions between the naturally-occurring antioxidant sinapic acid (SA) and the very damaging ·NO2 and ·OH were investigated through the density functional theory (DFT). Two most possible reaction mechanisms were studied: hydrogen atom transfer (HAT) and radical adduct formation (RAF). Different reaction channels of neutral and anionic sinapic acid (SA-) scavenging radicals in both atmosphere and water medium were traced independently, and the thermodynamic and kinetic parameters were calculated. We find the most active site of SA/SA- scavenging ·NO2 and ·OH is the -OH group in benzene ring by HAT mechanism, while the RAF mechanism for SA/SA- scavenging ·NO2 seems thermodynamically unfavorable. In water phase, at 298 K, the total rate constants of SA eliminating ·NO2 and ·OH are 1.30×108 and 9.20×109 M-1 S-1 respectively, indicating that sinapic acid is an efficient scavenger for both ·NO2 and ·OH. PMID:27622460

  8. The role of radical and molecular reactions in the processes of ozonization of aqueous solutions of non-dissociating compounds

    NASA Astrophysics Data System (ADS)

    Ignat'ev, A. N.; Pryakhin, A. N.; Lunin, V. V.

    2010-04-01

    A theoretical approach to determining regions where ozonation proceeds by radical and molecular mechanisms is proposed. Ozonation of aqueous solutions of non-dissociating substances in open and closed reactors is considered. The effect of the values of the rate constants of reactions between the substrate and ozone, OH radicals, and O- ions, as well as that of the conditions of ozonation (pH of the solution, concentration of the reagents, and so on) on the role of radical and molecular reactions in the ozonation of chemical compounds is analyzed.

  9. Kinetic and mechanistic study of the reaction of atomic chlorine with dimethyl sulfide

    SciTech Connect

    Stickel, R.E.; Nicovich, J.M.; Wang, S.; Zhao, Z.; Wine, P.H.

    1992-11-26

    Time-resolved resonance fluorescence detection of Cl({sup 2}P{sub J}) following 266-nm laser flash photolysis of Cl{sub 2}CO/CH{sub 3}SCH{sub 3}(DMS)/N{sub 2} mixtures has been employed to study the kinetics of the title reaction over the temperature and pressure ranges 240-421 K and 3-700 Torr. The reaction is found to be very fast, occurring on essentially every Cl({sup 2}P{sub J}) + DMS encounter. The reaction rate increases with decreasing temperature and shows a significant pressure dependence. At 297 K, for example, the rate coefficient increases from a low-pressure limit value of approximately 1.8 x 10{sup {minus}10} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} to a value of (3.3 {+-} 0.5) x 10{sup {minus}10} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} at P = 700 Torr. A few experiments were carried out with CD{sub 3}SCD{sub 3} or C{sub 2}H{sub 5}SC{sub 2}H{sub 5} replacing DMS as the sulfide reactant; within experimental uncertainty, no dependence of the rate coefficient on the identity of the sulfide reactant was observed. In a separate study, time-resolved tunable diode laser spectroscopic detection of HCl has been coupled with 248-nm laser flash photolysis of Cl{sub 2}CO/DMS/CO{sub 2}/N{sub 2} mixtures to measure the HCl product yield from the title reaction as a function of pressure at T = 297 K. The HCl yield approaches unity as P {yields} 0 but decreases with increasing pressure to a value of {approximately}0.5 at P = 203 Torr. The yield experiments demonstrate that hydrogen abstraction is the dominant reaction mechanism in the low-pressure limit. With increasing pressure, stabilization of a (CH{sub 3}){sub 2}SCl adduct apparently becomes competitive with the hydrogen abstraction pathway. The potential role of the title reaction in marine atmospheric chemistry is discussed. 59 refs., 7 figs., 3 tabs.

  10. Kinetics of hydrogen abstraction reactions of butene isomers by OH radical

    SciTech Connect

    Sun, Hongyan; Law, Chung K.

    2010-11-26

    The rate coefficients of H-abstraction reactions of butene isomers by the OH radical were determined by both canonical variational transition-state theory and transition-state theory, with potential energy surfaces calculated at the CCSD(T)/6-311++G(d,p)//BH&HLYP/6-311G(d,p) level and CCSD(T)/6-311++G(d,p)//BH&HLYP/cc-pVTZ level and quantum mechanical tunneling effect corrected by either the small-curvature tunneling method or the Eckart method. While 1-butene contains allylic, vinylic, and alkyl hydrogens that can be abstracted to form different butene radicals, results reveal that s-allylic H-abstraction channels have low and broad energy barriers, and they are the most dominant channels which can occur via direct and indirect H-abstraction channels. For the indirect H-abstraction s-allylic channel, the reaction can proceed via forming two van der Waals prereactive complexes with energies that are 2.7-2.8 kcal mol-1 lower than that of the entrance channel at 0 K. Assuming that neither mixing nor crossover occurs between different reaction pathways, the overall rate coefficient was calculated by summing the rate coefficients of the s-allyic, methyl, and vinyl H-abstraction paths and found to agree well with the experimentally measured OH disappearance rate. Furthermore, the rate coefficients of p-allylic H abstraction of cis-2-butene, trans-2-butene, and isobutene by the OH radical were also determined at 300-1500 K, with results analyzed and compared with available experimental data.

  11. Theoretical investigation on H abstraction reaction mechanisms and rate constants of Isoflurane with the OH radical

    NASA Astrophysics Data System (ADS)

    Ren, Hongjiang; Li, Xiaojun

    2015-12-01

    The mechanism of H abstraction reactions for Isoflurane with the OH radical was investigated using density functional theory and G3(MP2) duel theory methods. The geometrical structures of all the species were fully optimised at B3LYP/6-311++G** level of theory. Thermochemistry data were obtained by utilising the high accurate model chemistry method G3(MP2) combined with the standard statistical thermodynamic calculations. Gibbs free energies were used for the reaction channels analysis. All the reaction channels were confirmed throughout the intrinsic reaction coordinate analysis. The results show that two channels were obtained, which correspond to P(1) and P(2) with the respective activation barriers of 63.03 and 54.82 kJ/mol. The rate constants for the two channels over a wide temperature range of 298.15-2000 K were predicted and the calculated data are in agreement with the experimental one. The results show that P(2) is the dominant reaction channel under 800 K and above 800 K, it can be found that P(1) will be more preferable reaction channel.

  12. Rapid reaction of nanomolar Mn(II) with superoxide radical in seawater and simulated freshwater

    USGS Publications Warehouse

    Hansard, S.P.; Easter, H.D.; Voelker, B.M.

    2011-01-01

    Superoxide radical (O2-) has been proposed to be an important participant in oxidation-reduction reactions of metal ions in natural waters. Here, we studied the reaction of nanomolar Mn(II) with O 2- in seawater and simulated freshwater, using chemiluminescence detection of O2- to quantify the effect of Mn(II) on the decay kinetics of O2-. With 3-24 nM added [Mn(II)] and <0.7 nM [O2-], we observed effective second-order rate constants for the reaction of Mn(II) with O2- of 6 ?? 106 to 1 ?? 107 M -1???s-1 in various seawater samples. In simulated freshwater (pH 8.6), the effective rate constant of Mn(II) reaction with O 2- was somewhat lower, 1.6 ?? 106 M -1???s-1. With higher initial [O2-], in excess of added [Mn(II)], catalytic decay of O 2- by Mn was observed, implying that a Mn(II/III) redox cycle occurred. Our results show that reactions with nanomolar Mn(II) could be an important sink of O2- in natural waters. In addition, reaction of Mn(II) with superoxide could maintain a significant fraction of dissolved Mn in the +III oxidation state. ?? 2011 American Chemical Society.

  13. Nickel-Catalyzed Allylic Alkylation with Diarylmethane Pronucleophiles: Reaction Development and Mechanistic Insights.

    PubMed

    Sha, Sheng-Chun; Jiang, Hui; Mao, Jianyou; Bellomo, Ana; Jeong, Soo A; Walsh, Patrick J

    2016-01-18

    Palladium-catalyzed allylic substitution reactions are among the most efficient methods to construct C-C bonds between sp(3)-hybridized carbon atoms. In contrast, much less work has been done with nickel catalysts, perhaps because of the different mechanisms of the allylic substitution reactions. Palladium catalysts generally undergo substitution by a "soft"-nucleophile pathway, wherein the nucleophile attacks the allyl group externally. Nickel catalysts are usually paired with "hard" nucleophiles, which attack the metal before C-C bond formation. Introduced herein is a rare nickel-based catalyst which promotes substitution with diarylmethane pronucleophiles by the soft-nucleophile pathway. Preliminary studies on the asymmetric allylic alkylation are promising. PMID:26756444

  14. Electrocatalysis in alkaline media: Mechanistic studies of fuel cell reactions on well-defined model catalysts

    NASA Astrophysics Data System (ADS)

    Spendelow, Jacob S.

    Scanning tunneling microscopy and electrochemical techniques have been used to study several electrocatalytic reactions occurring on Pt(111) and Pt(111)/Ru surfaces in alkaline media. The reactions chosen, CO oxidation, methanol oxidation, and oxygen reduction, are relevant to direct methanol fuel cells (DMFCs). Each is relatively slow, and therefore requires high loading of precious metal catalysts to achieve sufficient fuel cell power density. The focus of these studies has been on determining mechanisms and limiting factors in each reaction. Special attention has been given to the role of adsorbed Ru and the role of Pt defects in enhancing catalytic activity. All defects were found to be more active than terraces for CO oxidation on Pt(111) in alkaline media at DMFC-relevant potentials. Step-typed defects enhance methanol dehydrogenation, but kink-type defects are inactive for this reaction. All defects are inactive for oxygen reduction. These observations can be explained in terms of the local geometric and electronic structure at defects. Adsorbate-adsorbate repulsions, with resultant effects on activation barriers, control the rates of CO oxidation, as well as methanol oxidation. In the case of CO, coverage-dependent CO-CO repulsions and OH-OH repulsions on defects both enhance kinetics. In the case of methanol, repulsive interactions with CO decrease the rate of methanol dehydrogenation, thus giving rise to the CO poisoning effect. Ru was found to promote both methanol dehydrogenation and CO oxidation on adjacent Pt sites. Ru enhances methanol dehydrogenation through two distinct ligand effects: it increases the intrinsic dehydrogenation activity of adjacent Pt sites, and it causes CO to diffuse away from these active sites, decreasing the CO poisoning effect. A Ru ligand effect also enhances CO oxidation by weakening the Pt-CO bond. Ru supplies adsorbed OH for bifunctional CO oxidation, but since Pt defects can also supply OH in alkaline media, the Ru

  15. [Utilizing fereducer reaction to enhance DC corona radical shower for benzene treatment].

    PubMed

    Li, Ming-Bo; Kang, Ying; Wu, Zu-cheng

    2005-11-01

    Fereducer reaction is introduced to enhance DC corona radicals shower for removal of benzene in air. In the presence of nozzle electrode gas containing Fereducer reagent, the enhanced decomposing efficiencies were 21% and 4.2% for benzene concentration of 953 mg/m3 and 63 mg/m3, respectively. The enhancement of benzene removal was remarkable in the presence of nozzle electrode gas (O2, H2O) with the highest removal rate of 89.6%. Lower initial concentration of benzene has higher removal efficiency. However, higher absolute removal rate would be achieved when initial concentration of benzene was higher. PMID:16447423

  16. Theoretical study of the reaction mechanism of a series of 4-hydroxycoumarins against the DPPH radical

    NASA Astrophysics Data System (ADS)

    Rodríguez, Sergio A.; Baumgartner, Maria T.

    2014-05-01

    Structural, electronic and energetic characteristics of a series of 4-hydroxycoumarin derivatives have been studied using DFT to elucidate the mechanisms involved in their antiradical activities against DPPH radical. Different mechanisms were examined. The thermodynamic parameters obtained were BDE, IP, ETE, PA and PDE, both in gas and methanolic phase. The evaluation of these parameters allowed to conclude that the most probable mechanism was HAT. In addition, the transition state (TS) and pre-TS complex for the reaction of hydroxycoumarins and DPPHrad were calculated. The results provide a physicochemical understanding of the hydrogen abstraction of a no-phenolic hydroxyl.

  17. Mechanistic Insights into RNA Transphosphorylation from Kinetic Isotope Effects and Linear Free Energy Relationships of Model Reactions

    PubMed Central

    Chen, Haoyuan; Giese, Timothy J.; Huang, Ming; Wong, Kin-Yiu; Harris, Michael E.; York, Darrin M.

    2015-01-01

    Phosphoryl transfer reactions are ubiquitous in biology, and the understanding of the mechanisms whereby these reactions are catalyzed by protein and RNA enzymes is central to reveal design principles for new therapeutics. Two of the most powerful experimental probes of chemical mechanism involve the analysis of linear free energy relations (LFERs) and the measurement of kinetic isotope effects (KIEs). These experimental data report directly on differences in bonding between the ground state and the rate-controlling transition state, which is the most critical point along the reaction free energy pathway. However, interpretation of LFER and KIE data in terms of transition state structure and bonding optimally requires the use of theoretical models. In this work, we apply density-functional calculations to determine KIEs for a series of phosphoryl transfer reactions of direct relevance to the 2’-O-transphosphorylation that leads to cleavage of the phosphodiester backbone of RNA. We first examine a well-studied series of phosphate and phosphorothioate mono-, di- and triesters that are useful as mechanistic probes and for which KIEs have been measured. Close agreement is demonstrated between the calculated and measured KIEs, establishing the reliability of our quantum model calculations. Next, we examine a series of RNA transesterification model reactions with a wide range of leaving groups in order to provide a direct connection between observed Brønsted coefficients and KIEs with the structure and bonding in the transition state. These relations can be used for prediction or to aid in the interpretation of experimental data for similar non-enzymatic and enzymatic reactions. Finally, we apply these relations to RNA phosphoryl transfer catalyzed by ribonuclease A, and demonstrate the reaction coordinate-KIE correlation is reasonably preserved. A prediction of the secondary deuterium KIE in this reaction is also provided. These results demonstrate the utility of

  18. Mechanistic Studies of the Solvolyses of Carbamoyl Chlorides and Related Reactions

    PubMed Central

    D’Souza, Malcolm J.; Kevill, Dennis N.

    2016-01-01

    Carbamoyl chlorides are important intermediates, both in the research laboratory and in industrial scale syntheses. The most studied and used are the disubstituted derivatives, incorporating either aryl or alkyl groups (Ar2NCOCl or R2NCOCl). Sometimes, the groups are tied back to give a ring and piperidino- and morpholino-derivatives are commonly encountered. Some studies have been made with two different groups attached. Solvolyses tend to occur at the carbonyl carbon, with replacement of the chloride ion. Studies of both rate and products are reviewed and the solvolysis reactions are usually SN1, although addition of an amine leads to a superimposable bimolecular component. Many of the studies under solvolytic conditions include the application of the extended Grunwald–Winstein equation. The monosubstituted derivatives (ArNHCOCl or RNHCOCl) are less studied. They are readily prepared by the addition of HCl to an isocyanate. In acetonitrile, they decompose to set up and reach equilibrium with the isocyanate (ArNCO or RNCO) and HCl. Considering that the structurally related formyl chloride (HOCOCl) is highly unstable (with formation of HCl + CO2), the unsubstituted carbamoyl chloride (H2NCOCl) is remarkably stable. Recommended synthetic procedures require it to survive reaction temperatures in the 300–400 °C range. There has been very little study of its reactions. PMID:26784185

  19. 6- and 14-Fluoro farnesyl diphosphate: mechanistic probes for the reaction catalysed by aristolochene synthase.

    PubMed

    Miller, David J; Yu, Fanglei; Knight, David W; Allemann, Rudolf K

    2009-03-01

    The catalytic mechanism of the enzyme aristolochene synthase from Penicillium roqueforti (PR-AS) has been probed with the farnesyl diphosphate analogues 6- and 14-fluoro farnesyl diphosphate (1a and 1c). Incubation of these analogues with PR-AS followed by analysis of the reaction products by GC-MS and NMR spectroscopy indicated that these synthetic FPP analogues were converted to the fluorinated germacrene A analogues 3b and 3c, respectively. In both cases the position of the fluorine atom prevented the formation of the eudesmane cation analogues 4b and 4c. These results highlight that germacrene A is an on-path reaction intermediate during PR-AS catalysis and shed light on the mechanism by which germacrene A is converted to eudesmane cation. They support the proposal that the role of PR-AS in the cyclisation is essentially passive in that it harnesses the inherent chemical reactivity present in the substrate by promoting the initial ionisation of farnesyl diphosphate and by acting as a productive template to steer the reaction through an effective series of cyclisations and rearrangements to (+)-aristolochene (7a). PMID:19225680

  20. Mechanistic Studies of the Solvolyses of Carbamoyl Chlorides and Related Reactions.

    PubMed

    D'Souza, Malcolm J; Kevill, Dennis N

    2016-01-01

    Carbamoyl chlorides are important intermediates, both in the research laboratory and in industrial scale syntheses. The most studied and used are the disubstituted derivatives, incorporating either aryl or alkyl groups (Ar2NCOCl or R2NCOCl). Sometimes, the groups are tied back to give a ring and piperidino- and morpholino-derivatives are commonly encountered. Some studies have been made with two different groups attached. Solvolyses tend to occur at the carbonyl carbon, with replacement of the chloride ion. Studies of both rate and products are reviewed and the solvolysis reactions are usually SN1, although addition of an amine leads to a superimposable bimolecular component. Many of the studies under solvolytic conditions include the application of the extended Grunwald-Winstein equation. The monosubstituted derivatives (ArNHCOCl or RNHCOCl) are less studied. They are readily prepared by the addition of HCl to an isocyanate. In acetonitrile, they decompose to set up and reach equilibrium with the isocyanate (ArNCO or RNCO) and HCl. Considering that the structurally related formyl chloride (HOCOCl) is highly unstable (with formation of HCl + CO2), the unsubstituted carbamoyl chloride (H2NCOCl) is remarkably stable. Recommended synthetic procedures require it to survive reaction temperatures in the 300-400 °C range. There has been very little study of its reactions. PMID:26784185

  1. Mechanistic insight into the Staudinger reaction catalyzed by N-heterocyclic carbenes.

    PubMed

    Hans, Morgan; Wouters, Johan; Demonceau, Albert; Delaude, Lionel

    2013-07-15

    Four zwitterions were prepared by treating 1,3-dimesitylimidazolin-2-ylidene (SIMes) or 1,3-dimesitylimidazol-2-ylidene (IMes) with either N-tosyl benzaldimine or diphenylketene. They were isolated in high yields and characterized by IR and NMR spectroscopy. The molecular structures of three of them were determined by using X-ray crystallography and their thermal stability was monitored by using thermogravimetric analysis. The imidazol(in)ium-2-amides were rather labile white solids that did not show any tendency to tautomerize into the corresponding 1,2,2-triaminoethene derivatives. They displayed a mediocre catalytic activity in the Staudinger reaction of N-tosyl benzaldimine with diphenylketene. In contrast, the imidazol(in)ium-2-enolates were orange-red crystalline materials that remained stable over extended periods of time. Despite their greater stability, these zwitterions turned out to be efficient promoters for the model cycloaddition under scrutiny. As a matter of fact, their catalytic activity matched those recorded with the free carbenes. Altogether, these results provide strong experimental insight into the mechanism of the Staudinger reaction catalyzed by N-heterocyclic carbenes. They also highlight the superior catalytic activity of the imidazole-based carbene IMes compared with its saturated analogue SIMes in the reaction under consideration. PMID:23754585

  2. The reactions of pyridinyl thioesters with triiron dodecacarbonyl: their novel diiron carbonyl complexes and mechanistic investigations.

    PubMed

    Long, Li; Xiao, Zhiyin; Zampella, Giuseppe; Wei, Zhenhong; De Gioia, Luca; Liu, Xiaoming

    2012-08-21

    Reaction of Fe(3)(CO)(12) with pyridinyl thioester ligand PyCH(2)SCOCH(3) (L(1), Py = pyridin-2-yl) produced complex, [Fe(2)(κ-COCH(3))(μ-SCH(2)Py)(CO)(5)] (1) (PyCH(2)S = pyridin-2-ylmethanethiolate). When complex 1 reacted with PPh(3), a monosubstituted complex, [Fe(2)(κ-COCH(3))(μ-SCH(2)Py)(CO)(4)PPh(3)] (2), was derived. Reaction of the same precursor with analogous thioester ligand PyCH(2)SCOPy (L(2)) generated three novel diiron complexes, [Fe(2)(κ-Py)(μ-SCH(2)Py)(CO)(5)] (3), [Fe(2)(κ-Py)'(μ-SCH(2)Py)(CO)(5)] (4), and [Fe(2)(κ-Py)(μ-SCH(2)Py)(CO)(6)] (5). Complexes 3 and 4 are structural isomers. Complex 5 could be converted into complex 4 but the conversion from complex 5 to the isomer 3 was not observed. All the five complexes were fully characterised using FTIR, NMR, and other techniques. Their structures were determined using X-ray single crystal diffraction analysis. The oxidative formation of complexes 1, 3, 4, and 5 involved C-S and/or C-C bonds cleavages. To probe possible mechanisms for these cleavages, DFT calculations were performed. From the calculations, viable reaction pathways leading to the formation of all the isolated products were delineated. The results of the theoretic calculations also allowed rationalisation of the experimental observations. PMID:22751866

  3. An ab initio investigation of possible intermediates in the reaction of the hydroxyl and hydroperoxyl radicals

    NASA Technical Reports Server (NTRS)

    Jackels, C. F.

    1985-01-01

    Ab initio quantum chemical techniques are used to investigate covalently-bonded and hydrogen-bonded species that may be important intermediates in the reaction of hydroxyl and hydroperoxyl radicals. Stable structures of both types are identified. Basis sets of polarized double zeta quality and large scale configuration interaction wave functions are utilized. Based on electronic energies, the covalently bonded HOOOH species is 26.4 kcal/mol more stable than the OH and HO2 radicals. Similarly, the hydrogen bonded HO---HO2 species has an electronic energy 4.7 kcal/mol below that of the component radicals, after correction is made for the basis set superposition error. The hydrogen bonded form is planar, possesses one relatively normal hydrogen bond, and has the lowest energy 3A' and 1A' states that are essentially degenerate. The 1A" and 3A" excited states produced by rotation of the unpaired OH electron into the molecular plane are very slightly bound.

  4. Evidence for a radical relay mechanism during reaction of surface-immobilized molecules

    SciTech Connect

    Buchanan, A.C. III; Britt, P.F.; Thomas, K.B.; Biggs, C.A.

    1996-03-06

    The impact of restricted mass transport on high-temperature, free-radical reactions has been explored through the use of organic compounds immobilized on silica surfaces by a thermally robust Si-O-C{sub aromatic} linkage. The rate of thermolysis of surface-immobilized 1,3-diphenylpropane(=DPP) at 375{degree}C under vacuum, by a free-radical chain pathway, was found to be very sensitive (factor of 40 variation) to the structure and orientation of a second, neighboring spacer molecule on the surface. Compared with the inert aromatic spacers, (e.g., biphenyl) it was found that spacer molecules containing reactive benzylic C-H bonds (e.g., diphenylmethane) are capable of accelerating the =DPP thermolysis by a process that is unique to diffusionally constrained systems. A mechanism involving rapid serial hydrogen transfer steps on the surface is proposed, which results in radical intermediates being relayed across the surface and hence overcoming classical diffusional limitations. 33 refs., 3 figs., 3 tabs.

  5. Effects of edaravone on experimental brain injury in view of free radical reaction.

    PubMed

    Nakamura, H; Uzura, M; Uchida, K; Nakayama, H; Furuya, Y; Hayashi, T; Sekino, H; Ominato, M; Owada, S

    2003-01-01

    The purpose of this study is to clarify the influence of a novel free radical scavenger edaravone on experimental brain injury. Male Wistar rats were anesthetized with 1-2% halothane. Brain injury was produced using a controlled cortical impact injury device. Experimental rats were divided into 2 groups. In the edaravone group, edaravone (3 mg/kg) was twice administered intravenously for 30 minutes. In the saline group, saline solution was administered in the same way. This administration of edaravone or saline solution made it possible to evaluate the relative effects of edaravone by assessment of free radical reaction and water content. As a result, the level of oxygen free radicals at 50 minutes after brain injury was significantly lower in the edaravone group than in the saline group. The water content in the injured brain at 180 minutes was significantly lower in the edaravone group than in the saline group. Therefore, we propose that edaravone may be effective for treatment in head injury. PMID:14753459

  6. Predicting the reaction rate constants of micropollutants with hydroxyl radicals in water using QSPR modeling.

    PubMed

    Jin, Xiaohui; Peldszus, Sigrid; Huck, Peter M

    2015-11-01

    Quantitative structure-property relationship (QSPR) models which predict hydroxyl radical rate constants (kOH) for a wide range of emerging micropollutants are a cost effective approach to assess the susceptibility of these contaminants to advanced oxidation processes (AOPs). A QSPR model for the prediction of kOH of emerging micropollutants from their physico-chemical properties was developed with special attention to model validation, applicability domain and mechanistic interpretation. In this study, 118 emerging micropollutants including those experimentally determined by the author and data collected from the literature, were randomly divided into the training set (n=89) and validation set (n=29). 951 DRAGON molecular descriptors were calculated for model development. The QSPR model was calibrated by applying forward multiple linear regression to the training set. As a result, 7 DRAGON descriptors were found to be important in predicting the kOH values which related to the electronegativity, polarizability, and double bonds, etc. of the compounds. With outliers identified and removed, the final model fits the training set very well and shows good robustness and internal predictivity. The model was then externally validated with the validation set showing good predictive power. The applicability domain of the model was also assessed using the Williams plot approach. Overall, the developed QSPR model provides a valuable tool for an initial assessment of the susceptibility of micropollutants to AOPs. PMID:26005810

  7. Mechanistic studies of the reaction of reduced methane monooxygenase hydroxylase with dioxygen and substrates

    SciTech Connect

    Valentine, A.M.; Stahl, S.S.; Lippard, S.J.

    1999-04-28

    Soluble methane monooxygenase (sMMO) catalyzes the oxidation of methane to methanol. Single-turnover reactions of sMMO from Methylococcus capsulatus (Bath) were studied by stopped-flow optical spectroscopy to examine further the activated dioxygen intermediates and their reactions with hydrocarbon substrates. A diiron(III) peroxo species designated H{sub peroxo} is the first intermediate observed in the reaction between the chemically reduced hydroxylase (H{sub red}) and dioxygen. The optical spectrum of this species determined by diode array detection is presented for the first time and exhibits visible absorption bands with {lambda}{sub max} {approx} 420 nm ({epsilon} = 4,000 M{sup {minus}1} cm{sup {minus}1}) and {lambda}{sub max} = 725 nm ({epsilon} = 1,800 M{sup {minus}1} cm{sup {minus}1}). The temperature dependences of the rate constants for formation and decay of H{sub peroxo} and for the subsequent intermediate, Q, were examined in the absence and in the presence of hydrocarbon substrates, and activation parameters for these reactions were determined. For single-turnover reaction kinetics monitored at 420 nm, the {lambda}{sub max} for Q, a nonlinear Eyring plot was obtained when acetylene or methane was present in sufficiently high concentration. This behavior reflects a two-step mechanism, Q formation followed by Q decay, in which the rate-determining step changes depending on the temperature. The rate of H{sub peroxo} formation does not depend on dioxygen concentration, indicating that an effectively irreversible step involving dioxygen precedes formation of the diiron(III) peroxo species. The rate constant observed at 4 C for H{sub peroxo} formation, 1--2 s{sup {minus}1}, is slower than that determined previously by Moessbauer and optical spectroscopy, {approximately}20--25 s{sup {minus}1} (Liu, K. E., et al. J. Am. Chem. Soc. 1995, 117, 4997--4998; 10174--10185). Possible explanations for this discrepancy include the existence of two distinct peroxo

  8. Mechanistic study of chemoselectivity in Ni-catalyzed coupling reactions between azoles and aryl carboxylates.

    PubMed

    Lu, Qianqian; Yu, Haizhu; Fu, Yao

    2014-06-11

    Itami et al. recently reported the C-O electrophile-controlled chemoselectivity of Ni-catalyzed coupling reactions between azoles and esters: the decarbonylative C-H coupling product was generated with the aryl ester substrates, while C-H/C-O coupling product was generated with the phenol derivative substrates (such as phenyl pivalate). With the aid of DFT calculations (M06L/6-311+G(2d,p)-SDD//B3LYP/6-31G(d)-LANL2DZ), the present study systematically investigated the mechanism of the aforementioned chemoselective reactions. The decarbonylative C-H coupling mechanism involves oxidative addition of C(acyl)-O bond, base-promoted C-H activation of azole, CO migration, and reductive elimination steps (C-H/Decar mechanism). This mechanism is partially different from Itami's previous proposal (Decar/C-H mechanism) because the C-H activation step is unlikely to occur after the CO migration step. Meanwhile, C-H/C-O coupling reaction proceeds through oxidative addition of C(phenyl)-O bond, base-promoted C-H activation, and reductive elimination steps. It was found that the C-O electrophile significantly influences the overall energy demand of the decarbonylative C-H coupling mechanism, because the rate-determining step (i.e., CO migration) is sensitive to the steric effect of the acyl substituent. In contrast, in the C-H/C-O coupling mechanism, the release of the carboxylates occurs before the rate-determining step (i.e., base-promoted C-H activation), and thus the overall energy demand is almost independent of the acyl substituent. Accordingly, the decarbonylative C-H coupling product is favored for less-bulky group substituted C-O electrophiles (such as aryl ester), while C-H/C-O coupling product is predominant for bulky group substituted C-O electrophiles (such as phenyl pivalate). PMID:24823646

  9. Products of the gas-phase reactions of 1,3-butadiene with OH and NO{sub 3} radicals

    SciTech Connect

    Tuazon, E.C.; Alvarado, A.; Aschmann, S.M.; Atkinson, R.; Arey, J.

    1999-10-15

    1,3-Butadiene is emitted into the atmosphere from a number of sources including combustion sources and is listed in the US as a hazardous air pollutant. In the atmosphere, 1,3-butadiene reacts with OH radicals, NO{sub 3} radicals, and O{sub 3} with the dominant tropospheric removal processes being daytime reaction with the OH radical and nighttime reaction with the NO{sub 3} radical. The authors have used gas chromatography, in situ Fourier transform infrared (FT-IR) absorption spectroscopy, and in situ atmospheric pressure ionization tandem mass spectrometry (API-MS) to identify and quantify the products formed from the reactions of 1,3-butadiene with OH radicals (in the presence of NO) and NO{sub 3} radicals. Acrolein, formaldehyde, and furan were identified and quantified from the OH radical-initiated reaction, with formation yields of 0.58 {+-} 0.04, 0.62 {+-} 0.05, and 0.03--0.04, respectively. Organic nitrates were observed by FT-IR spectroscopy with an estimated yield of 0.07 {+-} 0.03, and the API-MS analyses indicated that these organic nitrates are mainly the hydroxynitrate HOCH{sub 2}CH=CHCH{sub 2}ONO{sub 2} and/or its isomers. API-MS analyses showed the formation of a hydroxycarbonyl with the formula C{sub 4}H{sub 6}O{sub 2}, attributed to HOCH{sub 2}CH=CHCHO and/or its isomers. The major products of the NO{sub 3} radical-initiated reaction were organic nitrates; the API-MS analyses indicated the formation of acrolein, 1,2-epoxy-3-butene, and unsaturated C{sub 4}-hydroxycarbonyls, hydroxynitrates, carbonyl nitrates, and nitrooxyhydroperoxides. Acrolein, HCHO, and furan were again quantified by gas chromatographic and FT-IR analyses. The data is compared with previous literature studies, and detailed reaction mechanisms are presented and discussed.

  10. Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics

    SciTech Connect

    Trevitt, Adam J.; Goulay, Fabien; Taatjes, Craig A.; Osborn, David L.; Leone, Stephen R.

    2009-12-23

    Low temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165 and 295 K is found to be relatively constant over this temperature range, 3.9 - 4.9 x 10-10 cm3 molecule-1 s-1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a slower rate coefficient of 1.3 x 10-10 cm3 molecule-1 s-1 at 105 K. At room temperature, non-exponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta and para isomers of cyanotoluene because of their similar ionization energies and the ~;; 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn?s moon Titan (~;;100 K) and are also likely to proceed at the temperature of interstellar clouds (10-20 K).

  11. Enhancement of hydroxyl radical generation in the Fenton reaction by alpha-hydroxy acid.

    PubMed

    Ali, M A; Konishi, T

    1998-09-01

    The effect of various organic acids on hydroxyl radical (.OH) generation in the Fenton reaction were examined by the ESR spin trapping technique, where 5,5-dimethyl-1-pyroline-N-nitroxide (DMPO) and alpha-phenyl-tert-butyl nitrone (PBN) were used as the spin trapping reagents. alpha-Hydroxy acids such as lactic acid, glycolic acid and 2-hydroxy isobutyric acid were found to markedly enhance .OH generation in the reaction. In contrast, beta-hydroxy acid, alpha-keto acid, esters of alpha-hydroxy acids, aldehydes and other straight chain organic acids had no such enhancing activity. alpha-Amino acids had also no enhancing effect. The results suggest that the alpha-hydroxy acid moiety is prerequisite for the enhancement of .OH generation in the Fenton reaction. Superoxide dismutase did not inhibit the enhancing effect of alpha-hydroxy acids whereas catalase completely inhibited the .OH generation. Thus, alpha-hydroxy acids directly enhanced the .OH generation via the Fenton reaction but not the Haber-Weiss reaction. Possible role of lactic acid manipulating .OH generation is discussed in relation to the ischemia-reperfusion cell damage. PMID:9784848

  12. Kinetics of Several Oxygen-Containing Carbon-Centered Free Radical Reactions with Nitric Oxide.

    PubMed

    Rissanen, Matti P; Ihlenborg, Marvin; Pekkanen, Timo T; Timonen, Raimo S

    2015-07-16

    Kinetics of four carbon-centered, oxygen-containing free radical reactions with nitric oxide (NO) were investigated as a function of temperature at a few Torr pressure of helium, employing flow tube reactors coupled to a laser-photolysis/resonance-gas-discharge-lamp photoionization mass spectrometer (LP-RPIMS). Rate coefficients were directly determined from radical (R) decay signals under pseudo-first-order conditions ([R]0 ≪ [NO]). The obtained rate coefficients showed negative temperature dependences, typical for a radical-radical association process, and can be represented by the following parametrizations (all in units of cm(3) molecule(-1) s(-1)): k(CH2OH + NO) = (4.76 × 10(-21)) × (T/300 K)(15.92) × exp[50700/(RT)] (T = 266-363 K, p = 0.79-3.44 Torr); k(CH3CHOH + NO) = (1.27 × 10(-16)) × (T/300 K)(6.81) × exp[28700/(RT)] (T = 241-363 K, p = 0.52-3.43 Torr); k(CH3OCH2 + NO) = (3.58 ± 0.12) × 10(-12) × (T/300 K)(-3.17±0.14) (T = 221-363 K, p = 0.50-0.80 Torr); k(T)3 = 9.62 × 10(-11) × (T/300 K)(-5.99) × exp[-7100/(RT)] (T = 221-473 K, p = 1.41-2.95 Torr), with the uncertainties given as standard errors of the fits and the overall uncertainties estimated as ±20%. The rate of CH3OCH2 + NO reaction was measured in two density ranges due to its observed considerable pressure dependence, which was not found in the studied hydroxyalkyl reactions. In addition, the CH3CO + NO rate coefficient was determined at two temperatures resulting in k298K(CH3CO + NO) = (5.6 ± 2.8) × 10(-13) cm(3) molecule(-1) s(-1). No products were found during these experiments, reasons for which are briefly discussed. PMID:26000890

  13. Kinetics and Mechanistic Studies on the Reaction between Cytochrome c and Tea Catechins

    PubMed Central

    Wang, Lihua; Santos, Elizabeth; Schenk, Desiree; Rabago-Smith, Montserrat

    2014-01-01

    Green tea is characterized by the presence of an abundance of polyphenolic compounds, also known as catechins, including epicatechin (EC), epigallocatechin (EGC), epicatechin gallate (EGC) and epigallocatechin gallate (EGCG). In addition to being a popular beverage, tea consumption has been suggested as a mean of chemoprevention. However, its mode of action is unclear. It was discovered that tea catechins can react with cytochrome c. When oxidized cytochrome c was mixed with catechins commonly found in green tea under non-steady-state conditions, a reduction of cytochrome c was observed. The reaction rate of the catechins was dependent on the pH and the nature of the catechin. The pseudo-first order rate constant obtained increased in the order of EC < ECG < EGC < EGCG, which is consistent with previously reported superoxide reduction activities and Cu2+ reduction activities of tea catechins. PMID:26785071

  14. Temperature dependent rate coefficients for the reaction of OH radicals with dimethylbenzoquinones

    NASA Astrophysics Data System (ADS)

    Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Wenger, John C.

