Science.gov

Sample records for radical stability directs

  1. Direct generation of oxygen-stabilized radicals by H• transfer from transition metal hydrides.

    PubMed

    Kuo, Jonathan L; Hartung, John; Han, Arthur; Norton, Jack R

    2015-01-28

    Transition-metal hydrides generate α-alkoxy radicals by H• transfer to enol ethers. We have measured the rate constant for transfer from CpCr(CO)3H to n-butyl vinyl ether and have examined the chemistry of radicals generated by such transfers. Radicals from appropriate substrates undergo 5-exo cyclization, with higher diastereoselectivity than the analogous all-carbon radicals. From such radicals it is straightforward to make substituted tetrahydrofurans.

  2. Competition of charge- versus radical-directed fragmentation of gas-phase protonated cysteine sulfinyl radicals.

    PubMed

    Love, Chasity B; Tan, Lei; Francisco, Joseph S; Xia, Yu

    2013-04-24

    The fragmentation behavior of various cysteine sulfinyl ions (intact, N-acetylated, and O-methylated), new members of the gas-phase amino acid radical ion family, was investigated by low-energy collision-induced dissociation (CID). The dominant fragmentation channel for the protonated cysteine sulfinyl radicals ((SO•)Cys) was the radical-directed Cα-Cβ homolytic cleavage, resulting in the formation of glycyl radical ions and loss of CH2SO. This channel, however, was not observed for protonated N-acetylated cysteine sulfinyl radicals (Ac-(SO•)Cys); instead, charge-directed H2O loss followed immediately by SH loss prevailed. Counterintuitively, the H2O loss did not derive from the carboxyl group but involved the sulfinyl oxygen, a proton, and a Cβ hydrogen atom. Theoretical calculations suggested that N-acetylation significantly increases the barrier (~14 kcal mol(-1)) for the radical-directed fragmentation channel because of its reduced capability to stabilize the thus-formed glycyl radical ions via the captodative effect. N-Acetylation also assists in moving the proton to the sulfinyl site, which reduces the barrier for H2O loss. Our studies demonstrate that for cysteine sulfinyl radical ions, the stability of the product ions (glycyl radical ions) and the location of the charge (proton) can significantly modulate the competition between radical- and charge-directed fragmentation.

  3. The stabilization energies of polyenyl radicals

    NASA Astrophysics Data System (ADS)

    Luo, Yu-Ran; Holmes, John L.

    1994-10-01

    The resonance stabilization energies, Es, of polyenyl radicals can be estimated by the equation Es( N)=-13.2+[3.95-15.8(2) -2/ n] kcal mol -1, where N is the number of C, C-π bonds in the polyenyl radicals. This correlation has been extended for predicting the weakest HC, CC and COH bond dissociation energies in vitamin A and similar compounds.

  4. Designed metalloprotein stabilizes a semiquinone radical

    NASA Astrophysics Data System (ADS)

    Ulas, Gözde; Lemmin, Thomas; Wu, Yibing; Gassner, George T.; Degrado, William F.

    2016-04-01

    Enzymes use binding energy to stabilize their substrates in high-energy states that are otherwise inaccessible at ambient temperature. Here we show that a de novo designed Zn(II) metalloprotein stabilizes a chemically reactive organic radical that is otherwise unstable in aqueous media. The protein binds tightly to and stabilizes the radical semiquinone form of 3,5-di-tert-butylcatechol. Solution NMR spectroscopy in conjunction with molecular dynamics simulations show that the substrate binds in the active site pocket where it is stabilized by metal-ligand interactions as well as by burial of its hydrophobic groups. Spectrochemical redox titrations show that the protein stabilized the semiquinone by reducing the electrochemical midpoint potential for its formation via the one-electron oxidation of the catechol by approximately 400 mV (9 kcal mol-1). Therefore, the inherent chemical properties of the radical were changed drastically by harnessing its binding energy to the metalloprotein. This model sets the basis for designed enzymes with radical cofactors to tackle challenging chemistry.

  5. Carbon radicals. Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH).

    PubMed

    Savee, John D; Papajak, Ewa; Rotavera, Brandon; Huang, Haifeng; Eskola, Arkke J; Welz, Oliver; Sheps, Leonid; Taatjes, Craig A; Zádor, Judit; Osborn, David L

    2015-02-06

    Oxidation of organic compounds in combustion and in Earth's troposphere is mediated by reactive species formed by the addition of molecular oxygen (O2) to organic radicals. Among the most crucial and elusive of these intermediates are hydroperoxyalkyl radicals, often denoted "QOOH." These species and their reactions with O2 are responsible for the radical chain branching that sustains autoignition and are implicated in tropospheric autoxidation that can form low-volatility, highly oxygenated organic aerosol precursors. We report direct observation and kinetics measurements of a QOOH intermediate in the oxidation of 1,3-cycloheptadiene, a molecule that offers insight into both resonance-stabilized and nonstabilized radical intermediates. The results establish that resonance stabilization dramatically changes QOOH reactivity and, hence, that oxidation of unsaturated organics can produce exceptionally long-lived QOOH intermediates.

  6. Haptoglobin Binding Stabilizes Hemoglobin Ferryl Iron and the Globin Radical on Tyrosine β145

    PubMed Central

    Schaer, Dominik J.; Buehler, Paul W.; Wilson, Michael T.; Reeder, Brandon J.; Silkstone, Gary; Svistunenko, Dimitri A.; Bulow, Leif; Alayash, Abdu I.

    2013-01-01

    Abstract Aim: Hemoglobin (Hb) becomes toxic when released from the erythrocyte. The acute phase protein haptoglobin (Hp) binds avidly to Hb and decreases oxidative damage to Hb itself and to the surrounding proteins and lipids. However, the molecular mechanism underpinning Hp protection is to date unclear. The aim of this study was to use electron paramagnetic resonance (EPR) spectroscopy, stopped flow optical spectrophotometry, and site-directed mutagenesis to explore the mechanism and specifically the role of specific tyrosine residues in this protection. Results: Following peroxide challenge Hb produces reactive oxidative intermediates in the form of ferryl heme and globin free radicals. Hp binding increases the steady state level of ferryl formation during Hb-catalyzed lipid peroxidation, while at the same time dramatically inhibiting the overall reaction rate. This enhanced ferryl stability is also seen in the absence of lipids and in the presence of external reductants. Hp binding is not accompanied by a decrease in the pK of ferryl protonation; the protonated ferryl species still forms, but is intrinsically less reactive. Ferryl stabilization is accompanied by a significant increase in the concentration of the peroxide-induced tyrosine free radical. EPR spectral parameters and mutagenesis studies suggest that this radical is located on tyrosine 145, the penultimate C-terminal amino acid on the beta Hb subunit. Innovation: Hp binding decreases both the ferryl iron and free radical reactivity of Hb. Conclusion: Hp protects against Hb-induced damage in the vasculature, not by preventing the primary reactivity of heme oxidants, but by rendering the resultant protein products less damaging. Antioxid. Redox Signal. 18, 2264–2273. PMID:22702311

  7. Effects of substituents on the stabilities of phosphonyl radicals and their hydroxyphosphinyl tautomers.

    PubMed

    Krenske, Elizabeth H; Coote, Michelle L

    2007-08-23

    High-level ab initio quantum chemical methods have been used to calculate the radical stabilization energies (RSEs) of phosphonyl radicals XYP(=O)* bearing a range of substituents X and Y. The main influences on these radicals' stabilities are sigma-effects. Due to the high positive charge on phosphorus, sigma-withdrawal is destabilizing, and sigma-donation is stabilizing. The pyramidal geometry at phosphorus minimizes the effect of stabilization by pi-delocalization, while the potentially stabilizing effect of lone-pair donation is outweighed by concomitant sigma-withdrawal. Thus, the calculated RSEs of phosphonyl radicals XHP(=O)* increase in the order X = F < Me(3)N+ < MeO < CF3 < tBu < Me(2)N < NC < H < Ph < MeS < Me(3)Si. The tautomeric hydroxyphosphinyl radicals X(OH)P. exhibit a different set of substituent effects, with RSEs increasing in the order X = CF3 < Me(2)N < Me(3)N+ < MeO < (t)Bu < H < MeS < Me(3)Si < F < NC < Ph. In these radicals, both the sigma- and pi-properties of the X substituent influence stability, in tandem with those of the OH group. A comparison of the absolute enthalpies of isomeric phosphonyl and hydroxyphosphinyl radicals indicates that the hydroxyphosphinyl radicals X(OH)P* are more stable than the phosphonyl radicals XYP(=O)*. This is not a common situation in phosphorus chemistry. It is primarily attributed to the greater phosphorus p character of the singly occupied molecular orbital (SOMO) in the hydroxyphosphinyl radicals compared with the phosphonyl tautomers. As in closed-shell phosphorus species, the magnitude of the effect is modulated by the electronegativity of the substituent X.

  8. Tested Demonstrations: The Effect of Free Radical Stability on the Rate of Bromination of Hydrocarbons.

    ERIC Educational Resources Information Center

    Gilbert, George L., Ed.; And Others

    1980-01-01

    Presents a demonstration of the effect of alkyl free radical stability on the rate of free radical halogenation of hydrocarbons. The arenes toluene, ethylbenzene and comene are photobrominated comparatively, using an overhead projector both to provide a light source for the chemical reaction and to project the results on a screen. (CS)

  9. Direct assembly of multiply oxygenated carbon chains by decarbonylative radical-radical coupling reactions

    NASA Astrophysics Data System (ADS)

    Masuda, Kengo; Nagatomo, Masanori; Inoue, Masayuki

    2016-10-01

    Pentoses and hexoses contain more than three oxygen-bearing stereocentres and are ideal starting materials for the synthesis of multiply oxygenated natural products such as sagittamide D, maitotoxin and hikizimycin. Here we demonstrate new radical-radical homocoupling reactions of sugar derivatives with minimal perturbation of their chiral centres. The radical exchange procedure using Et3B/O2 converted sugar-derived α-alkoxyacyl tellurides into α-alkoxy radicals via decarbonylation and rapidly dimerized the monomeric radicals. The robustness of this process was demonstrated by a single-step preparation of 12 stereochemically diverse dimers with 6-10 secondary hydroxy groups, including the C5-C10 stereohexad of sagittamide D and the enantiomer of the C51-C60 stereodecad of maitotoxin. Furthermore, the optimally convergent radical-radical cross-coupling reaction achieved a one-step assembly of the protected C1-C11 oxygenated carbon chain of the anthelmintic hikizimycin. These exceptionally efficient homo- and heterocoupling methods together provide a powerful strategy for the expedited total synthesis of contiguously hydroxylated natural products.

  10. Spectroscopy and Ionization Thresholds of Isoelectronic 1-PHENYLALLYL and Benzylallenyl Resonance Stabilized Radicals

    NASA Astrophysics Data System (ADS)

    Sebree, Joshua A.; Kidwell, Nathan; Buchanan, Evan; Zwier, Timothy S.; Zgierski, Marek

    2011-06-01

    In recent years it has been proposed that resonance-stabilized radicals (RSRs) may play an important role as intermediates in the formation of polycyclic aromatic hydrocarbons (PAHs). RSRs gain extra stability by delocalizing the unpaired electron through a neighboring conjugated π-system. Because of this extra stability, RSRs are able to build up in concentration, allowing for the creation of larger, more complex systems through their recombination with other RSRs. Mass-selective two-color resonant two-photon ionization spectra of two RSRs, phenylallyl and benzylallenyl radicals, have been recorded under jet-cooled conditions. These two radicals, while sharing the same radical conjugation, have unique properties. The phenylallyl and benzylallenyl radicals were respectively produced via discharge of trans-β-methylstyrene and benzylallene in argon prior to supersonic expansion. The D0-D1 origin of the phenylallyl radical was found at 19204 wn and was found to have a strong vertical ionization energy of 6.905(2) eV. By comparison, the benzylallenyl radical has an origin at 19703 wn and, while showing similar Franck-Condon activity to phenylallyl, has an IP curve indicative of a large geometry change between the ground state and the ion 7.50(2) eV. Visible-visible holeburning was used to show that each radical exists in one conformeric form in the expansion. The CH stretch region of each radical was taken using D0-Resonant Ion Dip Infrared Spectroscopy in a novel four laser experiment. A combination of this and DFT calculations was used to show that each radical exists in a trans geometry.

  11. The properties and Roles of Resonance-Stabilized Radicals in Photochemical Pathways in Titan's Atmosphere

    NASA Astrophysics Data System (ADS)

    Sebree, Joshua A.; Kidwell, Nathan; Zwier, Timothy

    2010-11-01

    In recent years, the Cassini satellite has been providing details about the composition of Titan's atmosphere. Recent data has shown the existence of polycyclic aromatic hydrocarbons (PAHs) at higher altitudes than previously expected including masses tentatively ascribed to naphthalene and anthracene. The formation of indene (C9H9) and naphthalene (C10H8), the simplest PAHs, and their derivatives are of great interest as similar mechanisms may lead to the formation of larger fused-ring systems. In recent years it has been proposed that resonance-stabilized radicals (RSRs) may play an important role as intermediates along these pathways. RSRs gain extra stability by delocalizing the unpaired electron through a neighboring conjugated π-system. Because of this extra stability, RSRs are able to build up in concentration, allowing for the creation of larger, more complex systems through their recombination with other RSRs. Mass-selective UV-visible spectra of two RSRs, phenylallyl and benzylallenyl radicals, have been recorded under jet-cooled conditions. These two radicals, while sharing the same radical conjugation, have unique properties. The roles these radicals may play in the formation of fused ring systems will be discussed along with recent photochemical results on reaction pathways starting from benzylallene through the benzylallenyl radical.

  12. Investigations of stabilizing additives. I. A model system for studying radical scavenging activity in solution. [Gamma radiation

    SciTech Connect

    Dunn, T.S.; Williams, E.E.; Williams, J.L.

    1982-06-01

    In the current study an electron spin resonance model was developed to compare the thermal stability and radical scavenging activity of stabilizers in solution. High-resolution spectra and the influence of molecular structure on radical stability provided a basis for the interpretation of spin concentration data in the model system. A correlation was established between the radical scavenging activity measured in the model system and actual behavior in irradiated polypropylene formulations measured by radiation-induced degradation of mechanical properties.

  13. Charge-transfer-directed radical substitution enables para-selective C-H functionalization

    NASA Astrophysics Data System (ADS)

    Boursalian, Gregory B.; Ham, Won Seok; Mazzotti, Anthony R.; Ritter, Tobias

    2016-08-01

    Efficient C-H functionalization requires selectivity for specific C-H bonds. Progress has been made for directed aromatic substitution reactions to achieve ortho and meta selectivity, but a general strategy for para-selective C-H functionalization has remained elusive. Herein we introduce a previously unappreciated concept that enables nearly complete para selectivity. We propose that radicals with high electron affinity elicit arene-to-radical charge transfer in the transition state of radical addition, which is the factor primarily responsible for high positional selectivity. We demonstrate with a simple theoretical tool that the selectivity is predictable and show the utility of the concept through a direct synthesis of aryl piperazines. Our results contradict the notion, widely held by organic chemists, that radical aromatic substitution reactions are inherently unselective. The concept of radical substitution directed by charge transfer could serve as the basis for the development of new, highly selective C-H functionalization reactions.

  14. Charge Transfer Directed Radical Substitution Enables para-Selective C–H Functionalization

    PubMed Central

    Boursalian, Gregory B.; Ham, Won Seok; Mazzotti, Anthony R.; Ritter, Tobias

    2016-01-01

    Efficient C–H functionalization requires selectivity for specific C–H bonds. Progress has been made for directed aromatic substitution reactions to achieve ortho- and meta- selectivity, but a general strategy for para-selective C–H functionalization has remained elusive. Herein, we introduce a previously unappreciated concept which enables nearly complete para selectivity. We propose that radicals with high electron affinity elicit areneto-radical charge transfer in the transition state of radical addition, which is the factor primarily responsible for high positional selectivity. We demonstrate that the selectivity is predictable by a simple theoretical tool and show the utility of the concept through a direct synthesis of aryl piperazines. Our results contradict the notion, widely held by organic chemists, that radical aromatic substitution reactions are inherently unselective. The concept of charge transfer directed radical substitution could serve as the basis for the development of new, highly selective C–H functionalization reactions. PMID:27442288

  15. EPR study of phenolic radical stabilization by grafting on SiO 2

    NASA Astrophysics Data System (ADS)

    Panagiota, Stathi; Louloudi, Maria; Deligiannakis, Yiannis

    2009-04-01

    A hybrid [SiO 2-GA] material has been synthesized by grafting Gallic acid (3,4,5-trihydroxybenzoic acid, GA) on SiO 2 via formation of amide bonds between amine groups on aminopropyl-silica and the carboxyl group of GA. The spatial fixation of GA prevents polymerization effects. EPR spectroscopy shows that GA radicals on [SiO 2-GA] show remarkable stability, comparable to that previously observed only for radicals in biological matrices on in soil organic matter. EPR reveals a bundle-like organization of the GA molecules on [SiO 2-GA] material. The relation of these factors to the enhanced radical stability is discussed.

  16. Future Directions of Structural Mass Spectrometry using Hydroxyl Radical Footprinting

    SciTech Connect

    J Kiselar; M Chance

    2011-12-31

    Hydroxyl radical protein footprinting coupled to mass spectrometry has been developed over the last decade and has matured to a powerful method for analyzing protein structure and dynamics. It has been successfully applied in the analysis of protein structure, protein folding, protein dynamics, and protein-protein and protein-DNA interactions. Using synchrotron radiolysis, exposure of proteins to a 'white' X-ray beam for milliseconds provides sufficient oxidative modification to surface amino acid side chains, which can be easily detected and quantified by mass spectrometry. Thus, conformational changes in proteins or protein complexes can be examined using a time-resolved approach, which would be a valuable method for the study of macromolecular dynamics. In this review, we describe a new application of hydroxyl radical protein footprinting to probe the time evolution of the calcium-dependent conformational changes of gelsolin on the millisecond timescale. The data suggest a cooperative transition as multiple sites in different molecular subdomains have similar rates of conformational change. These findings demonstrate that time-resolved protein footprinting is suitable for studies of protein dynamics that occur over periods ranging from milliseconds to seconds. In this review, we also show how the structural resolution and sensitivity of the technology can be improved as well. The hydroxyl radical varies in its reactivity to different side chains by over two orders of magnitude, thus oxidation of amino acid side chains of lower reactivity are more rarely observed in such experiments. Here we demonstrate that the selected reaction monitoring (SRM)-based method can be utilized for quantification of oxidized species, improving the signal-to-noise ratio. This expansion of the set of oxidized residues of lower reactivity will improve the overall structural resolution of the technique. This approach is also suggested as a basis for developing hypothesis

  17. 14 CFR 23.177 - Static directional and lateral stability.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 1 2012-01-01 2012-01-01 false Static directional and lateral stability... Flight Stability § 23.177 Static directional and lateral stability. Link to an amendment published at 76 FR 75754, December 2, 2011. (a) The static directional stability, as shown by the tendency to...

  18. 14 CFR 25.177 - Static lateral-directional stability.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 1 2013-01-01 2013-01-01 false Static lateral-directional stability. 25... AIRCRAFT AIRWORTHINESS STANDARDS: TRANSPORT CATEGORY AIRPLANES Flight Stability § 25.177 Static lateral-directional stability. (a) The static directional stability (as shown by the tendency to recover from a...

  19. 14 CFR 23.177 - Static directional and lateral stability.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 1 2011-01-01 2011-01-01 false Static directional and lateral stability... Flight Stability § 23.177 Static directional and lateral stability. (a) The static directional stability... first, and at speeds from 1.2 VS1 to VO, the rudder pedal force must not reverse. (b) The static...

  20. 14 CFR 25.177 - Static lateral-directional stability.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 1 2014-01-01 2014-01-01 false Static lateral-directional stability. 25... AIRCRAFT AIRWORTHINESS STANDARDS: TRANSPORT CATEGORY AIRPLANES Flight Stability § 25.177 Static lateral-directional stability. (a) The static directional stability (as shown by the tendency to recover from a...

  1. 14 CFR 23.177 - Static directional and lateral stability.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 1 2010-01-01 2010-01-01 false Static directional and lateral stability... Flight Stability § 23.177 Static directional and lateral stability. (a) The static directional stability... first, and at speeds from 1.2 VS1 to VO, the rudder pedal force must not reverse. (b) The static...

  2. The stability of allyl radicals following the photodissociation of allyl iodide at 193 nm.

    SciTech Connect

    Fan, H.; Pratt, S. T.; Chemistry

    2006-01-01

    The photodissociation of allyl iodide (C{sub 3}H{sub 5}I) at 193 nm was investigated by using a combination of vacuum-ultraviolet photoionization of the allyl radical, resonant multiphoton ionization of the iodine atoms, and velocity map imaging. The data provide insight into the primary C-I bond fission process and into the dissociative ionization of the allyl radical to produce C{sub 3}H{sup 3+}. The experimental results are consistent with the earlier results of Szpunar et al. [J. Chem. Phys. 119, 5078 (2003)], in that some allyl radicals with internal energies higher than the secondary dissociation barrier are found to be stable. This stability results from the partitioning of available energy between the rotational and vibrational degrees of freedom of the radical, the effects of a centrifugal barrier along the reaction coordinate, and the effects of the kinetic shift in the secondary dissociation of the allyl radical. The present results suggest that the primary dissociation of allyl iodide to allyl radicals plus I*({sup 2}P{sub 1/2}) is more important than previously suspected.

  3. Understanding the stability of pyrolysis tars from biomass in a view point of free radicals.

    PubMed

    He, Wenjing; Liu, Qingya; Shi, Lei; Liu, Zhenyu; Ci, Donghui; Lievens, Caroline; Guo, Xiaofen; Liu, Muxin

    2014-03-01

    Fast pyrolysis of biomass has attracted increasing attention worldwide to produce bio-tars that can be upgraded into liquid fuels and chemicals. However, the bio-tars are usually poor in quality and stability and are difficult to be upgraded. To better understand the nature of the bio-tars, this work reveals radical concentration of tars derived from pyrolysis of two kinds of biomass. The tars were obtained by condensing the pyrolysis volatiles in 3s. It shows that the tars contain large amounts of radicals, at a level of 10(16)spins/g, and are able to generate more radicals at temperatures of 573K or higher, reaching a level of 10(19)spins/g at 673K in less than 30min. The radical generation in the tar samples is attributed to the formation of THF insoluble matters (coke), which also contain radicals. The radical concentrations of the aqueous liquids obtained in pyrolysis are also studied.

  4. Thrust vectoring for lateral-directional stability

    NASA Technical Reports Server (NTRS)

    Peron, Lee R.; Carpenter, Thomas

    1992-01-01

    The advantages and disadvantages of using thrust vectoring for lateral-directional control and the effects of reducing the tail size of a single-engine aircraft were investigated. The aerodynamic characteristics of the F-16 aircraft were generated by using the Aerodynamic Preliminary Analysis System II panel code. The resulting lateral-directional linear perturbation analysis of a modified F-16 aircraft with various tail sizes and yaw vectoring was performed at several speeds and altitudes to determine the stability and control trends for the aircraft compared to these trends for a baseline aircraft. A study of the paddle-type turning vane thrust vectoring control system as used on the National Aeronautics and Space Administration F/A-18 High Alpha Research Vehicle is also presented.

  5. Photodissociation of TEMPO-modified peptides: new approaches to radical-directed dissociation of biomolecules.

    PubMed

    Marshall, David L; Hansen, Christopher S; Trevitt, Adam J; Oh, Han Bin; Blanksby, Stephen J

    2014-03-14

    Radical-directed dissociation of gas phase ions is emerging as a powerful and complementary alternative to traditional tandem mass spectrometric techniques for biomolecular structural analysis. Previous studies have identified that coupling of 2-[(2,2,6,6-tetramethylpiperidin-1-oxyl)methyl]benzoic acid (TEMPO-Bz) to the N-terminus of a peptide introduces a labile oxygen-carbon bond that can be selectively activated upon collisional activation to produce a radical ion. Here we demonstrate that structurally-defined peptide radical ions can also be generated upon UV laser photodissociation of the same TEMPO-Bz derivatives in a linear ion-trap mass spectrometer. When subjected to further mass spectrometric analyses, the radical ions formed by a single laser pulse undergo identical dissociations as those formed by collisional activation of the same precursor ion, and can thus be used to derive molecular structure. Mapping the initial radical formation process as a function of photon energy by photodissociation action spectroscopy reveals that photoproduct formation is selective but occurs only in modest yield across the wavelength range (300-220 nm), with the photoproduct yield maximised between 235 and 225 nm. Based on the analysis of a set of model compounds, structural modifications to the TEMPO-Bz derivative are suggested to optimise radical photoproduct yield. Future development of such probes offers the advantage of increased sensitivity and selectivity for radical-directed dissociation.

  6. 14 CFR 23.177 - Static directional and lateral stability.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 1 2013-01-01 2013-01-01 false Static directional and lateral stability... Flight Stability § 23.177 Static directional and lateral stability. (a)(1) The static directional... is reached, whichever occurs first, and at speeds from 1.2 VS1 to VO. (b)(1) The static...

  7. 14 CFR 23.177 - Static directional and lateral stability.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 1 2014-01-01 2014-01-01 false Static directional and lateral stability... Flight Stability § 23.177 Static directional and lateral stability. (a)(1) The static directional... is reached, whichever occurs first, and at speeds from 1.2 VS1 to VO. (b)(1) The static...