    2015-10-01

    Rate coefficients for the gas-phase reaction of hydroxyl (OH) radicals with two methylated benzoquinones have been measured at atmospheric pressure over the temperature range 284-313 K using the relative rate method. The following Arrhenius expressions (in cm3 molecule-1 s-1) have been obtained: k(25DMBQ) = (8.59 ± 4.70) × 10-12exp[(228 ± 163)/T] and k(26DMBQ) = (5.11 ± 2.79) × 10-12exp[(399 ± 165)/T] for 2,5-dimethylbenzoquinone (2,5DMBQ) and 2,6-dimethylbenzoquinone (2,6DMBQ), respectively, with corresponding values at 298 K: k(25DMBQ) = (2.05 ± 0.46) × 10-11 and k(26DMBQ) = (1.93 ± 0.12) × 10-11. The rate coefficients are compared to those reported for similar compounds and discussed in terms of structure-activity relationships. The results are also used to calculate atmospheric lifetimes for 2,5DMBQ and 2,6DMBQ with respect to reaction with OH radicals.

  15. Growth of polyphenyls via ion-molecule reactions: An experimental and theoretical mechanistic study

    SciTech Connect

    Aysina, Julia; Tosi, Paolo; Ascenzi, Daniela; Maranzana, Andrea; Tonachini, Glauco

    2013-05-28

    The reactivity of biphenylium cations C{sub 12}H{sub 9}{sup +} with benzene C{sub 6}H{sub 6} is investigated in a joint experimental and theoretical approach. Experiments are performed by using a triple quadruple mass spectrometer equipped with an atmospheric pressure chemical ion source to generate C{sub 12}H{sub 9}{sup +} via dissociative ionization of various isomers of the neutral precursor hydroxybiphenyl (C{sub 12}H{sub 10}O). C-C coupling reactions leading to hydrocarbon growth are observed. The most abundant ionic products are C{sub 18}H{sub 15}{sup +}, C{sub 18}H{sub 13}{sup +}, C{sub 17}H{sub 12}{sup +}, and C{sub 8}H{sub 7}{sup +}. The dependence of product ion yields on the kinetic energy of reagent ions, as well as further experiments performed using partial isotopic labelling of reagents, support the idea that the reaction proceeds via a long lived association product, presumably the covalently bound protonated terphenyl C{sub 18}H{sub 15}{sup +}. Its formation is found to be exothermic and barrierless and, therefore, might occur under the low pressure and temperature conditions typical of planetary atmospheres and the interstellar medium. Theoretical calculations have focussed on the channel leading to C{sub 8}H{sub 7}{sup +} plus C{sub 10}H{sub 8}, identifying, as the most probable fragments, the phenylethen-1-ylium cation and naphthalene, thus suggesting that the pathway leading to them might be of particular interest for the synthesis of polycyclic aromatic hydrocarbons. Both experiments and theory agree in finding this channel exoergic but hampered by small barriers of 2.7 and 3.7 kcal mol{sup -1} on the singlet potential energy surface.

  16. Time-resolved study on the reactions of organic selenides with hydroxyl and oxide radicals, hydrated electrons, and H-atoms in aqueous solution, and DFT calculations of transients in comparison with sulfur analogues.

    PubMed

    Tobien, Thomas; Bonifacić, Marija; Naumov, Sergej; Asmus, Klaus-Dieter

    2010-07-01

    A complementary experimental and quantum chemical study has been undertaken on the reactivity, formation and properties of transients generated in the reaction of selected organic selenides with hydroxyl radicals, oxide radical ions, hydrated electrons and hydrogen atoms in aqueous solution. A detailed study of the OH and O (-) reactions with Me(2)Se revealed the formation of the respective adduct-radicals as precursors of (Me(2)Se thereforeSeMe(2))(+) radical cations. In case of the neutral adduct radical Me(2)Se (OH) the conversion into the three-electron bonded dimer species proceeds, in part, via the molecular (Me(2)Se thereforeOH(2))(+) radical cation. Absolute rate constants have been determined for all the underlying processes. The respective reactions with hydrated electrons and hydrogen atoms indicate that selenides exhibit a higher reactivity towards redox-active species than sulfides. A most interesting finding is that the reaction of Me(2)Se with H atoms is faster (k = 4.1 x 10(9) M(-1) s(-1)) than the reduction by hydrated electrons (k = 2.1 x 10(8) M(-1) s(-1)), precluding an electron transfer as mechanistic background. The rationale is rather an effective dissociative attack of the hydrogen atom on the selenium. Both, the e(aq)(-)- and H -induced reductions of Me(2)Se and Me(2)S lead, under cleavage of CH(3) radicals, to the direct formation of selenol and thiol, respectively. Complementary quantum chemical studies, performed with Density Functional Theory (DFT) BHandHLYP methods, confirm this mechanism. They also reveal a generally higher thermodynamic stability of the Se-centered radicals relative to the S-centered ones, e.g., for the molecular radical anions (Me(2)Se) (-) (DeltaH-27 kJ mol(-1)) and (Me(2)S) (-) (DeltaH-16 kJ mol(-1)). Despite of these stabilization energies the calculations indicate an instantaneous Se/S-CH(3) bond lengthening in the respective molecular radical anions. The same applies for the reaction of Me(2)S and Me(2)Se with

  17. Modelling Population Dynamics in Realistic Landscapes with Linear Elements: A Mechanistic-Statistical Reaction-Diffusion Approach.

    PubMed

    Roques, Lionel; Bonnefon, Olivier

    2016-01-01

    We propose and develop a general approach based on reaction-diffusion equations for modelling a species dynamics in a realistic two-dimensional (2D) landscape crossed by linear one-dimensional (1D) corridors, such as roads, hedgerows or rivers. Our approach is based on a hybrid "2D/1D model", i.e, a system of 2D and 1D reaction-diffusion equations with homogeneous coefficients, in which each equation describes the population dynamics in a given 2D or 1D element of the landscape. Using the example of the range expansion of the tiger mosquito Aedes albopictus in France and its main highways as 1D corridors, we show that the model can be fitted to realistic observation data. We develop a mechanistic-statistical approach, based on the coupling between a model of population dynamics and a probabilistic model of the observation process. This allows us to bridge the gap between the data (3 levels of infestation, at the scale of a French department) and the output of the model (population densities at each point of the landscape), and to estimate the model parameter values using a maximum-likelihood approach. Using classical model comparison criteria, we obtain a better fit and a better predictive power with the 2D/1D model than with a standard homogeneous reaction-diffusion model. This shows the potential importance of taking into account the effect of the corridors (highways in the present case) on species dynamics. With regard to the particular case of A. albopictus, the conclusion that highways played an important role in species range expansion in mainland France is consistent with recent findings from the literature. PMID:26986201

  18. Modelling Population Dynamics in Realistic Landscapes with Linear Elements: A Mechanistic-Statistical Reaction-Diffusion Approach

    PubMed Central

    2016-01-01

    We propose and develop a general approach based on reaction-diffusion equations for modelling a species dynamics in a realistic two-dimensional (2D) landscape crossed by linear one-dimensional (1D) corridors, such as roads, hedgerows or rivers. Our approach is based on a hybrid “2D/1D model”, i.e, a system of 2D and 1D reaction-diffusion equations with homogeneous coefficients, in which each equation describes the population dynamics in a given 2D or 1D element of the landscape. Using the example of the range expansion of the tiger mosquito Aedes albopictus in France and its main highways as 1D corridors, we show that the model can be fitted to realistic observation data. We develop a mechanistic-statistical approach, based on the coupling between a model of population dynamics and a probabilistic model of the observation process. This allows us to bridge the gap between the data (3 levels of infestation, at the scale of a French department) and the output of the model (population densities at each point of the landscape), and to estimate the model parameter values using a maximum-likelihood approach. Using classical model comparison criteria, we obtain a better fit and a better predictive power with the 2D/1D model than with a standard homogeneous reaction-diffusion model. This shows the potential importance of taking into account the effect of the corridors (highways in the present case) on species dynamics. With regard to the particular case of A. albopictus, the conclusion that highways played an important role in species range expansion in mainland France is consistent with recent findings from the literature. PMID:26986201

  19. Methane to acetic acid over Cu-exchanged zeolites: mechanistic insights from a site-specific carbonylation reaction.

    PubMed

    Narsimhan, Karthik; Michaelis, Vladimir K; Mathies, Guinevere; Gunther, William R; Griffin, Robert G; Román-Leshkov, Yuriy

    2015-02-11

    The selective low temperature oxidation of methane is an attractive yet challenging pathway to convert abundant natural gas into value added chemicals. Copper-exchanged ZSM-5 and mordenite (MOR) zeolites have received attention due to their ability to oxidize methane into methanol using molecular oxygen. In this work, the conversion of methane into acetic acid is demonstrated using Cu-MOR by coupling oxidation with carbonylation reactions. The carbonylation reaction, known to occur predominantly in the 8-membered ring (8MR) pockets of MOR, is used as a site-specific probe to gain insight into important mechanistic differences existing between Cu-MOR and Cu-ZSM-5 during methane oxidation. For the tandem reaction sequence, Cu-MOR generated drastically higher amounts of acetic acid when compared to Cu-ZSM-5 (22 vs 4 μmol/g). Preferential titration with sodium showed a direct correlation between the number of acid sites in the 8MR pockets in MOR and acetic acid yield, indicating that methoxy species present in the MOR side pockets undergo carbonylation. Coupled spectroscopic and reactivity measurements were used to identify the genesis of the oxidation sites and to validate the migration of methoxy species from the oxidation site to the carbonylation site. Our results indicate that the Cu(II)-O-Cu(II) sites previously associated with methane oxidation in both Cu-MOR and Cu-ZSM-5 are oxidation active but carbonylation inactive. In turn, combined UV-vis and EPR spectroscopic studies showed that a novel Cu(2+) site is formed at Cu/Al <0.2 in MOR. These sites oxidize methane and promote the migration of the product to a Brønsted acid site in the 8MR to undergo carbonylation. PMID:25562431

  20. Mechanism and kinetic study on the gas-phase reactions of OH radical with carbamate insecticide isoprocarb

    NASA Astrophysics Data System (ADS)

    Zhang, Chenxi; Yang, Wenbo; Bai, Jing; Zhao, Yuyang; Gong, Chen; Sun, Xiaomin; Zhang, Qingzhu; Wang, Wenxing

    2012-12-01

    As one of the most important carbamate insecticides, isoprocarb [2-(1-methylethyl) phenyl methylcarbamate, MIPC] is widely used in agricultural and cotton spraying. The atmospheric chemical reaction mechanism and kinetics of MIPC with OH radical have been researched using the density functional theory in this paper. The study shows that OH radical is more easily added to the C atoms of aromatic ring than to carbon-oxygen double bond, while the H atom is abstracted more difficulty from -CONH- group and aromatic ring than from the -CH3- group and the -CH- group. At room temperature, the total rate constant of MIPC with OH radical is about 5.1 × 10-12 cm3 molecule-l s-l. OH radical addition reaction and H atom abstraction reaction are both important for the OH-initiated reaction of MIPC. The energy-rich adducts (MIPC-OH) and the MIPC's radical isomers are open-shell activated radicals and can be further oxidized in the atmosphere.

  1. In situ electrochemical-electron spin resonance investigations of multi-electron redox reaction for organic radical cathodes

    NASA Astrophysics Data System (ADS)

    Huang, Qian; Walter, Eric D.; Cosimbescu, Lelia; Choi, Daiwon; Lemmon, John P.

    2016-02-01

    The multi-electron redox reaction of an organic radical based composite cathode comprised of poly(2,2,6,6- tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA)-Ketjenblack is investigated using an in situ electrochemical-electron spin resonance (ESR) methodology. The experiments allow each electrochemical state to be associated with the chemical state (or environment) of the radical species upon the cell cycling. In situ ESR spectra of the composite cathode demonstrate a two-electron redox reaction of PTMA that is from an aminoxy anion (n-type, at 2.5-2.6 V vs. Li/Li+) via a radical (at 3.2-3.5 V vs. Li/Li+) to an oxoammonium cation (p-type, at 3.7-4.0 V vs. Li/Li+). In particular, an adjustable n-type doping process of PTMA is first observed during the discharging process. Moreover, two different local environments of radical species are found in the PTMA-Ketjenblack composite electrode that includes both concentrated and isolated radicals. These two types of radical species, showing similarities during the redox reaction process while behaving quite different in the non-faradic reaction of ion sorption/desorption on the electrode surface, govern the electrochemical behavior of PTMA based composite electrode.

  2. Mechanistic elucidation of linker and ancillary ligand substitution reactions in Pt(II) dinuclear complexes.

    PubMed

    Ongoma, Peter O; Jaganyi, Deogratius

    2013-02-28

    The rate of substitution of aqua ligands by three nucleophiles, thiourea (TU), N,N-dimethylthiourea (DMTU) and N,N,N,N-tetramethylthiourea (TMTU), for the complexes [cis-{PtOH2(NH3)2}2-μ-pyrazine](ClO4)2 (pzn), [cis-{PtOH2(NH3)2}2-μ-2,3-dimethylpyrazine](ClO4)2 (2,3pzn), [cis-{PtOH2(NH3)2}2-μ-2,5-pyrazine](ClO4)2 (2,5pzn) and [cis-{PtOH2(NH3)2}2-μ-2,6-dimethylpyrazine](ClO4)2 (2,6pzn) was investigated under pseudo first-order conditions as a function of concentration and temperature by stopped-flow and UV-Visible spectrophotometry. The reaction proceeded in three consecutive steps; each step follows first order kinetics with respect to each complex and nucleophile. The pseudo first-order rate constants, k(obs(1/2/3)), for sequential substitution of the aqua ligands and subsequent displacement of the linker obeyed the rate law: k(obs(1/2/3)) = k((1/2/3))[nucleophile]. The steric hindrance properties of the pyrazine-bridging ligand control the overall reaction pattern. The order of reactivity of the complexes is 2,3pzn ≈ 2,5pzn < 2,6pzn < pzn. The difference in reactivity attributed to the steric crowding at the Pt(II) centre imposed by the methyl groups reduces the lability of the aqua complexes. The order of reactivity of the nucleophiles decreases with the increase in steric demand TU > DMTU > TMTU. 1H and 195Pt NMR spectroscopic results confirmed the observed dissociation of the bridging ligand from the metal centre of the cis-dinuclear complexes and its derivatives in the third step. The dissociation process is accelerated by the introduction of the steric effect on the linker in conjunction with the increased ligand field strength imparted by additional thiourea ligands at each metal centre. The large negative entropy of activation ΔS(≠) values in all cases support an associative substitution mechanism. PMID:23223554

  3. Fine-tuning of a radical-based reaction by radical S-adenosyl-L-methionine tryptophan lyase.

    PubMed

    Sicoli, Giuseppe; Mouesca, Jean-Marie; Zeppieri, Laura; Amara, Patricia; Martin, Lydie; Barra, Anne-Laure; Fontecilla-Camps, Juan C; Gambarelli, Serge; Nicolet, Yvain

    2016-03-18

    The radical S-adenosyl-L-methionine tryptophan lyase NosL converts L-tryptophan into 3-methylindolic acid, which is a precursor in the synthesis of the thiopeptide antibiotic nosiheptide. Using electron paramagnetic resonance spectroscopy and multiple L-tryptophan isotopologues, we trapped and characterized radical intermediates that indicate a carboxyl fragment migration mechanism for NosL. This is in contrast to a proposed fragmentation-recombination mechanism that implied Cα-Cβ bond cleavage of L-tryptophan. Although NosL resembles related tyrosine lyases, subtle substrate motions in its active site are responsible for a fine-tuned radical chemistry, which selects the Cα-C bond for disruption. This mechanism highlights evolutionary adaptation to structural constraints in proteins as a route to alternative enzyme function. PMID:26989252

  4. Hydroxyl-radical production in physiological reactions. A novel function of peroxidase.

    PubMed

    Chen, S X; Schopfer, P

    1999-03-01

    Peroxidases catalyze the dehydrogenation by hydrogen peroxide (H2O2) of various phenolic and endiolic substrates in a peroxidatic reaction cycle. In addition, these enzymes exhibit an oxidase activity mediating the reduction of O2 to superoxide (O2.-) and H2O2 by substrates such as NADH or dihydroxyfumarate. Here we show that horseradish peroxidase can also catalyze a third type of reaction that results in the production of hydroxyl radicals (.OH) from H2O2 in the presence of O2.-. We provide evidence that to mediate this reaction, the ferric form of horseradish peroxidase must be converted by O2.- into the perferryl form (Compound III), in which the haem iron can assume the ferrous state. It is concluded that the ferric/perferryl peroxidase couple constitutes an effective biochemical catalyst for the production of .OH from O2.- and H2O2 (iron-catalyzed Haber-Weiss reaction). This reaction can be measured either by the hydroxylation of benzoate or the degradation of deoxyribose. O2.- and H2O2 can be produced by the oxidase reaction of horseradish peroxidase in the presence of NADH. The .OH-producing activity of horseradish peroxidase can be inhibited by inactivators of haem iron or by various O2.- and .OH scavengers. On an equimolar Fe basis, horseradish peroxidase is 1-2 orders of magnitude more active than Fe-EDTA, an inorganic catalyst of the Haber-Weiss reaction. Particularly high .OH-producing activity was found in the alkaline horseradish peroxidase isoforms and in a ligninase-type fungal peroxidase, whereas lactoperoxidase and soybean peroxidase were less active, and myeloperoxidase was inactive. Operating in the .OH-producing mode, peroxidases may be responsible for numerous destructive and toxic effects of activated oxygen reported previously. PMID:10103001

  5. Triethylaluminum- or triethylborane-induced free radical reaction of alkyl iodides and alpha,beta-unsaturated compounds.

    PubMed

    Liu, Jing-Yuan; Jang, Yoeng-Jiunn; Lin, Wen-Wei; Liu, Ju-Tsung; Yao, Ching-Fa

    2003-05-16

    A series of alpha,beta-unsaturated compounds, 1a-c, 9, 13, and 17, were used as reactants in free radical conjugate addition reactions with different radicals generated from alkyl iodides such as 3, 4, or 5 in the presence of triethylborane-oxygen in air or via the use of triethylaluminum-benzoyl peroxide as a free radical initiator. When the reactions were carried out using triethylborane-air, the products, in most cases, were clean and were easily purified. However, higher yields of the 1,4-adducts and less side reactions occurred when less reactive substrates were used as Michael acceptors in reactions with triethylaluminum-benzoyl peroxide and alkyl iodide under similar conditions. A mechanism for this is proposed in Scheme 1. PMID:12737587

  6. Hydroxyl radical (OH•) reaction with guanine in an aqueous environment: a DFT study.

    PubMed

    Kumar, Anil; Pottiboyina, Venkata; Sevilla, Michael D

    2011-12-22

    The reaction of hydroxyl radical (OH(•)) with DNA accounts for about half of radiation-induced DNA damage in living systems. Previous literature reports point out that the reaction of OH(•) with DNA proceeds mainly through the addition of OH(•) to the C═C bonds of the DNA bases. However, recently it has been reported that the principal reaction of OH(•) with dGuo (deoxyguanosine) is the direct hydrogen atom abstraction from its exocyclic amine group rather than addition of OH(•) to the C═C bonds. In the present work, these two reaction pathways of OH(•) attack on guanine (G) in the presence of water molecules (aqueous environment) are investigated using the density functional theory (DFT) B3LYP method with 6-31G* and 6-31++G** basis sets. The calculations show that the initial addition of the OH(•) at C(4)═C(5) double bond of guanine is barrier free and the adduct radical (G-OH(•)) has only a small activation barrier of ca. 1-6 kcal/mol leading to the formation of a metastable ion-pair intermediate (G(•+)---OH(-)). The formation of ion-pair is a result of the highly oxidizing nature of the OH(•) in aqueous media. The resulting ion-pair (G(•+)---OH(-)) deprotonates to form H(2)O and neutral G radicals favoring G(N(1)-H)(•) with an activation barrier of ca. 5 kcal/mol. The overall process from the G(C(4))-OH(•) (adduct) to G(N(1)-H)(•) and water is found to be exothermic in nature by more than 13 kcal/mol. (G-OH(•)), (G(•+)---OH(-)), and G(N(1)-H)(•) were further characterized by the CAM-B3LYP calculations of their UV-vis spectra and good agreement between theory and experiment is achieved. Our calculations for the direct hydrogen abstraction pathway from N(1) and N(2) sites of guanine by the OH(•) show that this is also a competitive route to produce G(N(2)-H)(•), G(N(1)-H)(•) and H(2)O. PMID:22050033

  7. Hydroxyl Radical (OH•) Reaction with Guanine in an Aqueous Environment: A DFT Study

    PubMed Central

    Kumar, Anil; Pottiboyina, Venkata; Sevilla, Michael D.

    2011-01-01

    The reaction of hydroxyl radical (OH•) with DNA accounts for about half of radiation-induced DNA damage in living systems. Previous literature reports point out that the reaction of OH• with DNA proceeds mainly through the addition of OH• to the C=C bond of the DNA bases. However, recently it has been reported that the principal reaction of OH• with dGuo (deoxyguanosine) is the direct hydrogen atom abstraction from its exocyclic amine group rather than addition of OH• to the C=C bond. In the present work, these two reaction pathways of OH• attack on guanine (G) in the presence of water molecules (aqueous environment) are investigated using the density functional theory (DFT) B3LYP method with 6-31G* and 6-31++G** basis sets. The calculations show that the initial addition of the OH• at C4=C5 double bond of guanine is barrier free and the adduct radical (G-OH•) has only a small activation barrier of ca. 1 – 6 kcal/mol leading to the formation of a metastable ion-pair intermediate (G•+---OH−). The formation of ion-pair is a result of the highly oxidizing nature of the OH• in aqueous media. The resulting ion-pair (G•+---OH−) deprotonates to form H2O and neutral G radicals favoring G(N1-H)• with an activation barrier of ca. 5 kcal/mol. The overall process from the G(C4)-OH• (adduct) to G(N1-H)• and water is found to be exothermic in nature by more than 13 kcal/mol. (G-OH•), (G•+---OH−), and G(N1-H)• were further characterized by the CAM-B3LYP calculations of their UV-visible spectra and good agreement between theory and experiment is achieved. Our calculations for the direct hydrogen abstraction pathway from N1 and N2 sites of guanine by the OH• show that this is also a competitive route to produce G(N2-H)•, G(N1-H)• and H2O. PMID:22050033

  8. Chain-amplified photochemical fragmentation of N-alkoxypyridinium salts: proposed reaction of alkoxyl radicals with pyridine bases to give pyridinyl radicals.

    PubMed

    Shukla, Deepak; Adiga, Shashishekar P; Ahearn, Wendy G; Dinnocenzo, Joseph P; Farid, Samir

    2013-03-01

    Photoinduced electron transfer to N-alkoxypyridiniums, which leads to N–O bond cleavage and alkoxyl radical formation, is highly chain amplified in the presence of a pyridine base such as lutidine. Density functional theory calculations support a mechanism in which the alkoxyl radicals react with lutidine via proton-coupled electron transfer (PCET) to produce lutidinyl radicals (BH•). A strong electron donor, BH• is proposed to reduce another alkoxypyridinium cation, leading to chain amplification, with quantum yields approaching 200. Kinetic data and calculations support the formation of a second, stronger reducing agent: a hydrogen-bonded complex between BH• and another base molecule (BH•···B). Global fitting of the quantum yield data for the reactions of four pyridinium salts (4-phenyl and 4-cyano with N-methoxy and N-ethoxy substituents) led to a consistent set of kinetic parameters. The chain nature of the reaction allowed rate constants to be determined from steady-state kinetics and independently determined chain-termination rate constants. The rate constant of the reaction of CH3O• with lutidine to form BH•, k1, is ~6 × 10(6) M(–1) s(–1); that of CH3CH2O• is ~9 times larger. Reaction of CD3O• showed a deuterium isotope effect of ~6.5. Replacing lutidine by 3-chloropyridine, a weaker base, decreases k1 by a factor of ~400. PMID:23181705

  9. Reaction kinetics of hydrogen abstraction reactions by hydroperoxyl radical from 2-methyltetrahydrofuran and 2,5-dimethyltetrahydrofuran.

    PubMed

    Chakravarty, Harish Kumar; Fernandes, Ravi X

    2013-06-20

    Highly accurate rate parameters for H-abstraction reactions by HO2 radicals are needed for development of predictive chemical kinetic models for ignition. In this article, we report the rate coefficients for reaction of hydroperoxyl radical (HO2) with 2-methyltetrahydrofuran (MTHF) and 2,5-dimethyltetrahydrofuran (DMTHF) computed employing CBS-QB3 and CCSD(T)/cc-pVTZ//B3LYP/cc-pVTZ level of theory in the temperature range of 500-2000 K. Conventional transition state theory (CTST) with hindered rotor approximation for low frequency torsional modes and RRHO (rigid-rotor harmonic oscillator) approximation for all other vibrational modes is employed to evaluate the high pressure rate constants as a function of temperature. Rate constant of each individual hydrogen abstraction channel is taken into account to calculate the overall rate constant. Three-parameter Arrhenius expressions have been obtained by fitting to the computed rate constants of all abstraction channels between 500 and 2000 K. Eight transition states have been identified for MTHF and four for slightly more stable trans-DMTHF. Intrinsic reaction coordinates (IRC) calculations were performed to verify the connectivity of all the transition states (TSs) with reactants and products. One dimensional Eckart's asymmetrical method has been used to calculate quantum mechanical tunneling effect. Results of the theoretically calculated rate coefficients indicate that the hydrogen abstraction by HO2 from the C2 carbon of both MTHF and DMTHF is the most dominant path among all reaction pathways attributed to its lowest barrier height. The total rate coefficients of the MTHF and DMTHF with HO2 at CCSD(T)/cc-pVTZ//B3LYP/cc-pVTZ level of theory are k(T) = 8.60T(3.54) exp(-8.92/RT) and k(T)= 3.17T(3.63) exp(-6.59/RT) cm(3) mol(-1) s(-1), respectively. At both the level of theories, the predicted total abstraction rate constant for DMTHF is found to be higher as compared to that of MTHF over an entire temperature range

  10. Kinetics of the Reactions of IO Radicals with NO and NO2

    NASA Technical Reports Server (NTRS)

    Daykin, E. P.; Wine, P. H.

    1997-01-01

    A laser flash photolysis-long path absorption technique has been employed to study the kinetics of the reactions of IO radicals with NO and NO2 as a function of temperature and pressure. The IO and NO rate coefficient is independent of pressure over the range 40-200 Torr of N2, and its temperature dependence over the range 242-359 K is adequately described by the Arrhenius expression k(sub 1) = (6.9 +/- 1.7) x 10(exp -12) exp[(328 +/- 71)/T] cu cm/(molecule.s) (errors are 2 sigma, precision only). These Arrhenius parameters are similar to those determined previously for the ClO + NO and BrO + NO reactions. The IO and NO2 association reaction is found to be in the falloff regime over the temperature and pressure ranges investigated (254-354 K and 40-750 Torr of N2). Assuming F(sub c) = 0.4 independent of temperature, a physically reasonable set of falloff parameters which adequately describe the data are k(sub 0) = 7.7 x 10(exp -31)(T/300)(exp -5.0) cm(exp 6)/(molecule(exp 2).s) and k(sub infinity) = 1.55 x 10(exp -11)cu cm/(molecule.s) independent of temperature. The IO + NO2 rate coefficients determined in this study are about a factor of 2 faster than those reported in the only previous study of this reaction.

  11. Kinetics and product yields of the acetyl peroxy + HO2 radical reaction studied by photoionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Dodson, L. G.; Shen, L.; Savee, J. D.; Eddingsaas, N. C.; Welz, O.; Taatjes, C. A.; Osborn, D. L.; Sander, S. P.; Okumura, M.

    2013-12-01

    The acetyl peroxy radical (CH3C(O)O2) is a key intermediate in the oxidation of carbonyl-containing hydrocarbons in the troposphere. Reaction of acetyl peroxy radicals with HO2 has been suggested as a source of OH radicals in low-NOx environments. Previous work on this reaction observed only two product channels forming (1) peracetic acid and (2) acetic acid. Recent experiments have shown that there is a third channel that generates the radicals OH and acetoxy: CH3C(O)O2 + HO2 → (1) CH3C(O)OOH + O2 (2) CH3C(O)OH + O3 (3) CH3C(O)O + O2 + OH This last pathway to OH formation would then contribute to the apparent isoprene OH recycling suggested by discrepancies between atmospheric models and field observations of OH. There have, however, been significant disagreements among experiments on the yield of OH from reaction of acetyl peroxy radicals with HO2. We report our preliminary studies of acetyl peroxy self-reaction and its reaction with HO2 at 298 K and 8 Torr. Experiments were conducted at the Advanced Light Source synchrotron at the Lawerence Berkeley National Laboratory using tunable VUV ionizing radiation coupled to the Sandia National Laboratory pulsed-laser-photolysis multiplexed photoionization mass spectrometer to detect the time- and isomer-resolved formation of radical intermediates and products. From these results, we report new branching fractions of the three product channels in the acetyl peroxy + HO2 radical reaction.

  12. Ab initio pressure-dependent reaction kinetics of methyl propanoate radicals.

    PubMed

    Tan, Ting; Yang, Xueliang; Ju, Yiguang; Carter, Emily A

    2015-12-14

    The unimolecular dissociation and isomerization kinetics of the three methyl propanoate (MP) radicals, CH3CH2C(=O)OĊH2 (MP-m), CH3ĊHC(=O)OCH3 (MP-α), and ĊH2CH2C(=O)OCH3 (MP-β), are theoretically investigated using high-level ab initio methods and the Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation (ME) theory. Stationary-point energies are obtained using the coupled cluster singles and doubles with perturbative triples correction (CCSD(T)), multi-reference singles and doubles configuration interaction (MRSDCI) with the Davidson-Silver (DS) correction, and multi-reference averaged coupled pair functional (MRACPF2) theories. The isomerization barriers between the three radicals are predicted to be generally lower than the corresponding bond dissociation channels, leading to a strongly coupled reaction system in subsequent kinetics studies. The phenomenological temperature- and pressure-dependent rate coefficients are computed using the RRKM/ME theory over a temperature range of 500 to 2000 K and at a pressure range of 0.01 atm to the high-pressure limit, which are then fitted to modified Arrhenius expressions. The β-scission rate coefficients of MP-α to CH3CHC(=O) and CH3O[combining dot above] are predicted to be the smallest because of its highest activation energy among all studied unimolecular reactions channels. Analysis of branching fractions shows that both MP-m and MP-α radicals mainly decompose to the bimolecular products CH3CH2Ċ(=O) and H2CO, whereas the MP-β radical primarily decomposes via cleavage of a C-C bond to form C2H4 and CH3OĊ(=O). The isomerization channels dominate at low temperatures, the branching fractions of which decrease with increasing temperature and become very minor at about 2000 K. Our accurate rate coefficients and branching fractions help to illuminate the unique combustion properties of MP. PMID:26536041

  13. Products and Mechanism of the Reaction of 1-Pentadecene with NO3 Radicals and the Effect of a -ONO2 Group on Alkoxy Radical Decomposition.

    PubMed

    Yeh, Geoffrey K; Claflin, Megan S; Ziemann, Paul J

    2015-10-29

    The linear C15 alkene, 1-pentadecene, was reacted with NO3 radicals in a Teflon environmental chamber and yields of secondary organic aerosol (SOA) and particulate β-hydroxynitrates, β-carbonylnitrates, and organic peroxides (β-nitrooxyhydroperoxides + dinitrooxyperoxides) were quantified using a variety of methods. Reaction occurs almost solely by addition of NO3 to the C═C double bond and measured yields of β-hydroxynitrate isomers indicate that 92% of addition occurs at the terminal carbon. Molar yields of reaction products determined from measurements, a proposed reaction mechanism, and mass-balance considerations were 0.065 for β-hydroxynitrates (0.060 and 0.005 for 1-nitrooxy-2-hydroxypentadecane and 1-hydroxy-2-nitrooxypentadecane isomers), 0.102 for β-carbonylnitrates, 0.017 for organic peroxides, 0.232 for β-nitrooxyalkoxy radical isomerization products, and 0.584 for tetradecanal and formaldehyde, the volatile C14 and C1 products of β-nitrooxyalkoxy radical decomposition. Branching ratios for decomposition and isomerization of β-nitrooxyalkoxy radicals were 0.716 and 0.284 and should be similar for other linear 1-alkenes ≥ C6 whose alkyl chains are long enough to allow for isomerization to occur. These branching ratios have not been measured previously, and they differ significantly from those estimated using structure-activity relationships, which predict >99% isomerization. It appears that the presence of a -ONO2 group adjacent to an alkoxy radical site greatly enhances the rate of decomposition relative to isomerization, which is otherwise negligible, and that the effect is similar to that of a -OH group. The results provide insight into the effects of molecular structure on mechanisms of oxidation of volatile organic compounds and should be useful for improving structure-activity relationships that are widely used to predict the fate of these compounds in the atmosphere and for modeling SOA formation and aging. PMID:26436557

  14. Activity of key enzymes in microsomal and mitochondrial membranes depends on the redox reactions involving lipid radicals.