  8. Stabilization of Two Radicals with One Metal: A Stepwise Coupling Model for Copper-Catalyzed Radical–Radical Cross-Coupling

    NASA Astrophysics Data System (ADS)

    Qi, Xiaotian; Zhu, Lei; Bai, Ruopeng; Lan, Yu

    2017-03-01

    Transition metal-catalyzed radical–radical cross-coupling reactions provide innovative methods for C–C and C–heteroatom bond construction. A theoretical study was performed to reveal the mechanism and selectivity of the copper-catalyzed C–N radical–radical cross-coupling reaction. The concerted coupling pathway, in which a C–N bond is formed through the direct nucleophilic addition of a carbon radical to the nitrogen atom of the Cu(II)–N species, is demonstrated to be kinetically unfavorable. The stepwise coupling pathway, which involves the combination of a carbon radical with a Cu(II)–N species before C–N bond formation, is shown to be probable. Both the Mulliken atomic spin density distribution and frontier molecular orbital analysis on the Cu(II)–N intermediate show that the Cu site is more reactive than that of N; thus, the carbon radical preferentially react with the metal center. The chemoselectivity of the cross-coupling is also explained by the differences in electron compatibility of the carbon radical, the nitrogen radical and the Cu(II)–N intermediate. The higher activation free energy for N–N radical–radical homo-coupling is attributed to the mismatch of Cu(II)–N species with the nitrogen radical because the electrophilicity for both is strong.

  9. Stabilization of Two Radicals with One Metal: A Stepwise Coupling Model for Copper-Catalyzed Radical–Radical Cross-Coupling

    PubMed Central

    Qi, Xiaotian; Zhu, Lei; Bai, Ruopeng; Lan, Yu

    2017-01-01

    Transition metal-catalyzed radical–radical cross-coupling reactions provide innovative methods for C–C and C–heteroatom bond construction. A theoretical study was performed to reveal the mechanism and selectivity of the copper-catalyzed C–N radical–radical cross-coupling reaction. The concerted coupling pathway, in which a C–N bond is formed through the direct nucleophilic addition of a carbon radical to the nitrogen atom of the Cu(II)–N species, is demonstrated to be kinetically unfavorable. The stepwise coupling pathway, which involves the combination of a carbon radical with a Cu(II)–N species before C–N bond formation, is shown to be probable. Both the Mulliken atomic spin density distribution and frontier molecular orbital analysis on the Cu(II)–N intermediate show that the Cu site is more reactive than that of N; thus, the carbon radical preferentially react with the metal center. The chemoselectivity of the cross-coupling is also explained by the differences in electron compatibility of the carbon radical, the nitrogen radical and the Cu(II)–N intermediate. The higher activation free energy for N–N radical–radical homo-coupling is attributed to the mismatch of Cu(II)–N species with the nitrogen radical because the electrophilicity for both is strong. PMID:28272407

  10. 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.

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

    DOE PAGES

    Wang, Qiang; Zheng, Jianming; Walter, Eric; ...

    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

  12. 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.

  13. Structural effects on the beta-scission reaction of alkoxyl radicals. Direct measurement of the absolute rate constants for ring opening of benzocycloalken-1-oxyl radicals.

    PubMed

    Bietti, Massimo; Lanzalunga, Osvaldo; Salamone, Michela

    2005-02-18

    [reaction: see text] The absolute rate constants for beta-scission of a series of benzocycloalken-1-oxyl radicals and of the 2-(4-methylphenyl)-2-butoxyl radical have been measured directly by laser flash photolysis. The benzocycloalken-1-oxyl radicals undergo ring opening with rates which parallel the ring strain of the corresponding cycloalkanes. In the 1-X-indan-1-oxyl radical series, ring opening is observed when X = H, Me, whereas exclusive C-X bond cleavage occurs when X = Et. The factors governing the fragmentation regioselectivity are discussed.

  14. In vivo triarylmethyl radical stabilization through encapsulation in Pluronic F-127 hydrogel

    NASA Astrophysics Data System (ADS)

    Abbas, Kahina; Boutier-Pischon, Audrey; Auger, Florian; Françon, Dominique; Almario, Antonio; Frapart, Yves-Michel

    2016-09-01

    In vivo electron paramagnetic resonance (EPR) imaging and spectroscopy are non-invasive technologies used to specifically detect and quantify paramagnetic species. However, the relative instability of spin probes such as triarylmethyl radicals limits their application to conduct oxygen quantification and mapping. In this study we encapsulated tetrathiatriarylmethyl radical (TAM; known as "Finland" probe) in Pluronic F-127 hydrogel (PF-127) in order to limit its degradation and evaluate its in vitro and in vivo EPR properties as a function of oxygen. Our results show that the EPR signal of encapsulated TAM in PF-127 hydrogel is similar to the one in solution. Although it is less sensitive to oxygen, it is suitable for oximetry. We also demonstrated that the incorporation of TAM in PF-127 hydrogel leads to an improved in vivo EPR stability of the radical under anesthesia. This new formulation enables high quality EPR imaging and oximetry and paves the way for the application of TAM radical-based probes in various biomedical fields.

  15. 14 CFR 25.177 - Static lateral-directional stability.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 1 2012-01-01 2012-01-01 false Static lateral-directional stability. 25... AIRCRAFT AIRWORTHINESS STANDARDS: TRANSPORT CATEGORY AIRPLANES Flight Stability § 25.177 Static lateral... is set forth as follows: § 25.177 Static lateral-directional stability. (a) The static...

  16. 14 CFR 29.177 - Static directional stability.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 1 2010-01-01 2010-01-01 false Static directional stability. 29.177 Section 29.177 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION... Static directional stability. (a) The directional controls must operate in such a manner that the...

  17. 14 CFR 29.177 - Static directional stability.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 1 2012-01-01 2012-01-01 false Static directional stability. 29.177 Section 29.177 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION... Static directional stability. (a) The directional controls must operate in such a manner that the...

  18. 14 CFR 29.177 - Static directional stability.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 1 2011-01-01 2011-01-01 false Static directional stability. 29.177 Section 29.177 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION... Static directional stability. (a) The directional controls must operate in such a manner that the...

  19. 14 CFR 29.177 - Static directional stability.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 1 2013-01-01 2013-01-01 false Static directional stability. 29.177 Section 29.177 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION... Static directional stability. (a) The directional controls must operate in such a manner that the...

  20. 14 CFR 29.177 - Static directional stability.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 1 2014-01-01 2014-01-01 false Static directional stability. 29.177 Section 29.177 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION... Static directional stability. (a) The directional controls must operate in such a manner that the...

  1. The role of hydration in the distribution of free radical trapping in directly ionized DNA.

    PubMed

    Purkayastha, Shubhadeep; Milligan, Jamie R; Bernhard, William A

    2006-07-01

    The purpose of this study was to elucidate the role of hydration (Gamma) in the distribution of free radical trapping in directly ionized DNA. Solid-state films of pUC18 (2686 bp) plasmids were hydrated to Gamma in the range 2.5 < or = Gamma < or = 22.5 mol water/mol nucleotide. Free radical yields, G(Sigmafr), measured by EPR at 4 K are seen to increase from 0.28 +/- 0.01 micromol/J at Gamma = 2.5 to 0.63 +/- 0.01 micromol/J at Gamma= 22.5, respectively. Based on a semi-empirical model of the free radical trapping events that follow the initial ionizations of the DNA components, we conclude that two-thirds of the holes formed on the inner solvation shell (Gamma < 10) transfer to the sugar-phosphate backbone. Likewise, of the holes produced by direct ionization of the sugar-phosphate, about one-third are trapped by deprotonation as neutral sugar-phosphate radical species, while the remaining two-thirds are found to transfer to the bases. This analysis provides the best measure to date for the probability of hole transfer (approximately 67%) into the base stack. It can thus be predicted that the distribution of holes formed in fully hydrated DNA at 4 K will be 78% on the bases and 22% on the sugar-phosphate. Adding the radicals due to electron attachment (confined to the pyrimidine bases), the distribution of all trapped radicals will be 89% on the bases and 11% on the sugar-phosphate backbone. This prediction is supported by partitioning results obtained from the high dose-response curves fitted to the two-component model. These results not only add to our understanding of how the holes redistribute after ionization but are also central to predicting the yield and location of strand breaks in DNA exposed to the direct effects of ionizing radiation.

  2. The natural polyamine spermine functions directly as a free radical scavenger

    PubMed Central

    Ha, Hyo Chol; Sirisoma, Nilantha S.; Kuppusamy, Periannan; Zweier, Jay L.; Woster, Patrick M.; Casero, Robert A.

    1998-01-01

    The polyamines are small organic cations that are absolutely required for eukaryotic cell growth. Although their growth requirements are well established, the molecular functions of the polyamines are ill-defined. Oxidative damage to DNA by reactive oxygen species is a continual problem that cells must guard against to survive. The polyamine spermine, which is normally found in millimolar concentrations in the nucleus, is shown here to function directly as a free radical scavenger, and adducts formed as a result of this function are identified. These data suggest that spermine is a major natural intracellular compound capable of protecting DNA from free radical attack. PMID:9736703

  3. Direct measurements of HOx radicals in the marine boundary layer: testing the current tropospheric chemistry mechanism.

    PubMed

    Kanaya, Yugo; Akimoto, Hajime

    2002-01-01

    OH and HO(2) radicals, atmospheric detergents, and the reservoir thereof, play central roles in tropospheric chemistry. In spite of their importance, we had no choice but to trust their concentrations predicted by modeling studies based on known chemical processes. However, recent direct measurements of these radicals have enabled us to test and revise our knowledge of the processes by comparing the predicted and observed values of the radical concentrations. We developed a laser-induced fluorescence (LIF) instrument and successfully observed OH and HO(2) at three remote islands of Japan (Oki Island, Okinawa Island, and Rishiri Island). At Okinawa Island, the observed daytime level of HO(2) agreed closely with the model estimates, suggesting that the photochemistry at Okinawa is well described by the current chemistry mechanism. At Rishiri Island, in contrast, the observed daytime level of HO(2) was consistently much lower than the calculated values. We proposed that iodine chemistry, usually not incorporated into the mechanism, is at least partly responsible for the discrepancy in the results. At night, HO(2) was detected at levels greater than 1 pptv at all three islands, suggesting the presence of processes in the dark that produce radicals. We showed that ozone reactions with unsaturated hydrocarbons, including monoterpenes, could significantly contribute to radical production.

  4. 213 nm Ultraviolet Photodissociation on Peptide Anions: Radical-Directed Fragmentation Patterns

    NASA Astrophysics Data System (ADS)

    Halim, Mohammad A.; Girod, Marion; MacAleese, Luke; Lemoine, Jérôme; Antoine, Rodolphe; Dugourd, Philippe

    2016-03-01

    Characterization of acidic peptides and proteins is greatly hindered due to lack of suitable analytical techniques. Here we present the implementation of 213 nm ultraviolet photodissociation (UVPD) in high-resolution quadrupole-Orbitrap mass spectrometer in negative polarity for peptide anions. Radical-driven backbone fragmentation provides 22 distinctive fragment ion types, achieving the complete sequence coverage for all reported peptides. Hydrogen-deficient radical anion not only promotes the cleavage of Cα-C bond but also stimulates the breaking of N-Cα and C-N bonds. Radical-directed loss of small molecules and specific side chain of amino acids are detected in these experiments. Radical containing side chain of amino acids (Tyr, Ser, Thr, and Asp) may possibly support the N-Cα backbone fragmentation. Proline comprising peptides exhibit the unusual fragment ions similar to reported earlier. Interestingly, basic amino acids such as Arg and Lys also stimulated the formation of abundant b and y ions of the related peptide anions. Loss of hydrogen atom from the charge-reduced radical anion and fragment ions are rationalized by time-dependent density functional theory (TDDFT) calculation, locating the potential energy surface (PES) of ππ* and repulsive πσ* excited states of a model amide system.

  5. The spinal accessory nerve plexus, the trapezius muscle, and shoulder stabilization after radical neck cancer surgery.

    PubMed Central

    Brown, H; Burns, S; Kaiser, C W

    1988-01-01

    A clinical and anatomic study of the spinal accessory, the eleventh cranial nerve, and trapezius muscle function of patients who had radical neck cancer surgery was conducted. This study was done not only to document the indispensibility of the trapezius muscle to shoulder-girdle stability, but also to clarify the role of the eleventh cranial nerve in the variable motor and sensory changes occurring after the loss of this muscle. Seventeen male patients, 49-69 years of age, (average of 60 years of age) undergoing a total of 23 radical neck dissections were examined for upper extremity function, particularly in regard to the trapezius muscle, and for subjective signs of pain. The eleventh nerve, usually regarded as the sole motor innervation to the trapezius, was cut in 17 instances because of tumor involvement. Dissection of four fresh and 30 preserved adult cadavers helped to reconcile the motor and sensory differences in patients who had undergone loss of the eleventh nerve. The dissections and clinical observations corroborate that the trapezius is a key part of a "muscle continuum" that stabilizes the shoulder. Variations in origins and insertions of the trapezius may influence its function in different individuals. As regards the spinal accessory nerve, it is concluded that varying motor and sensory connections form a plexus with the eleventh nerve, accounting, in part, for the variations in motor innervation and function of the trapezius, as well as for a variable spectrum of sensory changes when the eleventh nerve is cut. For this reason, it is suggested that the term "spinal accessory nerve plexus" be used to refer to the eleventh nerve when it is considered in the context of radical neck cancer surgery. Images Fig. 4. Fig. 6. Fig. 7. Fig. 8. PMID:3056289

  6. Direct detection of radical generation in rat liver nuclei on treatment with tumour-promoting hydroperoxides and related compounds.

    PubMed

    Greenley, T L; Davies, M J

    1994-04-12

    EPR spin trapping has been employed to directly detect radical production in isolated rat liver nuclei on exposure to a variety of hydroperoxides and related compounds which are known, or suspect, tumour promoters. The hydroperoxides, in the absence of reducing equivalents, undergo oxidative cleavage, generating peroxyl radicals. In the presence of NADPH (and to a lesser extent NADH) reductive cleavage of the O-O bond generates alkoxyl radicals. These radicals undergo subsequent rearrangements and reactions (dependent on the structure of the alkoxyl radical), generating carbon-centred radicals. Acyl peroxides and peracids appear to undergo only reductive cleavage of the O-O bond. With peracids this cleavage can generate aryl carboxyl (RCO2.) or hydroxyl radicals (HO.); with acyl peroxides, aryl carboxyl radicals are formed and, in the case of t-butyl peroxybenzoate, alkoxyl radicals (RO.). The radicals detected with each peroxide are similar in type to those detected in the rat liver microsomal fraction, although the extent of radical production is lower. The subsequent reactions of the initially generated radicals are similar to those determined in homogeneous chemical systems, suggesting that they are in free solution. Experiments with NADPH/NADH, heat denaturation of the nuclei and various inhibitors suggest that radical generation is an enzymatic process catalysed by haemoproteins, in particular cytochrome P-450, and that NADPH/cytochrome P-450 reductase is involved in the reductive cleavage of the O-O bond. The generation of these radicals by the rat liver nuclear fraction is potentially highly damaging for the cell due to the proximity of the generating source to DNA. Several previous studies have shown that some of the radicals detected in this study, such as aryl carboxyl and aryl radicals, can damage DNA, via various reactions which result in the generation of strand breaks and adducts to DNA bases: these processes are suggested to play an important role

  7. Stabilities of nitrogen containing heterocyclic radicals and geometrical influences on non-radiative processes in organic molecules

    NASA Technical Reports Server (NTRS)

    Evleth, E. M.

    1972-01-01

    Stabilities of nitrogen containing heterocyclic radicals were studied to detect radicals of the type R-N-R, and to theoretically rationalize their electronic structure. The computation of simple potential energy surfaces for ground and excited states is discussed along with the photophysical properties of indolizine. Methods of calculation and problems associated with the calculations are presented. Results, tables, diagrams, discussions, and references are included.

  8. Direct measurement of the fundamental rotational transitions of the OH radical by laser sideband spectroscopy

    NASA Technical Reports Server (NTRS)

    Farhoomand, J.; Pickett, H. M.; Blake, G. A.

    1985-01-01

    The direct (zero-field) spectra of the fundamental rotational transitions of the OH radical in its Omega = 3/2 and 1/2 states at 2509.9 and 1834.7 GHz are obtained using a recently developed far-infrared laser sideband spectrometer. These measurements have verified and refined the predictions of previous laser magnetic resonance work, thereby confirming the far-infrared detection of interstellar OH. The increased accuracy of these direct measurements will be useful to future astronomical and atmospheric studies of these important transitions.

  9. Direct Administration of Nerve-Specific Contrast to Improve Nerve Sparing Radical Prostatectomy

    PubMed Central

    Barth, Connor W.; Gibbs, Summer L.

    2017-01-01

    Nerve damage remains a major morbidity following nerve sparing radical prostatectomy, significantly affecting quality of life post-surgery. Nerve-specific fluorescence guided surgery offers a potential solution by enhancing nerve visualization intraoperatively. However, the prostate is highly innervated and only the cavernous nerve structures require preservation to maintain continence and potency. Systemic administration of a nerve-specific fluorophore would lower nerve signal to background ratio (SBR) in vital nerve structures, making them difficult to distinguish from all nervous tissue in the pelvic region. A direct administration methodology to enable selective nerve highlighting for enhanced nerve SBR in a specific nerve structure has been developed herein. The direct administration methodology demonstrated equivalent nerve-specific contrast to systemic administration at optimal exposure times. However, the direct administration methodology provided a brighter fluorescent nerve signal, facilitating nerve-specific fluorescence imaging at video rate, which was not possible following systemic administration. Additionally, the direct administration methodology required a significantly lower fluorophore dose than systemic administration, that when scaled to a human dose falls within the microdosing range. Furthermore, a dual fluorophore tissue staining method was developed that alleviates fluorescence background signal from adipose tissue accumulation using a spectrally distinct adipose tissue specific fluorophore. These results validate the use of the direct administration methodology for specific nerve visualization with fluorescence image-guided surgery, which would improve vital nerve structure identification and visualization during nerve sparing radical prostatectomy. PMID:28255352

  10. Direct Administration of Nerve-Specific Contrast to Improve Nerve Sparing Radical Prostatectomy.

    PubMed

    Barth, Connor W; Gibbs, Summer L

    2017-01-01

    Nerve damage remains a major morbidity following nerve sparing radical prostatectomy, significantly affecting quality of life post-surgery. Nerve-specific fluorescence guided surgery offers a potential solution by enhancing nerve visualization intraoperatively. However, the prostate is highly innervated and only the cavernous nerve structures require preservation to maintain continence and potency. Systemic administration of a nerve-specific fluorophore would lower nerve signal to background ratio (SBR) in vital nerve structures, making them difficult to distinguish from all nervous tissue in the pelvic region. A direct administration methodology to enable selective nerve highlighting for enhanced nerve SBR in a specific nerve structure has been developed herein. The direct administration methodology demonstrated equivalent nerve-specific contrast to systemic administration at optimal exposure times. However, the direct administration methodology provided a brighter fluorescent nerve signal, facilitating nerve-specific fluorescence imaging at video rate, which was not possible following systemic administration. Additionally, the direct administration methodology required a significantly lower fluorophore dose than systemic administration, that when scaled to a human dose falls within the microdosing range. Furthermore, a dual fluorophore tissue staining method was developed that alleviates fluorescence background signal from adipose tissue accumulation using a spectrally distinct adipose tissue specific fluorophore. These results validate the use of the direct administration methodology for specific nerve visualization with fluorescence image-guided surgery, which would improve vital nerve structure identification and visualization during nerve sparing radical prostatectomy.

  11. Direct dynamics study of hydrogen-transfer isomerization of 1-pentyl and 1-hexyl radicals.

    PubMed

    Zheng, Jingjing; Truhlar, Donald G

    2009-10-29

    The rate constants of three intramolecular hydrogen-transfer isomerization reactions, namely, 1-4 isomerization of the 1-pentyl radical and 1-4 and 1-5 isomerizations of the 1-hexyl radical, are calculated using variational transition state theory with multidimensional tunneling, in particular by using canonical variational theory (CVT, which is the version of variational transition state theory in which the transition state dividing surface is optimized for a canonical ensemble) with small-curvature tunneling (SCT) for the transmission coefficient. The required potential energy surfaces were obtained implicitly by direct dynamics employing interpolated variational transition state theory with mapping (IVTST-M) and variational transition state theory with interpolated single-point energies (VTST-ISPE). Single-level direct dynamics calculations were performed for all of the reactions by IVTST-M using M06-2X/MG3S or M08-HX/cc-pVTZ+ potential energy surfaces or both. The stationary points of 1-4 isomerization of 1-pentyl and the stationary points for the forward reactions of 1-4 and 1-5 isomerizations of 1-hexyl were also optimized by BMC-CCSD, and for all three reactions we also performed dual-level direct dynamics calculations using VTST-ISPE in which MCG3-MPW single-point energies served as the higher level. The calculated MCG3-MPW//M06-2X/MG3S rate constants agree well with experimental values for 1-4 isomerization of the 1-pentyl radical at high temperature, and this validates the accuracy of this theoretical method for 1-4 isomerization. The MCG3-MPW//M06-2X/MG3S method was therefore used to make a reliable prediction for the rata constants of 1-4 isomerization of the 1-hexyl radical for which a direct experimental measurement is not available. The calculated CVT/SCT/M08-HX/cc-pVTZ+ rate constants agree well with experimental values for 1-5 isomerization of the 1-hexyl radical, and they show that the tunneling effect for these reactions was underestimated in

  12. Direct Dynamics Study of Hydrogen-Transfer Isomerization of 1-Pentyl and 1-Hexyl Radicals

    NASA Astrophysics Data System (ADS)

    Zheng, Jingjing; Truhlar, Donald G.

    2009-07-01

    The rate constants of three intramolecular hydrogen-transfer isomerization reactions, namely, 1-4 isomerization of the 1-pentyl radical and 1-4 and 1-5 isomerizations of the 1-hexyl radical, are calculated using variational transition state theory with multidimensional tunneling, in particular by using canonical variational theory (CVT, which is the version of variational transition state theory in which the transition state dividing surface is optimized for a canonical ensemble) with small-curvature tunneling (SCT) for the transmission coefficient. The required potential energy surfaces were obtained implicitly by direct dynamics employing interpolated variational transition state theory with mapping (IVTST-M) and variational transition state theory with interpolated single-point energies (VTST-ISPE). Single-level direct dynamics calculations were performed for all of the reactions by IVTST-M using M06-2X/MG3S or M08-HX/cc-pVTZ+ potential energy surfaces or both. The stationary points of 1-4 isomerization of 1-pentyl and the stationary points for the forward reactions of 1-4 and 1-5 isomerizations of 1-hexyl were also optimized by BMC-CCSD, and for all three reactions we also performed dual-level direct dynamics calculations using VTST-ISPE in which MCG3-MPW single-point energies served as the higher level. The calculated MCG3-MPW//M06-2X/MG3S rate constants agree well with experimental values for 1-4 isomerization of the 1-pentyl radical at high temperature, and this validates the accuracy of this theoretical method for 1-4 isomerization. The MCG3-MPW//M06-2X/MG3S method was therefore used to make a reliable prediction for the rata constants of 1-4 isomerization of the 1-hexyl radical for which a direct experimental measurement is not available. The calculated CVT/SCT/M08-HX/cc-pVTZ+ rate constants agree well with experimental values for 1-5 isomerization of the 1-hexyl radical, and they show that the tunneling effect for these reactions was underestimated in

  13. Highly durable organic electrode for sodium-ion batteries via a stabilized α-C radical intermediate

    PubMed Central

    Wu, Shaofei; Wang, Wenxi; Li, Minchan; Cao, Lujie; Lyu, Fucong; Yang, Mingyang; Wang, Zhenyu; Shi, Yang; Nan, Bo; Yu, Sicen; Sun, Zhifang; Liu, Yao; Lu, Zhouguang

    2016-01-01

    It is a challenge to prepare organic electrodes for sodium-ion batteries with long cycle life and high capacity. The highly reactive radical intermediates generated during the sodiation/desodiation process could be a critical issue because of undesired side reactions. Here we present durable electrodes with a stabilized α-C radical intermediate. Through the resonance effect as well as steric effects, the excessive reactivity of the unpaired electron is successfully suppressed, thus developing an electrode with stable cycling for over 2,000 cycles with 96.8% capacity retention. In addition, the α-radical demonstrates reversible transformation between three states: C=C; α-C·radical; and α-C− anion. Such transformation provides additional Na+ storage equal to more than 0.83 Na+ insertion per α-C radical for the electrodes. The strategy of intermediate radical stabilization could be enlightening in the design of organic electrodes with enhanced cycling life and energy storage capability. PMID:27819293

  14. 14 CFR 25.177 - Static lateral-directional stability.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 1 2011-01-01 2011-01-01 false Static lateral-directional stability. 25.177 Section 25.177 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION AIRCRAFT AIRWORTHINESS STANDARDS: TRANSPORT CATEGORY AIRPLANES Flight Stability § 25.177 Static...

  15. 14 CFR 25.177 - Static lateral-directional stability.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 1 2010-01-01 2010-01-01 false Static lateral-directional stability. 25.177 Section 25.177 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION AIRCRAFT AIRWORTHINESS STANDARDS: TRANSPORT CATEGORY AIRPLANES Flight Stability § 25.177 Static...