    PubMed

    Dmitriev, L F

    2001-07-01

    The work reviews membrane processes, such as monooxygenase reaction and oxidative phosphorylation with special reference to hydroxylation of a xenobiotic benzo(a)pyrene and the effects of the radical scavenger propyl gallate and radical generator Fe2+ ions on the reaction kinetics. A possibility is discussed that tocopherol provides for the activity of the lipid-radical cycles involving cytochrome b5. The lipid-radical cycles protect membrane lipids from oxidation and control the kinetics of membrane processes. The NADPH oxidation energy is transformed into the energy of lipid pulsations and this energy is used for activation of membrane enzymes. To account for the role of lipid pulsations in membrane processes, a new parameter is introduced - the internal temperature. It is supposed that there should be the equilibrium between the pro- and antioxidant factors in the membranes, and the presence of exogenous antioxidants (propyl gallate etc.) should be considered as a negative factor. PMID:11699868

  15. Radical S-Adenosylmethionine (SAM) Enzymes in Cofactor Biosynthesis: A Treasure Trove of Complex Organic Radical Rearrangement Reactions*

    PubMed Central

    Mehta, Angad P.; Abdelwahed, Sameh H.; Mahanta, Nilkamal; Fedoseyenko, Dmytro; Philmus, Benjamin; Cooper, Lisa E.; Liu, Yiquan; Jhulki, Isita; Ealick, Steven E.; Begley, Tadhg P.

    2015-01-01

    In this minireview, we describe the radical S-adenosylmethionine enzymes involved in the biosynthesis of thiamin, menaquinone, molybdopterin, coenzyme F420, and heme. Our focus is on the remarkably complex organic rearrangements involved, many of which have no precedent in organic or biological chemistry. PMID:25477515

  16. Radical S-adenosylmethionine (SAM) enzymes in cofactor biosynthesis: a treasure trove of complex organic radical rearrangement reactions.

    PubMed

    Mehta, Angad P; Abdelwahed, Sameh H; Mahanta, Nilkamal; Fedoseyenko, Dmytro; Philmus, Benjamin; Cooper, Lisa E; Liu, Yiquan; Jhulki, Isita; Ealick, Steven E; Begley, Tadhg P

    2015-02-13

    In this minireview, we describe the radical S-adenosylmethionine enzymes involved in the biosynthesis of thiamin, menaquinone, molybdopterin, coenzyme F420, and heme. Our focus is on the remarkably complex organic rearrangements involved, many of which have no precedent in organic or biological chemistry. PMID:25477515

  17. Lamb shift in radical-ion pairs produces a singlet-triplet energy splitting in photosynthetic reaction centers

    NASA Astrophysics Data System (ADS)

    Vitalis, K. M.; Kominis, I. K.

    2014-09-01

    Radical-ion pairs, fundamental for understanding photosynthesis and the avian magnetic compass, were recently shown to be biological open quantum systems. We here show that the coupling of the radical-pair spin degrees of freedom to its decohering vibrational reservoir leads to a shift of the radical-pair magnetic energy levels. The Lamb shift Hamiltonian is diagonal in the singlet-triplet basis, and results in a singlet-triplet energy splitting physically indistinguishable from an exchange interaction. This could have significant implications for understanding the energy level structure and the dynamics of photosynthetic reaction centers.

  18. Reaction of C-type cytochromes with the iron hexacyanides. Mechanistic implications.

    PubMed

    Ohno, N; Cusanovich, M A

    1981-12-01

    The reaction of c-cytochromes with iron hexacyanides is similar in mechanism to the interaction of cytochromes with their physiological oxidants and reductants in that the formation of complexes precedes electron transfer. Analysis of the kinetics of oxidation and reduction of a number of c-cytochromes by solving the simultaneous differential equations defining the mechanism is possible, and allows assignment of all six rate constants describing a minimum three-step mechanism [cyto(Fe(+3)) + Fe(+2) right harpoon over left harpoon cyto (Fe(+3)) - Fe(+2) right harpoon over left harpoon cyto(Fe(+2)) - Fe(+3) right harpoon over left harpoon cyto(Fe(+2)) + Fe(+3)]. We find that the usual steady-state approximations are not valid. Furthermore, the ratio of first-order rate constants for electron transfer was approximately 1.0, and no correlation was found between any of the six rate constants and the differences in oxidation-reduction potential of the iron-hexacyanides and different cytochromes c. However, it was found that the ratio of the rate constants for complex formation between ferricytochrome c and potassium ferrocyanide and ferrocytochrome c and potassium ferricyanide was proportional to the difference in oxidation-reduction potentials. Thus the minimum three-step mechanism given above accurately describes the observed kinetic data. However, this mechanism leads to a number of conceptual difficulties. Specifically, the mechanism requires that the collision complexes formed [cyto(Fe(+3)) - Fe(CN)(6) (-4) and cyto(Fe(+2)) - Fe(CN)(6) (-3)] have very different equilibrium constants, and further requires that formation of the collision complexes be accompanied by "chemistry" to make the intermediates isoenergetic. A more complex five-step mechanism which requires that the reactants [Fe(CN)(6) (-4) and ferricytochrome c or Fe(CN)(6) (-3) and ferrocytochrome c] form a collision complex followed by a first-order process before electron transfer, was found to yield

  19. High-throughput identification of off-targets for the mechanistic study of severe adverse drug reactions induced by analgesics

    SciTech Connect

    Pan, Jian-Bo; Ji, Nan; Pan, Wen; Hong, Ru; Wang, Hao; Ji, Zhi-Liang

    2014-01-01

    Drugs may induce adverse drug reactions (ADRs) when they unexpectedly bind to proteins other than their therapeutic targets. Identification of these undesired protein binding partners, called off-targets, can facilitate toxicity assessment in the early stages of drug development. In this study, a computational framework was introduced for the exploration of idiosyncratic mechanisms underlying analgesic-induced severe adverse drug reactions (SADRs). The putative analgesic-target interactions were predicted by performing reverse docking of analgesics or their active metabolites against human/mammal protein structures in a high-throughput manner. Subsequently, bioinformatics analyses were undertaken to identify ADR-associated proteins (ADRAPs) and pathways. Using the pathways and ADRAPs that this analysis identified, the mechanisms of SADRs such as cardiac disorders were explored. For instance, 53 putative ADRAPs and 24 pathways were linked with cardiac disorders, of which 10 ADRAPs were confirmed by previous experiments. Moreover, it was inferred that pathways such as base excision repair, glycolysis/glyconeogenesis, ErbB signaling, calcium signaling, and phosphatidyl inositol signaling likely play pivotal roles in drug-induced cardiac disorders. In conclusion, our framework offers an opportunity to globally understand SADRs at the molecular level, which has been difficult to realize through experiments. It also provides some valuable clues for drug repurposing. - Highlights: • A novel computational framework was developed for mechanistic study of SADRs. • Off-targets of drugs were identified in large scale and in a high-throughput manner. • SADRs like cardiac disorders were systematically explored in molecular networks. • A number of ADR-associated proteins were identified.

  20. Ab initio study of the reaction of propionyl (C2H5CO) radical with oxygen (O2).

    PubMed

    Hou, Hua; Wang, Baoshan

    2007-08-01

    The reaction of propionyl radical with oxygen has been studied using the full coupled cluster theory with the complete basis set. This is the first time to gain a conclusive insight into the reaction mechanism and kinetics for this important reaction in detail. The reaction takes place via a chemical activation mechanism. The barrierless association of propionyl with oxygen produces the propionylperoxy radical, which decomposes to form the hydroxyl radical and the three-center alpha-lactone predominantly or the four-center beta-propiolactone. The oxidation of propionyl radical to carbon monoxide or carbon dioxide is not straightforward rather via the secondary decomposition of alpha-lactone and beta-propiolactone. Kinetically, the overall rate constant is almost pressure independent and it approaches the high-pressure limit around tens of torr of helium. At temperatures below 600 K, the rate constant shows negative temperature dependence. The experimental yields of the hydroxyl radical can be well reproduced, with the average energy transferred per collision -DeltaE=20-25 cm(-1) at 213 and 295 K (helium bath gas). At low pressures, together with the hydroxy radical, alpha-lactone is the major product, while beta-propiolactone only accounts for about one-fifth of alpha-lactone. At the high-pressure limit, the production of the propionylperoxy radical is dominant together with a fraction of the isomers. The infrared spectroscopy or the mass spectroscopy techniques are suggested to be employed in the future experimental study of the C2H5CO+O2 reaction. PMID:17688339

  1. The reaction rate of edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one (MCI-186)) with hydroxyl radical.

    PubMed

    Abe, Shinji; Kirima, Kazuyoshi; Tsuchiya, Koichiro; Okamoto, Masumi; Hasegawa, Toyoshi; Houchi, Hitoshi; Yoshizumi, Masanori; Tamaki, Toshiaki

    2004-02-01

    The pyrazoline derivative edaravone is a potent hydroxyl radical scavenger that has been approved for attenuation of brain damage caused by ischemia-reperfusion. In the present work, we first determined the rate constant, k(r), at which edaravone scavenges radicals generated by a Fenton reaction in aqueous solution in the presence of the spin trap agent, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), which competed with edaravone. We detected the edaravone radicals in the process of hydroxyl radical scavenging and found that edaravone reacts with hydroxyl radical around the diffusion limit (k(r)=3.0 x 10(10) M(-1) s(-1)). The EPR (electron paramagnetic resonance) spectrum of the edaravone radical was observed by oxidation with a horseradish peroxidase-hydrogen peroxide system using the fast-flow method. This radical species is unstable and changed to another radical species with time. In addition, it was found that edaravone consumed molecular oxygen when it was oxidized by horseradish peroxidase (HRP)-H(2)O(2) system, and that edaravone was capable of providing two electrons to the electrophiles. The possible mechanisms for oxidation of edaravone were investigated from these findings. PMID:14758002

  2. Pressure and Temperature Dependence of the Reaction of Vinyl Radical with Ethylene

    NASA Technical Reports Server (NTRS)

    Ismail, Huzeifa; Goldsmith, C. Franklin; Abel, Paul R.; Howe, Pui-Teng; Fahr, Askar; Halpern, Joshua B.; Jusinski, Leonard E.; Georgievskii, Yuri; Taatjes, Craig A.; Green, William H.

    2007-01-01

    This work reports measurements of absolute rate coefficients and Rice-Ramsperger-Kassel-Marcus (RRKM) master equation simulations of the C2H3 + C2H4 reaction. Direct kinetic studies were performed over a temperature range of 300-700 K and pressures of 20 and 133 mbar. Vinyl radicals (H2C=CH) were generated by laser photolysis of vinyl iodide (C2H31) at 266 nm, and time-resolved absorption spectroscopy was used to probe vinyl radicals through absorption at 423.2 nm. Measurements at 20 mbar are in good agreement with previous determinations at higher temperature. A weighted three-parameter Arrhenius fit to the experimental rate constant at 133 mbar, with the temperature exponent fixed, gives k = (7 +/- 1) x 10(exp -l4) cu cm/molecule/s (T/298 K)(exp 2) exp[-(1430 +/- 70) K/T]. RRKM master equation simulations, based on G3 calculations of stationary points on the C4H7 potential energy surface, were carried out to predict rate coefficients and product branching fractions. The predicted branching to 1-methylallyl product is relatively small under the conditions of the present experiments but increases as the pressure is lowered. Analysis of end products of 248 nm photolysis of vinyl iodide/ethylene mixtures at total pressures between 27 and 933 mbar provides no direct evidence for participation of I -methylallyl.

  3. Free radical depolymerization of hyaluronan by Maillard reaction products: role in liquefaction of aging vitreous.

    PubMed

    Deguine, V; Menasche, M; Ferrari, P; Fraisse, L; Pouliquen, Y; Robert, L

    1998-02-01

    The degradation of hyaluronan was followed by viscosimetry and by HPLC in order to study the possible role of Maillard products (lysine-glucose) on the alteration of the vitreous gel in aging and diabetes. Lysine-glucose generated Maillard products produced a decrease of viscosity and of the number average molecular weight (Mn) of hyaluronan during a 1 h incubation at 37 degrees C. This effect was comparable to that produced by 1 U/ml of testicular hyaluronidase but was weaker than the effect of a Fenton-type reagent (Udenfriend's reagent). The polydispersity of hyaluronan incubated with Maillard products appeared higher than with hyaluronidase suggesting a more random reaction. Antioxydant enzymes (SOD, catalase), the iron chelators (desferrioxamine, transferrin) and the free radical scavengers (uric acid, carnosine) inhibited the degradation by Maillard products confirming its free radical nature and the intervention of trace metals. Maillard products have been detected in diabetic vitreous and may play a role in its accelerated modifications (liquefaction) in diabetes as compared to normal aging. PMID:9513812

  4. ENDOR studies of the intermediate electron acceptor radical anion I-. in Photosystem II reaction centers.

    PubMed

    Lubitz, W; Isaacson, R A; Okamura, M Y; Abresch, E C; Plato, M; Feher, G

    1989-11-23

    The EPR and ENDOR characteristics of the intermediate electron acceptor radical anion I-. in Photosystem II (PS II) are shown to be identical in membrane particles and in the D1D2 cytochrome b-559 complex (Nanba, O. and Satoh, K. (1987) Proc. Natl. Acad. Sci. USA 84, 109-112). These findings provide further evidence that the D1D2 complex is the reaction center of PS II and show that the pheophytin binding site is intact. A hydrogen bond between I-. and the protein (GLU D1-130) is postulated on the basis of D2O exchange experiments. The ENDOR data of I-. and of the pheophytin a radical anion in different organic solvents are compared and the observed differences are related to structural changes of the molecule on the basis of molecular orbital calculations (RHF-INDO/SP). The importance of the orientation of the vinyl group (attached to ring I) on electron transfer is discussed. PMID:2553112

  5. Kinetics of nitrosamine and amine reactions with NO3 radical and ozone related to aqueous particle and cloud droplet chemistry

    NASA Astrophysics Data System (ADS)

    Weller, Christian; Herrmann, Hartmut

    2015-01-01

    Aqueous phase reactivity experiments with the amines dimethylamine (DMA), diethanolamine (DEA) and pyrrolidine (PYL) and their corresponding nitrosamines nitrosodimethylamine (NDMA), nitrosodiethanolamine (NDEA) and nitrosopyrrolidine (NPYL) have been performed. NO3 radical reaction rate coefficients for DMA, DEA and PYL were measured for the first time and are 3.7 × 105, 8.2 × 105 and 8.7 × 105 M-1 s-1, respectively. Rate coefficients for NO3 + NDMA, NDEA and NPYL are 1.2 × 108, 2.3 × 108 and 2.4 × 108 M-1 s-1. Compared to OH radical rate coefficients for reactions with amines, the NO3 radical will most likely not be an important oxidant but it is a potential nighttime oxidant for nitrosamines in cloud droplets or deliquescent particles. Ozone is unreactive towards amines and nitrosamines and upper limits of rate coefficients suggest that aqueous ozone reactions are not important in atmospheric waters.

  6. Pathway and kinetic analysis on the propyl radical + 02 reaction system

    SciTech Connect

    Bozzelli, J.W.; Pitz, W.J.

    1997-05-01

    In this study of the reaction of alkyl radicals with molecular oxygen, we analyze the propyl + 02 reaction system using thermochemical kinetics, Transition State Theory (TST), molecular thermodynamic properties, quantum Kassel analysis (quantum RRK) for k(E) and modified strong collision analysis for fall off. Cyclic transition states for both hydrogen transfer and the H02 concerted elimination from propylperoxy are calculated using semi-empirical (MOPAC PM3) calculations [8] in addition to transition states for H02 elimination and epoxide formation from hydroperoxy-isopropyl. Computed rate constants for propyl + 02 are compared to the values of Gulati and Walker who measured the rate constants at 50 torr and over a temperature range of 653 to 773 K. Computed rate constants are also used in a detailed chemical kinetic mechanism and compared to the n- propyl + 02 data of Slagle. They measured the rate of disappearance of n-propyl by reaction with 02 over a temperature range of 297 to 635 K and a pressure range of 0.4 to 7 Torr, as well as the fall off data of the Kaiser and Wallington.

  7. Reactions of hydroxyl radical with humic substances: bleaching, mineralization, and production of bioavailable carbon substrates.

    PubMed

    Goldstone, J V; Pullin, M J; Bertilsson, S; Voelker, B M

    2002-02-01

    In this study, we examine the role of the hydroxyl (OH*) radical as a mechanism for the photodecomposition of chromophoric dissolved organic matter (CDOM) in sunlit surface waters. Using gamma-radiolysis of water, OH* was generated in solutions of standard humic substances in quantities comparable to those produced on time scales of days in sunlit surface waters. The second-order rate coefficients of OH* reaction with Suwannee River fulvic (SRFA; 2.7 x 10(4) s(-1) (mg of C/L)(-1)) and humic acids (SRHA; 1.9 x 10(4) s(-1) (mg of C/L)(-1)) are comparable to those observed for DOM in natural water samples and DOM isolates from other sources but decrease slightly with increasing OH* doses. OH* reactions with humic substances produced dissolved inorganic carbon (DIC) with a high efficiency of approximately 0.3 mol of CO2/mol of OH*. This efficiency stayed approximately constant from early phases of oxidation until complete mineralization of the DOM. Production rates of low molecular weight (LMW) acids including acetic, formic, malonic, and oxalic acids by reaction of SRFA and SRHA with OH* were measured using HPLC. Ratios of production rates of these acids to rates of DIC production for SRHA and for SRFA were similar to those observed upon photolysis of natural water samples. Bioassays indicated that OH* reactions with humic substances do not result in measurable formation of bioavailable carbon substrates other than the LMW acids. Bleaching of humic chromophores by OH* was relatively slow. Our results indicate that OH* reactions with humic substances are not likely to contribute significantly to observed rates of DOM photomineralization and LMW acid production in sunlit waters. They are also not likely to be a significant mechanism of photobleaching except in waters with very high OH* photoformation rates. PMID:11871550

  8. Theoretical investigations of the gas phase reaction of limonene (C10H16) with OH radical

    NASA Astrophysics Data System (ADS)

    Ranjan Dash, Manas; Rajakumar, B.

    2015-11-01

    The rate coefficients of hydroxyl radical (OH) reaction with limonene were computed using canonical variational transition state theory with small-curvature tunnelling between 275 and 400 K. The geometries and frequencies of all the stationary points are calculated using hybrid density functional theory methods M06-2X and MPWB1K with 6-31+G(d,p), 6-311++G(d,p), and 6-311+G(2df,2p) basis sets. Both addition and abstraction channels of the title reaction were explored. The rate coefficients obtained over the temperature range of 275-400 K were used to derive the Arrhenius expressions: k(T) = 4.06×10-34 T7.07 exp[4515/T] and k(T) = 7.37×10-25 T3.9 exp[3169/T] cm3 molecule-1 s-1 at M06-2X/6-311+G(2df,2p) and MPWB1K/6-311+G(2df,2p) levels of theory, respectively. Kinetic study indicated that addition reactions are major contributors to the total reaction in the studied temperature range. The atmospheric lifetime (τ) of limonene due to its reactions with various tropospheric oxidants was calculated and concluded that limonene is lost in the atmosphere within a few hours after it is released. The ozone production potential of limonene was computed to be (14-18) ppm, which indicated that degradation of limonene would lead to a significant amount of ozone production in the troposphere.

  9. Kinetics investigation of the hydrogen abstraction reaction between CH3SS and CN radicals.

    PubMed

    Yan, Liu; Wenliang, Wang; Zhongwen, Liu; Hongjiang, Ren

    2016-01-01

    The reaction mechanisms and rates for the H abstraction reactions between CH3SS and CN radicals in the gas phase were investigated with density functional theory (DFT) methods. The geometries, harmonic vibrational frequencies, and energies of all stationary points were obtained at B3PW91/6-311G(d,p) level of theory. Relationships between the reactants, intermediates, transition states and products were confirmed, with the frequency and the intrinsic reaction coordinate (IRC) analysis at the same theoretical level. High accurate energy information was provided by the G3(MP2) method combined with the standard statistical thermodynamics. Gibbs free energies at 298.15 K for all of the reaction steps were reported, and were used to describe the profile diagrams of the potential energy surface. The rate constants were evaluated with both the classical transition state theory and the canonical variational transition state theory, in which the small-curvature tunneling correction was included. A total number of 9 intermediates (IMs) and 17 transition states (TSs) were obtained. It is shown that IM1 is the most stable intermediate by the largest energy release, and the channel of CH3SS + CN → IM3 → TS10  → P1(CH2SS + HCN) is the dominant reaction with the lowest energy barrier of 144.7 kJ mol(-1). The fitted Arrhenius expressions of the calculated CVT/SCT rate constants for the rate-determining step of the favorable channel is k =7.73 × 10(6)  T (1.40)exp(-14,423.8/T) s(-1) in the temperature range of 200-2000 K. The apparent activation energy E a(app.) for the main channel is -102.5 kJ mol(-1), which is comparable with the G3(MP2) energy barrier of -91.8 kJ mol(-1) of TS10 (relative to the reactants). PMID:26781664

  10. Water mediated hydrogen abstraction mechanism in the radical reaction between HOSO and NO2

    NASA Astrophysics Data System (ADS)

    Lesar, Antonija; Tušar, Simona

    2016-05-01

    The effect of water molecules on the direct hydrogen abstraction from HOSO by NO2 was investigated for the first time. Stationary points were located at the B3LYP/6-311+G(2df,2pd) and CCSD/aug-cc-pVDZ levels of theory whereas energetics was further improved by CBS-QB3 and G4 composite methods. The fractions of hydrated radical complexes were estimated in order to assess atmospheric relevance of the title reaction. The energy barrier of the water mediated process becomes negligible. The formations of post-reactive complexes from pre-reactive complexes are energetically very favorable and the processes are spontaneous suggesting that they should be very feasible under atmospheric conditions.

  11. Solvent effects on the rate constants for reaction of trichloromethylperoxyl radicals with organic reductants

    SciTech Connect

    Alfassi, Z.B.; Huie, R.E.; Neta, P. )

    1993-07-15

    Absolute rate constants for the reactions of trichloromethylperoxyl radicals with chloropromazine and trolox have been determined by pulse radiolysis in 16 different solvents. The rate constants were found to vary over two orders of magnitude (10[sup 7]-10[sup 9] L mol[sup [minus]1] s[sup [minus]1]) and to correlate with the Hildebrand solubility parameter (cohesive energy density) of the solvent better than with any other single solvent parameter. The correlation was satisfactory for ClPz and did not improve significantly by including additional parameters. For trolox, however, the correlation was relatively poor but was improved considerably by taking into account the basicity of the solvent. This effect is due to the transfer of a proton upon the oxidation of trolox. 21 refs., 3 figs., 2 tabs.

  12. Identification of the radicals formed in the reactions of some endogenous photosensitizers with oleic acid under the UVA irradiation.

    PubMed

    Mori, Hiroko; Iwahashi, Hideo

    2012-11-01

    Electron spin resonance measurements were performed for the reactions of some endogenous photosensitizers (flavin mononucleotide or flavin adenine dinucleotide or folic acid or β-nicotinamide adenine dinucleotide or β-nicotinamide adenine dinucleotide phosphate or pyridoxal-5'-phosphate or urocanic acid) with oleic acid under the ultraviolet light A irradiation using α-(4-pyridyl-1-oxide)-N-tert-butylnitrone as a spin trap reagent. Of the endogenous photosensitizers, prominent electron spin resonance signals (α(N) = 1.58 mT and α(H)β = 0.26 mT) were observed for the reaction mixture of flavin mononucleotide (or flavin adenine dinucleotide or folic acid), suggesting that radical species form in the reaction mixtures. Singlet oxygen seems to participate in the formation of the radicals because the electron spin resonance peak heights increased for the reactions in D(2)O to a great extent. A high performance liquid chromatography-electron spin resonance-mass spectrometry was employed to identify the radicals formed in the reactions of the endogenous photosensitizers (flavin mononucleotide or flavin adenine dinucleotide or folic acid) with oleic acid under the ultraviolet light A irradiation. The high performance liquid chromatography-electron spin resonance-mass spectrometry analyses showed that 7-carboxyheptyl and 1-(3-carboxypropyl)-4-hydroxybutyl radicals form in the reaction mixture of flavin mononucleotide (or flavin adenine dinucleotide or folic acid). PMID:23170043

  13. Atmospheric Degradation of CH2═C(CH3)C(O)OCH3 Initiated by OH Radicals: Mechanistic Study and Quantification of CH3C(O)C(O)OCH3 in NOx Free Air.

    PubMed

    Gibilisco, Rodrigo G; Uranga, Jorge G; Santiago, Ana N; Teruel, Mariano A

    2015-08-20

    The product distribution of the gas-phase reaction of OH radicals with methyl methacrylate (CH2═C(CH3)C(O)OCH3, MMA) in the absence of NOx was studied at 298 K and atmospheric pressure of air. The experiments were performed in a Teflon chamber using solid-phase microextraction (SPME) with GC-MS and GC-FID for product identification and quantification, respectively. In the absence of NOx, methyl pyruvate (CH3C(O)C(O)OCH3) was identified with a yield of 76 ± 13% in accordance with the decomposition of the 1,2-hydroxyalkoxy radicals formed. In addition, a detailed quantum chemical study of the degradation of MMA was performed by density functional theory (DFT) methods using the MPWB1K functional. This calculation suggests that formation of methyl pyruvate, from C1-C2 scission of 1,2-hydroxyalkoxy radical, is kinetically and thermodynamically the most favorable reaction path taking into account the electronic properties of reaction intermediates and transition states. The difference observed on the degradation mechanism of MMA in the presence and absence of NOx was explained in terms of the associated thermochemistry. Furthermore, this study propose that reaction between peroxy radical (RO2(•)) and hydroxyl radical (OH) became relevant at NOx-free environments. This statement is in agreement with recent studies concerning small peroxy radicals such as CH3OO(•). PMID:26213280

  14. The mechanism of the retro-Diels-Alder reaction in 4-vinylcyclohexene cation radical

    NASA Astrophysics Data System (ADS)

    Pancíř, J.; Tureček, F.

    1984-06-01

    Butadiene cation radicals are produced symmetrically from the ring and side-chain of the vinylcyclohexene cation radical near the onset of the fragmentation. The appearance energies of C 4H 6+- and C 4H 2D 4+- from (3,3,6,6-D 4)vinylcyclohex ene were measured as 11.07 ± 0.05 and 11.06 ± 0.06 eV, respectively. This sets the barrier to retro-Diels-Alder decomposition at 1140 kJ mol -1 above the energy of 1 and 44 kJ mol -1 above the thermochemical threshold corresponding to C 4H 6+- + C 4H 6. Topological molecular orbital calculations indicate that this lowest-energy path involves a sequential rupture of the C 3C 4 and C 5C 6 bonds, with a calculated barrier of 211 kJ mol -1. The second, two-step reaction channel proceeds by subsequent fission of the C 5C 6 and C 3C 4 bonds with a barrier of 299 kJ mol -1. This channel is found experimentally as a break on the ionization efficiency curve at 12.1 eV. Both the supra-supra and the supra-antara pericyclic reactions go through energy maxima and are therefore forbidden. The supra-supra process is the most favorable route for decomposition from the first excited state, the activation energy being 333 kJ mol -1. The preference for the two-step mechanism is due to hyperconjugative stabilization of intermediate molecular configurations.

  15. Mechanistic Significance of the Si–O–Pd Bond in the Palladium-Catalyzed Cross-Coupling Reactions of Arylsilanolates

    PubMed Central

    2016-01-01

    Through the combination of reaction kinetics (both stoichiometric and catalytic), solution- and solid-state characterization of arylpalladium(II) arylsilanolates, and computational analysis, the intermediacy of covalent adducts containing Si–O–Pd linkages in the cross-coupling reactions of arylsilanolates has been unambiguously established. Two mechanistically distinct pathways have been demonstrated: (1) transmetalation via a neutral 8-Si-4 intermediate that dominates in the absence of free silanolate (i.e., stoichiometric reactions of arylpalladium(II) arylsilanolate complexes), and (2) transmetalation via an anionic 10-Si-5 intermediate that dominates in the cross-coupling under catalytic conditions (i.e., in the presence of free silanolate). Arylpalladium(II) arylsilanolate complexes bearing various phosphine ligands have been isolated, fully characterized, and evaluated for their kinetic competence under thermal (stoichiometric) and anionic (catalytic) conditions. Comparison of the rates for thermal and anionic activation suggested, but did not prove, that intermediates containing the Si–O–Pd linkage were involved in the cross-coupling process. The isolation of a coordinatively unsaturated, T-shaped arylpalladium(II) arylsilanolate complex ligated with t-Bu3P allowed the unambiguous demonstration of the operation of both pathways involving 8-Si-4 and 10-Si-5 intermediates. Three kinetic regimes were identified: (1) with 0.5–1.0 equiv of added silanolate (with respect to arylpalladium bromide), thermal transmetalation via a neutral 8-Si-4 intermediate; (2) with 1.0–5.0 equiv of added silanolate, activated transmetalation via an anionic 10-Si-5 intermediate; and (3) with >5.0 equiv of added silanolate, concentration-independent (saturation) activated transmetalation via an anionic 10-Si-5 intermediate. Transition states for the intramolecular transmetalation of neutral (8-Si-4) and anionic (10-Si-5) intermediates have been located computationally

  16. The importance of OH radical-neutral low temperature tunnelling reactions in interstellar clouds using a new model

    NASA Astrophysics Data System (ADS)

    Acharyya, K.; Herbst, E.; Caravan, R. L.; Shannon, R. J.; Blitz, M. A.; Heard, D. E.

    2015-08-01

    Recent laboratory experiments using a pulsed Laval nozzle apparatus have shown that reactions between a neutral molecule and the radical OH can occur efficiently at low temperatures despite activation energy barriers if there is a hydrogen-bonded complex in the entrance channel which allows the system to tunnel efficiently under the barrier. Since OH is a major radical in the interstellar medium, this class of reactions may well be important in the chemistry that occurs in the gas phase of interstellar clouds. Using a new gas-grain chemical network with both gas-phase reactions and reactions on the surfaces of dust particles, we studied the role of OH-neutral reactions in dense interstellar clouds at 10, 50, and 100 K. We determined that at least one of these reactions can be significant, especially at the lowest temperatures studied, where the rate constants are large. It was found in particular that the reaction between CH3OH and OH provides an effective and unambiguous gas-phase route to the production of the gaseous methoxy radical (CH3O), which has been recently detected in cold, dense interstsellar clouds. The role of other reactions in this class is explored.

  17. Characterization of a Cross-Linked Protein-Nucleic Acid Substrate Radical in the Reaction Catalyzed by RlmN

    SciTech Connect

    Silakov, Alexey; Grove, Tyler L.; Radle, Matthew I.; Bauerle, Matthew R.; Green, Michael T.; Rosenzweig, Amy C.; Boal, Amie K.; Booker, Squire J.

    2014-08-14

    RlmN and Cfr are methyltransferases/methylsynthases that belong to the radical S-adenosylmethionine superfamily of enzymes. RlmN catalyzes C2 methylation of adenosine 2503 (A2503) of 23S rRNA, while Cfr catalyzes C8 methylation of the exact same nucleotide, and will subsequently catalyze C2 methylation if the site is unmethylated. A key feature of the unusual mechanisms of catalysis proposed for these enzymes is the attack of a methylene radical, derived from a methylcysteine residue, onto the carbon center undergoing methylation to generate a paramagnetic protein–nucleic acid cross-linked species. This species has been thoroughly characterized during Cfr-dependent C8 methylation, but does not accumulate to detectible levels in RlmN-dependent C2 methylation. Herein, we show that inactive C118S/A variants of RlmN accumulate a substrate-derived paramagnetic species. Characterization of this species by electron paramagnetic resonance spectroscopy in concert with strategic isotopic labeling shows that the radical is delocalized throughout the adenine ring of A2503, although predominant spin density is on N1 and N3. Moreover, 13C hyperfine interactions between the radical and the methylene carbon of the formerly [methyl-13C]Cys355 residue show that the radical species exists in a covalent cross-link between the protein and the nucleic acid substrate. X-ray structures of RlmN C118A show that, in the presence of SAM, the substitution does not alter the active site structure compared to that of the wild-type enzyme. Together, these findings have new mechanistic implications for the role(s) of C118 and its counterpart in Cfr (C105) in catalysis, and suggest involvement of the residue in resolution of the cross-linked species via a radical mediated process

  18. Characterization of a Cross-Linked Protein–Nucleic Acid Substrate Radical in the Reaction Catalyzed by RlmN

    PubMed Central

    2015-01-01

    RlmN and Cfr are methyltransferases/methylsynthases that belong to the radical S-adenosylmethionine superfamily of enzymes. RlmN catalyzes C2 methylation of adenosine 2503 (A2503) of 23S rRNA, while Cfr catalyzes C8 methylation of the exact same nucleotide, and will subsequently catalyze C2 methylation if the site is unmethylated. A key feature of the unusual mechanisms of catalysis proposed for these enzymes is the attack of a methylene radical, derived from a methylcysteine residue, onto the carbon center undergoing methylation to generate a paramagnetic protein–nucleic acid cross-linked species. This species has been thoroughly characterized during Cfr-dependent C8 methylation, but does not accumulate to detectible levels in RlmN-dependent C2 methylation. Herein, we show that inactive C118S/A variants of RlmN accumulate a substrate-derived paramagnetic species. Characterization of this species by electron paramagnetic resonance spectroscopy in concert with strategic isotopic labeling shows that the radical is delocalized throughout the adenine ring of A2503, although predominant spin density is on N1 and N3. Moreover, 13C hyperfine interactions between the radical and the methylene carbon of the formerly [methyl-13C]Cys355 residue show that the radical species exists in a covalent cross-link between the protein and the nucleic acid substrate. X-ray structures of RlmN C118A show that, in the presence of SAM, the substitution does not alter the active site structure compared to that of the wild-type enzyme. Together, these findings have new mechanistic implications for the role(s) of C118 and its counterpart in Cfr (C105) in catalysis, and suggest involvement of the residue in resolution of the cross-linked species via a radical mediated process. PMID:24806349

  19. Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

    NASA Technical Reports Server (NTRS)

    Hynes, A. J.; Wine, P. H.