  16. Influence of "remote" intramolecular hydrogen bonds on the stabilities of phenoxyl radicals and benzyl cations.

    PubMed

    Foti, Mario C; Amorati, Riccardo; Pedulli, Gian Franco; Daquino, Carmelo; Pratt, Derek A; Ingold, K U

    2010-07-02

    Remote intramolecular hydrogen bonds (HBs) in phenols and benzylammonium cations influence the dissociation enthalpies of their O-H and C-N bonds, respectively. The direction of these intramolecular HBs, para --> meta or meta --> para, determines the sign of the variation with respect to molecules lacking remote intramolecular HBs. For example, the O-H bond dissociation enthalpy of 3-methoxy-4-hydroxyphenol, 4, is about 2.5 kcal/mol lower than that of its isomer 3-hydroxy-4-methoxyphenol, 5, although group additivity rules would predict nearly identical values. In the case of 3-methoxy-4-hydroxybenzylammonium and 3-hydroxy-4-methoxybenzylammonium ions, the CBS-QB3 level calculated C-N eterolytic dissociation enthalpy is about 3.7 kcal/mol lower in the former ion. These effects are caused by the strong electron-withdrawing character of the -O(*) and -CH(2)(+) groups in the phenoxyl radical and benzyl cation, respectively, which modulates the strength of the HB. An O-H group in the para position of ArO(*) or ArCH(2)(+) becomes more acidic than in the parent molecules and hence forms stronger HBs with hydrogen bond acceptors (HBAs) in the meta position. Conversely, HBAs, such as OCH(3), in the para position become weaker HBAs in phenoxyl radicals and benzyl cations than in the parent molecules. These product thermochemistries are reflected in the transition states for, and hence in the kinetics of, hydrogen atom abstraction from phenols by free radicals (dpph(*) and ROO(*)). For example, the 298 K rate constant for the 4 + dpph(*) reaction is 22 times greater than that for the 5 + dpph(*) reaction. Fragmentation of ring-substituted benzylammonium ions, generated by ESI-MS, to form the benzyl cations reflects similar remote intramolecular HB effects.

  17. Anisotropic flow in the forward directions at {radical}s{sub NN} = 200 GeV

    SciTech Connect

    Oldenburg, Markus D.

    2004-03-09

    The addition of the two Forward TPCs to the STAR detector allows one to measure anisotropic flow at forward pseudorapidities. This made possible the first measurement of directed flow at collision energies of {radical}s{sub NN} = 200 GeV. PHOBOS' results on elliptic flow at forward rapidities were confirmed, and the sign of v{sub 2} was determined to be positive for the first time at RHIC energies. The higher harmonic, v{sub 4}, is consistent with the recently suggested v{sub 2}2 scaling behavior.

  18. Degradation pathways of lamotrigine under advanced treatment by direct UV photolysis, hydroxyl radicals, and ozone.

    PubMed

    Keen, Olya S; Ferrer, Imma; Michael Thurman, E; Linden, Karl G

    2014-12-01

    Lamotrigine is recently recognized as a persistent pharmaceutical in the water environment and wastewater effluents. Its degradation was studied under UV and ozone advanced oxidation treatments with reaction kinetics of lamotrigine with ozone (≈4 M(-1)s(-1)), hydroxyl radical [(2.1 ± 0.3) × 10(9)M(-1)s(-1)] and by UV photolysis with low and medium pressure mercury vapor lamps [quantum yields ≈0 and (2.7 ± 0.4)× 10(-4) respectively] determined. All constants were measured at pH 6 and at temperature ≈20°C. The results indicate that lamotrigine is slow to respond to direct photolysis or oxidation by ozone and no attenuation of the contaminant is expected in UV or ozone disinfection applications. The compound reacts rapidly with hydroxyl radicals indicating that advanced oxidation processes would be effective for its treatment. Degradation products were identified under each treatment process using accurate mass time-of-flight spectrometry and pathways of decay were proposed. The main transformation pathways in each process were: dechlorination of the benzene ring during direct photolysis; hydroxyl group addition to the benzene ring during the reaction with hydroxyl radicals; and triazine ring opening after reaction with ozone. Different products that form in each process may be to a varying degree less environmentally stable than the parent lamotrigine. In addition, a novel method of ozone quenching without addition of salts is presented. The new quenching method would allow subsequent mass spectrometry analysis without a solid phase extraction clean-up step. The method involves raising the pH of the sample to approximately 10 for a few seconds and lowering it back and is therefore limited to applications for which temporary pH change is not expected to affect the outcome of the analysis.

  19. Ab initio study of the influence of resonance stabilization on intramolecular ring closure reactions of hydrocarbon radicals.

    PubMed

    Wang, Kun; Villano, Stephanie M; Dean, Anthony M

    2016-03-28

    The intramolecular ring closure reactions of unsaturated hydrocarbon radicals potentially play an important role for the formation of molecular weight growth species, especially during the pyrolysis and oxidation of alkenes under low to intermediate temperatures. In this work we investigated a series of intramolecular cycloaddition reactions of both allylic- and alkyl-type dienyl radicals. In the first set of reactions, a resonant linear radical is converted into a non-resonant cyclic radical. In the second set, a non-resonant linear alkenyl radical isomerizes to either a resonant cyclic radical or a cyclic carbinyl radical. In both cases, three different reaction schemes are examined based on the location of the partially-formed resonance structure in the cyclic transition state. For each reaction scheme, both the endo- and exo-pathways were investigated. High pressure rate parameters are obtained from the results of CBS-QB3 electronic structure calculations combined with canonical transition state theory calculations. The results are discussed in the context of a Benson-type model to examine the impact of the partially-formed resonance stabilization on both the activation energies and pre-exponential factors. The results are compared to previously reported rate parameters for cycloaddition reactions of alkenyl radicals. The differences in the activation energies are primarily due to the bimolecular component of the activation energy. However, in some cases, the presence of the partial resonance structure significantly increases the strain energy for the ring that is formed in the transition state. The pre-exponential factors are also impacted by the formation of a partial resonance structure in the transition state. Lastly, the C6H9 potential energy surface is examined to show how the trends that are outlined here can be used to estimate rate parameters, which are needed to analyze pressure-dependent reaction systems.

  20. Stability and abundance of the trisulfur radical ion S3- in hydrothermal fluids

    NASA Astrophysics Data System (ADS)

    Pokrovski, Gleb S.; Dubessy, Jean

    2015-02-01

    The interpretation of sulfur behavior in geological fluids and melts is based on a long-standing paradigm that sulfate, sulfide, and sulfur dioxide are the major sulfur compounds. This paradigm was recently challenged by the discovery of the trisulfur ion S3- in aqueous S-bearing fluids from laboratory experiments at elevated temperatures. However, the stability and abundance of this potentially important sulfur species remain insufficiently quantified at hydrothermal conditions. Here we used in situ Raman spectroscopy on model thiosulfate, sulfide, and sulfate aqueous solutions across a wide range of sulfur concentration (0.5-10.0 wt%), acidity (pH 3-8), temperature (200-500 °C), and pressure (15-1500 bar) to identify the different sulfur species and determine their concentrations. Results show that in the low-density (< 0.2 g /cm3) vapor phase, H2S is the only detectable sulfur form. By contrast, in the denser liquid and supercritical fluid phase, together with sulfide and sulfate, the trisulfur radical ion S3- is a ubiquitous and thermodynamically stable species from 200 °C to at least 500 °C. In addition, the disulfur radical ion S2- is detected at 450-500 °C in most solutions, and polymeric molecular sulfur with a maximum abundance around 300 °C in S-rich solutions. These results, combined with revised literature data, allow the thermodynamic properties of S3- to be constrained, enabling quantitative predictions of its abundance over a wide temperature and pressure range of crustal fluids. These predictions suggest that S3- may account for up to 10% of total dissolved sulfur (Stot) at 300-500 °C in fluids from arc-related magmatic-hydrothermal systems, and more than 50% Stot at 600-700 °C in S-rich fluids produced via prograde metamorphism of pyrite-bearing rocks. The trisulfur ion may favor the mobility of sulfur itself and associated metals (Au, Cu, Pt, Mo) in geological fluids over a large range of depth and provide the source of these elements for

  1. Stability and properties of the two-dimensional hexagonal boron nitride monolayer functionalized by hydroxyl (OH) radicals: a theoretical study.

    PubMed

    Wang, Hong-mei; Liu, Yue-jie; Wang, Hong-xia; Zhao, Jing-xiang; Cai, Qing-hai; Wang, Xuan-zhang

    2013-12-01

    Motivated by the great advance in graphene hydroxide--a versatile material with various applications--we performed density functional theory (DFT) calculations to study the functionalization of the two-dimensional hexagonal boron nitride (h-BN) sheet with hydroxyl (OH) radicals, which has been achieved experimentally recently. Particular attention was paid to searching for the most favorable site(s) for the adsorbed OH radicals on a h-BN sheet and addressing the roles of OH radical coverage on the stability and properties of functionalized h-BN sheet. The results indicate that, for an individual OH radica, the most stable configuration is that it is adsorbed on the B site of the h-BN surface with an adsorption energy of -0.88 eV and a magnetic moment of 1.00 μ(B). Upon adsorption of more than one OH radical on a h-BN sheet, however, these adsorbates prefer to adsorb in pairs on the B and its nearest N atoms from both sides of h-BN sheet without magnetic moment. An energy diagram of the average adsorption energy of OH radicals on h-BN sheet as a function of its coverage indicates that when the OH radical coverage reaches to 60 %, the functionalized h-BN sheet is the most stable among all studied configurations. More importantly, this configuration exhibits good thermal and dynamical stability at room temperature. Owing to the introduction of certain impurity levels, the band gap of h-BN sheet gradually decreases with increasing OH coverage, thereby enhancing its electrical conductivity.

  2. Formation and Stabilization of Combustion-Generated, Environmentally Persistent Radicals on Ni(II)O Supported on a Silica Surface

    PubMed Central

    Vejerano, Eric; Lomnicki, Slawomir M.; Dellinger, Barry

    2013-01-01

    Previous studies have indicated Environmentally Persistent Free Radicals (EPFRs) are formed when hydroxyl- and chlorine-substituted aromatics chemisorbed on Cu(II)O and Fe(III)2O3 surfaces and were stabilized through their interactions with the surface metal cation. The current study reports our laboratory investigation on the formation and stabilization of EPFRs on an Ni(II)O surface. The EPFRs were produced by the chemisorption of adsorbates on the supported metal oxide surface and transfer of an electron from the adsorbate to the metal center, resulting in reduction of the metal cation. Depending on the temperature and the nature of the adsorbate, more than one type of organic radical was formed. A phenoxyl-type radical, with g-value between 2.0029 and 2.0044, and a semiquinone-type radical, with g-value from 2.0050 to as high as 2.0081, were observed. The half-lives on Ni(II)O were long and ranged from 1.5 to 5.2 days, which were similar to what were observed on Fe(III)2O3,. The yields of the EPFRs formed on Ni(II)O was ~ 8x higher than on Cu(II)O and ~50x higher than on Fe(III)2O3. PMID:22831558

  3. Formation and Stabilization of Environmentally Persistent Free Radicals Induced by the Interaction of Anthracene with Fe(III)-Modified Clays.

    PubMed

    Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Zhu, Yunqing; Wang, Chuanyi

    2016-06-21

    Environmentally persistent free radicals (EPFRs) are occasionally detected in Superfund sites but the formation of EPFRs induced by polycyclic aromatic hydrocarbons (PAHs) is not well understood. In the present work, the formation of EPFRs on anthracene-contaminated clay minerals was quantitatively monitored via electron paramagnetic resonance (EPR) spectroscopy, and surface/interface-related environmental influential factors were systematically explored. The obtained results suggest that EPFRs are more readily formed on anthracene-contaminated Fe(III)-montmorillonite than in other tested systems. Depending on the reaction condition, more than one type of organic radicals including anthracene-based radical cations with g-factors of 2.0028-2.0030 and oxygenic carbon-centered radicals featured by g-factors of 2.0032-2.0038 were identified. The formed EPFRs are stabilized by their interaction with interlayer surfaces, and such surface-bound EPFRs exhibit slow decay with 1/e-lifetime of 38.46 days. Transformation pathway and possible mechanism are proposed on the basis of experimental results and quantum mechanical simulations. Overall, the formation of EPFRs involves single-electron-transfer from anthracene to Fe(III) initially, followed by H2O addition on formed aromatic radical cation. Because of their potential exposure in soil and atmosphere, such clay surface-associated EPFRs might induce more serious toxicity than PAHs and exerts significant impacts on human health.

  4. Two tyrosyl radicals stabilize high oxidation states in cytochrome c oxidase for efficient energy conservation and proton translocation

    NASA Astrophysics Data System (ADS)

    Rousseau, Denis

    2012-02-01

    The reaction of hydrogen peroxide (H2O2) with oxidized bovine cytochrome c oxidase (bCcO) was studied by electron paramagnetic resonance (EPR) to determine the properties of radical intermediates. Two distinct radicals with widths of 12 and 46 G are directly observed by X-band CW-EPR in the reaction of bCcO with H2O2 at pH 6 and pH 8. High-frequency EPR (D-band) provides assignments to tyrosine for both radicals based on well-resolved g-tensors. The 46 G wide radical has extensive hyperfine structure and can be fit with parameters consistent with Y129. However, the 12 G wide radical has minimal hyperfine structure and can be fit using parameters unique to the post-translationally modified Y244 in CcO. The results are supported by mixed quantum mechanics and molecular mechanics calculations. This study reports spectroscopic evidence of a radical formed on the modified tyrosine in CcO and resolves the much debated controversy of whether the wide radical seen at low pH in the bovine system is a tyrosine or tryptophan. A model is presented showing how radical formation and migration may play an essential role in proton translocation. This work was done in collaboration with Michelle A. Yu, Tsuyoshi Egawa, Syun-Ru Yeh and Gary J. Gerfen from Albert Einstein College of Medicine; Kyoko Shinzawa-Itoh and Shinya Yoshikawa from the University of Hyogo; and Victor Guallar from the Barcelona Supercomputing Center.

  5. Direct rate constant measurement of radical disulphide anion formation for cysteine and cysteamine in aqueous solution

    NASA Astrophysics Data System (ADS)

    Mezyk, Stephen P.

    1995-03-01

    The techniques of pulse radiolysis, laser photolysis and absorption spectroscopy have been used to directly determine rate constants for radical disulphide anion formation for cysteine and cysteamine in aqueous solution. The measured values for cysteine, over the pH range 7-12, allowed calculation of individual rate constants for the constituent reactions RS . + RSH → RSSR -. + H + and RS . + RS - → RSSR -. as (3.39 ± 0.31) × 10 8 and (1.21 ± 0.04) × 10 9 dm 3 mol -1 s -1, respectively. Analogous values for cysteamine were also determined by this technique as (3.06 ± 0.16) × 10 8 and (3.65 ± 0.07) × 10 9 dm 3 mol -1 s -1.

  6. Potential role of stabilized Criegee radicals in sulfuric acid production in a high biogenic VOC environment.

    PubMed

    Kim, Saewung; Guenther, Alex; Lefer, Barry; Flynn, James; Griffin, Robert; Rutter, Andrew P; Gong, Longwen; Cevik, Basak Karakurt

    2015-03-17

    We present field observations made in June 2011 downwind of Dallas-Fort Worth, TX, and evaluate the role of stabilized Criegee radicals (sCIs) in gaseous sulfuric acid (H2SO4) production. Zero-dimensional model calculations show that sCI from biogenic volatile organic compounds composed the majority of the sCIs. The main uncertainty associated with an evaluation of H2SO4 production from the sCI reaction channel is the lack of experimentally determined reaction rates for sCIs formed from isoprene ozonolysis with SO2 along with systematic discrepancies in experimentally derived reaction rates between other sCIs and SO2 and water vapor. In general, the maximum of H2SO4 production from the sCI channel is found in the late afternoon as ozone increases toward the late afternoon. The sCI channel, however, contributes minor H2SO4 production compared with the conventional OH channel in the mid-day. Finally, the production and the loss rates of H2SO4 are compared. The application of the recommended mass accommodation coefficient causes significant overestimation of H2SO4 loss rates compared with H2SO4 production rates. However, the application of a lower experimental value for the mass accommodation coefficient provides good agreement between the loss and production rates of H2SO4. The results suggest that the recommended coefficient for the H2O surface may not be suitable for this relatively dry environment.

  7. 14 CFR 27.177 - Static directional stability.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 1 2011-01-01 2011-01-01 false Static directional stability. 27.177 Section 27.177 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION AIRCRAFT AIRWORTHINESS STANDARDS: NORMAL CATEGORY ROTORCRAFT Flight Flight Characteristics § 27.177...

  8. 14 CFR 27.177 - Static directional stability.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 1 2012-01-01 2012-01-01 false Static directional stability. 27.177 Section 27.177 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION AIRCRAFT AIRWORTHINESS STANDARDS: NORMAL CATEGORY ROTORCRAFT Flight Flight Characteristics § 27.177...

  9. 14 CFR 27.177 - Static directional stability.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 1 2014-01-01 2014-01-01 false Static directional stability. 27.177 Section 27.177 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION AIRCRAFT AIRWORTHINESS STANDARDS: NORMAL CATEGORY ROTORCRAFT Flight Flight Characteristics § 27.177...

  10. 14 CFR 27.177 - Static directional stability.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 1 2010-01-01 2010-01-01 false Static directional stability. 27.177 Section 27.177 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION AIRCRAFT AIRWORTHINESS STANDARDS: NORMAL CATEGORY ROTORCRAFT Flight Flight Characteristics § 27.177...

  11. 14 CFR 27.177 - Static directional stability.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 1 2013-01-01 2013-01-01 false Static directional stability. 27.177 Section 27.177 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION AIRCRAFT AIRWORTHINESS STANDARDS: NORMAL CATEGORY ROTORCRAFT Flight Flight Characteristics § 27.177...

  12. Influence of wheelchair front caster wheel on reverse directional stability.

    PubMed

    Guo, Songfeng; Cooper, Rory A; Corfman, Tom; Ding, Dan; Grindle, Garrett

    2003-01-01

    The purpose of this research was to study directional stability during reversing of rear-wheel drive, electric powered wheelchairs (EPW) under different initial front caster orientations. Specifically, the weight distribution differences caused by certain initial caster orientations were examined as a possible mechanism for causing directional instability that could lead to accidents. Directional stability was quantified by measuring the drive direction error of the EPW by a motion analysis system. The ground reaction forces were collected to determine the load on the front casters, as well as back-emf data to attain the speed of the motors. The drive direction error was found to be different for various initial caster orientations. Drive direction error was greatest when both casters were oriented 90 degrees to the left or right, and least when both casters were oriented forward. The results show that drive direction error corresponds to the loading difference on the casters. The data indicates that loading differences may cause asymmetric drag on the casters, which in turn causes unbalanced torque load on the motors. This leads to a difference in motor speed and drive direction error.

  13. What fraction of DNA double-strand breaks produced by the direct effect is accounted for by radical pairs?

    PubMed

    Peoples, Anita R; Mercer, Kermit R; Bernhard, William A

    2010-07-22

    The purpose of this investigation was to determine what fraction of double strand breaks (dsb's), generated by the direct effect of ionizing radiation on DNA, can be accounted for by radical pairs. A radical pair is defined as two radicals trapped within a separation distance of <3 nm. Q-band EPR was used to measure the yield of radical pairs in calf thymus DNA films X-irradiated at 4 K. The EPR spectrum of DNA showed no evidence of radical pairs. To determine the relative sensitivity for radical pair detection via Q-band EPR, we measured the yield of radical pairs in single crystals of thymine, G(rp-Thy). Under the same conditions employed for DNA, G(rp-Thy) was approximately 8 nmol/J. The value of G(rp-Thy), in conjunction with the measured signal-to-noise, was used to calculate an upper limit for the yield of radical pairs in DNA, G(max)(rp-DNA) < 0.7-1.4 nmol/J. The upper limit, G(max)(rp-DNA), was compared with the yield of dsb's, G(total)(dsb) = 10 nmol/J, previously measured in pUC18 DNA films by Purkayastha, S.; Milligan, J. R.; Bernhard, W. A. Radiat. Res. 2007, 168, 357. We found that G(total)(dsb) > 2 x G(max)(rp-DNA), implying that a significant fraction of dsb's were not derived from a pair of trappable radicals. At least one of the two precursors needed to form a dsb was a diamagnetic (molecular) product. The hypothesis is that EPR silent lesions are formed through a molecular pathway. For example, a two-electron oxidation of deoxyribose would result in a deoxyribose carbocation intermediate that ultimately leads to a strand break.

  14. Naphthoxanthenyl, a new stable phenalenyl type radical stabilized by electronic effects.

    PubMed

    Anamimoghadam, Ommid; Symes, Mark D; Busche, Christoph; Long, De-Liang; Caldwell, Stuart T; Flors, Cristina; Nonell, Santi; Cronin, Leroy; Bucher, Götz

    2013-06-21

    Naphthoxanthenyl 1 is a new stable phenalenyl-type radical. Electrochemical studies indicate that 1 has two reversible redox processes that occur on comparatively short time scales. Crystals containing 1 can be grown by electrocrystallization, suggesting that they are conductive.

  15. Tactile pavement for guiding walking direction: An assessment of heading direction and gait stability.

    PubMed

    Pluijter, Nanda; de Wit, Lieke P W; Bruijn, Sjoerd M; Plaisier, Myrthe A

    2015-10-01

    For maintaining heading direction while walking we heavily rely on vision. Therefore, walking in the absence of vision or with visual attention directed elsewhere potentially leads to dangerous situations. Here we investigated whether tactile information from the feet can be used as a (partial) substitute for vision in maintaining a stable heading direction. If so, participants should be better able to keep a constant heading direction on tactile pavement that indicates directionality than on regular flat pavement. However, such a pavement may also be destabilizing. Thus we asked participants to walk straight ahead on regular pavement, and on tactile pavement (tiles with ridges along the walking direction) while varying the amount of vision. We assessed the effects of the type of pavement as well as the amount of vision on the variability of the heading direction as well as gait stability. Both of these measures were calculated from accelerations and angular velocities recorded from a smartphone attached to the participants trunk. Results showed that on tactile pavement participants had a less variations in their heading direction than on regular pavement. The drawback, however, was that the tactile pavement used in this study decreased gait stability. In sum, tactile pavement can be used as a partial substitute for vision in maintaining heading direction, but it can also decrease gait stability. Future work should focus on designing tactile pavement that does provided directional clues, but is less destabilizing.

  16. The elimination of free radicals in irradiated UHMWPEs with and without vitamin E stabilization by annealing under pressure.

    PubMed

    Oral, Ebru; Ghali, Bassem W; Muratoglu, Orhun K

    2011-04-01

    Radiation crosslinking of ultrahigh molecular weight polyethylene (UHMWPE) has been used to decrease the wear of joint implant bearing surfaces. While radiation crosslinking has been successful in decreasing femoral head penetration into UHMWPE acetabular liners in vivo, postirradiation thermal treatment of the polymer is required to ensure the oxidative stability of joint implants in the long term. Two types of thermal treatment have been used: (i) annealing below the melting point preserves the mechanical properties but the residual free radicals trapped in the crystalline regions are not completely eliminated, leading to oxidation in the long-term and (ii) annealing above the melting point (melting) eliminates the free radicals but leads to a decrease in mechanical properties through loss of crystallinity during the melting process. In this study, we hypothesized that free radicals could be reduced by annealing below the melting point under pressure effectively without melting due to the elevation of the melting point. By avoiding the complete melting of UHMWPE, mechanical properties would be preserved. Our hypothesis tested positive in that we found the radiation-induced free radicals to be markedly reduced (below the detection limit of state-of-the-art electron spin resonance) by thermal annealing under pressure in radiation crosslinked virgin UHMWPE and UHMWPE/vitamin-E blends without loss of mechanical properties.

  17. The elimination of free radicals in irradiated UHMWPEs with and without vitamin E stabilization by annealing under pressure

    PubMed Central

    Oral, Ebru; Ghali, Bassem W.; Muratoglu, Orhun K.

    2013-01-01

    Radiation crosslinking of ultrahigh molecular weight polyethylene (UHMWPE) has been used to decrease the wear of joint implant bearing surfaces. While radiation crosslinking has been successful in decreasing femoral head penetration into UHMWPE acetabular liners in vivo, postirradiation thermal treatment of the polymer is required to ensure the oxidative stability of joint implants in the long term. Two types of thermal treatment have been used: (i) annealing below the melting point preserves the mechanical properties but the residual free radicals trapped in the crystalline regions are not completely eliminated, leading to oxidation in the long-term and (ii) annealing above the melting point (melting) eliminates the free radicals but leads to a decrease in mechanical properties through loss of crystallinity during the melting process. In this study, we hypothesized that free radicals could be reduced by annealing below the melting point under pressure effectively without melting due to the elevation of the melting point. By avoiding the complete melting of UHMWPE, mechanical properties would be preserved. Our hypothesis tested positive in that we found the radiation-induced free radicals to be markedly reduced (below the detection limit of state-of-the-art electron spin resonance) by thermal annealing under pressure in radiation crosslinked virgin UHMWPE and UHMWPE/vitamin-E blends without loss of mechanical properties. PMID:21381192

  18. Comparison of commercial uv lamps for radical oxidation and direct photolysis in water

    SciTech Connect

    Haag, W; Wang, F T

    1999-08-01

    Lawrence Livermore National Laboratory (LLNL) is charged with developing methods for treating contaminated sites and destroying waste organic compounds that are currently being accumulated, including Trimsol (machining oil), trichloroethene (ICE), tributyl phosphate (TBP), kerosene, and many other organics. These organics are sometimes present mixed with radioactive waste, and in these cases it is important to destroy the organics in such a way as to not increase the total volume of the waste and to ensure that no radioactivity is released in the process. Among the most promising techniques for treating aqueous mixed wastes are ultraviolet light (UV) oxidation and the molten salt process, as opposed to methods like incineration or supercritical water oxidation that might lead to air emissions of radioactivity if not very carefully controlled. The purpose of the present study was to compare the energy efficiency of various commercial UV lamp systems designed for photooxidation. Two type of tests were conducted: (1) direct photolysis of a chlorinated compound and (2) photolysis of hydrogen peroxide, which is an additive often used to photooxidize compounds that are not amenable to direct photolysis. The results should allow LLNL to select the most cost-effective system for treating wastes by UV- enhanced radical oxidation processes.

  19. The effect of free radical inhibitor on the sensitized radiation crosslinking and thermal processing stabilization of polyurethane shape memory polymers.

    PubMed

    Hearon, Keith; Smith, Sarah E; Maher, Cameron A; Wilson, Thomas S; Maitland, Duncan J

    2013-02-01

    The effects of free radical inhibitor on the electron beam crosslinking and thermal processing stabilization of novel radiation crosslinkable polyurethane shape memory polymers (SMPs) blended with acrylic radiation sensitizers have been determined. The SMPs in this study possess novel processing capabilities-that is, the ability to be melt processed into complex geometries as thermoplastics and crosslinked in a secondary step using electron beam irradiation. To increase susceptibility to radiation crosslinking, the radiation sensitizer pentaerythritol triacrylate (PETA) was solution blended with thermoplastic polyurethane SMPs made from 2-butene-1,4-diol and trimethylhexamethylene diisocyanate (TMHDI). Because thermoplastic melt processing methods such as injection molding are often carried out at elevated temperatures, sensitizer thermal instability is a major processing concern. Free radical inhibitor can be added to provide thermal stabilization; however, inhibitor can also undesirably inhibit radiation crosslinking. In this study, we quantified both the thermal stabilization and radiation crosslinking inhibition effects of the inhibitor 1,4-benzoquinone (BQ) on polyurethane SMPs blended with PETA. Sol/gel analysis of irradiated samples showed that the inhibitor had little to no inverse effects on gel fraction at concentrations of 0-10,000 ppm, and dynamic mechanical analysis showed only a slight negative correlation between BQ composition and rubbery modulus. The 1,4-benzoquinone was also highly effective in thermally stabilizing the acrylic sensitizers. The polymer blends could be heated to 150°C for up to five hours or to 125°C for up to 24 hours if stabilized with 10,000 ppm BQ and could also be heated to 125°C for up to 5 hours if stabilized with 1000 ppm BQ without sensitizer reaction occurring. We believe this study provides significant insight into methods for manipulation of the competing mechanisms of radiation crosslinking and thermal stabilization

  20. The effect of free radical inhibitor on the sensitized radiation crosslinking and thermal processing stabilization of polyurethane shape memory polymers

    PubMed Central

    Hearon, Keith; Smith, Sarah E.; Maher, Cameron A.; Wilson, Thomas S.; Maitland, Duncan J.

    2012-01-01

    The effects of free radical inhibitor on the electron beam crosslinking and thermal processing stabilization of novel radiation crosslinkable polyurethane shape memory polymers (SMPs) blended with acrylic radiation sensitizers have been determined. The SMPs in this study possess novel processing capabilities—that is, the ability to be melt processed into complex geometries as thermoplastics and crosslinked in a secondary step using electron beam irradiation. To increase susceptibility to radiation crosslinking, the radiation sensitizer pentaerythritol triacrylate (PETA) was solution blended with thermoplastic polyurethane SMPs made from 2-butene-1,4-diol and trimethylhexamethylene diisocyanate (TMHDI). Because thermoplastic melt processing methods such as injection molding are often carried out at elevated temperatures, sensitizer thermal instability is a major processing concern. Free radical inhibitor can be added to provide thermal stabilization; however, inhibitor can also undesirably inhibit radiation crosslinking. In this study, we quantified both the thermal stabilization and radiation crosslinking inhibition effects of the inhibitor 1,4-benzoquinone (BQ) on polyurethane SMPs blended with PETA. Sol/gel analysis of irradiated samples showed that the inhibitor had little to no inverse effects on gel fraction at concentrations of 0-10,000 ppm, and dynamic mechanical analysis showed only a slight negative correlation between BQ composition and rubbery modulus. The 1,4-benzoquinone was also highly effective in thermally stabilizing the acrylic sensitizers. The polymer blends could be heated to 150°C for up to five hours or to 125°C for up to 24 hours if stabilized with 10,000 ppm BQ and could also be heated to 125°C for up to 5 hours if stabilized with 1000 ppm BQ without sensitizer reaction occurring. We believe this study provides significant insight into methods for manipulation of the competing mechanisms of radiation crosslinking and thermal

  1. The effect of free radical inhibitor on the sensitized radiation crosslinking and thermal processing stabilization of polyurethane shape memory polymers

    NASA Astrophysics Data System (ADS)

    Hearon, Keith; Smith, Sarah E.; Maher, Cameron A.; Wilson, Thomas S.; Maitland, Duncan J.

    2013-02-01

    The effects of free radical inhibitor on the electron beam crosslinking and thermal processing stabilization of novel radiation crosslinkable polyurethane shape memory polymers (SMPs) blended with acrylic radiation sensitizers have been determined. The SMPs in this study possess novel processing capabilities—that is, the ability to be melt processed into complex geometries as thermoplastics and crosslinked in a secondary step using electron beam irradiation. To increase susceptibility to radiation crosslinking, the radiation sensitizer pentaerythritol triacrylate (PETA) was solution blended with thermoplastic polyurethane SMPs made from 2-butene-1,4-diol and trimethylhexamethylene diisocyanate (TMHDI). Because the thermoplastic melt processing methods such as injection molding are often carried out at elevated temperatures, sensitizer thermal instability is a major processing concern. Free radical inhibitor can be added to provide thermal stabilization; however, inhibitor can also undesirably inhibit radiation crosslinking. In this study, we quantified both the thermal stabilization and radiation crosslinking inhibition effects of the inhibitor 1,4-benzoquinone (BQ) on polyurethane SMPs blended with PETA. Sol/gel analysis of irradiated samples showed that the inhibitor had little to no inverse effects on gel fraction at concentrations of 0-10,000 ppm, and dynamic mechanical analysis showed only a slight negative correlation between BQ composition and rubbery modulus. The 1,4-benzoquinone was also highly effective in thermally stabilizing the acrylic sensitizers. The polymer blends could be heated to 150 °C for up to 5 h or to 125 °C for up to 24 h if stabilized with 10,000 ppm BQ and could also be heated to 125 °C for up to 5 h if stabilized with 1000 ppm BQ without sensitizer reaction occurring. We believe this study provides significant insight into methods for manipulation of the competing mechanisms of radiation crosslinking and thermal stabilization of

  2. A method for direct measurement of protein stability in vivo.

    PubMed

    Ignatova, Zoya; Gierasch, Lila M

    2009-01-01

    The stability of proteins is tuned by evolution to enable them to perform their cellular functions for the success of an organism. Yet, most of the arsenal of biophysical techniques at our disposal to characterize the thermodynamic stability of proteins is limited to in vitro samples. We describe an approach that we have developed to observe a protein directly in a cell and to monitor a fluorescence signal that reports the unfolding transition of the protein, yielding quantitatively interpretable stability data in vivo. The method is based on incorporation of structurally nonperturbing, specific binding motifs for a bis-arsenical fluorescein derivative in sites that result in dye fluorescence differences between the folded and unfolded states of the protein under study. This fluorescence labeling approach makes possible the determination of thermodynamic stability by direct urea titration in Escherichia coli cells. The specific case study we describe was carried out on the predominantly beta-sheet intracellular lipid-binding protein, cellular retinoic acid-binding protein (CRABP), expressed in E. coli.

  3. Are gait variability and stability measures influenced by directional changes?

    PubMed Central

    2014-01-01

    Background Many gait variability and stability measures have been proposed in the literature, with the aim to quantify gait impairment, degree of neuro-motor control and balance disorders in healthy and pathological subjects. These measures are often obtained from lower trunk acceleration data, typically acquired during rectilinear gait, but relevant experimental protocols and data processing techniques lack in standardization. Since directional changes represent an essential aspect of gait, the assessment of their influence on such measures is essential for standardization. In addition, their investigation is needed to evaluate the applicability of these measures in laboratory trials and in daily life activity analysis. A further methodological aspect to be standardized concerns the assessment of the sampling frequency, which could affect stability measures. The aim of the present study was hence to assess if gait variability and stability measures are affected by directional changes, and to evaluate the influence of sampling frequency of trunk acceleration data on the results. Methods Fifty-one healthy young adults performed a 6-minute walk test along a 30 m straight pathway, turning by 180 deg at each end of the pathway. Nine variability and stability measures (Standard deviation, Coefficient of variation, Poincaré plots, maximum Floquet multipliers, short-term Lyapunov exponents, Recurrence quantification analysis, Multiscale entropy, Harmonic ratio and Index of harmonicity) were calculated on stride duration and trunk acceleration data (acquired at 100 Hz and 200 Hz) coming from straight walking windows and from windows including both straight walking and the directional change. Results Harmonic ratio was the only measure that resulted to be affected by directional changes and sampling frequency, decreasing with the presence of a directional change task. HR was affected in the AP and V directions for the 200 Hz, but only in AP direction for the 100 Hz group

  4. Direct observation of hexamethylbenzenium radical cations generated during zeolite methanol-to-olefin catalysis: an ESR study.

    PubMed

    Kim, Sun Jung; Jang, Hoi-Gu; Lee, Jun Kyu; Min, Hyung-Ki; Hong, Suk Bong; Seo, Gon

    2011-09-07

    The generation of hexamethylbenzenium radical cations as the key reaction intermediate in chabazite-type molecular sieve acids (i.e., H-SAPO-34 and H-SSZ-13) during the methanol-to-olefin process has been directly evidenced by ESR spectroscopy.

  5. Instantaneous Directional Growth of Block Copolymer Nanowires During Heterogeneous Radical Polymerization (HRP).

    PubMed

    Lu, Chunliang; Urban, Marek W

    2016-04-13

    Polymeric nanowires that consist of ultrahigh molecular weight block copolymers were instantaneously prepared via one-step surfactant-free heterogeneous radical polymerization (HRP). Under heterogeneous reaction and initiator-starvation conditions, the sequential copolymerization of hydrophilic and hydrophobic monomers facilitates the formation of amphiphilic ultrahigh molecular weight block copolymers, which instantaneously assemble to polymeric nanowires. As polymerization progresses, initially formed nanoparticles exhibit the directional growth due to localized repulsive forces of hydrophilic blocks and confinement of the hydrophobic blocks that adopt favorable high aspect ratio nanowire morphologies. Using one-step synthetic approach that requires only four ingredients (water as a solvent, two polymerizable monomers (one hydrophilic and one hydrophobic), and water-soluble initiator), block copolymer nanowires ∼70 nm in diameter and hundreds of microns in length are instantaneously grown. For example, when 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) and styrene (St) were copolymerized, high aspect ratio nanowires consist of ultrahigh (>10(6) g/mol) molecular weight pDMAEMA-b-St block copolymers and the presence of temperature responsive pDMAEMA blocks facilitates nanowire diameter changes as a function of temperature. These morphologies may serve as structural components of the higher order biological constructs at micro and larger length scales, ranging from single strand nanowires to engineered biomolecular networks capable of responding to diverse and transient environmental signals, and capable of dimensional changes triggered by external stimuli.

  6. Direct dynamics study on hydrogen abstraction reaction of CF 3CHOHCF 3 with OH radical

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Liu, Jing-Yao; Li, Ze-Sheng

    2007-05-01

    Dual-level direct dynamics method is employed to investigate the H-abstraction reaction CF 3CHOHCF 3 with OH radical. Two hydrogen-abstraction reaction channels are possible: one from the methylene (-CH-) position and the other from the hydroxyl (-OH) position. The minimum energy path is calculated at the B3LYP/6-311G(d,p) level, and the energetic information is further refined by a new powerful and inexpensive BMC-CCSD method. To testify the accuracy of the structures and the energies, the recently developed hybrid density functional theory BB1K and higher level MC-QCISD are applied to this system. Hydrogen-bonded complexes are presented at both reactants and products sides of these two channels, which indicating that the reaction may proceed via an indirect mechanism. The rate constants for each reaction channel are evaluated by canonical variational transition state theory (CVT) with a small-curvature tunneling correction (SCT) over a wide range of temperatures from 200 to 2000 K. The calculated CVT/SCT rate constants are in good agreement with the available experimental values in the temperature region 250-430 K. The present results indicate that the two channels are competitive. At lower temperature, the reaction occurs mainly via the hydroxyl-H-abstraction channel, while the methylene-H-abstraction channel is preferred when the temperature is higher than 273 K.

  7. Stability of a directional solidification front in subdiffusive media.

    PubMed

    Hamed, Mohammad Abu; Nepomnyashchy, Alexander A

    2014-01-01

    The efficiency of crystal growth in alloys is limited by the morphological instability, which is caused by a positive feedback between the interface deformation and the diffusive flux of solute at the front of the phase transition. Usually this phenomenon is described in the framework of the normal diffusion equation, which stems from the linear relation between time and the mean squared displacement of molecules 〈x2(t)〉∼K1t (K1 is the classical diffusion coefficient) that is characteristic of Brownian motion. However, in some media (e.g., in gels and porous media) the random walk of molecules is hindered by obstacles, which leads to another power law, 〈x2(t)〉∼Kαtα, where 0<α≤1. As a result, the diffusion is anomalous, and it is governed by an integro-differential equation including a fractional derivative in time variable, i.e., a memory. In the present work, we investigate the stability of a directional solidification front in the case of an anomalous diffusion. Linear stability of a moving planar directional solidification front is studied, and a generalization of the Mullins-Sekerka stability criterion is obtained. Also, an asymptotic nonlinear long-wave evolution equation of Sivashinsky's type, which governs the cellular structures at the interface, is derived.

  8. Ultraviolet photolysis of HCHO: absolute HCO quantum yields by direct detection of the HCO radical photoproduct.

    PubMed

    Carbajo, Paula Gorrotxategi; Smith, Shona C; Holloway, Anne-Louise; Smith, Carina A; Pope, Francis D; Shallcross, Dudley E; Orr-Ewing, Andrew J

    2008-12-04

    Absolute quantum yields for the radical (H + HCO) channel of HCHO photolysis, Phi(HCO), have been measured for the tropospherically relevant range of wavelengths (lambda) between 300 and 330 nm. The HCO photoproduct was directly detected by using a custom-built, combined ultra-violet (UV) absorption and cavity ring down (CRD) detection spectrometer. This instrument was previously employed for high-resolution (spectral resolution approximately 0.0035 nm) measurements of absorption cross-sections of HCHO, sigma(HCHO)(lambda), and relative HCO quantum yields. Absolute Phi(HCO) values were measured at seven wavelengths, lambda = 303.70, 305.13, 308.87, 314.31, 320.67, 325.59, and 329.51 nm, using an independent calibration technique based on the simultaneous UV photolysis of HCHO and Cl(2). These Phi(HCO) measurements display greater variability as a function of wavelength than the current NASA-JPL recommendations for Phi(HCO). The absolute Phi(HCO)(lambda) determinations and previously measured sigma(HCHO)(lambda) were used to scale an extensive set of relative HCO yield measurements. The outcome of this procedure is a full suite of data for the product of the absolute radical quantum yield and HCHO absorption cross-section, Phi(HCO)(lambda)sigma(HCHO)(lambda), at wavelengths from 302.6 to 331.0 nm with a wavelength resolution of 0.005 nm. This product of photochemical parameters is combined with high-resolution solar photon flux data to calculate the integrated photolysis rate of HCHO to the radical (H + HCO) channel, J(HCO). Comparison with the latest NASA-JPL recommendations, reported at 1 nm wavelength resolution, suggests an increased J(HCO) of 25% at 0 degrees solar zenith angle (SZA) increasing to 33% at high SZA (80 degrees). The differences in the calculated photolysis rate compared with the current HCHO data arise, in part, from the higher wavelength resolution of the current data set and highlight the importance of using high-resolution spectroscopic

  9. Direct Numerical Simulation of a Cavity-Stabilized Ethylene/Air Premixed Flame

    NASA Astrophysics Data System (ADS)

    Chen, Jacqueline; Konduri, Aditya; Kolla, Hemanth; Rauch, Andreas; Chelliah, Harsha

    2016-11-01

    Cavity flame holders have been shown to be important for flame stabilization in scramjet combustors. In the present study the stabilization of a lean premixed ethylene/air flame in a rectangular cavity at thermo-chemical conditions relevant to scramjet combustors is simulated using a compressible reacting multi-block direct numerical simulation solver, S3D, incorporating a 22 species ethylene-air reduced chemical model. The fuel is premixed with air to an equivalence ratio of 0.4 and enters the computational domain at Mach numbers between 0.3 and 0.6. An auxiliary inert channel flow simulation is used to provide the turbulent velocity profile at the inlet for the reacting flow simulation. The detailed interaction between intense turbulence, nonequilibrium concentrations of radical species formed in the cavity and mixing with the premixed main stream under density variations due to heat release rate and compressibility effects is quantified. The mechanism for flame stabilization is quantified in terms of relevant non-dimensional parameters, and detailed analysis of the flame and turbulence structure will be presented. We acknowledge the sponsorship of the AFOSR-NSF Joint Effort on Turbulent Combustion Model Assumptions and the DOE Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.

  10. Beer thiol-containing compounds and redox stability: kinetic study of 1-hydroxyethyl radical scavenging ability.

    PubMed

    de Almeida, Natália E C; Lund, Marianne N; Andersen, Mogens L; Cardoso, Daniel R

    2013-10-02

    The 1-hydroxyethyl radical is a central intermediate in oxidative reactions occurring in beer. The reactivity of thiol-containing compounds toward 1-hydroxyethyl radical was evaluated in beer model solutions using a competitive kinetic approach, employing the spin-trap 4-POBN as a probe and by using electron paramagnetic resonance to detect the generated 1-hydroxyethyl/4-POBN spin adduct. Thiol-containing compounds were highly reactive toward the 1-hydroxyethyl radical with apparent second-order rate constants close to the diffusion limit in water and ranging from 0.5 × 10⁹ L mol⁻¹ s⁻¹ for the His-Cys-Lys-Phe-Trp-Trp peptide to 6.1 × 10⁹ L mol⁻¹ s⁻¹ for the reduced lipid transfer protein 1 (LTP1) isolated from beer. The reactions gave rise to a moderate kinetic isotope effect (k(H)/k(D) = 2.3) suggesting that reduction of the 1-hydroxyethyl radical by thiol-containing compounds takes place by hydrogen atom abstraction from the RSH group rather than electron transfer. The content of reduced thiols in different beers was determined using a previously established method based on ThioGlo-1 as the thiol derivatization reagent and detection of the derivatized thiols by reverse-phase liquid chromatography coupled to a fluorescence detector. The total level of thiol in beer (oxidized and reduced) was determined after a reduction step employing 3,3',3″-phosphanetriyltripropanoic acid (TCEP) as the disulfide reductant. A good correlation among total protein and total thiol content in different beers was observed. The results suggest a similar ratio between reduced thiols and disulfides in all of the tested beers, which indicates a similar redox state.

  11. Human Cryptochrome-1 Confers Light Independent Biological Activity in Transgenic Drosophila Correlated with Flavin Radical Stability

    PubMed Central

    Vieira, Jacqueline; Jones, Alex R.; Danon, Antoine; Sakuma, Michiyo; Hoang, Nathalie; Robles, David; Tait, Shirley; Heyes, Derren J.; Picot, Marie; Yoshii, Taishi; Helfrich-Förster, Charlotte; Soubigou, Guillaume; Coppee, Jean-Yves; Klarsfeld, André; Rouyer, Francois; Scrutton, Nigel S.; Ahmad, Margaret

    2012-01-01

    Cryptochromes are conserved flavoprotein receptors found throughout the biological kingdom with diversified roles in plant development and entrainment of the circadian clock in animals. Light perception is proposed to occur through flavin radical formation that correlates with biological activity in vivo in both plants and Drosophila. By contrast, mammalian (Type II) cryptochromes regulate the circadian clock independently of light, raising the fundamental question of whether mammalian cryptochromes have evolved entirely distinct signaling mechanisms. Here we show by developmental and transcriptome analysis that Homo sapiens cryptochrome - 1 (HsCRY1) confers biological activity in transgenic expressing Drosophila in darkness, that can in some cases be further stimulated by light. In contrast to all other cryptochromes, purified recombinant HsCRY1 protein was stably isolated in the anionic radical flavin state, containing only a small proportion of oxidized flavin which could be reduced by illumination. We conclude that animal Type I and Type II cryptochromes may both have signaling mechanisms involving formation of a flavin radical signaling state, and that light independent activity of Type II cryptochromes is a consequence of dark accumulation of this redox form in vivo rather than of a fundamental difference in signaling mechanism. PMID:22427812

  12. Melt flow effect on interface stability during directional solidification

    NASA Astrophysics Data System (ADS)

    Fedorov, O. P.; Mashkovskiy, A. G.

    2015-03-01

    In the framework of the phenomenological macroscopic continuum theory using the approximation of a flat frontier layer the stability of solid-liquid interface at the directional solidification under melt motion along the interface is studied. The stability conditions are reduced to determination of eigenvalues of boundary value problem for infinitesimal disturbances of stationary process. In case of stagnant melt it is shown that in the plane "wave number-pulling rate" there are two areas of instability for low and large pulling rates divided by the area of steady-steady growth. Neutral stability curve calculated for rather large pulling rates for succinonitrile-acetone (SCN-Ac) system is close to the relevant values received by Mullins and Sekerka, while the absolute values of critical growth rates are of the same order of magnitude as the experimental ones. Melt flow along the interface leads to emergence of the third area of instability which is characterized by small values of wave numbers. When increasing the melt flow rate the area of instability extends towards great values of wave numbers.

  13. Direct observation of photodissociation products from phenylperoxyl radicals isolated in the gas phase.

    PubMed

    Maccarone, Alan T; Kirk, Benjamin B; Hansen, Christopher S; Griffiths, Thomas M; Olsen, Seth; Trevitt, Adam J; Blanksby, Stephen J

    2013-06-19

    Gas phase peroxyl radicals are central to our chemical understanding of combustion and atmospheric processes and are typically characterized by strong absorption in the UV (λ(max) ≈ 240 nm). The analogous maximum absorption feature for arylperoxyl radicals is predicted to shift to the visible but has not previously been characterized nor have any photoproducts arising from this transition been identified. Here we describe the controlled synthesis and isolation in vacuo of an array of charge-substituted phenylperoxyl radicals at room temperature, including the 4-(N,N,N-trimethylammonium)methyl phenylperoxyl radical cation (4-Me3N([+])CH2-C6H4OO(•)), using linear ion-trap mass spectrometry. Photodissociation mass spectra obtained at wavelengths ranging from 310 to 500 nm reveal two major photoproduct channels corresponding to homolysis of aryl-OO and arylO-O bonds resulting in loss of O2 and O, respectively. Combining the photodissociation yields across this spectral window produces a broad (FWHM ≈ 60 nm) but clearly resolved feature centered at λ(max) = 403 nm (3.08 eV). The influence of the charge-tag identity and its proximity to the radical site are investigated and demonstrate no effect on the identity of the two dominant photoproduct channels. Electronic structure calculations have located the vertical B ← X transition of these substituted phenylperoxyl radicals within the experimental uncertainty and further predict the analogous transition for unsubstituted phenylperoxyl radical (C6H5OO(•)) to be 457 nm (2.71 eV), nearly 45 nm shorter than previous estimates and in good agreement with recent computational values.

  14. Direct evidence for destruction of polychlorobiphenyls by OH radicals in the subtropical troposphere.

    PubMed

    Mandalakis, Manolis; Berresheim, Harald; Stephanou, Euripides G

    2003-02-01

    Although laboratory studies have indicated that OH radicals readily oxidize polychorobiphenyls (PCBs) in the gas-phase, this mechanism has never been positively demonstrated under real atmospheric conditions. By applying elaborated sampling and analytical techniques we achieved for the first time simultaneously a field study of the diurnal atmospheric cycle of OH radical and PCBs in a remote site of eastern Mediterranean. In all cases, the concentration of sigmaPCB (sum of 27 congeners) showed a characteristic depletion during daytime, while the concentration of OH radicals was at the maximum levels. By assuming that the depletion of PCBs was caused solely by the destruction from OH radicals, PCB-OH rate constants (KOH) of different PCB congeners were determined from field data by applying the relative rate method. Our field-determined KOH values were notably coherent with those previously measured in laboratory experiments. In all measurement periods, the KOH values consistently decreased in sequence for those compounds showing an increasing degree of chlorination on the biphenyl group. By taking into account KOH values and latitude-dependent concentration of OH radicals, it was estimated that, near to tropical and subtropical regions, the atmospheric lifetimes of PCBs 8 and 110 should be substantially low (10 and 20 days, respectively). A significant fraction of PCBs should be destroyed during their residence over tropical/subtropical regions, due to the intensive destruction by OH.

  15. Factors affecting the stability and equilibria of free radicals. XIII. N-alkoxy- and N-aralkoxypicrylamines and ESR spectra of the corresponding capto-dative persistent aminyls

    NASA Astrophysics Data System (ADS)

    Stanciuc, Gabriela; Caproiu, M. Teodor; Caragheorgheopol, Agneta; Caldararu, Horia; Balaban, Alexandru T.; Walter, Robert I.

    Five O-alkylhydroxylamines and three aralkylhydroxylamines have been picrylated to give O-alkyl- N-picrylhydroxylamines. These were converted to the corresponding N-(ar)alkoxy-picryl-aminyl radicals in toluene solution, and the ESR spectra were recorded. Simulations of the spectra with reasonable parameters and g values confirm the expected radical structures. Hyperfine coupling constants for nuclei in the picryl (acceptor) ring are smaller than those for the (ar)alkoxy group. This indication of competitive electron pair delocalization to the picryl ring, together with the long lifetimes of these radicals (compared with the symmetrically substituted diphenylaminyls), both support the concept of captodative stabilization.

  16. Direct ab initio dynamics studies of the hydrogen abstraction reactions of hydrogen atom with n-propyl radical and isopropyl radical.