    1997-01-01

    The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic

  20. Evaluation of a new copper(II)-curcumin complex as superoxide dismutase mimic and its free radical reactions.

    PubMed

    Barik, Atanu; Mishra, Beena; Shen, Liang; Mohan, Hari; Kadam, R M; Dutta, S; Zhang, Hong-Yu; Priyadarsini, K Indira

    2005-09-15

    A mononuclear (1:1) copper complex of curcumin, a phytochemical from turmeric, was synthesized and examined for its superoxide dismutase (SOD) activity. The complex was characterized by elemental analysis, IR, NMR, UV-VIS, EPR, mass spectroscopic methods and TG-DTA, from which it was found that a copper atom is coordinated through the keto-enol group of curcumin along with one acetate group and one water molecule. Cyclic voltammetric studies of the complex showed a reversible Cu(2+)/Cu(+) couple with a potential of 0.402 V vs NHE. The Cu(II)-curcumin complex is soluble in lipids and DMSO, and insoluble in water. It scavenges superoxide radicals with a rate constant of 1.97 x 10(5) M(-1) s(-1) in DMSO determined by stopped-flow spectrometer. Subsequent to the reaction with superoxide radicals, the complex was found to be regenerated completely, indicating catalytic activity in neutralizing superoxide radicals. Complete regeneration of the complex was observed, even when the stoichiometry of superoxide radicals was 10 times more than that of the complex. This was further confirmed by EPR monitoring of superoxide radicals. The SOD mimicking activity of the complex was determined by xanthine/xanthine oxidase assay, from which it has been found that 5 microg of the complex is equivalent to 1 unit of SOD. The complex inhibits radiation-induced lipid peroxidation and shows radical-scavenging ability. It reacts with DPPH radicals with rate constant 10 times less than that of curcumin. Pulse radiolysis-induced one-electron oxidation of the complex by azide radicals in TX-100 micellar solutions produced strongly absorbing ( approximately 500 nm) phenoxyl radicals, indicating that the phenolic moiety of curcumin remained intact on complexation with copper. The results confirm that the new Cu(II)-curcumin complex possesses SOD activity, free radical neutralizing ability, and antioxidant potential. Quantum chemical calculations with density functional theory have been performed

  1. Kinetic study of the gas phase reactions of a series of alcohols with the NO3 radical.

    PubMed

    Moreno, Alberto; Salgado, M Sagrario; Martín, M Pilar; Martínez, Ernesto; Cabañas, Beatriz

    2012-10-25

    The rate coefficients for the reaction of NO(3) radical with 2-butanol, 3-methyl-2-butanol, and 2,3-dimethyl-2-butanol were determined using relative rate technique in a 50 L glass pyrex photoreactor using in situ FT-IR spectroscopy at room temperature and a pressure of 350-670 Torr. The rate coefficient for the reaction of 2-methyl-2-butanol with NO(3) radical was also determined using, in this case, GC/MS. The rate coefficients calculated (in units of cm(3) molecule(-1) s(-1)) were (2.51 ± 0.42) × 10(-15), (3.06 ± 0.52) × 10(-15), (2.67 ± 0.3) × 10(-15), and (1.57 ± 0.16) × 10(-15), respectively. Results indicate that the reaction occurs by an initial H-abstraction of the alcohols by the NO(3) radical and that NO(3) is more reactive toward a H atom attached to a tertiary carbon than that attached to a secondary or primary carbon. Results are also discussed as related to their homologous structural alkanes and in comparison with the reactivity of other atmospheric oxidants. Atmospheric relevance of the considered reactions is evaluated, concluding that they are potential ozone generators, they have no significant influence on global warming, and the dominant atmospheric loss process for these alcohols is their daytime reaction with OH radicals. PMID:23030849

  2. Solution phase and membrane immobilized iron-based free radical reactions: Fundamentals and applications for water treatment

    NASA Astrophysics Data System (ADS)

    Lewis, Scott Romak

    Membrane-based separation processes have been used extensively for drinking water purification, wastewater treatment, and numerous other applications. Reactive membranes synthesized through functionalization of the membrane pores offer enhanced reactivity due to increased surface area at the polymer-solution interface and low diffusion limitations. Oxidative techniques utilizing free radicals have proven effective for both the destruction of toxic organics and non-environmental applications. Most previous work focuses on reactions in the homogeneous phase; however, the immobilization of reactants in membrane pores offers several advantages. The use of polyanions immobilized in a membrane or chelates in solution prevents ferric hydroxide precipitation at near-neutral pH, a common limitation of iron(Fe(II/III))-catalyzed hydrogen peroxide (H 2O2) decomposition. The objectives of this research are to develop a membrane-based platform for the generation of free radicals, degrade toxic organic compounds using this and similar solution-based reactions, degrade toxic organic compounds in droplet form, quantify hydroxyl radical production in these reactions, and develop kinetic models for both processes. In this study, a functionalized membrane containing poly(acrylic acid) (PAA) was used to immobilize iron ions and conduct free radical reactions by permeating H2O2 through the membrane. The membrane's responsive behavior to pH and divalent cations was investigated and modeled. The conversion of Fe(II) to Fe(III) in the membrane and its effect on the decomposition of hydrogen peroxide were monitored and used to develop kinetic models for predicting H2O2 decomposition in these systems. The rate of hydroxyl radical production, and hence contaminant degradation can be varied by changing the residence time, H2O2 concentration, and/or iron loading. Using these membrane-immobilized systems, successful removal of toxic organic compounds, such as pentachlorophenol (PCP), from water

  3. Reaction between CH3O2 and BrO radicals: a new source of upper troposphere lower stratosphere hydroxyl radicals.

    PubMed

    Shallcross, Dudley E; Leather, Kimberley E; Bacak, Asan; Xiao, Ping; Lee, Edmond P F; Ng, Maggie; Mok, Daniel K W; Dyke, John M; Hossaini, Ryan; Chipperfield, Martyn P; Khan, M Anwar H; Percival, Carl J

    2015-05-14

    Over the last two decades it has emerged that measured hydroxyl radical levels in the upper troposphere are often underestimated by models, leading to the assertion that there are missing sources. Here we report laboratory studies of the kinetics and products of the reaction between CH3O2 and BrO radicals that shows that this could be an important new source of hydroxyl radicals:BrO + CH3O2 → products (1). The temperature dependent value in Arrhenius form of k(T) is k1 = (2.42–0.72+1.02) × 10–14 exp[(1617 ± 94)/T] cm3 molecule–1 s–1. In addition, CH2OO and HOBr are believed to be the major products. Global model results suggest that the decomposition of H2COO to form OH could lead to an enhancement in OH of up to 20% in mid-latitudes in the upper troposphere and in the lower stratosphere enhancements in OH of 2–9% are inferred from model integrations. In addition, reaction 1 aids conversion of BrO to HOBr and slows polar ozone loss in the lower stratosphere. PMID:25768043

  4. Methyl radical also reacts by the frontside mechanism: an ab initio study of some homolytic substitution reactions of methyl radical at silicon, germanium and tin.

    PubMed

    Matsubara, Hiroshi; Horvat, Sonia M; Schiesser, Carl H

    2003-04-01

    Ab initio calculations using 6-311G**, cc-pVDZ, aug-cc-pVDZ, and a (valence) double-zeta pseudopotential (DZP) basis sets, with (MP2, QCISD, CCSD(T)) and without (UHF) the inclusion of electron correlation, and density functional (B3LYO) calculations predict that homolytic substitution reactions of the methyl radical at the silicon atom in disilane can proceed via both backside and frontside attack mechanisms. At the highest level of theory (CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ), energy barriers (delta E) of 47.4 and 48.6 kJ mol-1 are calculated for the backside and frontside reactions respectively. Similar results are obtained for reactions involving germanium and tin with energy barriers (delta E) of between 46.5 and 67.3, and 41.0 and 73.3 kJ mol-1 for the backside and frontside mechanisms, respectively. These data suggest that homolytic substitution reactions of methyl radical at silicon, germanium, and tin can proceed via either homolytic substitution mechanism. PMID:12926395

  5. Reactions of OOH radical with beta-carotene, lycopene, and torulene: hydrogen atom transfer and adduct formation mechanisms.

    PubMed

    Galano, Annia; Francisco-Marquez, Misaela

    2009-08-13

    The relative free radical scavenging activity of beta-carotene, lycopene, and torulene toward OOH radicals has been studied using density functional theory. Hydrogen atom transfer (HAT) and radical adduct formation (RAF) mechanisms have been considered. All the possible reaction sites have been included in the modeling, and detailed branching ratios are reported for the first time. The reactions of hydrocarbon carotenoids (Car) with peroxyl radicals, in both polar and nonpolar environments, are predicted to proceed via RAF mechanism, with contributions higher than 98% to the overall OOH + Car reactions. Lycopene and torulene were found to be more reactive than beta-carotene. In nonpolar environments the reactivity of the studied carotenoids toward peroxyl radical follows the trend LYC > TOR > BC, whereas in aqueous solutions it is TOR > LYC > BC. OOH adducts are predicted to be formed mainly at the terminal sites of the conjugated polyene chains. The main addition sites were found to be C5 for beta-carotene and lycopene and C30 for torulene. The general agreement between the calculated magnitudes and the available experimental data supports the predictions from this work. PMID:19627101

  6. Experimental and theoretical studies on gas-phase reactions of NO3 radicals with three methoxyphenols: Guaiacol, creosol, and syringol

    NASA Astrophysics Data System (ADS)

    Yang, Bo; Zhang, Haixu; Wang, Youfeng; Zhang, Peng; Shu, Jinian; Sun, Wanqi; Ma, Pengkun

    2016-01-01

    Methoxyphenols, lignin pyrolysis products, are major biomass combustion components and are considered potential tracers for wood smoke emissions. Their atmospheric reactivity, however, has not been well characterized. Guaiacol, creosol, and syringol are three typical methoxyphenols generated in relatively high concentrations in fresh wood smoke. In this study, the gas-phase reactions of NO3 radicals with these methoxyphenols were investigated using a laboratory-built vacuum ultraviolet photoionization gas time-of-flight mass spectrometer (VUV-GTOFMS) and off-line GC-MS. By combining experimental and theoretical methods, 4-nitroguaiacol, 6-nitroguaiacol, and 4,6-dinitroguaiacol were determined as the primary degradation products for guaiacol; similarly, 6-nitrocreosol and 3-nitrosyringol were identified for creosol and syringol, respectively. Using the relative rate method, rate constants at 298 K and 1 atm for the gas-phase reactions of guaiacol, creosol, and syringol with NO3 radicals were measured to be 3.2 × 10-12, 2.4 × 10-13, and 4.0 × 10-13 cm3 molecule-1 s-1, respectively. At a typical tropospheric concentration of NO3 radicals (5 × 108 molecule cm-3), atmospheric lifetimes for guaiacol, creosol, and syringol toward NO3 radicals were 0.2, 2.3, and 1.4 h, respectively. These results indicate that the reaction with NO3 radicals can be a major sink for methoxyphenols at night.

  7. Quenching and radical formation in the reaction of photoexcited benzophenone with thiols and thioethers (sulfides). Nanosecond flash studies

    SciTech Connect

    Inbar, S.; Linschitz, H.; Cohen, S.G.

    1982-01-01

    Laser flash measurements have been made of rate constants and primary radical yields in the reactions of triplet benzophenone with aliphatic and aromatic thiols and with dialkyl and aryl alkyl sulfides. Reaction with n-pentylthiol in benzene leads mainly to quenching, with k/sub ir/ = 9 x 10/sup 6/ M/sup -1/ s/sup -1/ and radical yield (ketyl) = 0.14; with mesitylene-2 thiol in benzene k/sub ir/ = 7 x 10/sup 8/ M/sup -1/ s/sup -1/ and hydrogen transfer is efficient, radical yield (ketyl) approx. 1.0. In reactions with both p-chlorophenyl ethyl and diisopropyl sulfides, k/sub ir/ increases and radical yield (ketyl) decreases with increasing solvent polarity. Values of k/sub ir/ are higher and those of radical yield (ketyl) are lower for the dialkyl than for the aryl alkyl sulfide. Results are discussed in terms of rapid interaction of the triplet with S, followed by quenching and/or hydrogen transfer. Quenching without hydrogen transfer occurs to a much greater extent with sulfides and aliphatic thiols than with amines.

  8. Rate coefficients of hydroxyl radical reactions with pesticide molecules and related compounds: A review

    NASA Astrophysics Data System (ADS)

    Wojnárovits, László; Takács, Erzsébet

    2014-03-01

    Rate coefficients published in the literature on hydroxyl radical reactions with pesticides and related compounds are discussed together with the experimental methods and the basic reaction mechanisms. Recommendations are made for the most probable values. Most of the molecules whose rate coefficients are discussed have aromatic ring: their rate coefficients are in the range of 2×109-1×1010 mol-1 dm3 s-1. The rate coefficients show some variation with the electron withdrawing-donating nature of the substituent on the ring. The rate coefficients for triazine pesticides (simazine, atrazine, prometon) are all around 2.5×109 mol-1 dm3 s-1. The values do not show variation with the substituent on the s-triazine ring. The rate coefficients for the non-aromatic molecules which have C=C double bonds or several C-H bonds may also be above 1×109 mol-1 dm3 s-1. However, the values for molecules without C=C double bonds or several C-H bonds are in the 1×107-1×109 mol-1 dm3 s-1 range.

  9. Oxygen dependency of one-electron reactions generating ascorbate radicals and hydrogen peroxide from ascorbic acid.

    PubMed

    Boatright, William L

    2016-04-01

    The effect of oxygen on the two separate one-electron reactions involved in the oxidation of ascorbic acid was investigated. The rate of ascorbate radical (Asc(-)) formation (and stability) was strongly dependent on the presence of oxygen. A product of ascorbic acid oxidation was measurable levels of hydrogen peroxide, as high as 32.5 μM from 100 μM ascorbic acid. Evidence for a feedback mechanism where hydrogen peroxide generated during the oxidation of ascorbic acid accelerates further oxidation of ascorbic acid is also presented. The second one-electron oxidation reaction of ascorbic acid leading to the disappearance of Asc(-) was also strongly inhibited in samples flushed with argon. In the range of 0.05-1.2 mM ascorbic acid, maximum levels of measurable hydrogen peroxide were achieved with an initial concentration of 0.2 mM ascorbic acid. Hydrogen peroxide generation was greatly diminished at ascorbic acid levels of 0.8 mM or above. PMID:26593628

  10. Strongly correlated mechanisms of a photoexcited radical reaction from the anti-Hermitian contracted Schrödinger equation

    NASA Astrophysics Data System (ADS)

    Foley, Jonathan J.; Rothman, Adam E.; Mazziotti, David A.

    2011-01-01

    Photoexcited radical reactions are critical to processes in both nature and materials, and yet they can be challenging for electronic structure methods due to the presence of strong electron correlation. Reduced-density-matrix (RDM) methods, based on solving the anti-Hermitian contracted Schrödinger equation (ACSE) for the two-electron RDM (2-RDM), are examined for studying the strongly correlated mechanisms of these reactions with application to the electrocyclic interconversion of allyl and cyclopropyl radicals. We combine recent extensions of the ACSE to excited states [G. Gidofalvi and D. A. Mazziotti, Phys. Rev. A 80, 022507 (2009)] and arbitrary spin states [A. E. Rothman, J. J. Foley IV, and D. A. Mazziotti, Phys. Rev. A 80, 052508 (2009)]. The ACSE predicts that the ground-state ring closure of the allyl radical has a high 52.5 kcal/mol activation energy that is consistent with experimental data, while the closure of an excited allyl radical can occur by disrotatory and conrotatory pathways whose transition states are essentially barrierless. Comparisons are made with multireference second- and third-order perturbation theories and multireference configuration interaction. While predicted energy differences do not vary greatly between methods, the ACSE appears to improve these differences when they involve a strongly and a weakly correlated radical by capturing a greater share of single-reference correlation that increases the stability of the weakly correlated radicals. For example, the ACSE predicts a -39.6 kcal/mol conversion of the excited allyl radical to the ground-state cyclopropyl radical in comparison to the -32.6 to -37.3 kcal/mol conversions predicted by multireference methods. In addition, the ACSE reduces the computational scaling with the number of strongly correlated orbitals from exponential (traditional multireference methods) to quadratic. Computed ground- and excited-state 2-RDMs are nearly N-representable.

  11. Photochemistry and kinetics of gas phase reactions involving HO and Cl radicals

    SciTech Connect

    Nelson, H.H.

    1980-11-01

    The kinetics of the reaction of the HO radical with HNO/sub 3/ and H/sub 2/O/sub 2/, the kinetics of Cl atom reactions with ClNO and ClNO/sub 2/, and the photochemistry of ClNO/sub 2/ and ClONO/sub 2/ were examined. The ultraviolet absorption cross sections of HNO/sub 3/ and ClNO/sub 2/ were also determined as part of the kinetics work. The rate constant for the reaction of HO with HNO/sub 3/ at room temperature was measured to be (8.2 +- 1.8) x 10/sup -14/ cm/sup 3/ molecule/sup -1/ s/sup -1/, where the uncertainty reported here and in all cases reflects twice the experimental standard deviation plus an estimate of systematic errors. The rate constant for the reaction HO + H/sub 2/O/sub 2/ was measured as (1.57 +- 0.23) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/. This agrees well with the two latest determinations and serves as a calibration of the experimental apparatus used. The Cl + ClNO reaction rate constant was determined to be (1.65 +- 0.32) x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/. The rate constant for the reaction of Cl + ClNO/sub 2/ was found to be (5.05 +- 0.75) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/. This is the first direct measurement of this rate constant. The photodissociation of ClNO/sub 2/ was studied in great detail. The absorption cross sections were measured in the ultraviolet and found to be substantially lower than the literature values in the Cl/sub 2/ absorption region (300 to 360 nm). Two product channels were investigated; products representative of the two channels were Cl and O atoms. Absolute calibration for the product detection systems was provided by Cl/sub 2/ and NO/sub 2/ photolysis respectively. The quantum uields measured for photolysis at 350 nm, calcualted using the absorption spectrum measured in this work, are: 0.93 +- 0.1 for Cl and less than or equal to 0.025 for O. An upper limit of 0.1 was measured for the O atom channel in ClOHO/sub 2/ photolysis.

  12. Linear free energy relationships between aqueous phase hydroxyl radical reaction rate constants and free energy of activation.

    PubMed

    Minakata, Daisuke; Crittenden, John

    2011-04-15

    The hydroxyl radical (HO(•)) is a strong oxidant that reacts with electron-rich sites on organic compounds and initiates complex radical chain reactions in aqueous phase advanced oxidation processes (AOPs). Computer based kinetic modeling requires a reaction pathway generator and predictions of associated reaction rate constants. Previously, we reported a reaction pathway generator that can enumerate the most important elementary reactions for aliphatic compounds. For the reaction rate constant predictor, we develop linear free energy relationships (LFERs) between aqueous phase literature-reported HO(•) reaction rate constants and theoretically calculated free energies of activation for H-atom abstraction from a C-H bond and HO(•) addition to alkenes. The theoretical method uses ab initio quantum mechanical calculations, Gaussian 1-3, for gas phase reactions and a solvation method, COSMO-RS theory, to estimate the impact of water. Theoretically calculated free energies of activation are found to be within approximately ±3 kcal/mol of experimental values. Considering errors that arise from quantum mechanical calculations and experiments, this should be within the acceptable errors. The established LFERs are used to predict the HO(•) reaction rate constants within a factor of 5 from the experimental values. This approach may be applied to other reaction mechanisms to establish a library of rate constant predictions for kinetic modeling of AOPs. PMID:21410278

  13. EXPERIMENTAL STUDY OF CO{sub 2} FORMATION BY SURFACE REACTIONS OF NON-ENERGETIC OH RADICALS WITH CO MOLECULES

    SciTech Connect

    Oba, Yasuhiro; Watanabe, Naoki; Kouchi, Akira; Hama, Tetsuya; Pirronello, Valerio

    2010-04-01

    Surface reactions between carbon monoxide and non-energetic hydroxyl radicals were carried out at 10 K and 20 K in order to investigate possible reaction pathways to yield carbon dioxide in dense molecular clouds. Hydroxyl radicals, produced by dissociating water molecules in microwave-induced plasma, were cooled down to 100 K prior to the introduction of CO. The abundances of species were monitored in situ using a Fourier transform infrared spectrometer. Formation of CO{sub 2} was clearly observed, even at 10 K, suggesting that reactions of CO with OH proceed with little or no activation barrier. The present results indicate that CO{sub 2} formation, due to reactions between CO and OH, occurs in tandem with H{sub 2}O formation, and this may lead to the formation of CO{sub 2} ice in polar environments, as typically observed in molecular clouds.

  14. Stereochemical Course of the Reaction Catalyzed by RimO, a Radical SAM Methylthiotransferase.

    PubMed

    Landgraf, Bradley J; Booker, Squire J

    2016-03-01

    RimO is a member of the growing radical S-adenosylmethionine (SAM) superfamily of enzymes, which use a reduced [4Fe-4S] cluster to effect reductive cleavage of the 5' C-S bond of SAM to form a 5'-deoxyadenosyl 5'-radical (5'-dA(•)) intermediate. RimO uses this potent oxidant to catalyze the attachment of a methylthio group (-SCH3) to C3 of aspartate 89 of protein S12, one of 21 proteins that compose the 30S subunit of the bacterial ribosome. However, the exact mechanism by which this transformation takes place has remained elusive. Herein, we describe the stereochemical course of the RimO reaction. Using peptide mimics of the S12 protein bearing deuterium at the 3 pro-R or 3 pro-S positions of the target aspartyl residue, we show that RimO from Bacteroides thetaiotaomicron (Bt) catalyzes abstraction of the pro-S hydrogen atom, as evidenced by the transfer of deuterium into 5'-deoxyadenosine (5'-dAH). The observed kinetic isotope effect on H atom versus D atom abstraction is ∼1.9, suggesting that this step is at least partially rate determining. We also demonstrate that Bt RimO can utilize the flavodoxin/flavodoxin oxidoreductase/NADPH reducing system from Escherichia coli as a source of requisite electrons. Use of this in vivo reducing system decreases, but does not eliminate, formation of 5'-dAH in excess of methylthiolated product. PMID:26871608

  15. Calculational and Experimental Investigations of the Pressure Effects on Radical - Radical Cross Combinations Reactions: C2H5 + C2H3

    NASA Technical Reports Server (NTRS)

    Fahr, Askar; Halpern, Joshua B.; Tardy, Dwight C.

    2007-01-01

    Pressure-dependent product yields have been experimentally determined for the cross-radical reaction C2H5 + C2H3. These results have been extended by calculations. It is shown that the chemically activated combination adduct, 1-C4H8*, is either stabilized by bimolecular collisions or subject to a variety of unimolecular reactions including cyclizations and decompositions. Therefore the "apparent" combination/disproportionation ratio exhibits a complex pressure dependence. The experimental studies were performed at 298 K and at selected pressures between about 4 Torr (0.5 kPa) and 760 Torr (101 kPa). Ethyl and vinyl radicals were simultaneously produced by 193 nm excimer laser photolysis of C2H5COC2H3 or photolysis of C2H3Br and C2H5COC2H5. Gas chromatograph/mass spectrometry/flame ionization detection (GC/MS/FID) were used to identify and quantify the final reaction products. The major combination reactions at pressures between 500 (66.5 kPa) and 760 Torr are (1c) C2H5 + C2H3 yields 1-butene, (2c) C2H5 + C2H5 yields n-butane, and (3c) C2H3 + C2H3 yields 1,3-butadiene. The major products of the disproportionation reactions are ethane, ethylene, and acetylene. At moderate and lower pressures, secondary products, including propene, propane, isobutene, 2-butene (cis and trans), 1-pentene, 1,4-pentadiene, and 1,5-hexadiene are also observed. Two isomers of C4H6, cyclobutene and/or 1,2-butadiene, were also among the likely products. The pressure-dependent yield of the cross-combination product, 1-butene, was compared to the yield of n-butane, the combination product of reaction (2c), which was found to be independent of pressure over the range of this study. The [ 1-C4H8]/[C4H10] ratio was reduced from approx.1.2 at 760 Torr (101 kPa) to approx.0.5 at 100 Torr (13.3 kPa) and approx.0.1 at pressures lower than about 5 Torr (approx.0.7 kPa). Electronic structure and RRKM calculations were used to simulate both unimolecular and bimolecular processes. The relative importance

  16. Are HO radicals produced in the reaction of O(3P) with 1-C4H8 ?

    NASA Technical Reports Server (NTRS)

    Luria, M.; Simonaitis, R.; Heicklen, J.

    1972-01-01

    The reaction of O(3P) with 1-C4H8 was examined in the presence of CO which scavenges HO radicals to produce CO2. From the CO2 quantum yield, an upper limit to the efficiency of HO production in the reaction of O(3P) with 1-C4H8 was found to be 0.020 at both 298 and 473 K.

  17. POLYCHLORINATED DIBENZO-P-DIOXINS AND DIBENZOFURANS: GAS-PHASE HYDROXYL RADICAL REACTIONS AND RELATED ATMOSPHERIC REMOVAL. (R825377)

    EPA Science Inventory

    Gas-phase reactions with the hydroxyl radical (OH) are
    expected to be an important removal pathway of polychlorinated dibenzo-p-dioxins and dibenzofurans
    (PCDD/F)
    in the atmosphere. Our laboratory recently developed
    a system to measure the rate constants of ...

  18. Proposed chemical mechanisms leading to secondary organic aerosol in the reactions of aliphatic amines with hydroxyl and nitrate radicals

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The presence and importance of amines in the atmosphere continues to gain more attention including aliphatic amines commonly associated with agricultural facilities. The atmospheric reaction mechanisms of these amines with key atmospheric radicals are important to predict both daytime and nighttime...

  19. FORMATION OF BETA-HYDROXYCARBONYLS FROM THE OH RADICAL-INITIATED REACTIONS OF SELECTED ALKENES (R825252)

    EPA Science Inventory

    -Hydroxycarbonyls can be formed from the gas-phase
    reactions of alkenes with the OH radical, both in the presence
    and in the absence of NO. To date, because of analytical
    difficulties, few data have been r...

  20. (16) O/(18) O Exchange of Aldehydes and Ketones caused by H2 (18) O in the Mechanistic Investigation of Organocatalyzed Michael, Mannich, and Aldol Reactions.

    PubMed

    Hayashi, Yujiro; Mukaiyama, Takasuke; Benohoud, Meryem; Gupta, Nishant R; Ono, Tsuyoshi; Toda, Shunsuke

    2016-04-18

    Organocatalyzed Michael, Mannich, and aldol reactions of aldehydes or ketones, as nucleophiles, have triggered several discussions regarding their reaction mechanism. H2 (18) O has been utilized to determine if the reaction proceeds through an enamine or enol mechanism by monitoring the ratio of (18) O incorporated into the final product. In this communication, we describe the risk of H2 (18) O as an evaluation tool for this mechanistic investigation. We have demonstrated that exchange of (16) O/(18) O occurs in the aldehyde or ketone starting material, caused by the presence of H2 (18) O and amine catalysts, before the Michael, Mannich, and aldol reactions proceed. Because the newly generated (18) O starting aldehydes or ketones and (16) O water affect the incorporation ratio of (18) O in the final product, the use of H2 (18) O would not be appropriate to distinguish the mechanism of these organocatalyzed reactions. PMID:26841358

  1. Coal liquefaction model studies: free radical chain decomposition of diphenylpropane, dibenzyl ether, and phenyl ether via. beta. -scission reactions

    SciTech Connect

    Gillert, K.E.; Gojewski, J.J.

    1982-12-03

    The thermal decompositions to 1,3-diphenylpropane (1), dibenzyl ether (2), and phenethyl phenyl ether (3) have been found to proceed by free radical chain processes. 1 gave toluene and styrene with a reaction order of 1.55, E/sub A/ = 51.4 kcal/mol, and log A = 12.5. The reaction could be initiated by benzyl phenyl ether but not by 1,2-diphenylethane. 2 gave toluene and benzaldehyde with a reaction order of 1.43,E/sub A/ = 48 kcal/mol, and log A = 12.6. The reaction could be initiated with benzyl phenyl ether. 3 gave phenol and styrene with a reaction order of 1.21, E/sub A/ = 50.3 kcal/mol, and log A =12.3. The reaction could be initiated by benzyl phenyl ether. All of the data are consistent with free radical processes with the reaction order determined by the termination reaction. No evidence for concerted reactions has been found.

  2. Oxidative stress and damage induced by abnormal free radical reactions and IgA nephropathy

    PubMed Central

    Chen, Jia-xi; Zhou, Jun-fu; Shen, Han-chao

    2005-01-01

    Objective: To estimate the oxidative stress and oxidative damage induced by abnormal free radical reactions in IgA nephropathy (IgAN) patients’ bodies. Methods: Seventy-two IgA N patients (IgANP) and 72 healthy adult volunteers (HAV) were enrolled in a random control study design, in which the levels of nitric oxide (NO) in plasma, lipoperoxide (LPO) in plasma and in erythrocytes, and vitamin C (VC), vitamin E (VE) and β-carotene (β-CAR) in plasma as well as the activities of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPX) in erythrocytes were determined with spectrophotometric mothods. Results: Compared with the HAV group, the averages of NO in plasma, and LPO in plasma and in erythrocytes in the IgANP group were significantly increased (P<0.0001), while those of VC, VE and β-CAR in plasma as well as those of SOD, CAT and GPX in erythrocytes in the IgANP group were significantly decreased (P<0.0001). Linear correlation analysis showed that with the increase of the values of NO, and LPO in plasma and in erythrocytes, and with the decrease of those of VC, VE, β-CAR, SOD, CAT and GPX in the IgAN patients, the degree of histological damage of tubulointerstitial regions was increased gradually (P<0.0001); and that with the prolongation of the duration of disease the values of NO, and LPO in plasma and erythrocytes were increased gradually, while those of VC, VE, β-CAR, SOD, CAT and GPX were decreased gradually (P<0.005). The discriminatory correct rates of the above biochemical parameters reflecting oxidative damage of the IgAN patients were 73.8%–92.5%, and the correct rates for the HAV were 70.0%–91.3% when independent discriminant analysis was used; and the correct rate for the IgAN patients was increased to 98.8%, the correct rate for the HAV was increased to 100% when stepwise discriminant analysis was used. The above biochemical parameters’ reliability coefficient (alpha) were used to estimate the oxidative damage of the

  3. Rh-Catalyzed Decarbonylation of Conjugated Ynones via Carbon–Alkyne Bond Activation: Reaction Scope and Mechanistic Exploration via DFT Calculations

    PubMed Central

    Dermenci, Alpay; Whittaker, Rachel E.; Gao, Yang; Cruz, Faben A.; Yu, Zhi-Xiang; Dong, Guangbin

    2015-01-01

    In this full article, detailed development of a catalytic decarbonylation of conjugated monoynones to synthesize disubstituted alkynes is described. The reaction scope and limitation has been thoroughly investigated, and a broad range of functional groups including heterocycles were compatible under the catalytic conditions. Mechanistic exploration via DFT calculations has also been executed. Through the computational study, a proposed catalytic mechanism has been carefully evaluated. These efforts are expected to serve as an important exploratory study for developing catalytic alkyne-transfer reactions via carbon−alkyne bond activation. PMID:26229587

  4. Reaction kinetics and efficiencies for the hydroxyl and sulfate radical based oxidation of artificial sweeteners in water.

    PubMed

    Toth, Janie E; Rickman, Kimberly A; Venter, Andre R; Kiddle, James J; Mezyk, Stephen P

    2012-10-11

    Over the past several decades, the increased use of artificial sweeteners as dietary supplements has resulted in rising concentrations of these contaminants being detected in influent waters entering treatment facilities. As conventional treatments may not quantitatively remove these sweeteners, radical-based advanced oxidation and reduction (AO/RP) treatments could be a viable alternative. In this study, we have established the reaction kinetics for both hydroxyl ((•)OH) and sulfate (SO(4)(•-)) radical reaction with five common artificial sweeteners, as well as their associated reaction efficiencies. Rate constants for acesulfame K, aspartame, rebaudioside A, saccharin, and sucralose were <2 × 10(7), (2.28 ± 0.02) × 10(9), (2.1 ± 0.1) × 10(8), <2 × 10(7), and (1.7 ± 0.1) × 10(8) M(-1) s(-1) for the sulfate radical, and (3.80 ± 0.27) × 10(9), (6.06 ± 0.05) × 10(9), (9.97 ± 0.12) × 10(9), (1.85 ± 0.01) × 10(9), and (1.50 ± 0.01) × 10(9) M(-1) s(-1) for the hydroxyl radical, respectively. These latter values have to be combined with their corresponding reaction efficiencies of 67.9 ± 0.9, 52.2 ± 0.7, 43.0 ± 2.5, 52.7 ± 2.9, and 98.3 ± 3.5% to give effective rate constants for the hydroxyl radical reaction that can be used in the modeling of the AOP based removal of these contaminants. PMID:22900636

  5. FeCl3-Mediated Radical Tandem Reactions of 3-Benzyl-2-oxindoles with Styrene Derivatives for the Stereoselective Synthesis of Spirocyclohexene Oxindoles.

    PubMed

    Wu, Hong-Ru; Cheng, Liang; Kong, De-Long; Huang, Hong-Yan; Gu, Chun-Ling; Liu, Li; Wang, Dong; Li, Chao-Jun

    2016-03-18

    A novel FeCl3-mediated reaction of 3-benzyl-2-oxindoles with styrene derivatives was developed. The reaction provided spirocyclohexene oxindoles in good yields and excellent diastereoselectivities via a tandem radical addition/cyclization process. PMID:26950164

  6. Analysis of Chemical Reactions between Radical Growth Precursors Adsorbed on Plasma-Deposited Silicon Thin-Film Surfaces

    NASA Astrophysics Data System (ADS)

    Bakos, Tamas; Valipa, Mayur; Maroudas, Dimitrios

    2006-03-01

    The dominant precursor in the plasma deposition of hydrogenated amorphous silicon (a-Si:H) thin films is the SiH3 radical. In this presentation, we report results of first-principles density functional theory calculations on the crystalline Si(001)-(2x1):H surface and molecular-dynamics simulations on a-Si:H surfaces for the interactions between SiH3 radicals adsorbed on Si thin-film surfaces. The analysis reveals that two SiH3 radicals may either form disilane (Si2H6) that desorbs from the surface or undergo a disproportionation reaction producing an SiH2 radical that is incorporated in the film and a silane molecule that is released in the gas phase. The corresponding activation barriers depend on the local atomic coordination of the surface Si atoms; Si2H6 formation is barrierless if both radicals are bonded to overcoordinated surface Si atoms and exhibits barriers in excess of 1 eV for two chemisorbed SiH3 radicals.