    PubMed

    Li, Qian Shu; Zhang, Yue; Zhang, Shaowen

    2005-02-01

    The kinetics of the hydrogen abstraction reactions of hydrogen atom with n-propyl radical and isopropyl radical were studied using the direct ab initio dynamics approach. BHandHLYP/cc-pVDZ method was employed to optimize the geometries of stationary points as well as the points on the minimum energy path (MEP). The energies of all the points for the two reactions were further refined at the QCISD(T)/cc-pVTZ level of theory. No barrier was found at the QCISD(T)/cc-pVTZ//BHandHLYP/cc-pVDZ level of theory for both reactions. The forward and reverse rate constants were evaluated with both canonical variational transition state theory (CVT) and microcanonical variational transition state theory (mu VT) in the temperature range of 300-2,500 K. The fitted three-parameter Arrhenius expression of the calculated CVT rate constants at the QCISD(T)/cc-pVTZ//BHandHLYP/cc-pVDZ level of theory are k(CVT) (n-C3H7) = 1.68 x 10(-14) T(0.84) e((319.5/T)) cm3 molecule(-1) s(-1) and k(CVT) (iso-C3H7)=4.99 x 10(-14) T(0.90) e((159.5/T)) cm3 molecule(-1) s(-1) for reactions of n-C3H7 + H and iso-C3H7 + H, respectively, which are in good agreement with available literature data. The variational effects were analysed.

  17. Intensity-dependent direct solar radiation- and UVA-induced radical damage to human skin and DNA, lipids and proteins.

    PubMed

    Haywood, Rachel; Andrady, Carima; Kassouf, Nick; Sheppard, Nick

    2011-01-01

    Skin can be exposed to high-intensity UV-radiation in hot countries and during sunbed use; however, the free-radical damage at these intensities is unknown. We used electron spin resonance spectroscopy to measure free-radical generation in ex vivo human skin/substitutes +/- the spin-trap 5,5 dimethyl-1-pyrroline N-oxide (DMPO) exposed to solar-irradiation equivalent to Mediterranean sunlight. Skin-substitutes, model DNA-photosensitizer systems, lipids and proteins were also irradiated with low-intensity UVA/visible light. Without DMPO a broad singlet was detected (using both irradiations) in skin/substitutes, nail-keratin, tendon-collagen, phospholipid and DNA+melanin or riboflavin. In addition to lipid-derived (tentatively tert-alkoxyl/acyl-) and protein radicals detected with DMPO at lower intensities, isotropic carbon-, additional oxygen- and hydrogen-adducts were detected in solar-irradiated skin/substitutes at higher intensities. Carbon-adducts were detected in UVA-irradiated human skin cells, DNA+melanin or riboflavin and soybean-phospholipid. Anisotropic protein-adducts, comparable to adducts in solar-irradiated tendon-collagen, were absent in UVA-irradiated skin fibroblasts suggesting the trapping of extracellular collagen radicals. Absence of hydrogen-adducts in fibroblasts implies formation in the extracellular compartment. We conclude damage at high intensities is part cellular (carbon- and oxygen-radicals) and part extracellular (protein- and hydrogen/H(+)+e(-) ), and skin substitutes are suitable for sunscreen testing. While UVA absorption and lipid-oxidation is direct, DNA and protein-oxidation require photosensitisation.

  18. EPR and DFT study on the stabilization of radiation-generated methyl radicals in dehydrated Na-A zeolite.

    PubMed

    Danilczuk, Marek; Pogocki, Dariusz; Lund, Anders; Michalik, Jacek

    2006-12-07

    Electron paramagnetic resonance (EPR) spectroscopy was applied to study paramagnetic species stabilized in Na-A zeolite exposed to gaseous methane and gamma-irradiated at 77 K. Two types of EPR spectra were recorded during thermal annealing of zeolite up to room temperature. Owing to the results for the zeolite exposed to (13)CH(4) the multiplet observed at 110 K was assigned to a (.-)CH(3)...Na(+) complex. After decay of the multiplet, the isotropic quartet of methyl radical was recorded in the temperature range of 170-280 K. On the basis of the EPR parameters it is postulated that (.-)CH(3) radicals in this temperature region are able to freely rotate inside the zeolite cage. The structures of the (.-)CH(3)...Na(+) adsorption complex and respective hyperfine coupling constants were calculated by applying DFT quantum chemical methods. Two different models were applied to represent the zeolite framework: the 6T structure of one six-membered ring and the 3T cluster. The hyperfine coupling constants calculated for the (.-)CH(3)...Na(+) adsorption complex for both applied models show very good agreement with those obtained experimentally.

  19. New insights into the aquatic photochemistry of fluoroquinolone antibiotics: Direct photodegradation, hydroxyl-radical oxidation, and antibacterial activity changes.

    PubMed

    Ge, Linke; Na, Guangshui; Zhang, Siyu; Li, Kai; Zhang, Peng; Ren, Honglei; Yao, Ziwei

    2015-09-15

    The ubiquity and photoreactivity of fluoroquinolone antibiotics (FQs) in surface waters urge new insights into their aqueous photochemical behavior. This study concerns the photochemistry of 6 FQs: ciprofloxacin, danofloxacin, levofloxacin, sarafloxacin, difloxacin and enrofloxacin. Methods were developed to calculate their solar direct photodegradation half-lives (td,E) and hydroxyl-radical oxidation half-lives (tOH,E) in sunlit surface waters. The td,E values range from 0.56 min to 28.8 min at 45° N latitude, whereas tOH,E ranges from 3.24h to 33.6h, suggesting that most FQs tend to undergo fast direct photolysis rather than hydroxyl-radical oxidation in surface waters. However, a case study for levofloxacin and sarafloxacin indicated that the hydroxyl-radical oxidation induced risky photochlorination and resulted in multi-degradation pathways, such as piperazinyl hydroxylation and clearage. Changes in the antibacterial activity of FQs caused by photodegradation in various waters were further examined using Escherichia coli, and it was found that the activity evolution depended on primary photodegradation pathways and products. Primary intermediates with intact FQ nuclei retained significant antibacterial activity. These results are important for assessing the fate and risk of FQs in surface waters.

  20. Tuning the Reactivity of Radical through a Triplet Diradical Cu(II) Intermediate in Radical Oxidative Cross-Coupling

    PubMed Central

    Zhou, Liangliang; Yi, Hong; Zhu, Lei; Qi, Xiaotian; Jiang, Hanpeng; Liu, Chao; Feng, Yuqi; Lan, Yu; Lei, Aiwen

    2015-01-01

    Highly selective radical/radical cross-coupling is paid more attention in bond formations. However, due to their intrinsic active properties, radical species are apt to achieve homo-coupling instead of cross-coupling, which makes the selective cross-coupling as a great challenge and almost untouched. Herein a notable strategy to accomplish direct radical/radical oxidative cross-coupling has been demonstrated, that is metal tuning a transient radical to a persistent radical intermediate followed by coupling with another transient radical. Here, a transient nitrogen-centered radical is tuned to a persistent radical complex by copper catalyst, followed by coupling with a transient allylic carbon-centered radical. Firstly, nitrogen-centered radical generated from N-methoxybenzamide stabilized by copper catalyst was successfully observed by EPR. Then DFT calculations revealed that a triplet diradical Cu(II) complex formed from the chelation N-methoxybenzamide nitrogen-centered radical to Cu(II) is a persistent radical species. Moreover, conceivable nitrogen-centered radical Cu(II) complex was observed by high-resolution electrospray ionization mass spectrometry (ESI-MS). Ultimately, various allylic amides derivatives were obtained in good yields by adopting this strategy, which might inspire a novel and promising landscape in radical chemistry. PMID:26525888

  1. Direct Measurement of the Radiative Lifetime of Vibrationally Excited OH Radicals

    SciTech Connect

    Meerakker, Sebastiaan Y.T. van de; Vanhaecke, Nicolas; Meijer, Gerard; Loo, Mark P.J. van der; Groenenboom, Gerrit C.

    2005-07-01

    Neutral molecules, isolated in the gas phase, can be prepared in a long-lived excited state and stored in a trap. The long observation time afforded by the trap can then be exploited to measure the radiative lifetime of this state by monitoring the temporal decay of the population in the trap. This method is demonstrated here and used to benchmark the Einstein A coefficients in the Meinel system of OH. A pulsed beam of vibrationally excited OH radicals is Stark decelerated and loaded into an electrostatic quadrupole trap. The radiative lifetime of the upper {lambda}-doublet component of the X {sup 2}{pi}{sub 3/2}, v=1, J=3/2 level is determined as 59.0{+-}2.0 ms, in good agreement with the calculated value of 58.0{+-}1.0 ms.

  2. Stabilization and isomerization of radical cations generated by fast electron irradiation of unsaturated organic molecules in a solid argon matrix

    NASA Astrophysics Data System (ADS)

    Feldman, V. I.; Sukhov, F. F.; Orlov, A. Yu.; Tyulpina, I. V.; Ivanchenko, V. K.

    2006-01-01

    Matrix isolation EPR spectroscopy was used to study the fate of "hot" unsaturated radical cations produced by fast electron irradiation in solid argon. It was found that the radical cations of cis-2-butene, trans-2-butene and ethyl vinyl ether resulting from highly exothermic hole transfer (excess energy>6 eV) underwent effective relaxation in an argon matrix. 1-Butene radical cation exhibits isomerization to cis-2-butene radical cation. The role of molecular structure of organic radical cations in excess energy relaxation is discussed.

  3. The production mechanisms of OH radicals in a pulsed direct current plasma jet

    SciTech Connect

    Liu, X. Y.; Pei, X. K.; Lu, X. P.; Liu, D. W.; Ostrikov, K.

    2014-09-15

    The production mechanism of OH radicals in a pulsed DC plasma jet is studied by a two-dimensional (2-D) plasma jet model and a one-dimensional (1-D) discharge model. For the plasma jet in the open air, electron-impact dissociation of H{sub 2}O, electron neutralization of H{sub 2}O{sup +}, as well as dissociation of H{sub 2}O by O(1D) are found to be the main reactions to generate the OH species. The contribution of the dissociation of H{sub 2}O by electron is more than the others. The additions of N{sub 2}, O{sub 2}, air, and H{sub 2}O into the working gas increase the OH density outside the tube slightly, which is attributed to more electrons produced by Penning ionization. On the other hand, the additions of O{sub 2} and H{sub 2}O into the working gas increase the OH density inside the tube substantially, which is attributed to the increased O (1D) and H{sub 2}O concentration, respectively. The gas flow will transport high density OH out of the tube during pulse off period. It is also shown that the plasma chemistry and reactivity can be effectively controlled by the pulse numbers. These results are supported by the laser induced fluorescence measurements and are relevant to several applications of atmospheric-pressure plasmas in health care, medicine, and materials processing.

  4. Effect of hydrogen pressure on free radicals in direct coal liquefaction/coprocessing

    SciTech Connect

    Seehra, M.S.; Ibrahim, M.M.

    1995-12-31

    The objective of this study was to investigate the coprocessing of coal with waste tires and commingled plastics and to characterize the relevant catalysts, using high pressure/high temperature in-situ ESR (Electron Spin Resonance) spectroscopy. The recent results from high pressure ESR spectroscopy are emphasized. During this period, considerable progress was made in developing the high pressure capabilities in in-situ ESR spectroscopy and new results carried out in 1000 psi of H{sub 2}gas are presented. In these experiments, sapphire tubes were used to contain the high pressures at temperatures up to 500{degrees}C. Results of the experiments carried out under 1000 psi of H{sub 2} are compared with those under 1000 psi of non-interacting argon and with the earlier experiments in flowing H{sub 2} gas where the volatiles are removed by the flowing gas. In these experiments, the free radical density N of the Blind Canyon coal was measured at each temperature and pressure by double integration of the ESR signal and calibrating it against a standard. The details of the experimental apparatus and procedures have been described in earlier publications.

  5. Direct observation of unimolecular decay of CH3CH2CHOO Criegee intermediates to OH radical products

    NASA Astrophysics Data System (ADS)

    Fang, Yi; Liu, Fang; Klippenstein, Stephen J.; Lester, Marsha I.

    2016-07-01

    The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH3CH2CHOO, following vibrational activation under collision-free conditions. Complementary statistical Rice-Ramsperger-Kassel-Marcus calculations of the microcanonical unimolecular decay rate for CH3CH2CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronic structure calculations, contributes significantly to the decay rate. Infrared transitions of CH3CH2CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH3CH2CHOO of ca. 107 s-1, which are slower than those obtained for syn-CH3CHOO or (CH3)2COO reported previously [Fang et al., J. Chem. Phys. 144, 061102 (2016)] at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH3CH2CHOO under atmospheric conditions, giving a rate of 279 s-1 at 298 K.

  6. Direct observation of unimolecular decay of CH3CH2CHOO Criegee intermediates to OH radical products.

    PubMed

    Fang, Yi; Liu, Fang; Klippenstein, Stephen J; Lester, Marsha I

    2016-07-28

    The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH3CH2CHOO, following vibrational activation under collision-free conditions. Complementary statistical Rice-Ramsperger-Kassel-Marcus calculations of the microcanonical unimolecular decay rate for CH3CH2CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronic structure calculations, contributes significantly to the decay rate. Infrared transitions of CH3CH2CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH3CH2CHOO of ca. 10(7) s(-1), which are slower than those obtained for syn-CH3CHOO or (CH3)2COO reported previously [Fang et al., J. Chem. Phys. 144, 061102 (2016)] at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH3CH2CHOO under atmospheric conditions, giving a rate of 279 s(-1) at 298 K.

  7. The enhanced stability of the cross-linked hylan structure to hydroxyl (OH) radicals compared with the uncross-linked hyaluronan

    NASA Astrophysics Data System (ADS)

    Al-Assaf, Saphwan; Phillips, Glyn O.; Deeble, D. J.; Parsons, Barry; Starnes, Hazel; Von Sonntag, C.

    1995-08-01

    A comparison has been made of the relative stabilities of hyaluronan and hylan to degradation by OH radicals produced by γ-irradiation of aqueous solutions in N 2O, when G (yield per 100 eV) for OH radicals is 5.6 and H atoms 0.6. Using low angle light scattering and viscometric methods, the change in molecular weight of the polysaccharides was measured with increasing dose. From the yield/dose curves (expressed as breaks per molecule), the initial G value for hyaluronan degradation is ˜ 4. A further slow post-irradiation decrease in molecular weight is observed, which can be brought to completion by incubating the solutions for 1 h at 60°C. Thereafter, the G value for degradation is ˜ 6. A similar post-irradiation degradation was found for hylan. A technique using tetranitromethane (TNM) has been used to distinguish between two types of radicals formed on the hyaluronan backbone. Radicals of the 1-hydroxy-2-alkoxy type (C-2, C-4, C-2 and C3 of the glucuronic acid) would induce strand breakage by alkoxy elimination. For the equivalent alkoxy radical at C6 of the acetamido monosaccharide, ring opening would occur with formation of a hemi-acetal, leading also to strand breakage. The C-2 and C-3 radicals would eliminate water rather than produce breaks by β-alkoxy elimination. Thus three out of the initially formed radicals would produce breaks by β-alkoxy formation. These can be stabilised with TNM and distinguished. It is concluded that these are the radicals involved in the post-irradiation thermal degradation process. Comparison of hylan and hyaluronan is, therefore, most valid when this post-irradiation process has been completed. Therefore, all G values for degradation were measured after incubation for 1 h at 60°. This investigation establishes the greater stability of hylan ( Gdegradation = 2) compared to hylan ( Gdegradation = 6). Therefore, in an environment such as supplementation of an inflammed joint where OH radicals are released, hylan is able to

  8. Direct Observation of Entropic Stabilization of bcc Crystals Near Melting

    NASA Astrophysics Data System (ADS)

    Sprakel, Joris; Zaccone, Alessio; Spaepen, Frans; Schall, Peter; Weitz, David A.

    2017-02-01

    Crystals with low latent heat are predicted to melt from an entropically stabilized body-centered cubic symmetry. At this weakly first-order transition, strongly correlated fluctuations are expected to emerge, which could change the nature of the transition. Here we show how large fluctuations stabilize bcc crystals formed from charged colloids, giving rise to strongly power-law correlated heterogeneous dynamics. Moreover, we find that significant nonaffine particle displacements lead to a vanishing of the nonaffine shear modulus at the transition. We interpret these observations by reformulating the Born-Huang theory to account for nonaffinity, illustrating a scenario of ordered solids reaching a state where classical lattice dynamics fail.

  9. Reductive Umpolung of Carbonyl Derivatives with Visible‐Light Photoredox Catalysis: Direct Access to Vicinal Diamines and Amino Alcohols via α‐Amino Radicals and Ketyl Radicals

    PubMed Central

    Fava, Eleonora; Millet, Anthony; Nakajima, Masaki; Loescher, Sebastian

    2016-01-01

    Abstract Visible‐light‐mediated photoredox‐catalyzed aldimine–aniline and aldehyde–aniline couplings have been realized. The reductive single electron transfer (SET) umpolung of various carbonyl derivatives enabled the generation of intermediary ketyl and α‐amino radical anions, which were utilized for the synthesis of unsymmetrically substituted 1,2‐diamines and amino alcohols. PMID:27136443

  10. Radical bonding: structure and stability of bis(phenalenyl) complexes of divalent metals from across the periodic table.

    PubMed

    Craciun, Smaranda; Donald, Kelling J

    2009-07-06

    We examine the bonding possibilities of the bis(phenalenyl) MP(2) sandwich complexes of the divalent metals M = Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg, at the B3LYP level of theory. The outcome is an extraordinarily diverse class of low symmetry bis(phenalenyl)metal complexes in which bonding preferences and binding enthalpies differ dramatically. The lowest energy group 2 metal MP(2) complexes include an intriguing eta(1),eta(3) BeP(2) structure, and bent eta(6),eta(6) systems for M = Ca, Sr, and Ba. The group 12 bis(phenalenyl) complexes are thermodynamically unstable eta(1),eta(1) slip-sandwich structures. To better understand changes in the structural preferences going from the (eta(6),eta(6)) group 2 to the (eta(1),eta(1)) group 12 complexes, we explored the bonding in the bis(phenalenyl) complexes of transition metals with stable +2 oxidations states between Ca and Zn in period 4. The computed binding enthalpies are large and negative for nearly all of the minimum energy bis(phenalenyl) complexes of the group 2 and the transition metals; they are tiny for MgP(2), and are quite positive for the group 12 systems. The structural preferences and stability of the complexes is a subtle negotiation of several influences: the (un)availability of (n - 1)d and np, orbitals for bonding, the cost of the rehybridization at carbon sites in the phenalenyl rings in preparation for bonding to the metals, and the (P---P) interaction between the phenalenyl radicals.

  11. Manganese complexes of curcumin analogues: evaluation of hydroxyl radical scavenging ability, superoxide dismutase activity and stability towards hydrolysis.

    PubMed

    Vajragupta, Opa; Boonchoong, Preecha; Berliner, Lawrence J

    2004-03-01

    In order to improve the antioxidant property of curcumin and its analogue, diacetylcurcumin, manganese was incorporated into the structures in order to enhance superoxide dismutase (SOD) activity. Manganese (Mn) complexes of curcumin (CpCpx) and diacetylcurcumin (AcylCpCpx) were synthesized and firstly investigated for SOD activity and hydroxyl radical (HO*) scavenging ability. SOD activity was evaluated by both the nitroblue tetrazolium (NBT) reduction assay and electron paramagnetic resonance (EPR) with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trapping agent. CpCpx and AcylCpCpx inhibited the NBT reduction and decreased the DMPO/OOH adduct much greater than corresponding antioxidants or ligands, with IC50 values of 29.9 and 24.7 microM (NBT), and 1.09 and 2.40 mM (EPR), respectively. For EPR, potassium superoxide (KO2) was used as a source of O2- where qualitative results suggested that CpCpx and AcylCpCpx were SOD mimics, which catalyze the conversion of O2- to dioxygen and hydrogen peroxide (H2O2). Additionally, CpCpx and AcylCpCpx exhibited the great inhibition of DMPO/OH adduct formation with an IC50 of 0.57 and 0.37mM, respectively, which were comparable to that of curcumin (IC50 of 0.64 mM), indicating that both Mn complexes are also an effective HO* scavenger. The stability against hydrolysis in water, various buffers and human blood/serum was carried out in vitro. It was found that both Mn complexes were pH and salt concentration dependent, being more stable in basic pH. In the human blood/serum test, CpCpx was more stable against hydrolysis than AcylCpCpx with about 10 and 20% of free Mn2+ releasing, respectively.

  12. Stability analysis of direct-detection cooperative optical beam tracking

    NASA Astrophysics Data System (ADS)

    Marola, Giovanni; Santerini, Daniele; Prati, Giancarlo

    1989-05-01

    The system under consideration is a cooperative spatial tracking system between two stations for laser beam communications, using a quadrant photodetector at each station. After determining the equilibrium points of the cooperative system for the case of periodical relative motion, the authors concentrate on the stability of the transient behavior around the equilibrium points for the case of uniform angular relative motion. This case corresponds to an assumption that the steady-state motion is slow with respect to transient phenomena, and is applicable to currently foreseen intersatellite and deep-space optical communications. The analysis is aimed at determining the combined effect of the basic system parameters, such as propagation delay time, tracking loop gains, DC servomotors time constant, and point-ahead velocity error, on the stability and the transient behavior of the overall tracking system. The stability conditions and the transient response around the steady-state trajectory provide a tool for evaluating the consistency of the design parameters for a given propagation delay.

  13. Myosin binding surface on actin probed by hydroxyl radical footprinting and site-directed labels.

    PubMed

    Oztug Durer, Zeynep A; Kamal, J K Amisha; Benchaar, Sabrina; Chance, Mark R; Reisler, Emil

    2011-11-25

    Actin and myosin are the two main proteins required for cell motility and muscle contraction. The structure of their strongly bound complex-rigor state-is a key for delineating the functional mechanism of actomyosin motor. Current knowledge of that complex is based on models obtained from the docking of known atomic structures of actin and myosin subfragment 1 (S1; the head and neck region of myosin) into low-resolution electron microscopy electron density maps, which precludes atomic- or side-chain-level information. Here, we use radiolytic protein footprinting for global mapping of sites across the actin molecules that are impacted directly or allosterically by myosin binding to actin filaments. Fluorescence and electron paramagnetic resonance spectroscopies and cysteine actin mutants are used for independent, residue-specific probing of S1 effects on two structural elements of actin. We identify actin residue candidates involved in S1 binding and provide experimental evidence to discriminate between the regions of hydrophobic and electrostatic interactions. Focusing on the role of the DNase I binding loop (D-loop) and the W-loop residues of actin in their interactions with S1, we found that the emission properties of acrylodan and the mobility of electron paramagnetic resonance spin labels attached to cysteine mutants of these residues change strongly and in a residue-specific manner upon S1 binding, consistent with the recently proposed direct contacts of these loops with S1. As documented in this study, the direct and indirect changes on actin induced by myosin are more extensive than known until now and attest to the importance of actin dynamics to actomyosin function.

  14. Perturbative stability along the supersymmetric directions of the landscape

    SciTech Connect

    Sousa, Kepa

    2015-02-01

    We consider the perturbative stability of non-supersymmetric configurations in N=1 supergravity models with a spectator sector not involved in supersymmetry breaking. Motivated by the supergravity description of complex structure moduli in Large Volume Compactifications of type IIB-superstrings, we concentrate on models where the interactions are consistent with the supersymmetric truncation of the spectator fields, and we describe their couplings by a random ensemble of generic supergravity theories. We characterise the mass spectrum of the spectator fields in terms of the statistical parameters of the ensemble and the geometry of the scalar manifold. Our results show that the non-generic couplings between the spectator and the supersymmetry breaking sectors can stabilise all the tachyons which typically appear in the spectator sector before including the supersymmetry breaking effects, and we find large regions of the parameter space where the supersymmetric sector remains stable with probability close to one. We discuss these results about the stability of the supersymmetric sector in two physically relevant situations: non-supersymmetric Minkowski vacua, and slow-roll inflation driven by the supersymmetry breaking sector. For the class of models we consider, we have reproduced the regimes in which the KKLT and Large Volume Scenarios stabilise all supersymmetric moduli. We have also identified a new regime in which the supersymmetric sector is stabilised at a very robust type of dS minimum without invoking a large mass hierarchy.

  15. Mid-IR beam direction stabilization scheme for vibrational spectroscopy, including dual-frequency 2DIR.

    PubMed

    Nyby, Clara M; Leger, Joel D; Tang, Jianan; Varner, Clyde; Kireev, Victor V; Rubtsov, Igor V

    2014-03-24

    A compact laser beam direction stabilization scheme is developed that provides the angular stability of better than 50 μrad over a wide range of frequencies from 800 to 4000 cm-1. The schematic is fully automated and features a single MCT quadrant detector. The schematic was tested to stabilize directions of the two IR beams used for dual-frequency two-dimensional infrared (2DIR) measurements and showed excellent results: automatic tuning of the beam direction allowed achieving the alignment quality within 10% of the optimal alignment obtained manually. The schematic can be easily implemented to any nonlinear spectroscopic measurements in the mid-IR spectral region.

  16. Spatial distribution of stabilizer-derived nitroxide radicals during thermal degradation of poly(acrylonitrile-butadiene-styrene) copolymers: a unified picture from pulsed ELDOR and ESR imaging.

    PubMed

    Jeschke, Gunnar; Schlick, Shulamith

    2006-09-21

    Double Electron-Electron Resonance (DEER) provides information on the spatial distribution of radicals on the length scale of a few nanometres, while Electron Spin Resonance Imaging (ESRI) provides information on a length scale of millimetres with a resolution of about 100 micrometres. Despite the gap between these length scales, results from the two techniques are found to complement and support each other in the characterization of the identity and distribution of nitroxide radicals derived from the Hindered Amine Stabilizer (HAS) Tinuvin 770 in poly(acrylonitrile-butadiene-styrene) (ABS) copolymers. DEER measurements demonstrate that there is no significant formation of biradicals from the bifunctional HAS, and provide the distributions of local radical concentrations. These distributions are poorly resolved for model-free analysis of the DEER data by the Tikhonov regularization; the resolution was significantly improved by utilizing information obtained by ESRI. DEER data can be fitted with only one adjustable parameter, namely the average radical concentration, if 1D and 2D spectral--spatial ESRI results on both the spatial distribution of nitroxides and their distribution between the acrylonitrile--styrene-rich (SAN) and butadiene-rich (B) microphases are considered.

  17. ESR spectra of free radicals formed during the gas-phase photo-oxidation of formaldehyde: thermal stability of the HOCH 2OO radical

    NASA Astrophysics Data System (ADS)

    Zabel, F.; Sahetchian, K. A.; Chachaty, C.

    1987-03-01

    Formaldehyde/oxygen/nitrogen mixtures were photolyzed with UV light in a gas flow system. The reaction mixtures were analyzed by pumping a small fraction of the flowing gas through a microprobe, trapping the condensable compounds on a cold finger ( T = 96 K), and measuring the ESR spectrum of the solid. The ESR spectra consisted of partly overlapping components from HO 2 and HOCH 2OO radicals, the latter having g-tensor values g1 = 2.0025, g2 = 2.0090 and g3 = 2.0320. By simulating the experimental spectra with appropriate amplitude factors for their HO 2 and HOCH 2OO components, the concentration ratio [HO 2]/[HOCH 2OO] was determined. From these values and the H 2CO concentrations, measured by UV absorption, equilibrium constants k1, k-1 for the reaction HO 2+H 2CO ⇌ HOCH 2OO were calculated. The expression k1/ k-1 = 2.4 × 10 -26 exp(15.2 kcal mol -1/ RT) cm 3 was obtained from measurements in the temperature range 30-100° C.

  18. Model of diffusion-assisted direct laser writing by means of nanopolymerization in the presence of radical quencher

    SciTech Connect

    Pikulin, Alexander Bityurin, Nikita; Sokolov, Viktor I.

    2015-12-15

    Diffusion-assisted direct laser writing (DA-DLW) by multiphoton polymerization has been recently shown to be one of the most promising methods for the high-resolution 3D nanofabrication [I. Sakellari, et al., ACS Nano 6, 2302 (2012)]. The improvement of the writing spatial resolution has been observed under certain conditions when the mobile radical quencher (polymerization inhibitor) is added to the photosensitive composition. In this work, we present a theoretical study of this method, focusing on the resolution capabilities and optimal writing parameters. The laser beam absorption in the polymerizable composition causes the localized depletion of the quencher molecules. If the quencher depletion is balanced by its diffusion from the outside of the focal volume, the quasi-stationary non-equillibrium concentration spatial profile with zero minimum can be obtained. The polymer is then effectively formed only in the domain where the quencher is depleted. The spatially-distributed quencher, in this case, has the effect similar to that of the vortex beam in STimulated Emission Microscopy (STED)

  19. Dual-level direct dynamics studies for the reactions of dimethyl ether with hydrogen atom and methyl radical.

    PubMed

    Wu, Jia-Yan; Liu, Jing-Yao; Li, Ze-Sheng; Huang, Xu-Ri; Sun, Chia-Chung

    2003-04-15

    The dual-level direct dynamics approach is employed to study the dynamics of the CH(3)OCH(3) + H (R1) and CH(3)OCH(3) + CH(3) (R2) reactions. Low-level calculations of the potential energy surface are carried out at the MP2/6-311+G(d,p) level of theory. High-level energetic information is obtained at the QCISD(T) level of theory with the 6-311+G(3df,3pd) basis set. The dynamics calculations are performed using variational transition state theory (VTST) with the interpolated single-point energies (ISPE) method, and small-curvature tunneling (SCT) is included. It is shown that the reaction of CH(3)OCH(3) with H (R1) may proceed much easier and with a lower barrier height than the reaction with CH(3) radical (R2). The calculated rate constants and activation energies are in good agreement with the experimental values. The calculated rate constants are fitted to k(R1) = 1.16 x 10(-19) T(3) exp(-1922/T) and k(R2) = 1.66 x 10(-28) T(5) exp(-3086/T) cm(3) mol(-1) s(-1) over a temperature range 207-2100 K. Furthermore, a small variational effect and large tunneling effect in the lower temperature range are found for the two reactions.

  20. Dynamics and stability of directional jumps in the desert locust

    PubMed Central

    Gvirsman, Omer

    2016-01-01

    Locusts are known for their ability to jump large distances to avoid predation. The jump also serves to launch the adult locust into the air in order to initiate flight. Various aspects of this important behavior have been studied extensively, from muscle physiology and biomechanics, to the energy storage systems involved in powering the jump, and more. Less well understood are the mechanisms participating in control of the jump trajectory. Here we utilise video monitoring and careful analysis of experimental directional jumps by adult desert locusts, together with dynamic computer simulation, in order to understand how the locusts control the direction and elevation of the jump, the residual angular velocities resulting from the jump and the timing of flapping-flight initiation. Our study confirms and expands early findings regarding the instrumental role of the initial body position and orientation. Both real-jump video analysis and simulations based on our expanded dynamical model demonstrate that the initial body coordinates of position (relative to the hind-legs ground-contact points) are dominant in predicting the jumps’ azimuth and elevation angles. We also report a strong linear correlation between the jumps’ pitch-angular-velocity and flight initiation timing, such that head downwards rotations lead to earlier wing opening. In addition to offering important insights into the bio-mechanical principles of locust jumping and flight initiation, the findings from this study will be used in designing future prototypes of a bio-inspired miniature jumping robot that will be employed in animal behaviour studies and environmental monitoring applications. PMID:27703846

  1. Estimation of Directional Stability Derivatives at Moderate Angles and Supersonic Speeds

    NASA Technical Reports Server (NTRS)

    Kaattari, George E.

    1959-01-01

    A study of some of the important aerodynamic factors affecting the directional stability of supersonic airplanes is presented. The mutual interference fields between the body, the lifting surfaces, and the stabilizing surfaces are analyzed in detail. Evaluation of these interference fields on an approximate theoretical basis leads to a method for predicting directional stability of supersonic airplanes. Body shape, wing position and plan form, vertical tail position and plan form, and ventral fins are taken into account. Estimates of the effects of these factors are in fair agreement with experiment.

  2. Direct evidence of iNOS-mediated in vivo free radical production and protein oxidation in acetone-induced ketosis

    PubMed Central

    Stadler, Krisztian; Bonini, Marcelo G.; Dallas, Shannon; Duma, Danielle; Mason, Ronald P.; Kadiiska, Maria B.

    2008-01-01

    Diabetic patients frequently encounter ketosis that is characterized by the breakdown of lipids with the consequent accumulation of ketone bodies. Several studies have demonstrated that reactive species are likely to induce tissue damage in diabetes, but the role of the ketone bodies in the process has not been fully investigated. In this study, electron paramagnetic resonance (EPR) spectroscopy combined with novel spin-trapping and immunological techniques has been used to investigate in vivo free radical formation in a murine model of acetone-induced ketosis. A six-line EPR spectrum consistent with the α-(4-pyridyl-1-oxide)-N-t-butylnitrone radical adduct of a carbon-centered lipid-derived radical was detected in the liver extracts. To investigate the possible enzymatic source of these radicals, inducible nitric oxide synthase (iNOS) and NADPH oxidase knockout mice were used. Free radical production was unchanged in the NADPH oxidase knockout but much decreased in the iNOS knockout mice, suggesting a role for iNOS in free radical production. Longer-term exposure to acetone revealed iNOS overexpression in the liver together with protein radical formation, which was detected by confocal microscopy and a novel immunospin-trapping method. Immunohistochemical analysis revealed enhanced lipid peroxidation and protein oxidation as a consequence of persistent free radical generation after 21 days of acetone treatment in control and NADPH oxidase knockout but not in iNOS knockout mice. Taken together, our data demonstrate that acetone administration, a model of ketosis, can lead to protein oxidation and lipid peroxidation through a free radical-dependent mechanism driven mainly by iNOS overexpression. PMID:18559982

  3. Direct evidence of iNOS-mediated in vivo free radical production and protein oxidation in acetone-induced ketosis.

    PubMed

    Stadler, Krisztian; Bonini, Marcelo G; Dallas, Shannon; Duma, Danielle; Mason, Ronald P; Kadiiska, Maria B

    2008-08-01

    Diabetic patients frequently encounter ketosis that is characterized by the breakdown of lipids with the consequent accumulation of ketone bodies. Several studies have demonstrated that reactive species are likely to induce tissue damage in diabetes, but the role of the ketone bodies in the process has not been fully investigated. In this study, electron paramagnetic resonance (EPR) spectroscopy combined with novel spin-trapping and immunological techniques has been used to investigate in vivo free radical formation in a murine model of acetone-induced ketosis. A six-line EPR spectrum consistent with the alpha-(4-pyridyl-1-oxide)-N-t-butylnitrone radical adduct of a carbon-centered lipid-derived radical was detected in the liver extracts. To investigate the possible enzymatic source of these radicals, inducible nitric oxide synthase (iNOS) and NADPH oxidase knockout mice were used. Free radical production was unchanged in the NADPH oxidase knockout but much decreased in the iNOS knockout mice, suggesting a role for iNOS in free radical production. Longer-term exposure to acetone revealed iNOS overexpression in the liver together with protein radical formation, which was detected by confocal microscopy and a novel immunospin-trapping method. Immunohistochemical analysis revealed enhanced lipid peroxidation and protein oxidation as a consequence of persistent free radical generation after 21 days of acetone treatment in control and NADPH oxidase knockout but not in iNOS knockout mice. Taken together, our data demonstrate that acetone administration, a model of ketosis, can lead to protein oxidation and lipid peroxidation through a free radical-dependent mechanism driven mainly by iNOS overexpression.

  4. Radicalization and Radical Catalysis of Biomass Sugars: Insights from First-principles Studies

    PubMed Central

    Yang, Gang; Zhu, Chang; Zou, Xianli; Zhou, Lijun

    2016-01-01

    Ab initio and density functional calculations are conducted to investigate the radicalization processes and radical catalysis of biomass sugars. Structural alterations due to radicalization generally focus on the radicalized sites, and radicalization affects H-bonds in D-fructofuranose more than in D-glucopyranose, potentially with outcome of new H-bonds. Performances of different functionals and basis sets are evaluated for all radicalization processes, and enthalpy changes and Gibbs free energies for these processes are presented with high accuracy, which can be referenced for subsequent experimental and theoretical studies. It shows that radicalization can be utilized for direct transformation of biomass sugars, and for each sugar, C rather than O sites are always preferred for radicalization, thus suggesting the possibility to activate C-H bonds of biomass sugars. Radical catalysis is further combined with Brønsted acids, and it clearly states that functionalization fundamentally regulates the catalytic effects of biomass sugars. In presence of explicit water molecules, functionalization significantly affects the activation barriers and reaction energies of protonation rather than dehydration steps. Tertiary butyl and phenyl groups with large steric hindrances or hydroxyl and amino groups resulting in high stabilities for protonation products drive the protonation steps to occur facilely at ambient conditions. PMID:27405843

  5. Radicalization and Radical Catalysis of Biomass Sugars: Insights from First-principles Studies

    NASA Astrophysics Data System (ADS)

    Yang, Gang; Zhu, Chang; Zou, Xianli; Zhou, Lijun

    2016-07-01

    Ab initio and density functional calculations are conducted to investigate the radicalization processes and radical catalysis of biomass sugars. Structural alterations due to radicalization generally focus on the radicalized sites, and radicalization affects H-bonds in D-fructofuranose more than in D-glucopyranose, potentially with outcome of new H-bonds. Performances of different functionals and basis sets are evaluated for all radicalization processes, and enthalpy changes and Gibbs free energies for these processes are presented with high accuracy, which can be referenced for subsequent experimental and theoretical studies. It shows that radicalization can be utilized for direct transformation of biomass sugars, and for each sugar, C rather than O sites are always preferred for radicalization, thus suggesting the possibility to activate C-H bonds of biomass sugars. Radical catalysis is further combined with Brønsted acids, and it clearly states that functionalization fundamentally regulates the catalytic effects of biomass sugars. In presence of explicit water molecules, functionalization significantly affects the activation barriers and reaction energies of protonation rather than dehydration steps. Tertiary butyl and phenyl groups with large steric hindrances or hydroxyl and amino groups resulting in high stabilities for protonation products drive the protonation steps to occur facilely at ambient conditions.

  6. [Anti-radical activity of products of processing of holothurian Cucumaria japonica and their practical application for lipid stabilization].

    PubMed

    Tabakaeva, O V; Kalenik, T K; Tabakaev, A V

    2015-01-01

    Products of technological and biotechnological modification (acid and enzymatic hydrolyzates and hydrothermal extracts) of the holothurian Cucumariajaponica from the Far East region are the complex multicomponent systems containing biologically active agents of a sea origin that has to provide them biological activity. The research objective consisted in quantitative studying of anti-radical properties of acid, enzymatic hydrolyzates and hydrothermal extracts from soft fabrics of a holothurian from the Far East region (Cucumaria japonica) and their influence on oxidation of lipids in fat emulsion products. The reaction with stable free 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical was used as a model system. Radical relating activity of hydrolyzates and extracts from Cucumaria japonica varied over a wide range from 48 to 78%. The maximum radical binding activity was noted for acid hydrolyzates. The activity of the hydrolyzate from a nimbus and feelers of Cucumaria japonica was comparable with activity of ionol. It has been defined that levels of manifestation of anti-radical activity depended on a way of technological and biotechnological processing of raw materials. Studying of fractional composition of melanoidins of hydrolyzates and extracts from Cucumaria japonica established that they can be divided into fractions--with molecular masses about 10,000 and 1000 Da. The maximum content of melanoidins has been defined in fraction weighing about 1000 Da. Introduction of acid, enzymatic hydrolyzates and hydrothermal extracts from Cucumaria japonica in the composition of oil-fat emulsion systems allowed to slow down processes of lipid oxidation and triglyceride hydrolysis in mayonnaise. Introduction of hydrolyzates and hydrothermal extracts from Cucumaria japonica in an oil-fat emulsion product allowed to reduce peroxide value by 22-45%, acid value by 12-35% on the 90th days of storage. Acid hydrolysates of Cucumaria Japonica most significantly reduce the rate of

  7. Beta-Carotene chemical stability in nanoemulsions was improved by stabilized with Beta-Lactoglobulin-Catechin conjugates through free radical method

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Beta-lactoglobulin (BLG)-catechin conjugates were prepared by a free radical method and investigated with sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE), electrospray ionization-mass spectrometry (ESI-MS), and far-UV circular dichroism (CD). Covalent binding between BLG and cat...

  8. Towards reducing DBP formation potential of drinking water by favouring direct ozone over hydroxyl radical reactions during ozonation.

    PubMed

    De Vera, Glen Andrew; Stalter, Daniel; Gernjak, Wolfgang; Weinberg, Howard S; Keller, Jurg; Farré, Maria José

    2015-12-15

    When ozonation is employed in advanced water treatment plants to produce drinking water, dissolved organic matter reacts with ozone (O3) and/or hydroxyl radicals (OH) affecting disinfection byproduct (DBP) formation with subsequently used chlorine-based disinfectants. This study presents the effects of varying exposures of O3 and •OH on DBP concentrations and their associated toxicity generated after subsequent chlorination. DBP formation potential tests and in vitro bioassays were conducted after batch ozonation experiments of coagulated surface water with and without addition of tertiary butanol (t-BuOH, 10 mM) and hydrogen peroxide (H2O2, 1 mg/mg O3), and at different pH (6-8) and transferred ozone doses (0-1 mg/mg TOC). Although ozonation led to a 24-37% decrease in formation of total trihalomethanes, haloacetic acids, haloacetonitriles, and trihaloacetamides, an increase in formation of total trihalonitromethanes, chloral hydrate, and haloketones was observed. This effect however was less pronounced for samples ozonated at conditions favoring molecular ozone (e.g., pH 6 and in the presence of t-BuOH) over •OH reactions (e.g., pH 8 and in the presence of H2O2). Compared to ozonation only, addition of H2O2 consistently enhanced formation of all DBP groups (20-61%) except trihalonitromethanes. This proves that •OH-transformed organic matter is more susceptible to halogen incorporation. Analogously, adsorbable organic halogen (AOX) concentrations increased under conditions that favor •OH reactions. The ratio of unknown to known AOX, however, was greater at conditions that promote direct O3 reactions. Although significant correlation was found between AOX and genotoxicity with the p53 bioassay, toxicity tests using 4 in vitro bioassays showed relatively low absolute differences between various ozonation conditions.

  9. Stability analysis of the rotor of ultrasonic motor driving fluid directly.

    PubMed

    Changliang, Xia; Mengli, Wang

    2005-06-01

    The stability of the rotor of ultrasonic motor driving fluid directly is a key to its applications and control. This paper introduced the acoustic streaming and acoustic viscous stress near the boundary layer. Following this, the effect of acoustic viscous force on the stability of the rotor of ultrasonic motor driving fluid directly was presented in detail. The result showed that this system can be equivalent to a mass-spring and the spring constant can be used to weigh the stability of the rotor. By this model and relevant experiments, factors that affect the stability of the rotor such as the driving frequency, the rotor's weight and radius, the saturated acoustic streaming velocity, the mode number of stator vibration, the fluid's height and type are investigated and useful guidelines for design and application are obtained.

  10. Beta-carotene chemical stability in Nanoemulsions was improved by stabilized with beta-lactoglobulin-catechin conjugates through free radical method.

    PubMed

    Yi, Jiang; Zhang, Yuzhu; Liang, Rong; Zhong, Fang; Ma, Jianguo

    2015-01-14

    Beta-lactoglobulin (BLG)–catechin conjugates were prepared by a free radical method and investigated with sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE), electrospray ionization–mass spectrometry (ESI-MS), and far-UV circular dichroism (CD). Covalent binding between BLG and catechin were confirmed with SDS-PAGE and ESI-MS. About 93% of beta-lactoglobulin was conjugated with catechin or catecin fragments according to the gel intensity analysis software. Far-UV CD results showed that the content of β-sheet decreased with a corresponding increase in unordered structures after grafting. Both nanoemulsions with mean particle size between 160 and 170 nm were prepared. Both the rate of particle growth and the total beta-carotene (BC) loss at 50 °C were significantly greater than at 4 and 25 °C. The retention rates of BC in nanoemulsions were 27.8% and 48.6% for BLG and BLG–catechin conjugates, respectively, after 30 days of storage at 50 °C. The BC retention encapsulated in nanoemulsion was significantly improved using BLG–catechin conjugates, compared with BLG alone. The increase of BC retention in nanoemulsions encapsulated with BLG–catechin conjugates was due to the significant improvement of antioxidative properties (reducing power, free radical scavenging activity, and hydroxyl radical scavenging activity) of BLG after covalent binding with catechin. The results indicated that the proteins modified with polyphenols can be widely used in a labile bioactive compounds encapsulation delivery system.

  11. The formation and stability of the superoxide radical (O2-) on rock-forming minerals: Band gaps, hydroxylation state, and implications for Mars oxidant chemistry

    NASA Astrophysics Data System (ADS)

    Zent, Aaron P.; Ichimura, Andrew S.; Quinn, Richard C.; Harding, Heather K.

    2008-09-01

    We have examined the generation and stability of O2 - on TiO2 and albite, a common Na feldspar. We were not able to produce thermally stable superoxide on albite, in contrast to the results of Yen et al., who reported the generation of O2 - that was stable up to 200°C on labradorite, another common feldspar. The superoxide radical did form under UV irradiation at 77 K on albite that was not dehydrated but decayed rapidly at room temperature. On dehydrated albite, no superoxide signal was observed. We studied the kinetics of O2 - decomposition on hydrated albite and derived an activation energy, E a = 15.2 kJ/mol. Assuming pseudo first-order kinetics, a simple thermal model of Mars' regolith demonstrates that the surface O2 - population does not go to zero overnight; superoxide extinction at the surface is only complete when the seasonal CO2 cap covers the surface and surface photolysis is inhibited. Depending on the specific quantum efficiency of the e-/h+ generation process, a finite, non-equilibrium population of O2 - should be observable on Martian surface materials throughout the Martian year. However, on the basis of our inability to generate stable O2 - on hydrated albite via direct UV irradiation, we do not believe that this mechanism is capable of explaining the O2 release in the Viking Gas Exchange (GEx) results, since O2 release in that case was observed even after samples had been stored for 143 sols in the dark at 10°C, then heated to 145°C for 3 hours. At least two other potential pathways to the generation of O2 - are identified in this article. The first possibility is that metal oxides common on the Martian surface, particularly hematite, may be photoactive on Mars and play a role analogous to TiO2 in surface catalysis. Secondly, we found that superoxide that formed during the sorption or drying of a 1% H2O2 solution on TiO2, and potentially other oxides seems to be stable indefinitely.

  12. System for imposing directional stability on a rocket-propelled vehicle

    NASA Technical Reports Server (NTRS)

    Perkins, H. (Inventor)

    1976-01-01

    An improved system for use in imposing directional stability on a rocket-propelled vehicle is described. The system includes a pivotally supported engine-mounting platform, a gimbal ring mounted on the platform and adapted to pivotally support a rocket engine and an hydraulic actuator connected to the platform for imparting selected pivotal motion. An accelerometer and a signal comparator circuit for providing error intelligence indicative of aberration in vehicle acceleration is included along with an actuator control circuit connected with the actuator and responsive to error intelligence for imparting pivotal motion to the platform. Relocation of the engine's thrust vector is thus achieved for imparting directional stability to the vehicle.

  13. Stabilities of nitrogen containing heterocyclic radicals and geometrical influences on non-radiative processes in organic molecules

    NASA Technical Reports Server (NTRS)

    Evleth, E. M.

    1971-01-01

    Theoretical and experimental work on generating radicals by removal of a hydrogen atom from pyrrole, imidazole, indole, and carbazole is reported. Photophysical studies on indolizine and related aza-derivatives show that materials having large S2-S1 energy gaps might exhibit upper state fluorescence. Photodecomposition quantum yields of a series of sterically hindered p-aminobenzene diazonium cations in water were found structurally and wavelength dependent and unquenched in aqueous sodium bromide solutions. Photodecomposition of diazonium materials did not produce a metastable species with a longer lifetime than 1 msec.

  14. A crossed molecular beams study on the formation and energetics of the resonantly stabilized free i-C4H3(X2A‧) radical and its isotopomers

    NASA Astrophysics Data System (ADS)

    Gu, Xibin; Guo, Ying; Zhang, Fangtong; Mebel, Alexander M.; Kaiser, Ralf I.

    2007-06-01

    The chemical dynamics of the formation of the i-C 4H 3(X 2A') radical together with its partially deuterated isotopomers were investigated in eight crossed molecular beams experiments of dicarbon molecules in their XΣg+ electronic ground and in first excited a 3Π u state with (partially deuterated) ethylene at collision energies between 12.1 and 40.9 kJ mol -1. The center-of-mass angular distributions suggest that the reaction dynamics on the singlet and triplet surfaces are indirect and involve butatriene reaction intermediates. In case of the C 2/C 2H 4 reaction, the 'symmetric' singlet butatriene intermediate would lead solely to a symmetric center-of-mass angular distribution; however, in combination with isotopically labeled reactants, we deduced that triplet butatriene intermediates excited to B/C like rotations likely account for the observed asymmetries in the center-of-mass angular distributions at higher collision energies. The translational energy distributions are also indicative of the involvement of both the triplet and singlet surfaces which lead both to the i-C 4H 3(X 2A') radicals through lose (singlet) and tight (triplet) exit transitions states. Also, our experiments helped to determine the enthalpy of formation of the i-C 4H 3(X 2A') radical to be about 504 ± 10 kJ mol -1 in good agreement with previous computational studies suggesting 498-499 kJ mol -1. The explicit identification of the resonance-stabilized i-C 4H 3(X 2A') radical proposes that the reaction of dicarbon with ethylene can lead to formation of i-C 4H 3(X 2A') in combustion flames; the n-C 4H 3(X 2A') isomer is not formed in this reaction. This conclusion correlates nicely with Hansen's et al. flame experiments at the advanced light source observing only the i-C 4H 3(X 2A') radical in hydrocarbon flames.

  15. Direct fiber comb stabilization to a gas-filled hollow-core photonic crystal fiber.

    PubMed

    Wu, Shun; Wang, Chenchen; Fourcade-Dutin, Coralie; Washburn, Brian R; Benabid, Fetah; Corwin, Kristan L

    2014-09-22

    We have isolated a single tooth from a fiber laser-based optical frequency comb for nonlinear spectroscopy and thereby directly referenced the comb. An 89 MHz erbium fiber laser frequency comb is directly stabilized to the P(23) (1539.43 nm) overtone transition of (12)C(2)H(2) inside a hollow-core photonic crystal fiber. To do this, a single comb tooth is isolated and amplified from 20 nW to 40 mW with sufficient fidelity to perform saturated absorption spectroscopy. The fractional stability of the comb, ~7 nm away from the stabilized tooth, is shown to be 6 × 10(-12) at 100 ms gate time, which is over an order of magnitude better than that of a comb referenced to a GPS-disciplined Rb oscillator.

  16. Hypersonic lateral and directional stability characteristics of aeroassist flight experiment configuration in air and CF4

    NASA Technical Reports Server (NTRS)

    Micol, John R.; Wells, William L.

    1993-01-01

    Hypersonic lateral and directional stability characteristics measured on a 60 deg half-angle elliptical cone, which was raked at an angle of 73 deg from the cone centerline and with an ellipsoid nose (ellipticity equal to 2.0 in the symmetry plane), are presented for angles of attack from -10 to 10 deg. The high normal-shock density ratio of a real gas was simulated by tests at a Mach number of 6 in air and CF4 (density ratio equal to 5.25 and 12.0, respectively). Tests were conducted in air at Mach 6 and 10 and in CF4 at Mach 6 to examine the effects of Mach number, Reynolds number, and normal-shock density ratio. Changes in Mach number from 6 to 10 in air or in Reynolds number by a factor of 4 at Mach 6 had a negligible effect on lateral and directional stability characteristics. Variations in normal-shock density ratio had a measurable effect on lateral and directional aerodynamic coefficients, but no significant effect on lateral and directional stability characteristics. Tests in air and CF4 indicated that the configuration was laterally and directionally stable through the test range of angle of attack.