  7. Rapid syntheses of dehydrodiferulates via biomimetic radical coupling reactions of ethyl ferulate.

    PubMed

    Lu, Fachuang; Wei, Liping; Azarpira, Ali; Ralph, John

    2012-08-29

    Dehydrodimerization of ferulates in grass cell walls provides a pathway toward cross-linking polysaccharide chains limiting the digestibility of carbohydrates by ruminant bacteria and in general affecting the utilization of grass as a renewable bioresource. Analysis of dehydrodiferulates (henceforth termed diferulates) in plant cell walls is useful in the evaluation of the quality of dairy forages as animal feeds. Therefore, there has been considerable demand for quantities of diferulates as standards for such analyses. Described here are syntheses of diferulates from ethyl ferulate via biomimetic radical coupling reactions using the copper(II)-tetramethylethylenediamine [CuCl(OH)-TMEDA] complex as oxidant or catalyst. Although CuCl(OH)-TMEDA oxidation of ethyl ferulate in acetonitrile produced mixtures composed of 8-O-4-, 8-5-, 8-8- (cyclic and noncyclic), and 5-5-coupled diferulates, a catalyzed oxidation using CuCl(OH)-TMEDA as catalyst and oxygen as an oxidant resulted in better overall yields of such diferulates. Flash chromatographic fractionation allowed isolation of 8-8- and 5-5-coupled diferulates. 8-5-Diferulate coeluted with 8-O-4-diferulate but was separated from it via crystallization; the 8-O-4 diferulate left in the mother solution was isolated by rechromatography following a simple tetrabutylammonium fluoride treatment that converted 8-5-diferulate to another useful diferulate, 8-5-(noncyclic) diferulate. Therefore, six of the nine (5-5, 8-O-4, 8-5-c, 8-5-nc, 8-5-dc, 8-8-c, 8-8-nc, 8-8-THF, 4-O-5) diferulic acids that have to date been found in the alkaline hydrolysates of plant cell walls can be readily synthesized by the CuCl(OH)-TMEDA catalyzed aerobic oxidative coupling reaction and subsequent saponification described here. PMID:22846085

  8. Comprehensive theoretical studies on the reaction of 1-bromo-3,3,3-trifluoropropene with OH free radicals.

    PubMed

    Zhang, Meiling; Song, Ce; Tian, Yan

    2013-01-01

    The potential energy surfaces (PES) for the reaction of 1-bromo-3,3,3-trifluoropropene (CF3CHCBrH) with hydroxyl (OH) free radicals is probed theoretically at the CCSD/aug-cc-pVDZ//B3LYP/6-311++G(d,p) level of theory. All the possible stationary and first-order saddle points along the reaction paths were verified by the vibrational analysis. The calculations account for all the product channels. Based on the calculated CCSD/aug-cc-pVDZ potential energy surface, the possible reaction mechanism is discussed. Six distinct reaction pathways of 1-bromo-3,3,3-trifluoropropene (BTP) with OH are investigated. The geometries, reaction enthalpies and energy barriers are determined. Canonical transition-state theory with Wigner tunneling correction was used to predict the rate constants for the temperature range of 290-3,000 K without any artificial adjustment, and the computed rate constants for elementary channels can be accurately fitted with three-parameter Arrhenius expressions. OH addition reaction channel and the H atom abstraction channels related to the carbon-carbon double bond are found to be the main reaction channels for the reaction of 1-bromo-3,3,3-trifluoropropene (CF3CHCBrH) with hydroxyl (OH) free radicals while the products leading to CF3CHCH + BrOH and COHF2CHCBrH + F play a negligible role. PMID:23884124

  9. A kinetic study of OH radical reactions with methane and perdeuterated methane

    SciTech Connect

    Dunlop, J.R.; Tully, F.P. )

    1993-10-28

    We measured absolute rate coefficients for the reactions of the hydroxyl radical with methane (k[sub 1]) and methane-d[sub 4] (k[sub 2]) using the laser photolysis/laser-induced fluorescence technique. We characterized k[sub 1] and k[sub 2] over the temperature range 293-800 K at pressures between 400 and 750 Torr of helium. We find excellent agreement between our results and the recent determinations of k[sub 1] at lower temperatures by Vaghjiani and Ravishankara. The measured rate coefficients, in the units cm[sup 3] molecule[sup [minus]1] s[sup [minus]1], fit well to the three-parameter expressions k[sub 1](T) = 9.65 [times] 10[sup [minus]20] T[sup 2.58] exp(-1082/T) and k[sub 2](T) = 8.70 x 10[sup [minus]22] T[sup 3.23] exp(-1334/T). The kinetic isotope effect for abstraction of the H and D atoms varies from 6.75 at 293 K to 1.96 at 800 K. We compare our results to recently reported calculations by Melissas and Truhlar. 10 refs., 3 figs., 1 tab.

  10. Kinetics and mechanism of the gas phase reaction of Cl atoms and OH radicals with bromobenzene

    NASA Astrophysics Data System (ADS)

    Nakano, Y.; Kawasaki, M.; Ponomarev, D. A.; Hurley, M. D.; Wallington, T. J.

    2002-02-01

    Relative rate techniques were used to study the kinetics and mechanism of the reaction of Cl atoms and OH radicals with bromobenzene (C 6H 5Br) in 20-700 Torr of N 2, O 2, or air diluent at 295±2 K. Using the observed rate constant ratios k(C 6H 5Br+Cl)/ k(C 2H 5Cl+Cl)=1.56±0.05 and k(C 6H 5Br+Cl)/ k(C 2H 6+Cl)=0.24±0.01, the C 6H 5Br+Cl rate constant is determined to be k( C6H5Br+ Cl)=(1.32±0.20)×10 -11 cm3 molecule-1 s-1 giving exclusively C 6H 5Cl through a displacement mechanism. Using the observed rate constant ratios k(C 6H 5Br+OH)/ k(C 6H 6+OH)=0.77±0.06 and k(C 6H 5Br+OH)/ k(C 2H 4+OH)=0.11±0.004, the C 6H 5Br+OH rate constant is determined to be k( C6H5Br+ OH)=(9.37±2.04)×10 -13 cm3 molecule-1 s-1. The product expected from a displacement mechanism, phenol, was not observed (<10% yield).

  11. Generation of Organic Radicals During Photocatalytic Reactions on TiO2

    SciTech Connect

    Henderson, Michael A.; Deskins, N. Aaron; Zehr, Robert T.; Dupuis, Michel

    2011-04-01

    Using a variety of organic carbonyl molecules (R1C(O)R2) and the rutile TiO2(110) surface as a model photocatalyst, we demonstrate both experimentally and theoretically that ejection of organic radicals from TiO2 surfaces is likely a prevalent reaction process occurring during heterogeneous photooxidationof organic molecules. Organic carbonyls react with coadsorbed oxygen species to form organic diolates which are more strongly bound to TiO2 than are the parent carbonyls. The parent carbonyls, when bound to TiO2(110) in an η1 configuration, are photo-inactive. However, the diolates are shown to photodecompose by ejection one of the two R substituents from the surface into the gas phase, leaving behind the carboxylate of the other R group. Theoretical calculations using DFT show that in most cases the choice of which R group is ejected can be predicted based on the C-R bond energies and, to a lesser extent, the stability of the ejected R group.

  12. Reaction of alcohol radicals with cyclic disulfides. An optical and conductimetric pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Anderson, Robert F.; Vojnovic, Borivoj; Patel, Kantilal B.; Michael, Barry D.

    The disulfides lipoamide (LIPA) and oxidized dithiothreitol ( ox-DTT) react with methanol, ethanol, isopropanol and t-butanol radicals in aqueous solution at pH10.8 to form disulfide radical anions. Electron transfer rates range from ca 10 7 dm 3 mol -1s -1 for t-butanol radicals with LIPA to 3.6 × 10 8 dm 3 mol -1s -1 for methanol radicals with LIPA. The formations of the disulfide radical anions were followed by simultaneously monitoring absorption changes at 400 nm and changes in conductance with time. The electron transfer efficiencies are higher for LIPA than for ox-DTT increasing in the series t-butanol ≪isopropanol radical formation on the alcohols.

  13. Experimental and Theoretical Study of Reactions of OH Radicals with Hexenols: An Evaluation of the Relative Importance of the H-Abstraction Reaction Channel.

    PubMed

    Gai, Yanbo; Lin, Xiaoxiao; Ma, Qiao; Hu, Changjin; Gu, Xuejun; Zhao, Weixiong; Fang, Bo; Zhang, Weijun; Long, Bo; Long, Zhengwen

    2015-09-01

    C6 hexenols are one of the most significant groups of volatile organic compounds with biogenic emissions. The lack of corresponding kinetic parameters and product information on their oxidation reactions will result in incomplete atmospheric chemical mechanisms and models. In this paper, experimental and theoretical studies are reported for the reactions of OH radicals with a series of C6 hexenols, (Z)-2-hexen-1-ol, (Z)-3-hexen-1-ol, (Z)-4-hexen-1-ol, (E)-2-hexen-1-ol, (E)-3-hexen-1-ol, and (E)-4-hexen-1-ol, at 298 K and 1.01 × 10(5) Pa. The corresponding rate constants were 8.53 ± 1.36, 10.1 ± 1.6, 7.86 ± 1.30, 8.08 ± 1.33, 9.10 ± 1.50, and 7.14 ± 1.20 (in units of 10(-11) cm(3) molecule(-1) s(-1)), respectively, measured by gas chromatography with a flame ionization detector (GC-FID), using a relative technique. Theoretical calculations concerning the OH-addition and H-abstraction reaction channels were also performed for these reactions to further understand the reaction mechanism and the relative importance of the H-abstraction reaction. By contrast to previously reported results, the H-abstraction channel is a non-negligible reaction channel for reactions of OH radicals with these hexenols. The rate constants of the H-abstraction channel are comparable with those for the OH-addition channel and contribute >20% for most of the studied alcohols, even >50% for (E)-3-hexen-1-ol. Thus, H-abstraction channels may have an important role in the reactions of these alcohols with OH radicals and must be considered in certain atmospheric chemical mechanisms and models. PMID:26274814

  14. The effect of spin-orbit splitting on the association kinetics of barrierless halogen atom-hydrocarbon radical reactions.

    SciTech Connect

    Jasper, A. W.; Klippenstein, S. J.; Harding, L. B.

    2010-01-01

    The effect of the geometry dependence of spin-orbit splitting on transition state theory (TST) predictions for radical-radical recombination rate coefficients is examined. The effects are illustrated with direct ab initio variable-reaction-coordinate (VRC)-TST calculations for the reactions of two types of hydrocarbon radicals (R = CH{sub 3} and CH{sub 2}CHCH{sub 2}) with three halogen atoms (X = F, Cl, and Br). These halogen atoms exhibit a range of spin-orbit interaction strengths, while their interactions with the two hydrocarbon radicals exhibit a range of attractiveness. The transition state dividing surfaces for these barrierless reactions occur over a range of R-X fragment separations ({approx}3-7 {angstrom}) where the magnitude of the spin-orbit splitting is strongly geometry dependent. Perturbative models for incorporating the energetic effect of spin-orbit splitting into barrierless kinetics are presented and tested. Simply neglecting the variation in the spin-orbit splitting is demonstrated to contribute an error of less than 15% to the predicted rate coefficients for all but the CH{sub 2}CHCH{sub 2} + Br reaction, where its neglect increases the rate by up to a factor of 2. For the CH{sub 2}CHCH{sub 2} + Br reaction, the effect of spin-orbit splitting is not perturbative and instead qualitatively changes the long-range interaction potential and association dynamics. The present theoretical predictions are compared with available experimental measurements and previous theoretical work. For the CH{sub 3} + F association reaction, the errors associated with limitations in the basis set and in the active space are studied, and a detailed comparison is made between VRC-TST and rigid rotor-harmonic oscillator variational TST.

  15. Proposed chemical mechanisms leading to secondary organic aerosol in the reactions of aliphatic amines with hydroxyl and nitrate radicals

    NASA Astrophysics Data System (ADS)

    Price, Derek J.; Clark, Christopher H.; Tang, Xiaochen; Cocker, David R.; Purvis-Roberts, Kathleen L.; Silva, Philip J.

    2014-10-01

    The presence and importance of amines in the atmosphere, including aliphatic amines, continues to gain more attention. The atmospheric reaction mechanisms of these amines with key atmospheric radicals are important to predict both daytime and nighttime atmospheric chemistry. While previous studies have focused on the production of amine salts, this analysis looks at the importance of peroxy radical reactions to the formation of secondary organic aerosol. Atmospheric oxidation mechanisms are presented to explain the observed chemistry. A series of environmental chamber experiments were conducted in which aliphatic tertiary and secondary amines were reacted with either hydroxyl radical (OH) or nitrate radical (NO3). Chemical composition of the aerosol products was obtained with a High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a Particle Into Liquid Sampler Time of Flight Mass Spectrometer (PILS-ToF-MS), while the chemical composition of the gas-phase products was obtained with a Selected Ion Flow Tube Mass Spectrometer (SIFT-MS). A number of aerosol-phase mass spectra showed highly oxidized fragments at a much higher molecular weight (MW) than the amine precursor. It is proposed that these larger compounds are oligomers formed through peroxy radical reactions with hydrogen rearrangement. Another reaction pathway observed was the formation of amine salts. The relative importance of each pathway to the overall production of aerosol is found to be dependent on the type of amine and oxidant. For example, the oligomers were observed in the tertiary methyl amines, while the formation of amine salts was more prevalent in the secondary and tertiary ethyl amines.

  16. Theoretical and kinetic study of the hydrogen atom abstraction reactions of unsaturated C6 methyl esters with hydroxyl radical

    NASA Astrophysics Data System (ADS)

    Wang, Quan-De; Ni, Zhong-Hai

    2016-04-01

    This work reports a systematic ab initio and chemical kinetic study of the rate constants for hydrogen atom abstraction reactions by hydroxyl radical (OH) on typical isomers of unsaturated C6 methyl esters at the CBS/QB3 level of theory. The high-pressure limit rate constants at different reaction sites for all the methyl esters in the temperature range from 500 to 2000 K are calculated via transition-state theory with the Wigner method for quantum tunneling effect and fitted to the modified three parameters Arrhenius expression using least-squares regression. Further, a branching ratio analysis for each reaction site has been performed.

  17. Visible-Light-Mediated Generation of Nitrogen-Centered Radicals: Metal-Free Hydroimination and Iminohydroxylation Cyclization Reactions

    PubMed Central

    Davies, Jacob; Booth, Samuel G; Essafi, Stephanie; Dryfe, Robert A W; Leonori, Daniele

    2015-01-01

    The formation and use of iminyl radicals in novel and divergent hydroimination and iminohydroxylation cyclization reactions has been accomplished through the design of a new class of reactive O-aryl oximes. Owing to their low reduction potentials, the inexpensive organic dye eosin Y could be used as the photocatalyst of the organocatalytic hydroimination reaction. Furthermore, reaction conditions for a unique iminohydroxylation were identified; visible-light-mediated electron transfer from novel electron donor–acceptor complexes of the oximes and Et3N was proposed as a key step of this process. PMID:26412046

  18. Dimethylselenide as a probe for reactions of halogenated alkoxyl radicals in aqueous solution. Degradation of dichloro- and dibromomethane.

    PubMed

    Makogon, Oksana; Flyunt, Roman; Tobien, Thomas; Naumov, Sergej; Bonifacić, Marija

    2008-07-01

    Using pulse radiolysis and steady-state gamma-radiolysis techniques, it has been established that, in air-saturated aqueous solutions, peroxyl radicals CH 2HalOO (*) (Hal = halogen) derived from CH 2Cl 2 and CH 2Br 2 react with dimethyl selenide (Me 2Se), with k on the order of 7 x 10 (7) M (-1) s (-1), to form HCO 2H, CH 2O, CO 2, and CO as final products. An overall two-electron oxidation process leads directly to dimethyl selenoxide (Me 2SeO), along with oxyl radical CH 2HalO (*). The latter subsequently oxidizes another Me 2Se molecule by a much faster one-electron transfer mechanism, leading to the formation of equal yields of CH 2O and the dimer radical cation (Me 2Se) 2 (*+). In absolute terms, these yields amount to 18% and 28% of the CH 2ClO (*) and CH 2BrO (*) yields, respectively, at 1 mM Me 2Se. In competition, CH 2HalO (*) rearranges into (*)CH(OH)Hal. These C-centered radicals react further via two pathways: (a) Addition of an oxygen molecule leads to the corresponding peroxyl radicals, that is, species prone to decomposition into H (+)/O 2 (*-) and formylhalide, HC(O)Hal, which further degrades mostly to H (+)/Hal (-) and CO. (b) Elimination of HHal yields the formyl radical H-C(*)=O with a rate constant of about 6 x 10 (5) s (-1) for Hal = Cl. In an air-saturated solution, the predominant reaction pathway of the H-C(*)=O radical is addition of oxygen. The formylperoxyl radical HC(O)OO (*) thus formed reacts with Me 2Se via an overall two-electron transfer mechanism, giving additional Me 2SeO and formyloxyl radicals HC(O)O(*). The latter rearrange via a 1,2 H-atom shift into (*)C(O)OH, which reacts with O2 to give CO2 and O2(*)(-). The minor fraction of H-C(*)=O undergoes hydration, with an estimated rate constant of k approximately 2 x 10(5) s(-1). The resulting HC(*)(OH)2 radical, upon reaction with O2, yields HCO 2H and H (+)/O2(*-). Some of the conclusions about the reactions of halogenated alkoxyl radicals are supported by quantum chemical

  19. The Tropospheric Lifetimes of Halocarbons and Their Reactions with OH Radicals: an Assessment Based on the Concentration of CO-14

    NASA Technical Reports Server (NTRS)

    Derwent, Richard G.; Volz-Thomas, Andreas

    1990-01-01

    Chemical reaction with hydroxyl radicals formed in the troposphere from ozone photolysis in the presence of methane, carbon monoxide and nitrogen oxides provides an important removal mechanism for halocarbons containing C-H and C = C double bonds. The isotropic distribution in atmospheric carbon monoxide was used to quantify the tropospheric hydroxyl radical distribution. Here, this methodology is reevaluated in the light of recent chemical kinetic data evaluations and new understandings gained in the life cycles of methane and carbon monoxide. None of these changes has forced a significant revision in the CO-14 approach. However, it is somewhat more clearly apparent how important basic chemical kinetic data are to the accurate establishment of the tropospheric hydroxyl radical distribution.

  20. Investigation of the O+allyl addition/elimination reaction pathways from the OCH(2)CHCH(2) radical intermediate.

    PubMed

    Fitzpatrick, Benjamin L; Lau, Kai-Chung; Butler, Laurie J; Lee, Shih-Huang; Lin, Jim Jr-Min

    2008-08-28

    These experiments study the preparation of and product channels resulting from OCH(2)CHCH(2), a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3 nm produces chlorine atoms and c-OCH(2)CHCH(2) radicals; these undergo a facile ring opening to the OCH(2)CHCH(2) radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8 eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33 kcalmol. To elucidate the product channels resulting from the OCH(2)CHCH(2) radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C(3)H(4)O (acrolein)+H, C(2)H(4)+HCO (formyl radical), and H(2)CO (formaldehyde)+C(2)H(3). A small signal from C(2)H(2)O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at me=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C(2)H(5)+CO, does not contribute significantly to the product branching. The higher internal energy onset of the acrolein+H product channel is consistent with the relative barriers en route to

  1. Kinetic of the gas-phase reactions of OH radicals and Cl atoms with diethyl ethylphosphonate and triethyl phosphate

    NASA Astrophysics Data System (ADS)

    Laversin, H.; El Masri, A.; Al Rashidi, M.; Roth, E.; Chakir, A.

    2016-02-01

    In this paper, the relative-rate technique has been used to obtain rate coefficients for the reaction of two organophosphorus compounds: Triethyl phosphate (TEP) and Diethyl ethylphosphonate (DEEP) with OH radicals and Cl atoms at atmospheric pressure and at different temperatures. The calculated rate constants were fitted to the Arrhenius expression over the temperature range 298-352 K. The following expressions (in cm3 molecule-1 s-1) were obtained for the reactions of OH and CL with DEEP and TEP: kOH+DEEP = (7.84 ± 0.65) × 10-14exp((1866 ± 824)/T), kOH+TEP = (6.54 ± 0.42) × 10-14exp((1897 ± 626)/T), kCl+DEEP = (5.27 ± 0.80) × 10-11exp(765 ± 140/T) and kCl+TEP = (5.23 ± 0.80) × 10-11exp(736 ± 110/T). These results show that the reaction of the studied compounds with Cl atoms proceeds more rapidly than that with OH radicals. The related tropospheric lifetimes suggest that once emitted into the atmosphere, TEP and DEEP can be removed within a few hours in areas close to their emission sources. TEP and DEEP are principally removed by OH radicals. However, in coastal areas where the Cl atoms' concentration is higher, TEP and DEEP removal by reaction with Cl atoms could be a competitive process.

  2. Effects of Vitamin E on the Oxidative Reaction of Free Radicals in Ultra-High Molecular Weight Polyethylene

    NASA Astrophysics Data System (ADS)

    Walters, Benjamin; Jahan, Muhammad

    2008-03-01

    Free radicals in gamma- or x-irradiated ultra-high molecular weight polyethylene (UHMWPE) are investigated as a function of vitamin E (alpha-tocopherol (α-T)). α-T is mixed with UHMWPE (GUR 1020) powder (e-PE) before (premix) or after (post-mix) irradiation. Pre-mix powder is also compression-molded (CM) to solid pucks (1'' thick and 2.5'' dia.) at 200^oC under constant force of 20-40 kN. Free radicals are detected using an X-band electron spin resonance (ESR) spectrometer, and oxidation index (OI) (1720 cm-1) by FTIR technique. As expected, no measurable OI is detected by FTIR and thus e-PE suffers no loss in its mechanical properties. ESR data, however, suggest that α-T quenches polyethylene radicals during and/or immediately after irradiation, but it does not have any effect on the long-term oxidative reaction. The difference between the pre- and post-mix powder is apparent only at the initial stage, and the terminal oxygen-induced radicals (OIR) are produced in all irradiated samples. Both pre- and post-mix powders are found to have equal amount of residual α-T radical (tocopheroxyl).

  3. Investigation of the formation of benzoyl peroxide, benzoic anhydride, and other potential aerosol products from gas-phase reactions of benzoylperoxy radicals

    NASA Astrophysics Data System (ADS)

    Strollo, Christen M.; Ziemann, Paul J.

    2016-04-01

    The secondary organic aerosol (SOA) products of the reaction of benzaldehyde with Cl atoms and with OH radicals in air in the absence of NOx were investigated in an environmental chamber in order to better understand the possible role of organic peroxy radical self-reactions in SOA formation. SOA products and authentic standards were analyzed using mass spectrometry and liquid chromatography, and results show that the yields of benzoyl peroxide (C6H5C(O)OO(O)CC6H5) and benzoic anhydride (C6H5C(O)O(O)CC6H5), two potential products from the gas-phase self-reaction of benzoylperoxy radicals (C6H5C(O)OO·), were less than 0.1%. This is in contrast to results of recent studies that have shown that the gas-phase self-reactions of β-nitrooxyperoxy radicals formed from reactions of isoprene with NO3 radicals form dialkyl peroxides that contribute significantly to gas-phase and SOA products. Such reactions have also been proposed to explain the gas-phase formation of extremely low volatility dimers from autooxidation of terpenes. The results obtained here indicate that, at least for benzoylperoxy radicals, the self-reactions form only benzoyloxy radicals. Analyses of SOA composition and volatility were inconclusive, but it appears that the SOA may consist primarily of oligomers formed through heterogeneous/multiphase reactions possibly involving some combination of phenol, benzaldehyde, benzoic acid, and peroxybenzoic acid.

  4. Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

    NASA Astrophysics Data System (ADS)

    Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

    2015-04-01

    Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

  5. Radiation-induced reactions of polymer radicals with ruthenium tris(bipyridyl)-OH adducts in aqueous solutions

    SciTech Connect

    Neta, P.; Silverman, J.; Markovic, V.; Rabani, J.

    1986-02-13

    Polymer radicals are produced by H abstraction from polyethylene glycol (PEG) and polybrene (PB) and by H abstraction and OH addition to polystyrenesulfonate (PSS). When ruthenium tris(bipyridyl) ions (Ru(bpy)/sub 3//sup 2 +/) are also present, they compete for OH and H radicals and produce the appropriate adducts. These adducts may disproportionate or react with the polymer radicals. The kinetic constants of these systems were measured by pulse radiolysis. The reaction products were also studied by dialysis of these systems following ..gamma..-irradiation. Under the conditions of these experiments the Ru(bpy)/sub 3//sup 2 +/-OH adduct (and probably also the corresponding H adduct) reacts with the polymer radicals. The products of these reactions are the appropriate polymer molecules with covalently bound Ru(bpy)/sub 3//sup 2 +/ residues. This method has a potential use in the synthesis of such compounds, which may be utilized for photochemical storage of light energy. 26 references, 4 figures, 1 table.

  6. A new insight of degradation reaction mechanism on desflurane radical with a catalyst of NO: A theoretical perspective

    NASA Astrophysics Data System (ADS)

    Ren, Hongjiang; Song, Jing; Li, Xiaojun; Liu, Yan

    2016-08-01

    The degradation reaction mechanism of desflurane radical in the presence of NO were investigated using density functional theory. The geometries of all the species were optimized at B3LYP/6-311++G∗∗ method. All the energy information are determined using configuration interaction method QCISD(T)/cc-pVTZ. Six connected reactions were found, which are labeled as Reaction 1, 2, 3, 4, 5 and 6 with the Gibbs barriers of 9.37, 13.74, 26.62, 0.99, 19.49 and 120.36 kJ/mol, respectively. The corresponding rate constants were also evaluated. The detailed reaction mechanism were analyzed and the results show that the Reaction 6 is a rate-determining one of all.

  7. Reactions between chlorine atom and acetylene in solid para-hydrogen: Infrared spectrum of the 1-chloroethyl radical

    SciTech Connect

    Golec, Barbara; Lee, Yuan-Pern

    2011-10-28

    We applied infrared matrix isolation spectroscopy to investigate the reactions between Cl atom and acetylene (C{sub 2}H{sub 2}) in a para-hydrogen (p-H{sub 2}) matrix at 3.2 K; Cl was produced via photodissociation at 365 nm of matrix-isolated Cl{sub 2} in situ. The 1-chloroethyl radical ({center_dot}CHClCH{sub 3}) and chloroethene (C{sub 2}H{sub 3}Cl) are identified as the main products of the reaction Cl + C{sub 2}H{sub 2} in solid p-H{sub 2}. IR absorption lines at 738.2, 1027.6, 1283.4, 1377.1, 1426.6, 1442.6, and 2861.2 cm{sup -1} are assigned to the 1-chloroethyl radical. For the reaction of Cl + C{sub 2}D{sub 2}, lines due to the {center_dot}CDClCH{sub 2}D radical and trans-CHDCDCl are observed; the former likely has a syn-conformation. These assignments are based on comparison of observed vibrational wavenumbers and {sup 13}C- and D-isotopic shifts with those predicted with the B3LYP/aug-cc-pVDZ and MP2/aug-cc-pVDZ methods. Our observation indicates that the primary addition product of Cl + C{sub 2}H{sub 2}, 2-chlorovinyl ({center_dot}CHCHCl) reacts readily with a neighboring p-H{sub 2} molecule to form {center_dot}CHClCH{sub 3} and C{sub 2}H{sub 3}Cl. Observation of {center_dot}CDClCH{sub 2}D and trans-CHDCDCl from Cl + C{sub 2}D{sub 2} further supports this conclusion. Although the reactivity of p-H{sub 2} appears to be a disadvantage for making highly reactive free radicals in solid p-H{sub 2}, the formation of 1-chloroethyl radical indicates that this secondary reaction might be advantageous in producing radicals that are difficult to prepare from simple photolysis or bimolecular reactions in situ.

  8. Reactions between chlorine atom and acetylene in solid para-hydrogen: Infrared spectrum of the 1-chloroethyl radical

    SciTech Connect

    Golec, Barbara; Lee, Yuan-Pern

    2011-11-07

    We applied infrared matrix isolation spectroscopy to investigate the reactions between Cl atom and acetylene (C{sub 2}H{sub 2}) in a para-hydrogen (p-H{sub 2}) matrix at 3.2 K; Cl was produced via photodissociation at 365 nm of matrix-isolated Cl{sub 2} in situ. The 1-chloroethyl radical ({center_dot}CHClCH{sub 3}) and chloroethene (C{sub 2}H{sub 3}Cl) are identified as the main products of the reaction Cl + C{sub 2}H{sub 2} in solid p-H{sub 2}. IR absorption lines at 738.2, 1027.6, 1283.4, 1377.1, 1426.6, 1442.6, and 2861.2 cm{sup -1} are assigned to the 1-chloroethyl radical. For the reaction of Cl + C{sub 2}D{sub 2}, lines due to the {center_dot}CDClCH{sub 2}D radical and trans-CHDCDCl are observed; the former likely has a syn-conformation. These assignments are based on comparison of observed vibrational wavenumbers and {sup 13}C- and D-isotopic shifts with those predicted with the B3LYP/aug-cc-pVDZ and MP2/aug-cc-pVDZ methods. Our observation indicates that the primary addition product of Cl + C{sub 2}H{sub 2}, 2-chlorovinyl ({center_dot}CHCHCl) reacts readily with a neighboring p-H{sub 2} molecule to form {center_dot}CHClCH{sub 3} and C{sub 2}H{sub 3}Cl. Observation of {center_dot}CDClCH{sub 2}D and trans-CHDCDCl from Cl + C{sub 2}D{sub 2} further supports this conclusion. Although the reactivity of p-H{sub 2} appears to be a disadvantage for making highly reactive free radicals in solid p-H{sub 2}, the formation of 1-chloroethyl radical indicates that this secondary reaction might be advantageous in producing radicals that are difficult to prepare from simple photolysis or bimolecular reactions in situ.

  9. A shock tube study of the reactions of the hydroxyl radical with combustion species and pollutants. Progress report

    SciTech Connect

    Cohen, N.

    1992-08-01

    To extend the database of reliable high temperature measurements of OH radicals with hydrocarbons and other fuels and their decomposition products, we undertook, a research program with both experimental and computational tasks. The experimental goal was to design a procedure for measuring, at combustion temperatures, the reaction rate coefficients of OH radicals with fuels and other species of importance in combustion or propulsion systems. The computational effort was intended to refine the semi-empirical thermochemical kinetics/ transition-state-theory (TK-TST) procedures for extrapolating rate coefficients of reactions of OH with combustion species of interest, for predicting rate coefficients for species not studied in the laboratory, and to examine the ability of the theory to predict rate coefficients for different pathways in cases where the reagent possessed nonequivalent H atoms.

  10. Correlation of Hydrogen-Atom Abstraction Reaction Efficiencies for Aryl Radicals with their Vertical Electron Affinities and the Vertical Ionization Energies of the Hydrogen Atom Donors

    PubMed Central

    Jing, Linhong; Nash, John J.

    2009-01-01

    The factors that control the reactivities of aryl radicals toward hydrogen-atom donors were studied by using a dual-cell Fourier-transform ion cyclotron resonance mass spectrometer (FT – ICR). Hydrogen-atom abstraction reaction efficiencies for two substrates, cyclohexane and isopropanol, were measured for twenty-three structurally different, positively-charged aryl radicals, which included dehydrobenzenes, dehydronaphthalenes, dehydropyridines, and dehydro(iso)quinolines. A logarithmic correlation was found between the hydrogen-atom abstraction reaction efficiencies and the (calculated) vertical electron affinities (EA) of the aryl radicals. Transition state energies calculated for three of the aryl radicals with isopropanol were found to correlate linearly with their (calculated) EAs. No correlation was found between the hydrogen-atom abstraction reaction efficiencies and the (calculated) enthalpy changes for the reactions. Measurement of the reaction efficiencies for the reactions of several different hydrogen-atom donors with a few selected aryl radicals revealed a logarithmic correlation between the hydrogen-atom abstraction reaction efficiencies and the vertical ionization energies (IE) of the hydrogen-atom donors, but not the lowest homolytic X – H (X = heavy atom) bond dissociation energies of the hydrogen-atom donors. Examination of the hydrogen-atom abstraction reactions of twenty-nine different aryl radicals and eighteen different hydrogen-atom donors showed that the reaction efficiency increases (logarithmically) as the difference between the IE of the hydrogen-atom donor and the EA of the aryl radical decreases. This dependence is likely to result from the increasing polarization, and concomitant stabilization, of the transition state as the energy difference between the neutral and ionic reactants decreases. Thus, the hydrogen-atom abstraction reaction efficiency for an aryl radical can be “tuned” by structural changes that influence either

  11. Molecular weight growth in Titan's atmosphere: branching pathways for the reaction of 1-propynyl radical (H3CC≡C˙) with small alkenes and alkynes.

    PubMed

    Kirk, Benjamin B; Savee, John D; Trevitt, Adam J; Osborn, David L; Wilson, Kevin R

    2015-08-28

    The reaction of small hydrocarbon radicals (i.e.˙CN, ˙C2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC[triple bond, length as m-dash]C˙), a likely product from the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (-H = 27%, -CH3 = 73%) and (-H = 14%, -CH3 = 86%), respectively. Together, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions. PMID:26204935

  12. Shock tube study of the reactions of the hydroxyl radical with combustion species and pollutants. Final report

    SciTech Connect

    Cohen, N.; Koffend, J.B.

    1998-02-01

    Shock heating t-butyl hydroperoxide behind a reflected shock wave has proved to be as a convenient source of hydroxyl radicals at temperatures near 1000 K. We applied this technique to the measurement of reaction rate coefficients of OH with several species of interest in combustion chemistry, and developed a thermochemical kinetics/transition state theory (TK-TST) model for predicting the temperature dependence of OH rate coefficients.

  13. Theoretical studies of nonadiabatic and spin-forbidden processes: Investigations of the reactions and spectroscopy of radical species relevant to combustion reactions and diagnostics

    SciTech Connect

    Yarkony, D.R.

    1993-12-01

    This research program focusses on studies of spin-forbidden and electronically nonadiabatic processes involving radical species relevant to combustion reactions and combustion diagnostics. To study the electronic structure aspects of these processes a unique and powerful system of electronic structure programs, developed over the past nine years, the BROOKLYN codes, is employed. These programs enable the authors to address questions basic to the understanding of elementary combustion processes not tractable using more standard quantum chemistry codes.

  14. Theoretical description of spin-selective reactions of radical pairs diffusing in spherical 2D and 3D microreactors

    NASA Astrophysics Data System (ADS)

    Ivanov, Konstantin L.; Sadovsky, Vladimir M.; Lukzen, Nikita N.

    2015-08-01

    In this work, we treat spin-selective recombination of a geminate radical pair (RP) in a spherical "microreactor," i.e., of a RP confined in a micelle, vesicle, or liposome. We consider the microreactor model proposed earlier, in which one of the radicals is located at the center of the micelle and the other one undergoes three-dimensional diffusion inside the micelle. In addition, we suggest a two-dimensional model, in which one of the radicals is located at the "pole" of the sphere, while the other one diffuses on the spherical surface. For this model, we have obtained a general analytical expression for the RP recombination yield in terms of the free Green function of two-dimensional diffusion motion. In turn, this Green function is expressed via the Legendre functions and thus takes account of diffusion over a restricted spherical surface and its curvature. The obtained expression allows one to calculate the RP recombination efficiency at an arbitrary magnetic field strength. We performed a comparison of the two models taking the same geometric parameters (i.e., the microreactor radius and the closest approach distance of the radicals), chemical reactivity, magnetic interactions in the RP and diffusion coefficient. Significant difference between the predictions of the two models is found, which is thus originating solely from the dimensionality effect: for different dimensionality of space, the statistics of diffusional contacts of radicals becomes different altering the reaction yield. We have calculated the magnetic field dependence of the RP reaction yield and chemically induced dynamic nuclear polarization of the reaction products at different sizes of the microreactor, exchange interaction, and spin relaxation rates. Interestingly, due to the intricate interplay of diffusional contacts of reactants and spin dynamics, the dependence of the reaction yield on the microreactor radius is non-monotonous. Our results are of importance for (i) interpreting

  15. Theoretical description of spin-selective reactions of radical pairs diffusing in spherical 2D and 3D microreactors.

    PubMed

    Ivanov, Konstantin L; Sadovsky, Vladimir M; Lukzen, Nikita N

    2015-08-28

    In this work, we treat spin-selective recombination of a geminate radical pair (RP) in a spherical "microreactor," i.e., of a RP confined in a micelle, vesicle, or liposome. We consider the microreactor model proposed earlier, in which one of the radicals is located at the center of the micelle and the other one undergoes three-dimensional diffusion inside the micelle. In addition, we suggest a two-dimensional model, in which one of the radicals is located at the "pole" of the sphere, while the other one diffuses on the spherical surface. For this model, we have obtained a general analytical expression for the RP recombination yield in terms of the free Green function of two-dimensional diffusion motion. In turn, this Green function is expressed via the Legendre functions and thus takes account of diffusion over a restricted spherical surface and its curvature. The obtained expression allows one to calculate the RP recombination efficiency at an arbitrary magnetic field strength. We performed a comparison of the two models taking the same geometric parameters (i.e., the microreactor radius and the closest approach distance of the radicals), chemical reactivity, magnetic interactions in the RP and diffusion coefficient. Significant difference between the predictions of the two models is found, which is thus originating solely from the dimensionality effect: for different dimensionality of space, the statistics of diffusional contacts of radicals becomes different altering the reaction yield. We have calculated the magnetic field dependence of the RP reaction yield and chemically induced dynamic nuclear polarization of the reaction products at different sizes of the microreactor, exchange interaction, and spin relaxation rates. Interestingly, due to the intricate interplay of diffusional contacts of reactants and spin dynamics, the dependence of the reaction yield on the microreactor radius is non-monotonous. Our results are of importance for (i) interpreting

  16. Theoretical description of spin-selective reactions of radical pairs diffusing in spherical 2D and 3D microreactors

    SciTech Connect

    Ivanov, Konstantin L. Lukzen, Nikita N.; Sadovsky, Vladimir M.

    2015-08-28

    In this work, we treat spin-selective recombination of a geminate radical pair (RP) in a spherical “microreactor,” i.e., of a RP confined in a micelle, vesicle, or liposome. We consider the microreactor model proposed earlier, in which one of the radicals is located at the center of the micelle and the other one undergoes three-dimensional diffusion inside the micelle. In addition, we suggest a two-dimensional model, in which one of the radicals is located at the “pole” of the sphere, while the other one diffuses on the spherical surface. For this model, we have obtained a general analytical expression for the RP recombination yield in terms of the free Green function of two-dimensional diffusion motion. In turn, this Green function is expressed via the Legendre functions and thus takes account of diffusion over a restricted spherical surface and its curvature. The obtained expression allows one to calculate the RP recombination efficiency at an arbitrary magnetic field strength. We performed a comparison of the two models taking the same geometric parameters (i.e., the microreactor radius and the closest approach distance of the radicals), chemical reactivity, magnetic interactions in the RP and diffusion coefficient. Significant difference between the predictions of the two models is found, which is thus originating solely from the dimensionality effect: for different dimensionality of space, the statistics of diffusional contacts of radicals becomes different altering the reaction yield. We have calculated the magnetic field dependence of the RP reaction yield and chemically induced dynamic nuclear polarization of the reaction products at different sizes of the microreactor, exchange interaction, and spin relaxation rates. Interestingly, due to the intricate interplay of diffusional contacts of reactants and spin dynamics, the dependence of the reaction yield on the microreactor radius is non-monotonous. Our results are of importance for (i) interpreting

  17. Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H2CCHCH2)Self Reaction

    NASA Technical Reports Server (NTRS)

    Selby, Talitha M.; Melini, giovanni; Goulay, Fabien; Leone, Stephen R.; Fahr, Askar; Taatjes, Craig A.; Osborn, David L.

    2008-01-01

    Product channels for the self-reaction of the resonance-stabilized allyl radical, C3H5 + C3H5, have been studied with isomeric specificity at temperatures from 300-600 K and pressures from 1-6 Torr using time-resolved multiplexed photoionization mass spectrometry. Under these conditions 1,5-hexadiene was the only C6H10 product isomer detected. The lack of isomerization of the C6H10 product is in marked contrast to the C6H6 product in the related C3H3 + C3H3 reaction, and is due to the more saturated electronic structure of the C6H10 system. The disproportionation product channel, yielding allene + propene, was also detected, with an upper limit on the branching fraction relative to recombination of 0.03. Analysis of the allyl radical decay at 298 K yielded a total rate coefficient of (2.7 +/- 0.8) x 10(exp -11) cu cm/molecule/s, in good agreement with pre.vious experimental measurements using ultraviolet kinetic absorption spectroscopy and a recent theoretical determination using variable reaction coordinate transition state theory. This result provides independent indirect support for the literature value of the allyl radical ultraviolet absorption cross-section near 223 nm.

  18. Radical Reaction of Sodium Hypophosphite with Terminal Alkynes: Synthesis of 1,1-bis-H-Phosphinates

    PubMed Central

    Gouault-Bironneau, Sonia; Deprèle, Sylvine; Sutor, Amber; Montchamp, Jean-Luc

    2008-01-01

    The room temperature radical addition of sodium hypophosphite to terminal alkynes produces the previously unknown 1-alkyl-1,1-bis-H-phosphinates in moderate yield. The reaction is initiated by R3B and air and proceeds under mild conditions in an open container. The bis-sodium salts precipitate spontaneously from the reaction mixtures, thus providing a simple purification procedure and the opportunity for multigram synthesis. The 1,1-bis-H-phosphinate products are novel precursors of the biologically important 1,1-bisphosphonates. PMID:16354097

  19. Visible-Light-Mediated Synthesis of Amidyl Radicals: Transition-Metal-Free Hydroamination and N-Arylation Reactions.

    PubMed

    Davies, Jacob; Svejstrup, Thomas D; Fernandez Reina, Daniel; Sheikh, Nadeem S; Leonori, Daniele

    2016-07-01

    The development of photoredox reactions of aryloxy-amides for the generation of amidyl radicals and their use in hydroamination-cyclization and N-arylation reactions is reported. Owing to the ease of single-electron-transfer reduction of the aryloxy-amides, the organic dye eosin Y was used as the photoredox catalyst, which results in fully transition-metal-free processes. These transformations exhibit a broad scope, are tolerant to several important functionalities, and have been used in the late-stage modification of complex and high-value N-containing molecules. PMID:27327358

  20. Extension of Structure-Reactivity Correlations for the Hydrogen Abstraction Reaction to Methyl Radical and Comparison to Chlorine Atom, Bromine Atom, and Hydroxyl Radical

    SciTech Connect

    Poutsma, Marvin L

    2016-01-01

    Recently we presented structure-reactivity correlations for the gas-phase rate constants for hydrogen abstraction from sp3-hybridized carbon by three electrophilic radicals (X + HCR3 XH + CR3; X = Cl , HO , and Br ); the reaction enthalpy effect was represented by the independent variable rH and the polar effect by the independent variables F and R, the Hammett-Taft constants for field/inductive and resonance effects. Here we present a parallel treatment for the less electronegative CH3 . In spite of a limited and scattered data base, the resulting least-squares fit [log k437(CH3 ) = 0.0251( rH) + 0.96( F) 0.56( R) 19.15] was modestly successful and useful for initial predictions. As expected, the polar effect appears to be minor and its directionality, i.e., the philicity of CH3 , may depend on the nature of the substituents.

  1. Multicomponent versus domino reactions: One-pot free-radical synthesis of β-amino-ethers and β-amino-alcohols.

    PubMed

    Rossi, Bianca; Pastori, Nadia; Prosperini, Simona; Punta, Carlo

    2015-01-01

    Following an optimized multicomponent procedure, an aryl amine, a ketone, and a cyclic ether or an alcohol molecule are assembled in a one-pot synthesis by nucleophilic radical addition of ketyl radicals to ketimines generated in situ. The reaction occurs under mild conditions by mediation of the TiCl4/Zn/t-BuOOH system, leading to the formation of quaternary β-amino-ethers and -alcohols. The new reaction conditions guarantee good selectivity by preventing the formation of secondary products. The secondary products are possibly derived from a competitive domino reaction, which involves further oxidation of the ketyl radicals. PMID:25670994

  2. Computerized pathway elucidation for hydroxyl radical-induced chain reaction mechanisms in aqueous phase advanced oxidation processes.

    PubMed

    Li, Ke; Crittenden, John

    2009-04-15

    The radical reaction mechanism that is involved in advanced oxidation processes is complex. An increasing number of trace contaminants and stringent drinking water standards call for a rule-based model to provide insight to the mechanism of the processes. A model was developed to predict the pathway of contaminant degradation and byproduct formation during advanced oxidation. The model builds chemical molecules as graph objects, which enables mathematic abstraction of chemicals and preserves chemistry information. The model algorithm enumerates all possible reaction pathways according to the elementary reactions (built as reaction rules) established from experimental observation. The method can predict minor pathways that could lead to toxic byproducts so that measures can be taken to ensure drinking water treatment safety. The method can be of great assistance to water treatment engineers and chemists who appreciate the mechanism of treatment processes. PMID:19475958

  3. Characterization of radicals and high-molecular weight species from alpha-pinene/ozone reaction and ambient aerosol samples

    NASA Astrophysics Data System (ADS)

    Pavlovic, Jelica

    Secondary organic aerosol formed during oxidation of different volatile organic compounds is composed from a number of final and intermediate reaction products. The final products include compounds in both low and high molecular weight range called also oligomer species. These compounds can be highly volatile, as well as being semi- or low-volatility compounds. This study characterized intermediate reactive radical products formed from previously often studied alpha-pinene/ozone reaction. In order to passivate those radical species nitrone spin traps were used. 5,5-dimethyl-4,5-dihydro-3H-pyrrole-N-oxide (DMPO), and 5-dietoxyphosphoryl-5-methyl-1-pyrroline-N-oxide (DEPMPO) traps were able to successfully trap oxygen- and carbon-centered radicals produced from alpha-pinene/ozone reaction. Electrospray ionization (ESI) in negative ion mode with mass spectrometry (MS) detection was used to scan spectra of formed spin trap adducts and the tandem mass spectrometry (MSn) to elucidate its structures as well as structures of captured radicals. The same method was applied to analyze radical species present in ambient PM2.5 samples. Few carbon- (alkyl) and oxygen- (alkoxyl) centered radicals were captured with DMPO and DEPMPO traps. The second part of this study was focused on high molecular weight (high-MW) species formed from the same reaction (alpha-pinene/ozone), but found also in fine particulate matter fractions of ambient samples. LC/MS/MS analysis of dimer species from chamber study revealed fragments that can originate from peroxide structures. Proposed reaction for these peroxide dimer formation is self reaction of two peroxyl radicals, followed by the loss of oxygen molecule. These findings emphasize the role of peroxyl (ROO) radicals in formation of high-MW products and are in line with the high O:C ratio results reported in other studies. Water soluble organic carbon (WSOC) extracts of three size fractions of the ambient aerosol, PM1--2.5, PM0.1--1, and PM<0

  4. Discovery and Mechanistic Studies of Facile N-Terminal Cα–C Bond Cleavages in the Dissociation of Tyrosine-Containing Peptide Radical Cations

    SciTech Connect

    Mu, Xiaoyan; Song, Tao; Xu, Minjie; Lai, Cheuk-Kuen; Siu, Chi-Kit; Laskin, Julia; Chu, Ivan K.

    2014-03-28

    Gas phase fragmentations of protein and peptide (M) ions in a mass spectrometer—induced by, for example, electron-capture dissociation1-2 and electron-transfer dissociation3-422 —form the foundation for top-down amino acid sequencing approaches for the rapid identification of protein components in complex biological samples. During these processes, protonated protein and peptide radicals ([M + nH]•(n – 1)+)5–8 are generated; their fragmentations are governed largely by the properties of the unpaired electron. Because of their importance in modern bioanalytical chemistry, considerable attention has been drawn recently toward understanding the radical cation chemistry behind the fragmentations of these odd-electron biomolecular ions in the gas phase.

  5. Regiochemical variations in reactions of methylcubane with tert-butoxyl radical, cytochrome P-450 enzymes, and a methane monooxygenase system

    SciTech Connect

    Choi, S.Y.; Hollenberg, P.F.; Newcomb, M.; Putt, D.A.; Eaton, P.E.; Upadhyaya, S.P.; Xiong, Y.; Liu, K.E.; Lippard, S.J.

    1996-07-17

    Reactions of methylcubane (1) with the tert-butoxyl radical (t-BuO{sup .}), with cytochrome P-450 enzymes, and with a methane monooxygenase (MMO) system have been studied. 2-Methylcubanecarboxylic acid (9b) is a new compound prepared from cubanecarboxylic acid. The key synthetic reactions were (1) metalation and subsequent iodination of the 2-position of (diisopropylcarbamoyl)cubane to effect the initial functionalization, (2) lithium-for-iodine exchange and methylation followed by reduction to give 2-methyl-l-[(diisopropylamino)methyl]-cubane, and (3) dimethyldioxirane oxidation of this amine to give 9b. Reaction of 1 with t-BuO{sup .} in the presence of 2,2,5,5-tetramethylisoindole-N-oxyl radical (TMIO{sup .}) at 40-55{degree}C gave mainly cube-substituted products in confirmation of the report that hydrogen atom abstraction by the electrophilic alkoxyl radical at low temperature occurs at the cubyl C-H positions. In a competition experiment at 42{degree}C, methylcubane was at least 3.5 times more reactive toward t-BuO{sup .} than cyclohexane, indicating that the cubyl positions in 1 are >= 40 times more reactive than the methyl positions in 1 (per hydrogen) toward the alkoxyl radical. Oxidation of 1 by enzymes gave alcohol products that were converted to their acetate derivatives for identification and quantitation. Microsomal cytochrome P-450 enzymes from rat and the rat purified P-450 isozyme CYP2B1 hydroxylated 1 at all positions, whereas the reconstituted MMO system from Methylococcus capsulatus (Bath) hydroxylated l only at the methyl position. 78 refs., 1 tab.

  6. Mechanistic studies of the reactions of the reduced vitamin B12 derivatives with the HNO donor Piloty's acid: further evidence for oxidation of cob(I)alamin by (H)NO.

    PubMed

    Subedi, Harishchandra; Brasch, Nicola E

    2016-01-01

    There is accumulating evidence for the existence of HNO in biological systems. Compared with NO (˙NO), much less is known about the chemical and biochemical reactivity of HNO. Kinetic and mechanistic studies have been carried out on the reaction between the vitamin B12-derived radical complex cob(II)alamin (Cbl(II)˙, Cbl(II)) with the widely used HNO donor Piloty's acid (PA). A stoichiometry of 1 : 2 Cbl(II) : PA was obtained and PA decomposition to HNO and benzenesulfinate (C6H5SO2(-)) is the rate-determining step. No evidence was found for nitrite (Griess assay), ammonia (Nessler's test) or NH2OH (indooxine test) in the product solution, and it is likely that HNO is instead reduced to N2. A mechanism is proposed in which reduction of Cbl(II) by (H)NO results in formation of cob(I)alamin (Cbl(I)(-)) and ˙NO. The Cbl(I)(-) intermediate is subsequently oxidized back to Cbl(II) by a second (H)NO molecule, and Cbl(II) reacts rapidly with ˙NO to form nitroxylcobalamin (NOCbl). Separate studies on the reaction between Cbl(I)(-) and PA shows that this system involves an additional step in which Cbl(I)(-) is first oxidized by (H)NO to Cbl(II), which reacts further with (H)NO to form NOCbl, with an overall stoichiometry of 1 : 3 Cbl(I)(-) : PA. Experiments in the presence of nitrite for both systems support the involvement of a Cbl(I)(-) intermediate in the Cbl(II)/PA reaction. These systems provide the second example of oxidation of cob(I)alamin by (H)NO. PMID:26618754

  7. Spectroscopic Characterization and Mechanistic Investigation of P-Methyl Transfer by a Radical SAM Enzyme from the Marine Bacterium Shewanella denitrificans OS217

    PubMed Central

    Allen, Kylie D.; Wang, Susan C

    2014-01-01

    Natural products containing carbon-phosphorus bonds elicit important bioactivity in many organisms. L-phosphinothricin contains the only known naturally-occurring carbon-phosphorus-carbon bond linkage. In actinomycetes, the cobalamin-dependent radical S-adenosyl-L-methionine (SAM) methyltransferase PhpK catalyzes the formation of the second C-P bond to generate the complete C-P-C linkage in phosphinothricin. Here we use electron paramagnetic resonance and nuclear magnetic resonance spectroscopies to characterize and demonstrate the activity of a cobalamin-dependent radical SAM methyltransferase denoted SD_1168 from Shewanella denitrificans OS217, a marine bacterium that has not been reported to synthesize phosphinothricin. Recombinant, refolded, and reconstituted SD_1168 binds a four-iron, four-sulfur cluster that interacts with SAM and cobalamin. In the presence of SAM, a reductant, and methylcobalamin, SD_1168 surprisingly catalyzes the P-methylation of N-acetyl-demethylphosphinothricin and demethylphosphinothricin to produce N-acetyl-phosphinothricin and phosphinothricin, respectively. In addition, this enzyme is active in the absence of methylcobalamin if the strong reductant titanium (III) citrate and hydroxocobalamin are provided. When incubated with [methyl-13C] cobalamin and titanium citrate, both [methyl-13C] and unlabeled N-acetylphosphinothricin are produced. Our results suggest that SD_1168 catalyzes P-methylation using radical SAM-dependent chemistry with cobalamin as a coenzyme. In light of recent genomic information, the discovery of this P-methyltransferase suggests that S. denitrificans produces a phosphinate natural product. PMID:25224746

  8. Non-photochemical Fluorescence Quenching in Photosystem II Antenna Complexes by the Reaction Center Cation Radical.

    PubMed

    Paschenko, V Z; Gorokhov, V V; Grishanova, N P; Korvatovskii, B N; Ivanov, M V; Maksimov, E G; Mamedov, M D

    2016-06-01

    In direct experiments, rate constants of photochemical (kP) and non-photochemical (kP(+)) fluorescence quenching were determined in membrane fragments of photosystem II (PSII), in oxygen-evolving PSII core particles, as well as in core particles deprived of the oxygen-evolving complex. For this purpose, a new approach to the pulse fluorometry method was implemented. In the "dark" reaction center (RC) state, antenna fluorescence decay kinetics were measured under low-intensity excitation (532 nm, pulse repetition rate 1 Hz), and the emission was registered by a streak camera. To create a "closed" [P680(+)QA(-)] RC state, a high-intensity pre-excitation pulse (pump pulse, 532 nm) of the sample was used. The time advance of the pump pulse against the measuring pulse was 8 ns. In this experimental configuration, under the pump pulse, the [P680(+)QA(-)] state was formed in RC, whereupon antenna fluorescence kinetics was measured using a weak testing picosecond pulsed excitation light applied to the sample 8 ns after the pump pulse. The data were fitted by a two-exponential approximation. Efficiency of antenna fluorescence quenching by the photoactive RC pigment in its oxidized (P680(+)) state was found to be ~1.5 times higher than that of the neutral (P680) RC state. To verify the data obtained with a streak camera, control measurements of PSII complex fluorescence decay kinetics by the single-photon counting technique were carried out. The results support the conclusions drawn from the measurements registered with the streak camera. In this case, the fitting of fluorescence kinetics was performed in three-exponential approximation, using the value of τ1 obtained by analyzing data registered by the streak camera. An additional third component obtained by modeling the data of single photon counting describes the P680(+)Pheo(-) charge recombination. Thus, for the first time the ratio of kP(+)/kP = 1.5 was determined in a direct experiment. The mechanisms of higher

  9. Does slow energy transfer limit the observed time constant for radical pair formation in photosystem II reaction centers?

    PubMed

    Rech, T; Durrant, J R; Joseph, D M; Barber, J; Porter, G; Klug, D R

    1994-12-13

    We have used spectrally photoselective femtosecond transient absorption spectroscopy on photosystem II reaction centers to show that there are at least two pools of chlorin molecules/states which can transfer excitation energy to P680, the primary electron donor in photosystem II. It has previously been shown that one chlorin pool equilibrates with P680 in 100 fs [Durrant et al. (1992) Proc. Natl. Acad. Sci. U.S.A. 89, 11632-11636], and we report here the observation of energy transfer from a second more weakly coupled chlorin pool. The effect of the weakly coupled pool is to increase the apparent time constant for radical pair formation from 21 ps when P680 is selectively excited to 27 ps when the accessory chlorins are excited. We conclude that it is possible to observe both radical pair formation somewhat slowed by an energy transfer step and radical pair formation not limited by this slow energy transfer, depending upon which chromophores are initially excited. These observations provide evidence that when using photoselective excitation of P680, the observed 21 ps time constant for radical pair formation is not limited by a slow energy transfer step. PMID:7993905

  10. Reaction mechanism between cell membranes of P. digitatum spores and oxygen radicals

    NASA Astrophysics Data System (ADS)

    Ito, Masafumi; Hashizume, Hiroshi; Ohta, Takayuki; Takeda, Keigo; Ishikawa, Kenji; Hori, Masaru

    2013-09-01

    P. digitatum spores were exposed to oxygen radicals 10 and 20 mm downstream from our developed atmospheric-pressure oxygen-radical source. Treated spores were stained by 1,1' -dioctadecyl-3,3,Y,3' -tetramethyl indocarbocyanine perchlorate (DiI), which has been used for investigation for functions of cell membranes. For control spores, DiI is not permeable into cells because cell membranes have selective permeability. Stained spores were observed by confocal laser microscopy. At 10 mm distance, 84% of total spores were intracellularly stained with 1.5-minute oxygen radical treatment. On the other hand, at 20 mm distance, about 80% of the total spores were intracellularly stained at least with 3-minute oxygen radical treatment. Based on the results of inactivation rates of P. digitatum spores and oxygen-radical densities, the results indicated that the increase of ratio of the number of intracellularly stained spores was correlated with the density of O(3Pj) rather than O2(1Δg) . These results and SEM observations suggest that O(3Pj) plays an important role as an inactivation factor by disturbing the normal function of cell membranes and influencing intracellular organelles without major deformation of the membranes.

  11. Visible-Light-Promoted Dual C-C Bond Formations of Alkynoates via a Domino Radical Addition/Cyclization Reaction: A Synthesis of Coumarins.

    PubMed

    Feng, Shangbiao; Xie, Xingang; Zhang, Weiwei; Liu, Lin; Zhong, Zhuliang; Xu, Dengyu; She, Xuegong

    2016-08-01

    A visible-light-promoted, mild, and direct difunctionalization of alkynoates has been accomplished. This procedure provides a new strategy toward synthesis of the coumarin core structure by photoredox-mediated oxidation to generate the α-oxo radical, which supervenes a domino radical addition/cyclization reaction in moderate to good yields with high regioselectivity at ambient temperature. PMID:27443889

  12. Molecular hydrogen regulates gene expression by modifying the free radical chain reaction-dependent generation of oxidized phospholipid mediators

    PubMed Central

    Iuchi, Katsuya; Imoto, Akemi; Kamimura, Naomi; Nishimaki, Kiyomi; Ichimiya, Harumi; Yokota, Takashi; Ohta, Shigeo

    2016-01-01

    We previously showed that H2 acts as a novel antioxidant to protect cells against oxidative stress. Subsequently, numerous studies have indicated the potential applications of H2 in therapeutic and preventive medicine. Moreover, H2 regulates various signal transduction pathways and the expression of many genes. However, the primary targets of H2 in the signal transduction pathways are unknown. Here, we attempted to determine how H2 regulates gene expression. In a pure chemical system, H2 gas (approximately 1%, v/v) suppressed the autoxidation of linoleic acid that proceeds by a free radical chain reaction, and pure 1-palmitoyl-2-arachidonyl-sn-glycero-3-phosphocholine (PAPC), one of the major phospholipids, was autoxidized in the presence or absence of H2. H2 modified the chemical production of the autoxidized phospholipid species in the cell-free system. Exposure of cultured cells to the H2-dependently autoxidized phospholipid species reduced Ca2+ signal transduction and mediated the expression of various genes as revealed by comprehensive microarray analysis. In the cultured cells, H2 suppressed free radical chain reaction-dependent peroxidation and recovered the increased cellular Ca2+, resulting in the regulation of Ca2+-dependent gene expression. Thus, H2 might regulate gene expression via the Ca2+ signal transduction pathway by modifying the free radical-dependent generation of oxidized phospholipid mediators. PMID:26739257

  13. Theoretical study of the rate constants for the hydrogen atom abstraction reactions of esters with (•)OH radicals.

    PubMed

    Mendes, Jorge; Zhou, Chong-Wen; Curran, Henry J

    2014-07-10

    A systematic investigation of the rate constants for hydrogen atom abstraction reactions by hydroxyl radicals on esters has been performed. The geometry optimizations and frequency calculations were obtained using the second-order Møller-Plesset method with the 6-311G(d,p) basis set. The same method was also used in order to determine the dihedral angle potential for each individual hindered rotor in each reactant and transition state. Intrinsic reaction coordinate calculations were used in order to connect each transition state to the corresponding local minimum. For the reactions of methyl ethanoate with an (•)OH radical, the relative electronic energies were calculated using the G3 and the CCSD(T)/cc-pVXZ (where X = D, T, and Q) methods, which were extrapolated to the complete basis set (CBS) limit. The electronic energies obtained using the G3 method were then benchmarked against the CBS results and were found to be within 1 kcal mol(-1) of one another. The high-pressure limit rate constants for every reaction channel were calculated by conventional transition-state theory, with an asymmetric Eckart tunneling correction, using the energies obtained with the G3 method. We report the individual, average, and total rate constants in the temperature range from 500 to 2200 K. Our calculated results are within a factor of 2 for methyl ethanoate and between 40% to 50% for methyl propanoate and methyl butanoate when compared to previously reported experimental data. PMID:24878337

  14. An ab-initio study of some homolytic substitution reactions of acyl radicals at silicon, germanium and tint.

    PubMed

    Matsubara, Hiroshi; Schiesser, Carl H

    2003-12-01

    Ab initio calculations using the 6-311G**, cc-pVDZ, and (valence) double-zeta pseudopotential (DZP) basis sets, with (MP2, QCISD, CCSD(T)) and without (UHF) the inclusion of electron correlation, and density functional (BHandHLYP, B3LYP) calculations predict that homolytic substitution reactions of acetyl radicals at the silicon atoms in disilane can proceed via both backside and frontside attack mechanisms. At the highest level of theory (CCSD(T)/cc-pVDZ//MP2/cc-pVDZ), energy barriers (deltaE double dagger) of 77.2 and 81.9 kJ mol(-1) are calculated for the backside and frontside reactions respectively. Similar results are obtained for reactions involving germanium and tin with energy barriers (deltaE double dagger) of 53.7-84.2, and 55.0-89.7 kJ mol(-1) for the backside and frontside mechanisms, respectively. These data suggest that both homolytic substitution mechanisms are feasible for homolytic substitution reactions of acetyl radicals at silicon, germanium, and tin. BHandHLYP calculations provide geometries and energy barriers for backside and frontside transition states in good agreement with those obtained by traditional ab initio techniques. PMID:14685338

  15. Reactivity of CHI3 with OH radicals: X-abstraction reaction pathways (X = H, I), atmospheric chemistry, and nuclear safety.

    PubMed

    Sudolská, Mária; Louis, Florent; Cernušák, Ivan

    2014-10-01

    The X-abstraction (X = H, I) pathways in the reaction of CHI3 with OH radical, a possible iodoform removal process relevant to the Earth's atmosphere and conditions prevailing in the case of a nuclear accident, have been studied applying highly correlated ab initio quantum chemistry methods and canonical transition-state theory to obtain reaction energy profiles and rate constants. Geometry optimizations of reactants, products, molecular complexes, and transition states determined at the MP2/cc-pVTZ level of theory have been followed by DK-CCSD(T)/ANO-RCC single-point energy calculations. Further improvement of electronic energies has been achieved by applying spin-orbit coupling, corrections toward full configuration interaction, vibration contributions, and tunneling corrections. Calculated reaction enthalpies at 0 K are -108.2 and -5.1 kJ mol(-1) for the H- and I-abstraction pathways, respectively; the strongly exothermic H-abstraction pathway is energetically favored over the modestly exothermic I-abstraction one. The overall rate constant at 298 K based on our ab initio calculations is 4.90 × 10(-11) cm(3) molecule(-1) s(-1), with the I-abstraction pathway being the major channel over the temperature range of 250-2000 K. The CHI3 atmospheric lifetime with respect to the removal reaction with OH radical is predicted to be about 6 h, very short compared to that of other halomethanes. PMID:25207959

  16. Theoretical and kinetic study of the hydrogen atom abstraction reactions of esters with H(O.)2 radicals.

    PubMed

    Mendes, Jorge; Zhou, Chong-Wen; Curran, Henry J

    2013-12-27

    This work details an ab initio and chemical kinetic study of the hydrogen atom abstraction reactions by the hydroperoxyl radical (HȮ2) on the following esters: methyl ethanoate, methyl propanoate, methyl butanoate, methyl pentanoate, methyl isobutyrate, ethyl ethanoate, propyl ethanoate, and isopropyl ethanoate. Geometry optimizations and frequency calculations of all of the species involved, as well as the hindrance potential descriptions for reactants and transition states, have been performed with the Møller-Plesset (MP2) method using the 6-311G(d,p) basis set. A validation of all of the connections between transition states and local minima was performed by intrinsic reaction coordinate calculations. Electronic energies for all of the species are reported at the CCSD(T)/cc-pVTZ level of theory in kcal mol(-1) with the zero-point energy corrections. The CCSD(T)/CBS (extrapolated from CCSD(T)/cc-pVXZ, in which X = D, T, Q) was used for the reactions of methyl ethanoate + HȮ2 radicals as a benchmark in the electronic energy calculations. High-pressure limit rate constants, in the temperature range 500-2000 K, have been calculated for all of the reaction channels using conventional transition state theory with asymmetric Eckart tunneling corrections. The 1-D hindered rotor approximation has been used for the low frequency torsional modes in both reactants and transition states. The calculated individual and total rate constants are reported for all of the reaction channels in each reaction system. A branching ratio analysis for each reaction site has also been investigated for all of the esters studied in this work. PMID:24175616

  17. Radical reactions of C 60Ph 5Cl: EPR study and DFT calculations

    NASA Astrophysics Data System (ADS)

    Kalina, O. G.; Tumanskii, B. L.; Chistyakov, A. L.; Stankevich, I. V.; Birkett, P. R.; Taylor, R.

    2003-10-01

    UV-irradiation of a toluene solution of C 60Ph 5Cl leads to the formation of the stable rad C 60Ph 5 cyclopentadienyl-type fullerenyl radical. Under UV-irradiation of a toluene solution of C 60Ph 5Cl containing Hg[P(O)(OPr i) 2] 2 (Pr i=CH(CH 3) 2), three isomers of the adducts of phosphoryl radicals with C 60Ph 5Cl are formed. Density functional (DFT) approach with the B3LYP functional was used for estimating of the enthalpies of the formation and hyperfine coupling constants for all possible adducts of phosphoryl radicals with C 60Ph 5Cl. Biradical particles rad C 60Ph 5[P(O)(OPr i) 2]- rad C 60Ph 5[P(O)(OPr i) 2] with a distance between unpaired electrons of about 10.5 Å, are also obtained.

  18. Reaction studies of hot silicon and germanium radicals. Progress report, September 1, 1979-August 31, 1980

    SciTech Connect

    Gaspar, P.P.

    1980-08-31

    The experimental approach to attaining the goals of this research program is briefly outlined and the progress made in the last year is reviewed in sections entitled: (a) primary steps in the reaction of recoiling silicon and germanium atoms and the identification of reactive intermediates in the recoil reactions; (b) thermally induced silylene and germylene reactions; (c) ion-molecule reaction studies.

  19. Mechanistic models

    SciTech Connect

    Curtis, S.B.

    1990-09-01

    Several models and theories are reviewed that incorporate the idea of radiation-induced lesions (repairable and/or irreparable) that can be related to molecular lesions in the DNA molecule. Usually the DNA double-strand or chromatin break is suggested as the critical lesion. In the models, the shoulder on the low-LET survival curve is hypothesized as being due to one (or more) of the following three mechanisms: (1) ``interaction`` of lesions produced by statistically independent particle tracks; (2) nonlinear (i.e., linear-quadratic) increase in the yield of initial lesions, and (3) saturation of repair processes at high dose. Comparisons are made between the various approaches. Several significant advances in model development are discussed; in particular, a description of the matrix formulation of the Markov versions of the RMR and LPL models is given. The more advanced theories have incorporated statistical fluctuations in various aspects of the energy-loss and lesion-formation process. An important direction is the inclusion of physical and chemical processes into the formulations by incorporating relevant track structure theory (Monte Carlo track simulations) and chemical reactions of radiation-induced radicals. At the biological end, identification of repair genes and how they operate as well as a better understanding of how DNA misjoinings lead to lethal chromosome aberrations are needed for appropriate inclusion into the theories. More effort is necessary to model the complex end point of radiation-induced carcinogenesis.

  20. Mechanistic models

    SciTech Connect

    Curtis, S.B.

    1990-09-01

    Several models and theories are reviewed that incorporate the idea of radiation-induced lesions (repairable and/or irreparable) that can be related to molecular lesions in the DNA molecule. Usually the DNA double-strand or chromatin break is suggested as the critical lesion. In the models, the shoulder on the low-LET survival curve is hypothesized as being due to one (or more) of the following three mechanisms: (1) interaction'' of lesions produced by statistically independent particle tracks; (2) nonlinear (i.e., linear-quadratic) increase in the yield of initial lesions, and (3) saturation of repair processes at high dose. Comparisons are made between the various approaches. Several significant advances in model development are discussed; in particular, a description of the matrix formulation of the Markov versions of the RMR and LPL models is given. The more advanced theories have incorporated statistical fluctuations in various aspects of the energy-loss and lesion-formation process. An important direction is the inclusion of physical and chemical processes into the formulations by incorporating relevant track structure theory (Monte Carlo track simulations) and chemical reactions of radiation-induced radicals. At the biological end, identification of repair genes and how they operate as well as a better understanding of how DNA misjoinings lead to lethal chromosome aberrations are needed for appropriate inclusion into the theories. More effort is necessary to model the complex end point of radiation-induced carcinogenesis.

  1. Kinetic and mechanistic studies on the reaction of the vitamin B12 complex aquacobalamin with the HNO donor Angeli's salt: Angeli's salt and HNO react with aquacobalamin.

    PubMed

    Subedi, Harishchandra; Hassanin, Hanaa A; Brasch, Nicola E

    2014-02-01

    We report the first studies on the reaction between an HNO donor compound and vitamin B12 complexes. Kinetic and mechanistic studies have been carried out on the reaction between the vitamin B12 derivative aquacobalamin (H2OCbl(+)/HOCbl; pKa = 7.8) and the HNO donor Angeli's salt. Studies were carried out with aquacobalamin in excess, since nitrite also reacts with aquacobalamin to form nitrocobalamin (NO2Cbl). At pH <9.90 aquacobalamin reacts directly with the monoprotonated form of Angeli's salt, HN2O3(-), to form nitroxylcobalamin (NO(-)-Cbl(III); NOCbl) and nitrite. At pH >10.80 the reaction instead switches predominantly to a mechanism in which spontaneous decomposition of Angeli's salt to give HNO and nitrite becomes the rate-determining step, followed by the rapid reaction between aquacobalamin and HNO/NO(-) to again give NOCbl. Both reactions proceed with a 1:1 stoichiometry and formation of nitrite is confirmed using the Griess assay. PMID:24437629

  2. Mechanistic aspects of the ethanol steam reforming reaction for hydrogen production on Pt, Ni, and PtNi catalysts supported on gamma-Al2O3.