  17. Generalized direct Lyapunov method for the analysis of stability and attraction in general time systems

    SciTech Connect

    Druzhinina, O V; Shestakov, A A

    2002-10-31

    A generalized direct Lyapunov method is put forward for the study of stability and attraction in general time systems of the following types: the classical dynamical system in the sense of Birkhoff, the general system in the sense of Zubov, the general system in the sense of Seibert, the general system with delay, and the general 'input-output' system. For such systems, with the help of generalized Lyapunov functions with respect to two filters, two quasifilters, or two filter bases, necessary and sufficient conditions for stability and attraction are obtained under minimal assumptions about the mathematical structure of the general system.

  18. Some effects of nonlinear variation in the directional-stability and damping-in-yawing derivatives on the lateral stability of an airplane

    NASA Technical Reports Server (NTRS)

    Sternfield, Leonard

    1951-01-01

    A theoretical investigation has been made to determine the effect of nonlinear stability derivatives on the lateral stability of an airplane. Motions were calculated on the assumption that the directional-stability and the damping-in-yawing derivatives are functions of the angle of sideslip. The application of the Laplace transform to the calculation of an airplane motion when certain types of nonlinear derivatives are present is described in detail. The types of nonlinearities assumed correspond to the condition in which the values of the directional-stability and damping-in-yawing derivatives are zero for small angle of sideslip.

  19. Increased functional stability and homogeneity of viral envelope spikes through directed evolution.

    PubMed

    Leaman, Daniel P; Zwick, Michael B

    2013-02-01

    The functional HIV-1 envelope glycoprotein (Env) trimer, the target of anti-HIV-1 neutralizing antibodies (Abs), is innately labile and coexists with non-native forms of Env. This lability and heterogeneity in Env has been associated with its tendency to elicit non-neutralizing Abs. Here, we use directed evolution to overcome instability and heterogeneity of a primary Env spike. HIV-1 virions were subjected to iterative cycles of destabilization followed by replication to select for Envs with enhanced stability. Two separate pools of stable Env variants with distinct sequence changes were selected using this method. Clones isolated from these viral pools could withstand heat, denaturants and other destabilizing conditions. Seven mutations in Env were associated with increased trimer stability, primarily in the heptad repeat regions of gp41, but also in V1 of gp120. Combining the seven mutations generated a variant Env with superior homogeneity and stability. This variant spike moreover showed resistance to proteolysis and to dissociation by detergent. Heterogeneity within the functional population of hyper-stable Envs was also reduced, as evidenced by a relative decrease in a proportion of virus that is resistant to the neutralizing Ab, PG9. The latter result may reflect a change in glycans on the stabilized Envs. The stabilizing mutations also increased the proportion of secreted gp140 existing in a trimeric conformation. Finally, several Env-stabilizing substitutions could stabilize Env spikes from HIV-1 clades A, B and C. Spike stabilizing mutations may be useful in the development of Env immunogens that stably retain native, trimeric structure.

  20. Safe storage of radical initiators within a polyaromatic nanocapsule

    NASA Astrophysics Data System (ADS)

    Yamashina, Masahiro; Sei, Yoshihisa; Akita, Munetaka; Yoshizawa, Michito

    2014-08-01

    2,2'-Azobisisobutyronitrile and its derivatives are standard reagents for polymer and organic syntheses that generate radical species on stimuli by light or heat. Radical initiators like the azo compounds are unstable so that they should be kept in the dark at low temperature to avoid photochemical and thermal decomposition as well as accidental explosion. Here we report the spontaneous and quantitative encapsulation of the radical initiators by a supramolecular nanocapsule in aqueous solution. We demonstrate the remarkable stability of the initiators toward light and heat in the well-defined cavity shielded by the polyaromatic capsule shell. The incarcerated and stabilized initiators can be directly utilized for the radical polymerization of olefins on spontaneous release of the initiators from the capsule under the reaction conditions.

  1. Direct production of OH radicals upon CH overtone activation of (CH3)2COO Criegee intermediates

    NASA Astrophysics Data System (ADS)

    Liu, Fang; Beames, Joseph M.; Lester, Marsha I.

    2014-12-01

    Ozonolysis of alkenes, a principle non-photolytic source of atmospheric OH radicals, proceeds through unimolecular decay of energized carbonyl oxide intermediates, known as Criegee intermediates. In this work, cold dimethyl-substituted Criegee intermediates are vibrationally activated in the CH stretch overtone region to drive the 1,4 hydrogen transfer reaction that leads to OH radical products. IR excitation of (CH3)2COO reveals the vibrational states with sufficient oscillator strength, coupling to the reaction coordinate, and energy to surmount the effective barrier (≤ 16.0 kcal mol-1) to reaction. Insight on the dissociation dynamics is gleaned from homogeneous broadening of the spectral features, indicative of rapid intramolecular vibrational energy redistribution and/or reaction, as well as the quantum state distribution of the OH X2Π (v = 0) products. The experimental results are compared with complementary electronic structure calculations, which provide the IR absorption spectrum and geometric changes along the intrinsic reaction coordinate. Additional theoretical analysis reveals the vibrational modes and couplings that permit (CH3)2COO to access to the transition state region for reaction. The experimental and theoretical results are compared with an analogous recent study of the IR activation of syn-CH3CHOO and its unimolecular decay to OH products [F. Liu, J. M. Beames, A. S. Petit, A. B. McCoy, and M. I. Lester, Science 345, 1596 (2014)].

  2. Convective stability in the Rayleigh-Benard and directional solidification problems - High-frequency gravity modulation

    NASA Technical Reports Server (NTRS)

    Wheeler, A. A.; Mcfadden, G. B.; Murray, B. T.; Coriell, S. R.

    1991-01-01

    The effect of vertical, sinusoidal, time-dependent gravitational acceleration on the onset of solutal convection during directional solidification is analyzed in the limit of large modulation frequency. When the unmodulated state is unstable, the modulation amplitude required to stabilize the system is determined by the method of averaging. When the unmodulated state is stable, resonant modes of instability occur at large modulation amplitude. These are analyzed using matched asymptotic expansions to elucidate the boundary-layer structure for both the Rayleigh-Benard and directional solidification configurations. Based on these analyses, a thorough examination of the dependence of the stability criteria on the unmodulated Rayleigh number, Schmidt number, and distribution coefficient, is carried out.

  3. Stability analysis of direct contact heat exchangers subject to system perturbations. Final report, Task 2

    SciTech Connect

    Jacobs, H.R.

    1985-01-01

    This report includes a project summary, copies of two papers resulting from the work and the Ph.D. Dissertation of Dr. Mehdi Golafshani entitled, ''Stability of a Direct Contact Heat Exchanger''. Specifically, the work deals with the operational stability of a spray column type heat exchanger subject to disturbances typical of those which can occur for geothermal applications. A computer program was developed to solve the one-dimensional transient two-phase flow problem and it was applied to the design of a spray column. The operation and design of the East Mesa 500kW/sub e/ direct contactor was assessed. It is shown that the heat transfer is governed by the internal resistance of the dispersed phase. In fact, the performance is well-represented by diffusion of heat within the drops. 5 refs.

  4. Direct Epoxidation of Propylene over Stabilized Cu+ Surface Sites on Ti Modified Cu2O

    DOE PAGES

    Yang, X.; Kattel, S.; Xiong, K.; ...

    2015-07-17

    Direct propylene epoxidation by O2 is a challenging reaction because of the strong tendency for complete combustion. Results from the current study demonstrate the feasibility to tune the epoxidation selectivity by generating highly dispersed and stabilized Cu+ active sites in a TiCuOx mixed oxide. The TiCuOx surface anchors the key surface intermediate, oxametallacycle, leading to higher selectivity for epoxidation of propylene.

  5. Lateral and Directional Stability and Control Characteristics of a C-54D Airplane

    NASA Technical Reports Server (NTRS)

    Talmage, Donald B; Reeder, John P

    1949-01-01

    Data are presented showing compliance of C-54D with Army and Navy lateral and directional stability and control specifications. The airplane met requirements except for the rolling effectiveness pb/2V, the aileron forces in rolling, and the rudder forces in the asymmetric power conditions which were marginal. Also, the results of special tests concerning asymmetric power, asymmetric loading, and pitch due to yaw requested by the Airplane Handling Qualities Subcommittee of the Air Transport Association are presented.

  6. A computational examination of directional stability for smooth and chined forebodies at high-alpha

    NASA Technical Reports Server (NTRS)

    Ravi, Ramakrishnan; Mason, William H.

    1992-01-01

    Computational Fluid Dynamics (CFD) has been used to study aircraft forebody flowfields at low-speed, angle-of-attack conditions with sideslip. The purpose is to define forebody geometries which provide good directional stability characteristics under these conditions. The flows over the experimentally investigated F-5A forebody and chine type configuration, previously computed by the authors, were recomputed with better grid topology and resolution. The results were obtained using a modified version of CFL3D (developed at NASA Langley) to solve either the Euler equations or the Reynolds equations employing the Baldwin-Lomax turbulence model with the Degani-Schiff modification to account for massive crossflow separation. Based on the results, it is concluded that current CFD methods can be used to investigate the aerodynamic characteristics of forebodies to achieve desirable high angle-of-attack characteristics. An analytically defined generic forebody model is described, and a parametric study of various forebody shapes was then conducted to determine which shapes promote a positive contribution to directional stability at high angle-of-attack. An unconventional approach for presenting the results is used to illustrate how the positive contribution arises. Based on the results of this initial parametric study, some guidelines for aerodynamic design to promote positive directional stability are presented.

  7. Radical Reaction Control in the AdoMet Radical Enzyme CDG Synthase (QueE): Consolidate, Destabilize, Accelerate

    PubMed Central

    2016-01-01

    Abstract Controlling radical intermediates and thus catalysing and directing complex radical reactions is a central feature of S‐adensosylmethionine (SAM)‐dependent radical enzymes. We report ab initio and DFT calculations highlighting the specific influence of ion complexation, including Mg2+, identified as a key catalytic component on radical stability and reaction control in 7‐carboxy‐7‐deazaguanine synthase (QueE). Radical stabilisation energies (RSEs) of key intermediates and radical clock‐like model systems of the enzyme‐catalysed rearrangement of 6‐carboxytetrahydropterin (CPH4), reveals a directing role of Mg2+ in destabilising both the substrate‐derived radical and corresponding side reactions, with the effect that the experimentally‐observed rearrangement becomes dominant over possible alternatives. Importantly, this is achieved with minimal disruption of the thermodynamics of the substrate itself, affording a novel mechanism for an enzyme to both maintain binding potential and accelerate the rearrangement step. Other mono and divalent ions were probed with only dicationic species achieving the necessary radical conformation to facilitate the reaction. PMID:27859789

  8. Impact of the N5-proximal Asn on the Thermodynamic and Kinetic Stability of the Semiquinone Radical in Photolyase*

    PubMed Central

    Damiani, Michael J.; Nostedt, Jordan J.; O'Neill, Melanie A.

    2011-01-01

    Flavoproteins can dramatically adjust the thermodynamics and kinetics of electron transfer at their flavin cofactor. A versatile regulatory tool is proton transfer. Here, we demonstrate the significance of proton-coupled electron transfer to redox tuning and semiquinone (sq) stability in photolyases (PLs) and cryptochromes (CRYs). These light-responsive proteins share homologous overall architectures and FAD-binding pockets, yet they have evolved divergent functions that include DNA repair, photomorphogenesis, regulation of circadian rhythm, and magnetoreception. We report the first measurement of both FAD redox potentials for cyclobutane pyrimidine dimer PL (CPD-PL, Anacystis nidulans). These values, E1(hq/sq) = −140 mV and E2(sq/ox) = −219 mV, where hq is FAD hydroquinone and ox is oxidized FAD, establish that the sq is not thermodynamically stabilized (ΔE = E2 − E1 = −79 mV). Results with N386D CPD-PL support our earlier hypothesis of a kinetic barrier to sq oxidation associated with proton transfer. Both E1 and E2 are upshifted by ∼100 mV in this mutant; replacing the N5-proximal Asn with Asp decreases the driving force for sq oxidation. However, this Asp alleviates the kinetic barrier, presumably by acting as a proton shuttle, because the sq in N386D CPD-PL oxidizes orders of magnitude more rapidly than wild type. These data clearly reveal, as suggested for plant CRYs, that an N5-proximal Asp can switch on proton transfer and modulate sq reactivity. However, the effect is context-dependent. More generally, we propose that PLs and CRYs tune the properties of their N5-proximal residue to adjust the extent of proton transfer, H-bonding patterns, and changes in protein conformation associated with electron transfer at the flavin. PMID:21131361

  9. Predicting solvent stability in aprotic electrolyte Li-air batteries: nucleophilic substitution by the superoxide anion radical (O2(•-)).

    PubMed

    Bryantsev, Vyacheslav S; Giordani, Vincent; Walker, Wesley; Blanco, Mario; Zecevic, Strahinja; Sasaki, Kenji; Uddin, Jasim; Addison, Dan; Chase, Gregory V

    2011-11-10

    There is increasing evidence that cyclic and linear carbonates, commonly used solvents in Li ion battery electrolytes, are unstable in the presence of superoxide and thus are not suitable for use in rechargeable Li-air batteries employing aprotic electrolytes. A detailed understanding of related decomposition mechanisms provides an important basis for the selection and design of stable electrolyte materials. In this article, we use density functional theory calculations with a Poisson-Boltzmann continuum solvent model to investigate the reactivity of several classes of aprotic solvents in nucleophilic substitution reactions with superoxide. We find that nucleophilic attack by O(2)(•-) at the O-alkyl carbon is a common mechanism of decomposition of organic carbonates, sulfonates, aliphatic carboxylic esters, lactones, phosphinates, phosphonates, phosphates, and sulfones. In contrast, nucleophilic reactions of O(2)(•-) with phenol esters of carboxylic acids and O-alkyl fluorinated aliphatic lactones proceed via attack at the carbonyl carbon. Chemical functionalities stable against nucleophilic substitution by superoxide include N-alkyl substituted amides, lactams, nitriles, and ethers. The results establish that solvent reactivity is strongly related to the basicity of the organic anion displaced in the reaction with superoxide. Theoretical calculations are complemented by cyclic voltammetry to study the electrochemical reversibility of the O(2)/O(2)(•-) couple containing tetrabutylammonium salt and GCMS measurements to monitor solvent stability in the presence of KO(2)(•) and a Li salt. These experimental methods provide efficient means for qualitatively screening solvent stability in Li-air batteries. A clear correlation between the computational and experimental results is established. The combination of theoretical and experimental techniques provides a powerful means for identifying and designing stable solvents for rechargeable Li-air batteries.

  10. Designing and building nanowires: directed nanocrystal self-assembly into radically branched and zigzag PbS nanowires

    NASA Astrophysics Data System (ADS)

    Xu, Fan; Ma, Xin; Gerlein, L. Felipe; Cloutier, Sylvain G.

    2011-07-01

    Lead sulfide nanowires with controllable optoelectronic properties would be promising building blocks for various applications. Here, we report the hot colloidal synthesis of radically branched and zigzag nanowires through self-attachment of star-shaped and octahedral nanocrystals in the presence of multiple surfactants. We obtained high-quality single-crystal nanowires with uniform diameter along the entire length, and the size of the nanowire can be tuned by tailoring the reaction parameters. This slow oriented attachment provides a better understanding of the intricacies of this complex nanocrystal assembly process. Meanwhile, these self-assembled nanowire structures have appealing lateral conformations with narrow side arms or highly faceted edges, where strong quantum confinement can occur. Consequently, the single-crystal nanowire structures exhibit strong photoluminescence in the near-infrared region with a large blue-shift compared to the bulk material.

  11. Development and validation of a simple high performance thin layer chromatography method combined with direct 1,1-diphenyl-2-picrylhydrazyl assay to quantify free radical scavenging activity in wine.

    PubMed

    Agatonovic-Kustrin, Snezana; Morton, David W; Yusof, Ahmad P

    2016-04-15

    The aim of this study was to: (a) develop a simple, high performance thin layer chromatographic (HPTLC) method combined with direct 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay to rapidly assess and compare free radical scavenging activity or anti-oxidant activity for major classes of polyphenolics present in wines; and (b) to investigate relationship between free radical scavenging activity to the total polyphenolic content (TPC) and total antioxidant capacity (TAC) in the wine samples. The most potent free radical scavengers that we tested for in the wine samples were found to be resveratrol (polyphenolic non-flavonoid) and rutin (flavonoid), while polyphenolic acids (caffeic acid and gallic acid) although present in all wine samples were found to be less potent free radical scavengers. Therefore, the total antioxidant capacity was mostly affected by the presence of resveratrol and rutin, while total polyphenolic content was mostly influenced by the presence of the less potent free radical scavengers gallic and caffeic acids.

  12. The effect of resistance exercise direction for hip joint stabilization on lateral abdominal muscle thickness

    PubMed Central

    Jung, Ju-Hyeon; Lee, Sang-Yeol

    2016-01-01

    The aim of this study was to determine the effects of resistance direction in hip joint stabilization exercise on change in lateral abdominal muscle thickness in healthy adults. Twenty-six healthy adults were randomly allocated to either a hip stabilization exercise by hip straight resistance group (n=12) or a hip diagonal resistance group (n=14). The outcome measures included contraction thickness ratio in transversus abdominis (TrA), internal oblique (IO) and external oblique, and TrA lateral slide were assessed during the abdominal drawing-in maneuver by b-mode ultrasound. The researcher measured the abdominal muscle thickness of each participant before the therapist began the intervention and at the moment intervention was applied. There was a significant difference in lateral abdominal muscle thickness between the straight resistance exercise of hip joint group and the diagonal resistance exercise of hip joint group. Significant differences were found between the two groups in the percentage of change of muscle thickness of the TrA (P=0.018) and in the thickness ratio of the TrA (P=0.018). Stability exercise accompanied by diagonal resistance on the hip joint that was applied in this study can induce automatic contraction of the IO and TrA, which provides stability to the lumbar spine. PMID:27807520

  13. Lateral-directional stability and control characteristics of the Quiet Short-Haul Research Aircraft (QSRA)

    NASA Technical Reports Server (NTRS)

    Stephenson, Jack D.; Jeske, James A.; Hardy, Gordon H.

    1990-01-01

    The results are presented of flight experiments to determine the lateral-directional stability and control characteristics of the Quiet Short-Haul Research Aircraft (QSRA), an experimental aircraft designed to furnish information on various aerodynamic characteristics of a transport type of airplane that makes use of the upper-surface blown (USB) flap technology to achieve short takeoff and landing (STOL) performance. The flight program designed to acquire the data consisted of maneuvers produced by rudder and control-wheel inputs with the airplane in several configurations that had been proposed for landing approach and takeoff operation. The normal stability augmentation system was not engaged during these maneuvers. Time-history records from the maneuvers were analyzed with a parameter estimation procedure to extract lateral-directional stability and control derivatives. For one aircraft configuration in which the USB flaps were deflected 50 deg, several maneuvers were performed to determine the effects of varying the average angle of attack, varying the thrust coefficient, and setting the airplane's upper surface spoilers at a 13 deg symmetrical bias angle . The effects on the lateral characteristics of deflecting the spoilers were rather small and generally favorable. The data indicate that for one test, conducted at low thrust (a thrust coefficient of 0.38), compared with results from tests at thrust coefficients of 0.77 and larger, there was a significant decrease in the lateral control effectiveness, in the yaw damping and in the directional derivative. The directional derivative was also decreased (by about 30 percent) when the average angle of attack of the test was increased from 3 to 16 deg.

  14. Direct Grout Stabilization of High Cesium Salt Waste: Cesium Leaching Studies

    SciTech Connect

    Langton, C.A.

    1999-09-19

    'The direct grout alternative is a viable option for treatment/stabilization and disposal of salt waste containing Cs-137 concentrations of 1-3 Ci/gal. The significant difference between these waste solutions is that the high cesium salt solution will contain between 1 and 3 Curies of Cs-137 per gallon compared to a negligible amount in the current salt solution. This difference will require special engineering and shielding for a direct grout processing facility and disposal units to achieve acceptable radiation exposure conditions. The higher cesium concentrations in the direct grout also require that the cesium leaching be evaluated as a function of curing temperature. ANS 16.1 leaching results and distribution ratios (approximations of distribution coefficients) as a function of temperature are presented in this report.'

  15. Transient Dynamics of Electric Power Systems: Direct Stability Assessment and Chaotic Motions

    NASA Astrophysics Data System (ADS)

    Chu, Chia-Chi

    A power system is continuously experiencing disturbances. Analyzing, predicting, and controlling transient dynamics, which describe transient behaviors of the power system following disturbances, is a major concern in the planning and operation of a power utility. Important conclusions and decisions are made based on the result of system transient behaviors. As today's power network becomes highly interconnected and much more complex, it has become essential to enhance the fundamental understanding of transient dynamics, and to develop fast and reliable computational algorithms. In this thesis, we emphasize mathematical rigor rather than physical insight. Nonlinear dynamical system theory is applied to study two fundamental topics: direct stability assessment and chaotic motions. Conventionally, power system stability is determined by calculating the time-domain transient behaviors for a given disturbance. In contrast, direct methods identify whether or not the system will remain stable once the disturbance is removed by comparing the corresponding energy value of the post-fault system to a calculated threshold value. Direct methods not only avoid the time-consuming numerical integration of the time domain approach, but also provide a quantitative measure of the degree of system stability. We present a general framework for the theoretical foundations of direct methods. Canonical representations of network-reduction models as well as network-preserving models are proposed to facilitate the analysis and the construction of energy functions of various power system models. An advanced and practical method, called the boundary of stability region based controlling unstable equilibrium point method (BCU method), of computing the controlling unstable equilibrium point is proposed along with its theoretical foundation. Numerical solution algorithms capable of supporting on-line applications of direct methods are provided. Further possible improvements and enhancements are

  16. Radical aminomethylation of imines.

    PubMed

    Fujii, Shintaro; Konishi, Takehito; Matsumoto, Yusuke; Yamaoka, Yousuke; Takasu, Kiyosei; Yamada, Ken-Ichi

    2014-09-05

    Taking advantage of the high level of performance of N-alkoxycarbonyl-imines, we achieved the first example of addition of the aminomethyl radical to imine. The reaction efficiency depended on the structure of the radical precursor, whether it is an iodide or a xanthate, and an electron-withdrawing group on the nitrogen atom of the radical. This reaction allows direct introduction of an N-substituted aminomethyl group onto imine to provide 1,2-diamine as well as the short-step synthesis of ICI-199,441.

  17. Stability transitions and directional flipping in a microswimmer with superparamagnetic links

    NASA Astrophysics Data System (ADS)

    Harduf, Yuval; Or, Yizhar

    2016-11-01

    The famous work of Dreyfus et al. (2005) introduced a microswimmer composed of a chain of superparamagnetic beads and actuated by a planar oscillating magnetic field. Further numerical simulations of the swimmer model by Gauger & Stark (2006) revealed that for large enough oscillation amplitude of the magnetic field's direction, the swimmer's mean orientation and net swimming direction both flip from the mean direction of the magnetic field to a direction perpendicular to it. This observation has been confirmed experimentally in Roper et al. (2008). In our work, we analyze this phenomenon theoretically by studying the simplest possible microswimmer model: two slender links connected by an elastic joint, while one link is superparamagnetic. The dynamic equations of motion are formulated explicitly, and approximated by a second-order system which resembles the well-known Kapitza pendulum with an oscillating pivot. Conditions for stability transitions induced by the system's parametric excitation are obtained numerically and analytically by using Hill's equation and infinite determinant. Remarkably, it is also found that there exist intermediate parameter regions of dynamic bistability where the aligned and perpendicular directions are both stable under different initial conditions.

  18. EPR spin-trapping evidence for the direct, one-electron reduction of tert-butylhydroperoxide to the tert-butoxyl radical by copper(II): paradigm for a previously overlooked reaction in the initiation of lipid peroxidation.

    PubMed

    Jones, Clare M; Burkitt, Mark J

    2003-06-11

    Lipid peroxidation is often initiated using Cu(II) ions. It is widely assumed that Cu(II) oxidizes preformed lipid hydroperoxides to peroxyl radicals, which propagate oxidation of the parent fatty acid via hydrogen atom abstraction. However, the oxidation of alkyl hydroperoxides by Cu(II) is thermodynamically unfavorable. An alternative means by which Cu(II) ions could initiate lipid peroxidation is by their one-electron reduction of lipid hydroperoxides to alkoxyl radicals, which would be accompanied by the generation of Cu(III). We have investigated by EPR spectroscopy, in conjunction with the spin trap 5,5-dimethyl-1-pyrroline N-oxide, the reactions of various Cu(II) chelates with tert-butylhydroperoxide. Spectra contained signals from the tert-butoxyl, methyl, and methoxyl radical adducts. In many previous studies, the signal from the methoxyl adduct has been assigned incorrectly to the tert-butylperoxyl adduct, which is now known to be unstable, releasing the tert-butoxyl radical upon decomposition. This either is trapped by 5,5-dimethyl-1-pyrroline N-oxide or undergoes beta-scission to the methyl radical, which either is trapped or reacts with molecular oxygen to give, ultimately, the methoxyl radical adduct. By using metal chelates that are known to be specific in either their oxidation or reduction of tert-butylhydroperoxide (the Cu(II) complex of bathocuproine disulfonic acid and the Fe(II) complex of diethylenetriaminepentaacetic acid, respectively) for comparison, we have been able to deduce, from the relative concentrations of the three radical adducts, that the Cu(II) complexes tested each reduce tert-butylhydroperoxide directly to the tert-butoxyl radical. These findings suggest that a previously overlooked reaction, namely the direct reduction of preformed lipid hydroperoxides to alkoxyl radicals by Cu(II), may be responsible for the initiation of lipid peroxidation by Cu(II) ions.