    PubMed

    Sanchez-Sanchez, Maria Cruz; Navarro Yerga, Rufino M; Kondarides, Dimitris I; Verykios, Xenophon E; Fierro, Jose Luis G

    2010-03-25

    Mechanistic aspects of ethanol steam reforming on Pt, Ni, and PtNi catalysts supported on gamma-Al(2)O(3) are investigated from the analysis of adsorbed species and gas phase products formed on catalysts during temperature-programmed desorption of ethanol and during ethanol steam reforming reaction. DRIFTS-MS analyses of ethanol decomposition and ethanol steam reforming reactions show that PtNi and Ni catalysts are more stable than the Pt monometallic counterpart. Ethanol TPD results on Ni, Pt, and NiPt catalysts point to ethanol dehydrogenation and acetaldehyde decomposition as the first reaction pathways of ethanol steam reforming over the studied catalysts. The active sites responsible for the acetaldehyde decomposition are easily deactivated in the first minutes on-stream by carbon deposits. For Ni and PtNi catalysts, a second reaction pathway, consisting in the decomposition of acetate intermediates formed over the surface of alumina support, becomes the main reaction pathway operating in steam reforming of ethanol once the acetaldehyde decomposition pathway is deactivated. Taking into account the differences observed in the mechanism of ethanol decomposition, the better stability observed for PtNi catalyst is proposed to be related with a cooperative effect between Pt and Ni activities together with the enhanced ability of Ni to gasify the methyl groups formed by decomposition of acetate species. On the contrary, monometallic catalysts are believed to dehydrogenate these methyl groups forming coke that leads to deactivation of metal particles. PMID:19824680

  3. Electronic nonadiabatic effects in low temperature radical-radical reactions. I. C({sup 3}P) + OH({sup 2}Π)

    SciTech Connect

    Maergoiz, A. I.; Nikitin, E. E.; Troe, J.

    2014-07-28

    The formation of collision complexes, as a first step towards reaction, in collisions between two open-electronic shell radicals is treated within an adiabatic channel approach. Adiabatic channel potentials are constructed on the basis of asymptotic electrostatic, induction, dispersion, and exchange interactions, accounting for spin-orbit coupling within the multitude of electronic states arising from the separated reactants. Suitable coupling schemes (such as rotational + electronic) are designed to secure maximum adiabaticity of the channels. The reaction between C({sup 3}P) and OH({sup 2}Π) is treated as a representative example. The results show that the low temperature association rate coefficients in general cannot be represented by results obtained with a single (generally the lowest) potential energy surface of the adduct, asymptotically reaching the lowest fine-structure states of the reactants, and a factor accounting for the thermal population of the latter states. Instead, the influence of non-Born–Oppenheimer couplings within the multitude of electronic states arising during the encounter markedly increases the capture rates. This effect extends up to temperatures of several hundred K.

  4. Rate Constant and Temperature Dependence for the Reaction of Hydroxyl Radicals with 2-Flouropropane (FC-281ea) and Comparison with an Estimated Rate Constant

    NASA Technical Reports Server (NTRS)

    DeMore, W.; Wilson, E., Jr.

    1998-01-01

    Relative rate experiments were used to measure the rate constant and temperature dependence of the reaction of OH radicals with 2-fluoropropane (HFC-281ea), using ethane, propane, ethyl chloride as reference standards.

  5. Vibrationally quantum-state-specific dynamics of the reactions of CN radicals with organic molecules in solution.

    PubMed

    Rose, Rebecca A; Greaves, Stuart J; Oliver, Thomas A A; Clark, Ian P; Greetham, Gregory M; Parker, Anthony W; Towrie, Michael; Orr-Ewing, Andrew J

    2011-06-28

    The dynamics of reactions of CN radicals with cyclohexane, d(12)-cyclohexane, and tetramethylsilane have been studied in solutions of chloroform, dichloromethane, and the deuterated variants of these solvents using ultraviolet photolysis of ICN to initiate a reaction. The H(D)-atom abstraction reactions produce HCN (DCN) that is probed in absorption with sub-picosecond time resolution using ∼500 cm(-1) bandwidth infrared (IR) pulses in the spectral regions corresponding to C-H (or C-D) and C≡N stretching mode fundamental and hot bands. Equivalent IR spectra were obtained for the reactions of CN radicals with the pure solvents. In all cases, the reaction products are formed at early times with a strong propensity for vibrational excitation of the C-H (or C-D) stretching (v(3)) and H-C-N (D-C-N) bending (v(2)) modes, and for DCN products there is also evidence of vibrational excitation of the v(1) mode, which involves stretching of the C≡N bond. The vibrationally excited products relax to the ground vibrational level of HCN (DCN) with time constants of ∼130-270 ps (depending on molecule and solvent), and the majority of the HCN (DCN) in this ground level is formed by vibrational relaxation, instead of directly from the chemical reaction. The time-dependence of reactive production of HCN (DCN) and vibrational relaxation is analysed using a vibrationally quantum-state specific kinetic model. The experimental outcomes are indicative of dynamics of exothermic reactions over an energy surface with an early transition state. Although the presence of the chlorinated solvent may reduce the extent of vibrational excitation of the nascent products, the early-time chemical reaction dynamics in these liquid solvents are deduced to be very similar to those for isolated collisions in the gas phase. The transient IR spectra show additional spectroscopic absorption features centered at 2037 cm(-1) and 2065 cm(-1) (in CHCl(3)) that are assigned, respectively, to CN

  6. Vibrationally quantum-state-specific dynamics of the reactions of CN radicals with organic molecules in solution

    NASA Astrophysics Data System (ADS)

    Rose, Rebecca A.; Greaves, Stuart J.; Oliver, Thomas A. A.; Clark, Ian P.; Greetham, Gregory M.; Parker, Anthony W.; Towrie, Michael; Orr-Ewing, Andrew J.

    2011-06-01

    The dynamics of reactions of CN radicals with cyclohexane, d12-cyclohexane, and tetramethylsilane have been studied in solutions of chloroform, dichloromethane, and the deuterated variants of these solvents using ultraviolet photolysis of ICN to initiate a reaction. The H(D)-atom abstraction reactions produce HCN (DCN) that is probed in absorption with sub-picosecond time resolution using ˜500 cm-1 bandwidth infrared (IR) pulses in the spectral regions corresponding to C-H (or C-D) and C≡N stretching mode fundamental and hot bands. Equivalent IR spectra were obtained for the reactions of CN radicals with the pure solvents. In all cases, the reaction products are formed at early times with a strong propensity for vibrational excitation of the C-H (or C-D) stretching (v3) and H-C-N (D-C-N) bending (v2) modes, and for DCN products there is also evidence of vibrational excitation of the v1 mode, which involves stretching of the C≡N bond. The vibrationally excited products relax to the ground vibrational level of HCN (DCN) with time constants of ˜130-270 ps (depending on molecule and solvent), and the majority of the HCN (DCN) in this ground level is formed by vibrational relaxation, instead of directly from the chemical reaction. The time-dependence of reactive production of HCN (DCN) and vibrational relaxation is analysed using a vibrationally quantum-state specific kinetic model. The experimental outcomes are indicative of dynamics of exothermic reactions over an energy surface with an early transition state. Although the presence of the chlorinated solvent may reduce the extent of vibrational excitation of the nascent products, the early-time chemical reaction dynamics in these liquid solvents are deduced to be very similar to those for isolated collisions in the gas phase. The transient IR spectra show additional spectroscopic absorption features centered at 2037 cm-1 and 2065 cm-1 (in CHCl3) that are assigned, respectively, to CN-solvent complexes and

  7. Aging Oxidation Reactions on Atmospheric Black Carbon by OH Radicals. A Theoretical Modeling Study.

    PubMed

    Rojas, Laura; Peraza, Alexander; Ruette, Fernando

    2015-12-31

    Aging processes of black carbon (BC) particles require knowledge of their chemical reactivities, which have impact on cloud condensation nuclei (CCN) activities, radiant properties and health problems related to air pollutions. In the present work, interactions between several OH radicals with BC (modeled with a coronene molecule) were calculated by using DFT and PM6 codes as described by Mysak et al. Water interaction with BC was also included. Results show that OH radical adsorption is preferred on border sites, independent of the theoretical method employed. Potential energy curves using DFT(TPSS-D3) approach for OH chemisorption showed small-energy barriers, as reported in previous work with PM6. A dipole moment has been created, and the hydrophobic coronene surface is transformed to hydrophilic after the first OH chemisorption. Several stages were found in the BC aging by OH radicals, thus (a) Hydroxylation of coronene by several OH radical would lead to H abstractions directly from the substrate. (b) Abstraction of H from adsorbed OH (at the border sites) drives a C-C bond breaking and the formation of carboxyl groups. (c) Hydrogen abstraction from carboxyl group produces decarboxylation (CO2 plus water) as experimentally obtained. Potential energy curves of one of the reactive path were calculated with the PM6 method. The formation of products was confirmed using DFT. Coronene interaction with O2 was also considered to have a realistic atmospheric environment. PMID:26605439

  8. Aqueous-Phase Reactions of Isoprene with Sulfoxy Radical Anions as a way of Wet Aerosol Formation in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Kuznietsova, I.; Rudzinski, K. J.; Szmigielski, R.; Laboratory of the Environmental Chemistry

    2011-12-01

    Atmospheric aerosols exhibit an important role in the environment. They have implications on human health and life, and - in the larger scale - on climate, the Earth's radiative balance and the cloud's formation. Organic matter makes up a significant fraction of atmospheric aerosols (~35% to ~90%) and may originate from direct emissions (primary organic aerosol, POA) or result from complex physico-chemical processes of volatile organic compounds (secondary organic aerosol, SOA). Isoprene (2-methyl-buta-1,3-diene) is one of the relevant volatile precursor of ambient SOA in the atmosphere. It is the most abundant non-methane hydrocarbon emitted to the atmosphere as a result of living vegetation. According to the recent data, the isoprene emission rate is estimated to be at the level of 500 TgC per year. While heterogeneous transformations of isoprene have been well documented, aqueous-phase reactions of this hydrocarbon with radical species that lead to the production of new class of wet SOA components such as polyols and their sulfate esters (organosulfates), are still poorly recognized. The chain reactions of isoprene with sulfoxy radical-anions (SRA) are one of the recently researched route leading to the formation of organosulfates in the aqueous phase. The letter radical species originate from the auto-oxidation of sulfur dioxide in the aqueous phase and are behind the phenomenon of atmospheric acid rain formation. This is a complicated chain reaction that is catalyzed by transition metal ions, such as manganese(II), iron(III) and propagated by sulfoxy radical anions . The presented work addresses the chemical interaction of isoprene with sulfoxy radical-anions in the water solution in the presence of nitrite ions and nitrous acid, which are important trace components of the atmosphere. We showed that nitrite ions and nitrous acid significantly altered the kinetics of the auto-oxidation of SO2 in the presence of isoprene at different solution acidity from 2 to 8

  9. Mechanisms before Reactions: A Mechanistic Approach to the Organic Chemistry Curriculum Based on Patterns of Electron Flow

    ERIC Educational Resources Information Center

    Flynn, Alison B.; Ogilvie, William W.

    2015-01-01

    A significant redesign of the introductory organic chemistry curriculum at the authors' institution is described. There are two aspects that differ greatly from a typical functional group approach. First, organic reaction mechanisms and the electron-pushing formalism are taught before students have learned a single reaction. The conservation of…

  10. Recent developments in copper-catalyzed radical alkylations of electron-rich π-systems

    PubMed Central

    2015-01-01

    Summary Recently, a number of papers have emerged demonstrating copper-catalyzed alkylation reactions of electron-rich small molecules. The processes are generally thought to be related to long established atom-transfer radical reactions. However, unlike classical reactions, these new transformations lead to simple alkylation products. This short review will highlight recent advances in alkylations of nitronate anions, alkenes and alkynes, as well as discuss current mechanistic understanding of these novel reactions. PMID:26734076

  11. EPR characterization of ascorbyl and sulfur dioxide anion radicals trapped during the reaction of bovine Cytochrome c Oxidase with molecular oxygen

    NASA Astrophysics Data System (ADS)

    Yu, Michelle A.; Egawa, Tsuyoshi; Yeh, Syun-Ru; Rousseau, Denis L.; Gerfen, Gary J.

    2010-04-01

    The reaction intermediates of reduced bovine Cytochrome c Oxidase (C cO) were trapped following its reaction with oxygen at 50 μs-6 ms by innovative freeze-quenching methods and studied by EPR. When the enzyme was reduced with either ascorbate or dithionite, distinct radicals were generated; X-band (9 GHz) and D-band (130 GHz) CW-EPR measurements support the assignments of these radicals to ascorbyl and sulfur dioxide anion radical ( SO2-rad ), respectively. The X-band spectra show a linewidth of 12 G for the ascorbyl radical and 11 G for the SO2-rad radical and an isotropic g-value of 2.005 for both species. The D-band spectra reveal clear distinctions in the g-tensors and powder patterns of the two species. The ascorbyl radical spectrum displays approximate axial symmetry with g-values of g x = 2.0068, g y = 2.0066, and g z = 2.0023. The SO2-rad radical has rhombic symmetry with g-values of g x = 2.0089, g y = 2.0052, and g z = 2.0017. When the contributions from the ascorbyl and SO2-rad radicals were removed, no protein-based radical on C cO could be identified in the EPR spectra.

  12. Development and application of ab initio QM/MM methods for mechanistic simulation of reactions in solution and in enzymes

    PubMed Central

    Hu, Hao; Yang, Weitao

    2013-01-01

    Determining the free energies and mechanisms of chemical reactions in solution and enzymes is a major challenge. For such complex reaction processes, combined quantum mechanics/molecular mechanics (QM/MM) method is the most effective simulation method to provide an accurate and efficient theoretical description of the molecular system. The computational costs of ab initio QM methods, however, have limited the application of ab initio QM/MM methods. Recent advances in ab initio QM/MM methods allowed the accurate simulation of the free energies for reactions in solution and in enzymes and thus paved the way for broader application of the ab initio QM/MM methods. We review here the theoretical developments and applications of the ab initio QM/MM methods, focusing on the determination of reaction path and the free energies of the reaction processes in solution and enzymes. PMID:24146439

  13. Online Monitoring Oxidative Products and Metabolites of Nicotine by Free Radicals Generation with Fenton Reaction in Tandem Mass Spectrometry

    PubMed Central

    Liang, Shih-Shin; Shiue, Yow-Ling; Kuo, Chao-Jen; Liao, Wei-Ting; Tsai, Eing-Mei

    2013-01-01

    In general, over 70% absorbed nicotine is metabolized to cotinine and trans-3′-hydroxycotinine by cytochrome oxidase P450, and nicotine is also a major addictive and the psychoactive component in cigarettes. As a xenobiotic metabolism, hydrophobic compounds are usually converted into more hydrophilic products through enzyme systems such as cytochrome oxidase P450, sulfotransferases, and UDP-glucuronosyltransferases to deliver drug metabolites out of the cell during the drug metabolic process. In this study, an electrodeless electrochemical oxidation (EEO) reaction via Fenton reaction by producing free radical to react with nicotine to immediately monitor the oxidative products and metabolic derivatives of nicotine by tandem mass spectrometer (MS) is done. Fenton reaction generates free radicals via ferrous ion (Fe2+) and hydrogen peroxide (H2O2) to oxidize DNA and to degrade proteins in cells. In the EEO method, the oxidative products of nicotine including cotinine, cotinine-N-oxide, trans-3′-hydroxycotinine, nornicotine, norcotinine, 4-oxo-4-(3-pyridyl)-butanoic acid, 4-hydroxy-4-(3-pyridyl)-butanoic acid, and nicotine-N′-oxide were detected by tandem mass spectrometer to simulate the changes of nicotine and its derivatives in a time-dependent manner. PMID:23983622

  14. Radical-Molecule Reaction C3H + H2O on Amorphous Water Ice: A Promising Route for Interstellar Propynal

    NASA Astrophysics Data System (ADS)

    Xie, Hong-bin; Shao, Chang-bin; Ding, Yi-hong

    2007-11-01

    Intriguing propynal (HCCCHO) has been attracting chemist's attention since 1955. However, to date, no satisfying conclusion concerning its formation mechanism in the interstellar medium (ISM) has been reached, although a variety of gas-reaction models, including ion-molecule, radical-molecule, and molecule-molecule, have been postulated. In this paper, we consider for the first time the gas-grain interaction model that involves heterogeneous reaction at the surface of dust grain or in the icy mantles to account for the propynal's formation. Based on the detailed density functional theory (DFT) and Gaussian-3 potential energy surface studies, we found that although the gaseous process C3H+H2O-->propynal+H must surmount a considerable entrance barrier (around 10 kcal mol-1), amorphous water ice can significantly catalyze the propynal's formation to be barrierless. So, this model should be a more reasonable one for propynal's formation in the low-temperature interstellar space. This result may also represent one rare case of the water-catalyzed reaction associated with a molecular radical in space. Future experimental studies are greatly desired to probe such interesting processes.

  15. Reaction studies of hot silicon and germanium radicals. Progress report, September 1, 1980-August 31, 1981

    SciTech Connect

    Gaspar, P.P.

    1981-08-31

    The experimental approach to attaining the goals of this research program is briefly outlined and the progress made in the last year is reviewed in sections entitled: a. Primary steps in the reaction of recoiling silicon and germanium atoms and the identification of reactive intermediates in the recoil reactions; b. Thermally and photochemically induced silylene and germylene reactions and the reactions of thermally evaporated silicon atoms.

  16. Rational Design in Catalysis: A Mechanistic Study of β-Hydride Eliminations in Gold(I) and Gold(III) Complexes Based on Features of the Reaction Valley.

    PubMed

    Castiñeira Reis, Marta; López, Carlos Silva; Kraka, Elfi; Cremer, Dieter; Faza, Olalla Nieto

    2016-09-01

    β-Hydride eliminations for ethylgold(III) dichloride complexes are identified as reactions with an unusually long prechemical stage corresponding to the conformational preparation of the reaction complex and spanning six phases. The prechemical process is characterized by a geared rotation of the L-Au-L group (L = Cl) driving methyl group rotation and causing a repositioning of the ligands. This requires more than 28 kcal/mol of the total barrier of 34.0 kcal/mol, according to the unified reaction valley approach, which also determines that the energy requirements of the actual chemical process leading to the β-elimination product are only about 5.5 kcal/mol. A detailed mechanistic analysis was used as a basis for a rational design of substrates (via substituents on the ethyl group) and/or ligands, which can significantly reduce the reaction barrier. This strategy takes advantage of either a higher trans activity of the ligands or a tuned electronic demand of the ethyl group. The β-hydride elimination of gold(I) was found to suffer from strong Coulomb and exchange repulsion when a positively charged hydrogen atom enforces a coordination position in a d(10)-configured gold atom, thus triggering an unassisted σ-π Au(I)-C conversion. PMID:27537214

  17. Ab initio reaction kinetics of hydrogen abstraction from methyl formate by hydrogen, methyl, oxygen, hydroxyl, and hydroperoxy radicals.

    PubMed

    Tan, Ting; Pavone, Michele; Krisiloff, David B; Carter, Emily A

    2012-08-23

    Combustion of renewable biofuels, including energy-dense biodiesel, is expected to contribute significantly toward meeting future energy demands in the transportation sector. Elucidating detailed reaction mechanisms will be crucial to understanding biodiesel combustion, and hydrogen abstraction reactions are expected to dominate biodiesel combustion during ignition. In this work, we investigate hydrogen abstraction by the radicals H·, CH(3)·, O·, HO(2)·, and OH· from methyl formate, the simplest surrogate for complex biodiesels. We evaluate the H abstraction barrier heights and reaction enthalpies, using multireference correlated wave function methods including size-extensivity corrections and extrapolation to the complete basis set limit. The barrier heights predicted for abstraction by H·, CH(3)·, and O· are in excellent agreement with derived experimental values, with errors ≤1 kcal/mol. We also predict the reaction energetics for forming reactant complexes, transition states, and product complexes for reactions involving HO(2)· and OH·. High-pressure-limit rate constants are computed using transition state theory within the separable-hindered-rotor approximation for torsions and the harmonic oscillator approximation for other vibrational modes. The predicted rate constants differ significantly from those appearing in the latest combustion kinetics models of these reactions. PMID:22830521

  18. Experimental measurements of low temperature rate coefficients for neutral-neutral reactions of interest for atmospheric chemistry of Titan, Pluto and Triton: reactions of the CN radical.

    PubMed

    Morales, Sébastien B; Le Picard, Sébastien D; Canosa, André; Sims, Ian R

    2010-01-01

    The kinetics of the reactions of cyano radical, CN (X2sigma+) with three hydrocarbons, propane (CH3CH2CH3), propene (CH3CH=CH2) and 1-butyne (CH[triple band]CCH2CH3) have been studied over the temperature range of 23-298 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in Uniform Supersonic Flow) apparatus combined with the pulsed laser photolysis-laser induced fluorescence technique. These reactions are of interest for the cold atmospheres of Titan, Pluto and Triton, as they might participate in the formation of nitrogen and carbon bearing molecules, including nitriles, that are thought to play an important role in the formation of hazes and biological molecules. All three reactions are rapid with rate coefficients in excess of 10(-10) cm3 molecule(-1) s(-1) at the lowest temperatures of this study and show behaviour characteristic of barrierless reactions. Temperature dependences, different for each reaction, are compared to those used in the most recent photochemical models of Titan's atmosphere. PMID:21302546

  19. Mechanistic Studies Lead to Dramatically Improved Reaction Conditions for the Cu-Catalyzed Asymmetric Hydroamination of Olefins.

    PubMed

    Bandar, Jeffrey S; Pirnot, Michael T; Buchwald, Stephen L

    2015-11-25

    Enantioselective copper(I) hydride (CuH)-catalyzed hydroamination has undergone significant development over the past several years. To gain a general understanding of the factors governing these reactions, kinetic and spectroscopic studies were performed on the CuH-catalyzed hydroamination of styrene. Reaction profile analysis, rate order assessment, and Hammett studies indicate that the turnover-limiting step is regeneration of the CuH catalyst by reaction with a silane, with a phosphine-ligated copper(I) benzoate as the catalyst resting state. Spectroscopic, electrospray ionization mass spectrometry, and nonlinear effect studies are consistent with a monomeric active catalyst. With this insight, targeted reagent optimization led to the development of an optimized protocol with an operationally simple setup (ligated copper(II) precatalyst, open to air) and short reaction times (<30 min). This improved protocol is amenable to a diverse range of alkene and alkyne substrate classes. PMID:26522837

  20. Cavity ring-down spectroscopy with an automated control feedback system for investigating nitrate radical surface chemistry reactions

    NASA Astrophysics Data System (ADS)

    Flemmer, Michael M.; Ham, Jason E.

    2012-08-01

    Nitrate radical (NO3•) surface chemistry of indoor environments has not been well studied due to the difficulty in generating and maintaining NO3• at low concentrations for long term exposures. This article presents the Surface Chemistry Reactant Air Delivery and Experiment System (SCRADES), a novel feedback controlled system developed to deliver nitrate radicals at specified concentrations (50-500 ppt, ±30 ppt) and flow rates (500-2000 ml min-1) to a variety of indoor surfaces to initiate reaction chemistry for periods of up to 72 h. The system uses a cavity ring-down spectrometer (CRDS), with a detection limit of 1.7 ppt, to measure the concentration of NO3• supplied to a 24 l experiment chamber. Nitrate radicals are introduced via thermal decomposition of N2O5 and diluted with clean dry air until the desired concentration is achieved. Additionally, this article addresses details concerning NO3• loss through the system, consistency of the NO3• concentration delivered, and stability of the CRDS cavity over long exposure durations (72 h).

  1. Extension of Structure-Reactivity Correlations for the Hydrogen Abstraction Reaction to the Methyl Radical and Comparison to the Chlorine Atom, Bromine Atom, and Hydroxyl Radical.

    PubMed

    Poutsma, Marvin L

    2016-07-01

    Recently, we presented structure-reactivity correlations for the gas-phase rate constants for hydrogen abstraction from sp(3)-hybridized carbon by three electrophilic radicals (X(•) + HCR3 → XH + (•)CR3; X = Cl(•), HO(•), and Br(•)); the reaction enthalpy effect was represented by the independent variable ΔrH and the "polar effect" by the independent variables F and R, the Hammett-Taft constants for field/inductive and resonance effects. Here we present a parallel treatment for the less electronegative CH3(•). In spite of a limited and scattered database, the resulting least-squares fit [log k437(CH3(•)) = -0.0251(ΔrH) + 0.96(ΣF) - 0.56(ΣR) - 19.15] was modestly successful and useful for initial predictions. As expected, the polar effect appears to be minor and its directionality, i.e., the "philicity" of CH3(•), may depend on the nature of the substituents. PMID:27266850

  2. Extension of structure-reactivity correlations for the hydrogen abstraction reaction to methyl radical and comparison to chlorine atom, bromine atom, and hydroxyl radical

    DOE PAGESBeta

    Poutsma, Marvin L.

    2016-06-07

    In this study, we presented structure-reactivity correlations for the gas-phase rate constants for hydrogen abstraction from sp3-hybridized carbon by three electrophilic radicals (X• + HCR3 → XH + •CR3; X = Cl•, HO•, and Br); the reaction enthalpy effect was represented by the independent variable ΔrH and the polar effect by the independent variables F and R, the Hammett-Taft constants for field/inductive and resonance effects. Here we present a parallel treatment for the less electronegative CH3•. In spite of a limited and scattered data base, the resulting least-squares fit [log k437(CH3•) = 0.0251(ΔrH) + 0.96(ΣF) 0.56(ΣR) – 19.15] was modestlymore » successful and useful for initial predictions. As expected, the polar effect appears to be minor and its directionality, i.e., the philicity of CH3, may depend on the nature of the substituents.« less

  3. Computational Study of the Reactions of Methanol with the Hydroperoxyl and Methyl Radicals. Part I: Accurate Thermochemistry and Barrier Heights

    SciTech Connect

    Alecu, I. M.; Truhlar, D. G.

    2011-04-07

    The reactions of CH3OH with the HO2 and CH3 radicals are important in the combustion of methanol and are prototypes for reactions of heavier alcohols in biofuels. The reaction energies and barrier heights for these reaction systems are computed with CCSD(T) theory extrapolated to the complete basis set limit using correlation-consistent basis sets, both augmented and unaugmented, and further refined by including a fully coupled treatment of the connected triple excitations, a second-order perturbative treatment of quadruple excitations (by CCSDT(2)Q), core–valence corrections, and scalar relativistic effects. It is shown that the M08-HX and M08-SO hybrid meta-GGA density functionals can achieve sub-kcal mol-1 agreement with the high-level ab initio results, identifying these functionals as important potential candidates for direct dynamics studies on the rates of these and homologous reaction systems.

  4. The gas phase reactions of hydroxyl radicals with a series of nitroalkanes over the temperature range 240-400 K

    NASA Astrophysics Data System (ADS)

    Liu, Renzhang; Huie, Robert E.; Kurylo, Michael J.; Nielsen, Ole J.

    1990-04-01

    Absolute rate constants were determined for the gas phase reactions of OH radicals with a series of nitroalkanes by the flash photolysis-resonance fluorescence technique. Experiments were performed at total pressures from 25 to 50 Torr using Ar as a diluent gas. Experiments with nitromethane and nitromethane- d3 at 296 K yielded rate constants of (1.58±0.09) × 10 -14 and (0.9±0.04) × 10 -14 cm 3 molecule -1 s -1, respectively. Data from experiments over the temperature range 240-400 K for nitroethane, 1-nitropropane, 2-nitropropane, 1-nitrobutane, and 1-nitropentane were used to evaluate their Arrhenius parameters. The results are discussed in terms of the reaction mechanism, and are compared to previous literature data.

  5. Formation of spiroiminodihydantoin due to the reaction between 8-oxoguanine and carbonate radical anion: A quantum computational study

    NASA Astrophysics Data System (ADS)

    Yadav, Amarjeet; Mishra, P. C.

    2014-01-01

    Reaction of 8-oxoguanine (8OG) with carbonate radical anion (CO3·-) producing spiroiminodihydantoin has been investigated using density functional theory. Geometries of reactant complex, intermediate complexes, product complexes and transition states were optimized at the B3LYP/6-31G(d,p) level of theory in gas phase which was followed by single point energy calculations employing the B3LYP, M06-2X and WB97XD functionals along with the AUG-cc-pVDZ basis set in gas phase and aqueous media. Solvent effect was treated employing the integral equation formalism of the polarizable continuum model. Possible roles of aeration, stirring and photoirradiation of reaction media which are performed in experimental studies have been explained.

  6. Radical formation in the FMN-photosensitized reactions of unsaturated fatty acids bearing double bonds at different positions.

    PubMed

    Nishihama, Nao; Iwahashi, Hideo

    2016-08-15

    -carboxybutyl, 7-carboxyheptyl and 9-carboxynonyl radicals formed in the control reaction mixtures of (z)-6-octadecenoic acid, (z)-9-octadecenoic acid {or (z, z)-9,12-octadecadienoic acid} and (z)-11-octadecenoic acid, respectively. The 4-carboxybutyl, 7-carboxyheptyl and 9-carboxynonyl radicals are all generated through β-scission of alkoxy radicals formed on carboxyl ends of the double bonds of the unsaturated fatty acids. Thus, we could reveal reactive sites of unsaturated fatty acids in the photosensitized reaction of flavin mononucleotide with unsaturated fatty acids bearing a double bond at different positions. PMID:27372435

  7. Simultaneous evaluation of one-electron reducing systems and radical reactions in cells by nitroxyl biradical as probe.

    PubMed

    Araki, Yoko; Koshiishi, Ichiro

    2016-07-01

    In the present study, a novel probe for the simultaneous evaluation of one-electron reducing systems (electron transport chain) and one-electron oxidizing systems (free radical reactions) in cells by electron chemical detection was developed. Six-membered cyclic nitroxyl radicals (2,2,6,6-tetramethylpiperidine-1-oxyl; TEMPO series) are sensitive to one-electron redox systems, generating the hydroxylamine form [TEMPO(H)] via one-electron reduction, and the secondary amine form [TEMPO(N)] via one-electron oxidation in the presence of thiols. In contrast, the sensitivities of five-membered cyclic nitroxyl radicals (2,2,5,5-tetramethylpyrrolidine-1-oxyl; PROXYL series) to the one-electron redox systems are comparatively low. The electron chemical detector can detect 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), TEMPO(H) and PROXYL but not TEMPO(N). Therefore, nitroxyl biradical, TEMPO-PROXYL, as a probe for the evaluation of one-electron redox systems was employed. TEMPO-PROXYL was synthesized by the conjunction of 4-amino-TEMPO with 3-carboxyl-PROXYL via the conventional dicyclohexyl carbodiimide reaction. TEMPO-PROXYL, TEMPO(H)-PROXYL and TEMPO(N)-PROXYL were simultaneously quantified by HPLC with Coularray detection. Calibration curves for the quantification of TEMPO-PROXYL, TEMPO(H)-PROXYL and TEMPO(N)-PROXYL were linear in the range from 80 nm to 80 μm, and the lowest quantification limit of each molecule was estimated to be <80 nm. The relative standard deviations at 0.8 and 80 μm were within 10% (n = 5). Copyright © 2015 John Wiley & Sons, Ltd. PMID:26613564

  8. Branching Ratios and Vibrational Distributions in Water-Forming Reactions of OH and OD Radicals with Methylamines.

    PubMed

    Butkovskaya, N I; Setser, D W

    2016-09-01

    Reactions of OH and OD radicals with (CH3)3N, (CH3)2NH, and CH3NH2 were studied by Fourier transform infrared emission spectroscopy (FTIR) of the water product molecules from a fast-flow reactor at 298 K. The rate constants (4.4 ± 0.5) × 10(-11), (5.2 ± 0.8) × 10(-11), and (2.0 ± 0.4) × 10(-11) cm(3) molecule(-1) s(-1) were determined for OD + (CH3)3N, (CH3)2NH, and CH3NH2, respectively, by comparing the HOD emission intensities to the HOD intensity from the OD reaction with H2S. Abstraction from the nitrogen site competes with abstraction from the methyl group, as obtained from an analysis of the HOD and D2O emission intensities from the OD reactions with the deuterated reactants, (CD3)2NH and CD3NH2. After adjustment for the hydrogen-deuterium kinetic isotope effect, the product branching fractions of the hydrogen abstraction from the nitrogen for di- and monomethylamine were found to be 0.34 ± 0.04 and 0.26 ± 0.05, respectively. Vibrational distributions of the H2O, HOD, and D2O molecules are typical for direct hydrogen atom abstraction from polar molecules, even though activation energies are negative because of the formation of pre-transition-state complexes. Comparison is made to the reactions of hydroxyl radicals with ammonia and with other compounds with primary C-H bonds to discuss specific features of disposal of energy to water product. PMID:27504785

  9. Reaction pathway of the degradation of the p-hydroxybenzoic acid by sulfate radical generated by ionizing radiations

    NASA Astrophysics Data System (ADS)

    Criquet, Justine; Leitner, Nathalie Karpel Vel

    2015-01-01

    The degradation of p-hydroxybenzoic acid (HBA) in aqueous solutions by ionizing radiation was studied. The phenolic pollutant was easily removed by the electron beam irradiation, as more than 80% of the initial 100 μM introduced was degraded for a dose of 600 Gy. It was shown that the addition of persulfate, producing the sulfate radical as additional reactive species, induced a change in the reaction pathway. LC-MS analyses were performed in order to identify the different by-products formed. In the absence of persulfate, the main by-product formed was 3,4-dihydroxybenzoic acid, while in presence of persulfate, 1,4-benzoquinone was detected and the hydroxylated by-products were not present. A reaction pathway of HBA degradation by hydroxyl and sulfate radicals was proposed from the identification of the chemical structure of the different by-products detected. The influences of pH and dissolved oxygen were also studied. A high decline of HBA degradation was observed at pH 11 compared to pH 4.5, this decrease was minimized in the presence of persulfate. The dissolved oxygen concentration was found to be a limiting parameter of HBA degradation, however an excess of dissolved oxygen in solution did not improve the degradation to a large extent.

  10. PRODUCTION OF ORGANIC NITRATES FROM HYDROXYL AND NITRATE RADICAL REACTION WITH PROPYLENE

    EPA Science Inventory

    Measurements of the gas-phase production rates of alpha-nitratoacetone, propylene glycol dinitrate, 2-hydroxy propyl nitrate, and 2-nitrato propyl alcohol (2-NPA) in a C3H6/N2O5/air dark reaction and a C3H6/NOX/air irradiation are reported. The probable operative reaction mechani...

  11. Structures of the reaction products of the AZADO radical with TCNQF4 or thiourea

    PubMed Central

    Suzuki, Hideto; Kawahara, Yuta; Akutsu, Hiroki; Yamada, Jun-ichi

    2013-01-01

    Summary While an addition product was formed by the reaction of AZADO (2-azaadamantane N-oxyl) with TCNQF4 (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), the reaction of AZADO with thiourea provided an inclusion compound, in which AZADO molecules are incorporated in cylindrical channels formed by thiourea molecules. PMID:23946847

  12. Synthesis of chiral cyclohexanes and carbasugars by 6-exo-dig radical cyclisation reactions

    PubMed Central

    Maudru, Elise; Wightman, Richard H; Morgan, Keith M

    2008-01-01

    Summary Treatment of 5-(tert-butyldimethylsilyl)-2,3-O-isopropylidene-D-ribose with lithium acetylides gave mixtures of syn- and anti-alkynols 2a– 2c which were separated following protection as methoxymethyl ethers. These were converted to the corresponding iodides which underwent 6-exo-dig radical cyclisation to afford chiral cyclohexanes and carbasugars. Oxidation of the primary alcohols 6a– b gave the corresponding aldehydes which on treatment with Grignard reagents afforded a mixture of alcohols. The corresponding iodides underwent similar 6-exo-dig cyclisation to give fully functionalised cyclohexanes. PMID:19104673

  13. Free radical reactions might contribute to severe alpha amanitin hepatotoxicity--a hypothesis.

    PubMed

    Zheleva, Antoaneta; Tolekova, Anna; Zhelev, Momchil; Uzunova, Veselina; Platikanova, Magdalena; Gadzheva, Vesselina

    2007-01-01

    Alpha amanitin is a powerful natural hepatotoxin that belongs to the amatoxins isolated from deadly poisonous Amanita phalloides mushroom. The basic molecular mechanism of their toxicity was attributed to inhibition of RNA polymerase II of the eukaryotic cells. At present, the most effective clinical antidote to acute Amanita phalloides mushroom poisoning is silybin, an antioxidant possessing free radical scavenger activity and inhibiting lipid peroxidation, stabilizing membrane structure and protecting enzymes under conditions of oxidative stress. Bearing in mind the biological mechanism of silybin action and the fact that for different amatoxins (alpha, beta, and est. amanitins) does not established straight correlation between their in vivo LD50 and inhibitory constants (Ki) toward RNA polymerase III in vitro determined we supposed some additional toxic effects of these toxins might contribute to their severe hepatotoxicity. Our formerly in vitro experiments demonstrated that alpha amanitin could act either as an antioxidant or as a prooxidant depending on the treatment conditions and toxin concentration. By UV-visible spectroscopy we also shown that alpha amanitin was sensitive to oxidation by a system of lactoperoxidase/H(2)O(2) and assumed formation of free radical toxin intermediates. Having in mind some exogenic compounds including natural toxins can induce increased production of reactive oxygen species (ROS) we suggested similar generation of ROS provoked by alpha amanitin. Our recently in vitro studies have demonstrated that the alpha amanitin could increase superoxide dismutase (SOD) activity and inhibit catalase (CAT) activity to a considerable degree after together incubation of the toxin with any of enzymes. We have also shown that in vitro increased SOD activity was due to superoxide anion radical scavenging activity (SSA) of the toxin. This therefore informed the decision to study the in vivo effect of alpha amanitin on SOD and CAT activity and the

  14. Radical prostatectomy

    MedlinePlus

    Prostatectomy - radical; Radical retropubic prostatectomy; Radical perineal prostatectomy; Laparoscopic radical prostatectomy; LRP; Robotic-assisted laparoscopic prostatectomy; RALP; Pelvic lymphadenectomy; ...

  15. Reactions of thiocarbamate, triazine and urea herbicides, RDX and benzenes on EPA Contaminant Candidate List with ozone and with hydroxyl radicals

    EPA Science Inventory

    Second-order rate constants of the direct ozone reactions (kO3,M) and the indirect OH radical reactions (kOH,M) for nine chemicals on the US EPA’s Drinking Water Contaminant Candidate List (CCL) were studied during the ozonation and ozone/hydrogen peroxide a...

  16. Ab Initio and RRKM Study of the Reaction of ClO with HOCO Radicals

    NASA Astrophysics Data System (ADS)

    Yu, Hua-Gen; Francisco, Joseph S.

    2009-10-01

    The reaction pathways for the ClO + HOCO reaction have been explored using the coupled-cluster method to locate and optimize the critical points on the ground-state potential-energy surface. Results show that the ClO + HOCO reaction can produce Cl + HOC(O)O, HOCl + CO2, HCl + CO3, and HClO + CO2 via an addition or a direct hydrogen abstraction reaction mechanism. The reaction kinetics has been studied using the variational RRKM theory. It is found that the ClO + HOCO reaction is fast and has a negative temperature dependence at low temperatures. At room temperature, the thermal rate coefficient is obtained as 4.26 × 10-12 cm3 molecules-1 s-1 with product branching fractions of Cl (0.518), HOCl (0.469), HCl (0.01), and HClO (0.003) at zero pressure. The Cl + HOC(O)O products are major, compared to the HOCl + CO2 products, because of the loose transition state along the dissociation pathway to eliminate Cl. In addition, the RRKM/master equation simulations indicate that the stabilization of the HOC(O)OCl intermediates is noticeable at moderate pressures as its thermal rate constants reach about 6.0 × 10-13 cm3 molecules-1 s-1. In contrast, the other product branching ratios for the ClO + HOCO reaction are weakly dependent on pressure.

  17. Kinetic Study of the Gas-Phase Reactions of Nitrate Radicals with Methoxyphenol Compounds: Experimental and Theoretical Approaches.

    PubMed

    Lauraguais, Amélie; El Zein, Atallah; Coeur, Cécile; Obeid, Emil; Cassez, Andy; Rayez, Marie-Thérèse; Rayez, Jean-Claude

    2016-05-01

    The gas-phase reactions of five methoxyphenols (three disubstituted and two trisubstituted) with nitrate radicals were studied in an 8000 L atmospheric simulation chamber at atmospheric pressure and 294 ± 2 K. The NO3 rate constants were investigated with the relative kinetic method using PTR-ToF-MS and GC-FID to measure the concentrations of the organic compounds. The rate constants (in units of cm(3) molecule(-1) s(-1)) determined were: 2-methoxyphenol (guaiacol; 2-MP), k(2-MP) = (2.69 ± 0.57 × 10(-11); 3-methoxyphenol (3-MP), k(3-MP) = (1.15 ± 0.21) × 10(-11); 4-methoxyphenol (4-MP), k(4-MP) = (13.75 ± 7.97) × 10(-11); 2-methoxy-4-methylphenol, k(2-M-4-MeP) = (8.41 ± 5.58) × 10(-11) and 2,6-dimethoxyphenol (syringol; 2,6-DMP), k(2,6-DMP) = (15.84 ± 8.10) × 10(-11). The NO3 rate constants of the studied methoxyphenols are compared with those of other substituted aromatics, and the differences in the reactivity are construed regarding the substituents (type, number and position) on the aromatic ring. This study was also supplemented by a theoretical approach of the methoxyphenol reactions with nitrate radicals. The upper limits of the NO3 overall rate constants calculated were in the same order of magnitude than those experimentally determined. Theoretical calculations of the minimum energies of the adducts formed from the reaction of NO3 radicals with the methoxyphenols were also performed using a DFT approach (M06-2X/6-31G(d,p)). The results indicate that the NO3 addition reactions on the aromatic ring of the methoxyphenols are exothermic, with energy values ranging between -13 and -21 kcal mol(-1), depending on the environment of the carbon on which the oxygen atom of NO3 is attached. These energy values allowed identifying the most suitable carbon sites for the NO3 addition on the aromatic ring of the methoxyphenols: at the exception of the 3-MP, the NO3 ipso-addition to the hydroxyl group is one of the favored sites for all the studies compounds

  18. n-Dopants Based on Dimers of Benzimidazoline Radicals: Structures and Mechanism of Redox Reactions.

    PubMed

    Zhang, Siyuan; Naab, Benjamin D; Jucov, Evgheni V; Parkin, Sean; Evans, Eric G B; Millhauser, Glenn L; Timofeeva, Tatiana V; Risko, Chad; Brédas, Jean-Luc; Bao, Zhenan; Barlow, Stephen; Marder, Seth R

    2015-07-20

    Dimers of 2-substituted N,N'-dimethylbenzimidazoline radicals, (2-Y-DMBI)2 (Y=cyclohexyl (Cyc), ferrocenyl (Fc), ruthenocenyl (Rc)), have recently been reported as n-dopants for organic semiconductors. Here their structural and energetic characteristics are reported, along with the mechanisms by which they react with acceptors, A (PCBM, TIPS-pentacene), in solution. X-ray data and DFT calculations both indicate a longer C-C bond for (2-Cyc-DMBI)2 than (2-Fc-DMBI)2 , yet DFT and ESR data show that the latter dissociates more readily due to stabilization of the radical by Fc. Depending on the energetics of dimer (D2 ) dissociation and of D2 -to-A electron transfer, D2 reacts with A to form D(+) and A(-) by either of two mechanisms, differing in whether the first step is endergonic dissociation or endergonic electron transfer. However, the D(+) /0.5 D2 redox potentials-the effective reducing strengths of the dimers-vary little within the series (ca. -1.9 V vs. FeCp2 (+/0) ) (Cp=cyclopentadienyl) due to cancelation of trends in the D(+/0) potential and D2 dissociation energy. The implications of these findings for use of these dimers as n-dopants, and for future dopant design, are discussed. PMID:26088609

  19. n-Dopants Based on Dimers of Benzimidazoline Radicals: Structures and Mechanism of Redox Reactions

    PubMed Central

    Zhang, Siyuan; Naab, Benjamin D.; Jucov, Evgheni V.; Parkin, Sean; Evans, Eric G. B.; Millhauser, Glenn L.; Timofeeva, Tatiana V.; Risko, Chad; Brédas, Jean-Luc; Bao, Zhenan; Barlow, Stephen; Marder, Seth R.

    2015-01-01

    Dimers of 2-substituted N,N'-dimethylbenzimidazoline radicals, (2-Y-DMBI)2 {Y = cyclohexyl (Cyc), ferrocenyl (Fc), ruthenocenyl (Rc)} have recently been reported as n-dopants for organic semiconductors. Here their structural and energetic characteristics are reported, along with the mechanisms by which they react with acceptors, A (PCBM, TIPS-pentacene), in solution. X-ray data and DFT both indicate a longer C—C bond for (2-Cyc-DMBI)2 than (2-Fc-DMBI)2, yet DFT and ESR data show that the latter dissociates more readily due to stabilization of the radical by Fc. Depending on the energetics of dimer (D2) dissociation and of D2-to-A electron transfer, D2 reacts with A to form D+ and A•– by either of two mechanisms, differing in whether the first step is endergonic dissociation or endergonic electron transfer. However, the D+/0.5D2 redox potentials – the effective reducing strengths of the dimers – vary little within the series (ca. –1.9 V vs. FeCp2+/0) due to cancelation of trends in the D+/0 potential and D2 dissociation energy. The implications of these findings for use of these dimers as n-dopants, and for future dopant design, are discussed. PMID:26088609

  20. A detailed mechanistic investigation into the reaction of 3-methylpentanoic acid with Meldrum's acid utilizing online NMR spectroscopy.

    PubMed

    Dunn, Anna L; Codina, Anna; Foley, David A; Marquez, Brian L; Zell, Mark T

    2016-06-01

    A thorough investigation into the mechanism of the reaction of 3-methylpentanoic acid and Meldrum's acid using online NMR spectroscopy is reported. This study is an expansion of a previous analysis of this chemical transformation in the synthesis of an active pharmaceutical ingredient imagabalin. The 3-methylpentanoic acid analogue reveals similar behavior under the reaction conditions. Online NMR spectroscopy and offline characterization experiments reveal new information about the mechanism, providing conclusive spectroscopic evidence for the previously hypothesized dimer anhydride intermediate species 3-methylpentanoic anhydride as a productive intermediate. The presence of an acyl chloride intermediate species, 3-methylpentanoyl chloride, is also revealed for the first time in this synthesis. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26332370

  1. A mechanistic study of the addition of alcohol to a five-membered ring silene via a photochemical reaction.

    PubMed

    Su, Ming-Der

    2016-03-21

    The mechanism for the photochemical rearrangement of a cyclic divinyldisilane (1-Si) in its first excited state ((1)π → (1)π*) is determined using the CAS/6-311G(d) and MP2-CAS/6-311++G(3df,3pd) levels of theory. The photoproduct, a cyclic silene, reacts with various alcohols to yield a mixture of cis- and trans- adducts. The two reaction pathways are denoted as the cis- addition path (path A) and the trans-addition path (path B). These model studies demonstrate that conical intersections play a crucial role in the photo-rearrangements of cyclic divinyldisilanes. The theoretical evidence also demonstrates that the addition of alcohol to a cyclic divinyldisilane follows the reaction path: cyclic divinyldisilane → Franck-Condon region → conical intersection → photoproduct (cyclic silene) → local intermediate (with alcohol) → transition state → cis- or trans-adduct. The theoretical studies demonstrate that the steric effects as well as the concentrations of CH3OH must have a dominant role in determining the yields of the final adducts by stereochemistry. The same mechanism for the carbon derivative (1-C) is also considered in this work. However, the theoretical results indicate that 1-C does not undergo a methanol addition reaction via the photochemical reaction pathway, since its energy of conical intersection (S1/S0-CI-C) is more than that of its FC (FC-C). The reason for these phenomena could be that the atomic radius of carbon is much smaller than that of silicon (77 and 117 pm, respectively). As a result, the conformation for 1-C is more sterically congested than that for 1-Si, along the 1,3-silyl-migration pathway. PMID:26928893

  2. Coordination Polymer Flexibility Leads to Polymorphism and Enables a Crystalline Solid–Vapour Reaction: A Multi-technique Mechanistic Study

    PubMed Central

    Vitórica-Yrezábal, Iñigo J; Libri, Stefano; Loader, Jason R; Mínguez Espallargas, Guillermo; Hippler, Michael; Fletcher, Ashleigh J; Thompson, Stephen P; Warren, John E; Musumeci, Daniele; Ward, Michael D; Brammer, Lee

    2015-01-01

    Despite an absence of conventional porosity, the 1D coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)3] (1; TMP=tetramethylpyrazine) can absorb small alcohols from the vapour phase, which insert into Ag–O bonds to yield coordination polymers [Ag4(O2C(CF2)2CF3)4(TMP)3(ROH)2] (1-ROH; R=Me, Et, iPr). The reactions are reversible single-crystal-to-single-crystal transformations. Vapour-solid equilibria have been examined by gas-phase IR spectroscopy (K=5.68(9)×10−5 (MeOH), 9.5(3)×10−6 (EtOH), 6.14(5)×10−5 (iPrOH) at 295 K, 1 bar). Thermal analyses (TGA, DSC) have enabled quantitative comparison of two-step reactions 1-ROH→1→2, in which 2 is the 2D coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)2] formed by loss of TMP ligands exclusively from singly-bridging sites. Four polymorphic forms of 1 (1-ALT, 1-AHT, 1-BLT and 1-BHT; HT=high temperature, LT=low temperature) have been identified crystallographically. In situ powder X-ray diffraction (PXRD) studies of the 1-ROH→1→2 transformations indicate the role of the HT polymorphs in these reactions. The structural relationship between polymorphs, involving changes in conformation of perfluoroalkyl chains and a change in orientation of entire polymers (A versus B forms), suggests a mechanism for the observed reactions and a pathway for guest transport within the fluorous layers. Consistent with this pathway, optical microscopy and AFM studies on single crystals of 1-MeOH/1-AHT show that cracks parallel to the layers of interdigitated perfluoroalkyl chains develop during the MeOH release/uptake process. PMID:25962844

  3. Temperature and pressure dependence of the absolute rate constant for the reactions of NH2 radicals with acetylene and ethylene

    NASA Technical Reports Server (NTRS)

    Bosco, S. R.; Nava, D. F.; Brobst, W. D.; Stief, L. J.

    1984-01-01

    The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.

  4. Intramolecular effects on the kinetics of unimolecular reactions of β-HOROO˙ and HOQ˙OOH radicals.

    PubMed

    Lizardo-Huerta, J C; Sirjean, B; Bounaceur, R; Fournet, R

    2016-04-28

    A theoretical study describing the influence of intramolecular effects on the energy barriers and rate constants of unimolecular reactions involving β-HOROO˙ and HOQ˙OOH radicals is proposed. The reactions considered are HO2˙ elimination, the Waddington mechanism, H-shift, cyclic ether formation and β-scission. All the calculations are performed at the CBS-QB3 level of theory along with canonical transition state theory and statistical thermodynamics, including a specific treatment of hindered rotors. Several structural parameters are investigated, such as the location of the hydroxyl function in the cyclic transition states or the substitution of H atoms by alkyl groups on carbon atoms involved in the reaction coordinate. It is shown that these molecular systems involve numerous transition states, especially for reactions such as 1,5 or 1,6 H-shift, and that, a priori simplification is not possible. It is also shown that the position of the -OH group in the transition state can largely modify both the barrier heights and the rate constants. However, opposite trends can be observed depending on the competition between energetic and entropic effects. Similar observations are made when H atoms are replaced by methyl or alkyl groups. These results can largely be explained by intramolecular effects such as hydrogen bonds, stabilization effects (from -OH or -CH3 groups), steric influences and by the coupling between them. The last point renders the classic establishment of the structure-reactivity relationship challenging. PMID:27080359

  5. Temperature Dual Enantioselective Control in a Rhodium-Catalyzed Michael-Type Friedel-Crafts Reaction: A Mechanistic Explanation.

    PubMed

    Méndez, Isabel; Rodríguez, Ricardo; Polo, Víctor; Passarelli, Vincenzo; Lahoz, Fernando J; García-Orduña, Pilar; Carmona, Daniel

    2016-07-25

    By changing the temperature from 283 to 233 K, the S (99 % ee) or R (96 % ee) enantiomer of the Friedel-Crafts (FC) adduct of the reaction between N-methyl-2-methylindole and trans-β-nitrostyrene can be obtained by using (SRh ,RC )-[(η(5) -C5 Me5 )Rh{(R)-Prophos}(H2 O)][SbF6 ]2 as the catalyst precursor. This catalytic system presents two other uncommon features: 1) The ee changes with reaction time showing trends that depend on the reaction temperature and 2) an increase in the catalyst loading results in a decrease in the ee of the S enantiomer. Detection and characterization of the intermediate metal-nitroalkene and metal-aci-nitro complexes, the free aci-nitro compound, and the FC adduct-complex, together with solution NMR measurements, theoretical calculations, and kinetic studies have allowed us to propose two plausible alternative catalytic cycles. On the basis of these cycles, all the above-mentioned observations can be rationalized. In particular, the reversibility of one of the cycles together with the kinetic resolution of the intermediate aci-nitro complexes account for the high ee values achieved in both antipodes. On the other hand, the results of kinetic measurements explain the unusual effect of the increment in catalyst loading. PMID:27345293

  6. A mechanistic hypothesis for the cytochrome P450-catalyzed cis-trans isomerization of 4-hydroxytamoxifen: an unusual redox reaction.

    PubMed

    Gao, Li; Tu, Yaoquan; Wegman, Pia; Wingren, Sten; Eriksson, Leif A

    2011-09-26

    We provide a detailed description of the cis-trans isomerization of 4-hydroxytamoxifen/endoxifen catalyzed by several isoforms from the cytochrome P450 (CYP) superfamily, including CYP1B1, CYP2B6, and CYP2C19. We show that the reactions mainly involve redox processes catalyzed by CYP. DFT calculation results strongly suggest that the isomerization occurs via a cationic intermediate. The cationic cis-isomer is more than 3 kcal/mol more stable than the trans form, resulting in an easier conversion from trans-to-cis than cis-to-trans. The cis-trans isomerization is a rarely reported CYP reaction and is ascribed to the lack of a second abstractable proton on the ethenyl group of the triarylvinyl class of substrates. The cationic intermediates thus formed instead of the stable dehydrogenation products allow for isomerization to occur. As a comparison, the reactions for the tamoxifen derivatives are compared to those of other substrates, 4-hydroxyacetanilide and raloxifene, for which the stable dehydrogenation products are formed. PMID:21870861

  7. Mechanistic insight on (E)-methyl 3-(2-aminophenyl)acrylate cyclization reaction by multicatalysis of solvent and substrate.

    PubMed

    Liu, Jiahui; Zheng, Yiying; Liu, Ying; Yuan, Haiyan; Zhang, Jingping

    2016-10-01

    The reaction mechanism of (E)-methyl 3-(2-aminophenyl)acrylate (A) with phenylisothiocyanate (B) as well as the vital roles of substrate A and solvent water were investigated under unassisted, water-assisted, substrate A-assisted, and water-A-assisted conditions. The reaction proceeds with four processes via nucleophilic addition, deprotonation and protonation, intramolecular cyclization with hydrogen transfer, and keto-enol tautomerization. According to the different H-shift mode, two possible types of H-shift P1 and P2 are carefully investigated to identify the most preferred pathway, differing in the NH2 group deprotonation and CH group of A protonation processes. It is found that substrate A and water not only act as reactant and solvent, but also as catalyst, proton shuttle, and stabilizer in effectively lowering the energy barrier. Therefore, the results demonstrate that the strong donating and accepting ability of NH2 group on A and the presence of bulk water are the keys to the title reaction proceed. © 2016 Wiley Periodicals, Inc. PMID:27487815

  8. EPR study of radical reactions of C 60 dimer connected by a silicon bridge and single bond (C 60SiPh 2C 60)

    NASA Astrophysics Data System (ADS)

    Tumanskii, B. L.; Kalina, O. G.; Sokolov, V. I.; Chistyakov, A. L.; Stankevich, I. V.; Han, A.; Murata, Y.; Komatsu, K.

    2004-09-01

    Radical reactions of C 60 dimer connected by a silicon bridge and single bond (C 60SiPh 2C 60) were studied by EPR-spectroscopy. Attack of phosphoryl radicals or 2,2,6,6-tetramethylpiperidine- N-oxyl on the silicon atom leads to radical substitution of the fullerene and formation of a new fullerenyl radical, the structure of the former being confirmed by quantum-chemical calculations (DFT). The formation of only one type of spin-adduct on addition of phosphoryl radicals to the fullerene core is associated with small distortion of the fullerene cage in C 60SiPh 2C 60. Geometry of fullerene core in dimer differs only slightly from C 60 owing probably to flexibility of Si-C and C-C bonds which share a five-membered ring.

  9. Lunasin peptide purified from Solanum nigrum L. protects DNA from oxidative damage by suppressing the generation of hydroxyl radical via blocking fenton reaction.

    PubMed

    Jeong, Jin Boo; De Lumen, Ben O; Jeong, Hyung Jin

    2010-07-01

    Oxidative DNA damage is the most critical factor implicated in carcinogenesis and other disorders. However, the protective effects of lunasin against oxidative DNA damage have not yet reported. In this study, we report here the protective effect of lunasin purified from Solanum nigrum L. against oxidative DNA. Lunasin protected DNA from the oxidative damage induced by Fe(2+) ion and hydroxyl radical. To better understand the mechanism for the protective effect of lunasin against DNA damage, the abilities to chelate Fe(2+), scavenge the generated hydroxyl radical and block the generation of hydroxyl radical were evaluated. Although it did not scavenge generated hydroxyl radical, lunasin blocked the generation of hydroxyl radical by chelating Fe(2+) ion. We conclude that lunasin protects DNA from oxidation by blocking fenton reaction between Fe(2+) and H(2)O(2) by chelating Fe(2+) and that consumption of lunasin may play an important role in the chemoprevention for the oxidative carcinogenesis. PMID:20083341

  10. Radical and Non-Radical States of the [Os(PIQ)] Core (PIQ = 9,10-Phenanthreneiminoquinone): Iminosemiquinone to Iminoquinone Conversion Promoted o-Metalation Reaction.

    PubMed

    Bera, Sachinath; Mondal, Sandip; Maity, Suvendu; Weyhermüller, Thomas; Ghosh, Prasanta

    2016-05-16

    The coordination and redox chemistry of 9,10-phenanthreneiminoquinone (PIQ) with osmium ion authenticating the [Os(II)(PIQ(•-))], [Os(III)(PIQ(•-))], [Os(III)(C,N-PIQ)], [Os(III)(PIQ)], and [Os(III)(PIQ(2-)) ] states of the [Os(PIQ)] core in the complexes of types trans-[Os(II)(PIQ(•-))(PPh3)2(CO)Br] (1), trans-[Os(III)(PIQ(•-))(PPh3)2Br2] (2), trans-[Os(III)(C,N-PIQ)(PPh3)2Br2]·2CH2Cl2 (3·2CH2Cl2), trans-[Os(III)(C,N-PIQ(Br))(PPh3)2Br2]·2CH2Cl2 (4·2CH2Cl2), trans-[Os(III)(C,N-PIQ(Cl2))(PPh3)2Br2] (6), trans-[Os(III)(PIQ(•-))(PPh3)2Br2](+)1/2I3(-)1/2Br(-) (1(+)1/2I3(-)1/2Br(-)), [Os(III)(PIQ)(PPh3)2Br2](+) (2(+)), and [Os(III)(PIQ(2-))(PPh3)2Br2](-) (2(-)) are reported (PIQ(•-) = 9,10-phenanthreneiminosemiquinonate anion radical; C,N-PIQ = ortho-metalated PIQ, C,N-PIQ(Br) = ortho-metalated 4-bromo PIQ, and C,N-PIQ(Cl2) = ortho-metalated 3,4-dichloro PIQ). Reduction of PIQ by [Os(II)(PPh3)3(H)(CO)Br] affords 1, while the reaction of PIQ with [Os(II)(PPh3)3Br2] furnishes 2. Oxidation of 1 with I2 affords 1(+)1/2I3(-)1/2Br(-), while the similar reactions of 2 with X2 (X = I, Br, Cl) produce the ortho-metalated derivatives 3·2CH2Cl2, 4·2CH2Cl2, and 6. PIQ and PIQ(2-) complexes of osmium(III), 2(+) and 2(-), are generated by constant-potential electrolysis. However, 2(+) ion is unstable in solution and slowly converts to 3 and partially hydrolyzes to trans-[Os(III)(PQ(•-))(PPh3)2Br2] (2PQ), a PQ(•-) analogue of 2. Conversion of 2(+) → 3 in solution excludes the formation of aryl halide as an intermediate for this unique ortho-metalation reaction at 295 K, where PIQ acts as a redox-noninnocent ambidentate ligand. In the complexes, the PIQ(•-) state where the atomic spin is more localized on the nitrogen atom is stable and is more abundant. The reaction of 2PQ, with I2 does not promote any ortho-metalation reaction and yields a PQ complex of type trans-[Os(III)(PQ)(PPh3)2Br2](+)I5(-)·2CH2Cl2 (5(+)I5(-)·2CH2Cl2). The molecular and electronic

  11. Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

    NASA Technical Reports Server (NTRS)

    DeMore, W.; Bayes, K.

    1998-01-01

    Relative rate experiements were used to measure rate constants and temperature denpendencies of the reactions of OH with propane, n-butane, n-pentane, n-hexane, cyclopropane, cyclobutane, cyclopentane, and dimethyl ether.

  12. Mechanistic studies of semicarbazone triapine targeting human ribonucleotide reductase in vitro and in mammalian cells: tyrosyl radical quenching not involving reactive oxygen species.

    PubMed

    Aye, Yimon; Long, Marcus J C; Stubbe, JoAnne

    2012-10-12

    Triapine® (3-aminopyridine-2-carboxaldehyde thiosemicarbazone (3-AP)) is a drug in Phase II trials. One of its established cellular targets is the β(2) subunit of ribonucleotide reductase that requires a diferric-tyrosyl-radical [(Fe(III)(2)-Y·)(Fe(III)(2))] cofactor for de novo DNA biosynthesis. Several mechanisms for 3-AP inhibition of β(2) have been proposed; one involves direct iron chelation from β(2), whereas a second involves Y· destruction by reactive oxygen species formed in situ in the presence of O(2) and reductant by Fe(II)-(3-AP). Inactivation of β(2) can thus arise from cofactor destruction by loss of iron or Y·. In vitro kinetic data on the rates of (55)Fe and Y· loss from [((55)Fe(III)(2)-Y·)((55)Fe(III)(2))]-β(2) under aerobic and anaerobic conditions reveal that Y· loss alone is sufficient for rapid β(2) inactivation. Oxyblot(TM) and mass spectrometric analyses of trypsin-digested inhibited β(2), and lack of Y· loss from H(2)O(2) and O(2)(•) treatment together preclude reactive oxygen species involvement in Y· loss. Three mammalian cell lines treated with 5 μm 3-AP reveal Y· loss and β(2) inactivation within 30-min of 3-AP-exposure, analyzed by whole-cell EPR and lysate assays, respectively. Selective degradation of apo- over [(Fe(III)(2)-Y·)(Fe(III)(2))]-β(2) in lysates, similar iron-content in β(2) immunoprecipitated from 3-AP-treated and untreated [(55)Fe]-prelabeled cells, and prolonged (12 h) stability of the inhibited β(2) are most consistent with Y· loss being the predominant mode of inhibition, with β(2) remaining iron-loaded and stable. A model consistent with in vitro and cell-based biochemical studies is presented in which Fe(II)-(3-AP), which can be cycled with reductant, directly reduces Y· of the [(Fe(III)(2)-Y·)(Fe(III)(2))] cofactor of β(2). PMID:22915594

  13. Kinetic studies of the reaction of the SO radical with NO2 and ClO from 210 to 363 K

    NASA Technical Reports Server (NTRS)

    Brunning, J.; Stief, L. J.

    1986-01-01

    The rates of the reactions of the SO radical with NO2 and ClO (significant in the upper atmosphere of earth and Venus) were determined in a discharge flow system near 1 torr pressure with detection of radical and molecular species using collision-free sampling mass spectrometry. The rate constants were obtained from the decay of SO radicals in the presence of an excess of NO2 and ClO. The NO2 reaction was examined between 210 and 363 K and found to be temperature invariant: SO + NO2 yields SO2 + NO; k1 = (1.37 + or - 0.10) x 10 to the -11th cu cm/s. In addition, the ClO reaction was observed to be independent of temperature between 248 and 363 K: SO + ClO yields SO2 + Cl; k2 = (3.22 + or - 0.48) x 10 to the -11th cu cm/s. A comparison was made with previous investigations of these reactions at room temperature and with other radical-radical reactions involving SO or ClO.

  14. Kinetics of the Reaction of CH3O2 Radicals with OH Studied over the 292-526 K Temperature Range.

    PubMed

    Yan, Chao; Kocevska, Stefani; Krasnoperov, Lev N

    2016-08-11

    Reaction of methyl peroxy radicals with hydroxyl radicals, CH3O2 + OH → CH3O + HO2 (1a) and CH3O2 + OH → CH2OO + H2O (1b) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 292-526 K temperature range and pressure 1 bar (bath gas He). Hydroxyl radicals were generated in the reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N2O at 193.3 nm, with H2O. Methyl peroxy radicals were generated in the reaction of methyl radicals, CH3, produced in the photolysis of acetone at 193.3 nm, and subsequent reaction of CH3 with O2. Temporal profiles of OH were monitored via transient absorption of light from a DC discharge H2O/Ar low-pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light was determined by accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The overall rate constant of the reaction is k1a+1b = (8.4 ± 1.7) × 10(-11)(T/298 K)(-0.81) cm(3) molecule(-1) s(-1) (292-526 K). The branching ratio of channel 1b at 298 K is less than 5%. PMID:27397742

  15. 4′-CyanoPLP presents better prospect for the experimental detection of elusive cyclic intermediate radical in the reaction of lysine 5,6-aminomutase

    SciTech Connect

    Maity, Amarendra Nath; Ke, Shyue-Chu

    2015-02-06

    Graphical abstract: The results of our calculations suggest that the reaction of 4′-cyanoPLP with lysine 5,6-aminomutase offers better prospect for the experimental detection of elusive cyclic azacyclopropylcarbinyl radical, which is proposed to be a key intermediate in the reaction of pyridoxal-5′-phosphate dependent radical aminomutases. - Highlights: • 4′-CyanoI{sup ·} is the lowest energy radical intermediate in the reaction of 5,6-LAM. • 4′-CyanoPLP offers good prospect for the experimental observation of elusive I{sup ·}. • The calculated HFCCs would help to characterize 4′-cyanoI{sup ·} by EPR. - Abstract: The results of our calculations suggest that the reaction of 4′-cyanoPLP with lysine 5,6-aminomutase offers better prospect for the experimental detection of elusive cyclic azacyclopropylcarbinyl radical (I{sup ·}), which is proposed to be a key intermediate in the reaction of pyridoxal-5′-phosphate dependent radical aminomutases. We have calculated the corresponding hyperfine coupling constants (HFCCs) for {sup 14}N and {sup 13}C of cyano group using several basis sets to help the characterization of 4′-cyanoI{sup ·}.

  16. Combining the Power of Irmpd with Ion-Molecule Reactions: the Structure and Reactivity of Radical Ions of Cysteine and its Derivatives

    NASA Astrophysics Data System (ADS)

    Lesslie, Michael; Osburn, Sandra; Berden, Giel; Oomens, J.; Ryzhov, Victor

    2015-06-01

    Most of the work on peptide radical cations has involved protons as the source of charge. Nonetheless, using metal ions as charge sources often offers advantages like stabilization of the structure via multidentate coordination and the elimination of the "mobile proton". Moreover, characterization of metal-bound amino acids is of general interest as the interaction of peptide side chains with metal ions in biological systems is known to occur extensively. In the current study, we generate thiyl radicals of cysteine and homocysteine in the gas phase complexed to alkali metal ions. Subsequently, we utilize infrared multiple-photon dissociation (IRMPD) and ion-molecule reactions (IMR) to characterize the structure and reactivity of these radical ions. Our group has worked extensively with the cysteine-based radical cations and anions, characterizing the gas-phase reactivity and rearrangement of the amino acid and several of its derivatives. In a continuation of this work, we are perusing the effects of metal ions as the charge bearing species on the reactivity of the sulfur radical. Our S-nitroso chemistry can easily be used in conjunction with metal ion coordination to produce initial S-based radicals in peptide radical-metal ion complexes. In all cases we have been able to achieve radical formation with significant yield to study reactivity. Ion-molecule reactions of metallated radicals with allyl iodide, dimethyl disulfide, and allyl bromide have all shown decreasing reactivity going down group 1A. Recently, we determined the experimental IR spectra for the homocysteine radical cation with Li+, Na+, and K+ as the charge bearing species at the FELIX facility. For comparison, the protonated IR spectrum of homocysteine has previously been obtained by our group. A preliminary match of the IR spectra has been confirmed. Finally, calculations are underway to determine the bond distances of all the metal adduct structures.

  17. Velocity Map Imaging Study of Ion-Radical Chemistry: Charge Transfer and Carbon-Carbon Bond Formation in the Reactions of Allyl Radicals with C(.).

    PubMed

    Pei, Linsen; Farrar, James M

    2016-08-11

    We present an experimental and computational study of the dynamics of collisions of ground state carbon cations with allyl radicals, C3H5, at a collision energy of 2.2 eV. Charge transfer to produce the allyl cation, C3H5(+), is exoergic by 3.08 eV and proceeds via energy resonance such that the electron transfer occurs without a significant change in nuclear velocities. The products have sufficient energy to undergo the dissociation process C3H5(+) → C3H4(+) + H. Approximately 80% of the reaction products are ascribed to charge transfer, with ∼40% of those products decaying via loss of a hydrogen atom. We also observe products arising from the formation of new carbon-carbon bonds. The experimental velocity space flux distributions for the four-carbon products are symmetric about the centroid of the reactants, providing direct evidence that the products are mediated by formation of a C4H5(+) complex living at least a few rotational periods. The primary four-carbon reaction products are formed by elimination of molecular hydrogen from the C4H5(+) complex. More than 75% of the nascent C4H3(+) products decay by C-H bond cleavage to yield a C4H2(+) species. Quantum chemical calculations at the MP2/6-311+g(d,p) level of theory support the formation of a nonplanar cyclic C4H5(+) adduct that is produced when the p-orbital containing the unpaired electron on C(+) ove