  19. Improving Kinetic or Thermodynamic Stability of an Azoreductase by Directed Evolution

    PubMed Central

    Brissos, Vânia; Gonçalves, Nádia; Melo, Eduardo P.; Martins, Lígia O.

    2014-01-01

    Protein stability arises from a combination of factors which are often difficult to rationalise. Therefore its improvement is better addressed through directed evolution than by rational design approaches. In this study, five rounds of mutagenesis/recombination followed by high-throughput screening (≈10,000 clones) yielded the hit 1B6 showing a 300-fold higher half life at 50°C than that exhibited by the homodimeric wild type PpAzoR azoreductase from Pseudomonas putida MET94. The characterization using fluorescence, calorimetry and light scattering shows that 1B6 has a folded state slightly less stable than the wild type (with lower melting and optimal temperatures) but in contrast is more resistant to irreversible denaturation. The superior kinetic stability of 1B6 variant was therefore related to an increased resistance of the unfolded monomers to aggregation through the introduction of mutations that disturbed hydrophobic patches and increased the surface net charge of the protein. Variants 2A1 and 2A1-Y179H with increased thermodynamic stability (10 to 20°C higher melting temperature than wild type) were also examined showing the distinctive nature of mutations that lead to improved structural robustness: these occur in residues that are mostly involved in strengthening the solvent-exposed loops or the inter-dimer interactions of the folded state. PMID:24475252

  20. Multi-directional Reach Test: An Investigation of the Limits of Stability of People Aged between 20-79 Years.

    PubMed

    Tantisuwat, Anong; Chamonchant, Dannaovarat; Boonyong, Sujitra

    2014-06-01

    [Purpose] The multi-directional reach test (MDRT) is a simple, inexpensive, reliable and valid screening tool for assessing the limits of stability in the anterorposterior and mediolateral directions. The aim of this study was to quantify the limits of stability of people aged between 20 and 79 years using the MDRT. [Subjects] One hundred and eighty subjects were divided into the following 6 age groups: 20-29, 30-39, 40-49, 50-59, 60-69 and 70-79 years (n=30 per group). [Methods] The MDRT was used to measure the limits of stability in four directions: forward, backward, leftward and rightward. Subjects performed maximal outstretched arm reach in each direction with their feet flat on the floor. [Results] All age groups performed the greatest values of the limit of stability in the forward direction. The 60-79 year group demonstrated significantly lower limits of stability in the forward, leftward and rightward directions compared to the 20-39 year group. [Conclusion] The limits of stability declined with age mainly in the forward, leftward and rightward directions. The MDRT appears to be a useful assessment tool for postural control and balance of those aged 60 years and over.

  1. Direct Grout Stabilization of High Cesium Salt Waste: Salt Alternative Phase III Feasibility Study

    SciTech Connect

    Langton, C.A.

    1998-12-07

    The direct grout alternative is a viable option for treatment/stabilization and disposal of salt waste containing Cs-137 concentrations of 1-3 Ci/gal. The composition of the direct grout salt solution is higher in sodium salts and contains up to a few hundred ppm Cs-137 more than the current reference salt solution. However it is still similar to the composition of the current reference salt solution. Consequently, the processing, setting, and leaching properties (including TCLP for Cr and Hg) of the direct grout and current saltstone waste forms are very similar. The significant difference between these waste solutions is that the high cesium salt solution will contain between 1 and 3 Curies of Cs-137 per gallon compared to a negligible amount in the current salt solution. This difference will require special engineering and shielding for a direct grout processing facility and disposal units to achieve acceptable radiation exposure conditions. The Cs-137 concentration in the direct grout salt solution will also affect the long-term curing temperature of the waste form since 4.84 Watts of energy are generated per 1000 Ci of Cs-137. The temperature rise of the direct grout during long-term curing has been calculated by A. Shaddy, SRTC.1 The effect of curing temperature on the strength, leaching and physical durability of the direct grout saltstone is described in this report. At the present time, long term curing at 90 degrees C appears to be unacceptable because of cracking which will affect the structural integrity as evaluated in the immersion test. (The experiments conducted in this feasibility study do not address the effect of cracking on leaching of contaminants other than Cr, Hg, and Cs.) No cracking of the direct grout or reference saltstone waste forms was observed for samples cured at 70 degrees C. At the present time the implications of waste form cracking at elevated curing temperatures has not been fully addressed. The direct grout falls within the

  2. Non-covalent interaction between dietary stilbenoids and human serum albumin: Structure-affinity relationship, and its influence on the stability, free radical scavenging activity and cell uptake of stilbenoids.

    PubMed

    Cao, Hui; Jia, Xueping; Shi, Jian; Xiao, Jianbo; Chen, Xiaoqing

    2016-07-01

    Dietary stilbenoids are associated with many benefits for human health, which depend on their bioavailability and bioaccessibility. The stilbenoid-human serum albumin (HSA) interactions are investigated to explore the structure-affinity relationship and influence on the stability, free radical scavenging activity and cell uptake of stilbenoids. The structure-affinity relationship of the stilbenoids-HSA interaction was found as: (1) the methoxylation enhanced the affinity, (2) an additional hydroxyl group increases the affinity and (3) the glycosylation significantly weakened the affinity. HSA obviously masked the free radical scavenging potential of stilbenoids. The stabilities of stilbenoids in different medium were determined as: HSA solution>human plasma>Dulbecco's modified Eagle's medium. It appears that the milk enhanced the cell uptake of stilbenoids with multi-hydroxyl groups and weakened the cell uptake of stilbenoids with methoxyl group on EA.hy 926 endothelial cells. The stilbenoids are hardly absorbed by human umbilical vein endothelial cells in the presence of milk.

  3. [10 YEARS' EXPERIENCE IN USING DIRECT URETEROINTESTINAL ANASTOMOSIS IN URINARY INTESTINAL DIVERSION AFTER RADICAL AND SIMPLE CYSTECTOMY].

    PubMed

    Loran, O B; Serjogin, I V; Hachatrjan, A L; Guspanov, R I

    2015-01-01

    147 patients who underwent urinary intestinal diversion from 2004 to 2014 were selected for the retrospective study. The authors carried out a comparative analysis of rates of complications that arise from the direct ureterointestinal anastomosis. The mean age of patients was 54.2 ± 3.0 (36-69) years. 60 (40.81%) patients of group 1 underwent Nesbit's direct ureterointestinal anastomosis, while in 87 (59.19%) patients of group 2 Wallace-1 and Wallace-2 anastomoses were performed. Average follow-up was 5.6 (2-10) years. Strictures of ureterointestinal anastomosis were detected in 2 (3.38%) patients of group 1 and in 1 (1.14%) patient of group 2. In all cases re-anastomosis was performed. The maximum postoperative concentration of serum creatinine in both groups was 231 mmol/l. According to radioisotope kidney scan, no differences in accumulative and excretory renal functions between two groups of patients were recorded. No kidney stone formation in both groups of patients during the follow-up period was observed. No ureteral reflux above grade 3 was noted. The clinical manifestation of reflux pyelonephritis was observed in 3.5% of the patients. Acute pyelonephritis was cured by antibacterial therapy.

  4. In vivo copper-mediated free radical production: an ESR spin-trapping study

    NASA Astrophysics Data System (ADS)

    Kadiiska, Maria B.; Mason, Ronald P.

    2002-04-01

    Copper has been suggested to facilitate oxidative tissue injury through a free radical-mediated pathway analogous to the Fenton reaction. By applying the electron spin resonance (ESR) spin-trapping technique, evidence for hydroxyl radical formation in vivo was obtained in rats treated simultaneously with copper and ascorbic acid or paraquat. A secondary radical spin-trapping technique was used in which the hydroxyl radical formed the methyl radical upon reaction with dimethylsulfoxide. The methyl radical was then detected by ESR spectroscopy as its adduct with the spin trap phenyl- N- t-butyl- nitrone (PBN). In contrast, lipid derived radical was detected in vivo in copper-challenged, vitamin E and selenium-deficient rats. These findings support the proposal that dietary selenium and vitamin E can protect against lipid peroxidation and copper toxicity. Since copper excreted into the bile from treated animals is expected to be maintained in the Cu(I) state (by ascorbic acid or glutathione), a chelating agent that would redox-stablilize it in the Cu(I) state was used to prevent ex vivo redox chemistry. Bile samples were collected directly into solutions of bathocuproinedisulfonic acid, a Cu(I)-stabilizing agent, and 2,2'-dipyridyl, a Fe(II)-stabilizing agent. If these precautions were not taken, radical adducts generated ex vivo could be mistaken for radical adducts produced in vivo and excreted into the bile.

  5. Rapid directed evolution of stabilized proteins with cellular high-throughput encapsulation solubilization and screening (CHESS).

    PubMed

    Yong, K J; Scott, D J

    2015-03-01

    Directed evolution is a powerful method for engineering proteins towards user-defined goals and has been used to generate novel proteins for industrial processes, biological research and drug discovery. Typical directed evolution techniques include cellular display, phage display, ribosome display and water-in-oil compartmentalization, all of which physically link individual members of diverse gene libraries to their translated proteins. This allows the screening or selection for a desired protein function and subsequent isolation of the encoding gene from diverse populations. For biotechnological and industrial applications there is a need to engineer proteins that are functional under conditions that are not compatible with these techniques, such as high temperatures and harsh detergents. Cellular High-throughput Encapsulation Solubilization and Screening (CHESS), is a directed evolution method originally developed to engineer detergent-stable G proteins-coupled receptors (GPCRs) for structural biology. With CHESS, library-transformed bacterial cells are encapsulated in detergent-resistant polymers to form capsules, which serve to contain mutant genes and their encoded proteins upon detergent mediated solubilization of cell membranes. Populations of capsules can be screened like single cells to enable rapid isolation of genes encoding detergent-stable protein mutants. To demonstrate the general applicability of CHESS to other proteins, we have characterized the stability and permeability of CHESS microcapsules and employed CHESS to generate thermostable, sodium dodecyl sulfate (SDS) resistant green fluorescent protein (GFP) mutants, the first soluble proteins to be engineered using CHESS.

  6. The near-failure of advance directives: why they should not be abandoned altogether, but their role radically reconsidered.

    PubMed

    Spranzi, Marta; Fournier, Véronique

    2016-12-01

    Advance directives (ADs) have been hailed for two decades as the best way to safeguard patients' autonomy when they are totally or partially incompetent. In many national contexts they are written into law and they are mostly associated with end-of-life decisions. Although advocates and critics of ADs exchange relevant empirical and theoretical arguments, the debate is inconclusive. We argue that this is so for good reasons: the ADs' project is fraught with tensions, and this is the reason why they are both important and deeply problematic. We outline six such tensions, and conclude with some positive suggestions about how to better promote patients' autonomy in end-of-life decision. We argue that ADs should continue to be an option but they cannot be the panacea that they are expected to be.

  7. Peptidyl Prolyl Isomerase PIN1 Directly Binds to and Stabilizes Hypoxia-Inducible Factor-1α

    PubMed Central

    Han, Hyeong-jun; Kwon, Nayoung; Choi, Min-A; Jung, Kyung Oh; Piao, Juan-Yu; Ngo, Hoang Kieu Chi; Kim, Su-Jung; Kim, Do-Hee; Chung, June-Key; Cha, Young-Nam; Youn, Hyewon; Choi, Bu Young; Min, Sang-Hyun; Surh, Young-Joon

    2016-01-01

    Peptidyl prolyl isomerase (PIN1) regulates the functional activity of a subset of phosphoproteins through binding to phosphorylated Ser/Thr-Pro motifs and subsequently isomerization of the phosphorylated bonds. Interestingly, PIN1 is overexpressed in many types of malignancies including breast, prostate, lung and colon cancers. However, its oncogenic functions have not been fully elucidated. Here, we report that PIN1 directly interacts with hypoxia-inducible factor (HIF)-1α in human colon cancer (HCT116) cells. PIN1 binding to HIF-1α occurred in a phosphorylation-dependent manner. We also found that PIN1 interacted with HIF-1α at both exogenous and endogenous levels. Notably, PIN1 binding stabilized the HIF-1α protein, given that their levels were significantly increased under hypoxic conditions. The stabilization of HIF-1α resulted in increased transcriptional activity, consequently upregulating expression of vascular endothelial growth factor, a major contributor to angiogenesis. Silencing of PIN1 or pharmacologic inhibition of its activity abrogated the angiogenesis. By utilizing a bioluminescence imaging technique, we were able to demonstrate that PIN1 inhibition dramatically reduced the tumor volume in a subcutaneous mouse xenograft model and angiogenesis as well as hypoxia-induced transcriptional activity of HIF-1α. These results suggest that PIN1 interacting with HIF-1α is a potential cancer chemopreventive and therapeutic target. PMID:26784107

  8. STABILITY OF THE DIRECTLY IMAGED MULTIPLANET SYSTEM HR 8799: RESONANCE AND MASSES

    SciTech Connect

    Fabrycky, Daniel C.; Murray-Clay, Ruth A.

    2010-02-20

    A new era of directly imaged extrasolar planets has produced a three-planet system, where the masses of the planets have been estimated by untested cooling models. We point out that the nominal circular, face-on orbits of the planets lead to a dynamical instability in {approx}10{sup 5} yr, a factor of at least 100 shorter than the estimated age of the star. Reduced planetary masses produce stability only for unreasonably small planets ({approx}<2 M{sub Jup}). Relaxing the face-on assumption, but still requiring circular orbits while fitting the observed positions, makes the instability time even shorter. A promising solution is that the inner two planets have a 2:1 commensurability between their periods, and they avoid close encounters with each other through this resonance. The fact that the inner resonance has lasted until now, in spite of the perturbations of the outer planet, leads to a limit {approx}<10 M{sub Jup} on the masses unless the outer two planets are also engaged in a 2:1 mean-motion resonance. In a double resonance, which is consistent with the current data, the system could survive until now even if the planets have masses of {approx}20 M{sub Jup}. Apsidal alignment can further enhance the stability of a mean-motion resonant system. A completely different dynamical configuration, with large eccentricities and large mutual inclinations among the planets, is possible but finely tuned.

  9. Stability robustness improvement of direct eigenspace assignment based feedback systems using singular value sensitivities

    NASA Technical Reports Server (NTRS)

    Garg, Sanjay

    1989-01-01

    A methodology to improve the stability robustness of feedback control systems designed using direct eigenspace assignment techniques is presented. The method consists of considering the sensitivity of the minimum singular value of the return difference transfer matrix at the plant input to small changes in the desired closed-loop eigenvalues and the specified elements of the desired closed-loop eigenvectors. Closed-form expressions for the gradient of the minimum return difference singular value with respect to desired closed-loop eigenvalue and eigenvector parameters are derived. Closed-form expressions for the gradients of the control feedback gains with respect to the specified eigenspace parameters are obtained as an intermediate step. The use of the gradient information to improve the guaranteed gain and phase margins in eigenspace assignment based designs is demonstrated by application to an advanced fighter aircraft.

  10. Osteoclast radicals.

    PubMed

    Silverton, S

    1994-11-01

    In biological research, new ideas arise and quickly spread to encompass the entire field. Thus, the evolution of molecular biology has significantly changed our methods of approaching our research. A similar far-reaching finding has been the advent of radical reactions into biology. Although radical chemistry has been utilized for many technological advances that affect our daily lives, the appreciation of this same process within our cells has opened an unexplored arena for research enquiry. As cellular messengers, radical molecules seem whimsically designed: they are evanescent, rapidly and apparently indiscriminately reactive, and barely detectable by most biological methods. Yet, our initial probing of these reactive agents in cells and organisms has led us to postulate a virtually undescribed system of communication within and among cells which may have significant effects in multiple organs. In bone, radical reactants have been attributed with an important role in the control of bone resorption.

  11. High-speed fuel tracer fluorescence and OH radical chemiluminescence imaging in a spark-ignition direct-injection engine.

    PubMed

    Smith, James D; Sick, Volker

    2005-11-01

    An innovative technique has been demonstrated to achieve crank-angle-resolved planar laser-induced fluorescence (PLIF) of fuel followed by OH* chemiluminescence imaging in a firing direct-injected spark-ignition engine. This study used two standard KrF excimer lasers to excite toluene for tracking fuel distribution. The intensified camera system was operated at single crank-angle resolution at 2000 revolutions per minute (RPM) for 500 consecutive cycles. Through this work, it has been demonstrated that toluene and OH* can be imaged through the same optical setup while similar signal levels are obtained from both species, even at these high rates. The technique is useful for studying correlations between fuel distribution and subsequent ignition and flame propagation without the limitations of phase-averaging imaging approaches. This technique is illustrated for the effect of exhaust gas recirculation on combustion and will be useful for studies of misfire causes. Finally, a few general observations are presented as to the effect of preignition fuel distribution on subsequent combustion.

  12. Dual-level direct dynamics studies for the reactions of OH radical with bromine-substituted ethanes.

    PubMed

    Wang, Li; Liu, Jing-yao; Gao, Hong; Wan, Su-qin; Li, Ze-sheng

    2009-03-01

    The dynamic properties of the multichannel hydrogen abstraction reactions of CH(3)CH(2)Br + OH --> products and CH(3)CHBr(2) + OH --> products are studied by dual-level direct dynamics method. For each reaction, three reaction channels, one for alpha-hydrogen abstraction and two for beta-hydrogen abstractions, have been identified. The minimum energy paths (MEPs) of both the reactions are calculated at the Becke's half-and-half (BH&H)-Lee-Yang-Parr (LYP)/6-311G(d, p) level and the energy profiles along the MEPs are further refined with interpolated single-point energies (ISPE) method at the G2M(RCC5)//BH&H-LYP level. There are complexes with energies less than those of the reactants or products located at the entrance or exit channels, which indicates that the reactions may proceed via an indirect mechanism. By canonical variational transition-state theory (CVT) the rate constants are calculated incorporating the small-curvature tunneling (SCT) correction in the temperature range of 220-2000 K. The agreement of the rate constants with available experimental values for two reactions is good in the measured temperature range. The calculated results show that alpha-hydrogen abstraction channel is the major reaction pathway in the lower temperature for two reactions, while the contribution of beta-hydrogen abstraction will increase with the increase in temperature.

  13. High-speed fuel tracer fluorescence and OH radical chemiluminescence imaging in a spark-ignition direct-injection engine

    NASA Astrophysics Data System (ADS)

    Smith, James D.; Sick, Volker

    2005-11-01

    An innovative technique has been demonstrated to achieve crank-angle-resolved planar laser-induced fluorescence (PLIF) of fuel followed by OH* chemiluminescence imaging in a firing direct-injected spark-ignition engine. This study used two standard KrF excimer lasers to excite toluene for tracking fuel distribution. The intensified camera system was operated at single crank-angle resolution at 2000 revolutions per minute (RPM) for 500 consecutive cycles. Through this work, it has been demonstrated that toluene and OH* can be imaged through the same optical setup while similar signal levels are obtained from both species, even at these high rates. The technique is useful for studying correlations between fuel distribution and subsequent ignition and flame propagation without the limitations of phase-averaging imaging approaches. This technique is illustrated for the effect of exhaust gas recirculation on combustion and will be useful for studies of misfire causes. Finally, a few general observations are presented as to the effect of preignition fuel distribution on subsequent combustion.

  14. O-GlcNAcylation stabilizes β-catenin through direct competition with phosphorylation at threonine 41

    PubMed Central

    Olivier-Van Stichelen, Stéphanie; Dehennaut, Vanessa; Buzy, Armelle; Zachayus, Jean-Luc; Guinez, Céline; Mir, Anne-Marie; El Yazidi-Belkoura, Ikram; Copin, Marie-Christine; Boureme, Didier; Loyaux, Denis; Ferrara, Pascual; Lefebvre, Tony

    2014-01-01

    Dysfunctions in Wnt signaling increase β-catenin stability and are associated with cancers, including colorectal cancer. In addition, β-catenin degradation is decreased by nutrient-dependent O-GlcNAcylation. Human colon tumors and colons from mice fed high-carbohydrate diets exhibited higher amounts of β-catenin and O-GlcNAc relative to healthy tissues and mice fed a standard diet, respectively. Administration of the O-GlcNAcase inhibitor thiamet G to mice also increased colonic expression of β-catenin. By ETD-MS/MS, we identified 4 O-GlcNAcylation sites at the N terminus of β-catenin (S23/T40/T41/T112). Furthermore, mutation of serine and threonine residues within the D box of β-catenin reduced O-GlcNAcylation by 75%. Interestingly, elevating O-GlcNAcylation in human colon cell lines drastically reduced phosphorylation at T41, a key residue of the D box responsible for β-catenin stability. Analyses of β-catenin O-GlcNAcylation mutants reinforced T41 as the most crucial residue that controls the β-catenin degradation rate. Finally, inhibiting O-GlcNAcylation decreased the β-catenin/α-catenin interaction necessary for mucosa integrity, whereas O-GlcNAcase silencing improved this interaction. These results suggest that O-GlcNAcylation regulates not only the stability of β-catenin, but also affects its localization at the level of adherens junctions. Accordingly, we propose that O-GlcNAcylation of β-catenin is a missing link between the glucose metabolism deregulation observed in metabolic disorders and the development of cancer.—Olivier-Van Stichelen, S., Dehennaut, V., Buzy, A., Zachayus, J.-L., Guinez, C., Mir, A.-M., El Yazidi-Belkoura, I., Copin, M.-C., Boureme, D., Loyaux, D., Ferrara, P., Lefebvre, T. O-GlcNAcylation stabilizes β-catenin through direct competition with phosphorylation at threonine 41. PMID:24744147

  15. Site-directed mutagenesis of an alkaline phytase: influencing specificity, activity and stability in acidic milieu.

    PubMed

    Tran, Thuy T; Mamo, Gashaw; Búxo, Laura; Le, Nhi N; Gaber, Yasser; Mattiasson, Bo; Hatti-Kaul, Rajni

    2011-07-10

    Site-directed mutagenesis of a thermostable alkaline phytase from Bacillus sp. MD2 was performed with an aim to increase its specific activity and activity and stability in an acidic environment. The mutation sites are distributed on the catalytic surface of the enzyme (P257R, E180N, E229V and S283R) and in the active site (K77R, K179R and E227S). Selection of the residues was based on the idea that acid active phytases are more positively charged around their catalytic surfaces. Thus, a decrease in the content of negatively charged residues or an increase in the positive charges in the catalytic region of an alkaline phytase was assumed to influence the enzyme activity and stability at low pH. Moreover, widening of the substrate-binding pocket is expected to improve the hydrolysis of substrates that are not efficiently hydrolysed by wild type alkaline phytase. Analysis of the phytase variants revealed that E229V and S283R mutants increased the specific activity by about 19% and 13%, respectively. Mutation of the active site residues K77R and K179R led to severe reduction in the specific activity of the enzyme. Analysis of the phytase mutant-phytate complexes revealed increase in hydrogen bonding between the enzyme and the substrate, which might retard the release of the product, resulting in decreased activity. On the other hand, the double mutant (K77R-K179R) phytase showed higher stability at low pH (pH 2.6-3.0). The E227S variant was optimally active at pH 5.5 (in contrast to the wild type enzyme that had an optimum pH of 6) and it exhibited higher stability in acidic condition. This mutant phytase, displayed over 80% of its initial activity after 3h incubation at pH 2.6 while the wild type phytase retained only about 40% of its original activity. Moreover, the relative activity of this mutant phytase on calcium phytate, sodium pyrophosphate and p-nitro phenyl phosphate was higher than that of the wild type phytase.

  16. A new technique for the direct detection of HO2 radicals using bromide chemical ionization mass spectrometry (Br-CIMS): initial characterization

    NASA Astrophysics Data System (ADS)

    Sanchez, Javier; Tanner, David J.; Chen, Dexian; Huey, L. Gregory; Ng, Nga L.

    2016-08-01

    Hydroperoxy radicals (HO2) play an important part in tropospheric photochemistry, yet photochemical models do not capture ambient HO2 mixing ratios consistently. This is likely due to a combination of uncharacterized chemical pathways and measurement limitations. The indirect nature of current HO2 measurements introduces challenges in accurately measuring HO2; therefore a direct technique would help constrain HOx chemistry in the atmosphere. In this work we evaluate the feasibility of using chemical ionization mass spectrometry (CIMS) and propose a direct HO2 detection scheme using bromide as a reagent ion. Ambient observations were made with a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) in Atlanta over the month of June 2015 to demonstrate the capability of this direct measurement technique. Observations displayed expected diurnal profiles, reaching daytime median values of ˜ 5 ppt between 2 and 3 p.m. local time. The HO2 diurnal profile was found to be influenced by morning-time vehicular NOx emissions and shows a slow decrease into the evening, likely from non-photolytic production, among other factors. Measurement sensitivities of approximately 5.1 ± 1.0 cps ppt-1 for a bromide ion (79Br-) count rate of 106 cps were observed. The relatively low instrument background allowed for a 3σ lower detection limit of 0.7 ppt for a 1 min integration time. Mass spectra of ambient measurements showed the 79BrHO2- peak was the major component of the signal at nominal mass-to-charge 112, suggesting high selectivity for HO2 at this mass-to-charge. More importantly, this demonstrates that these measurements can be achieved using instruments with only unit mass resolution capability.

  17. Selective stabilization of microtubules oriented toward the direction of cell migration.

    PubMed Central

    Gundersen, G G; Bulinski, J C

    1988-01-01

    A small subset of the microtubule (MT) array in many cultured cells does not exhibit the rapid turnover (t 1/2 approximately equal to 10 min) shown by most cellular MTs. The function of the stable class of MTs is unknown and has been confounded by the apparent lack of organization of stable MTs within cells. Using an antibody against detyrosinated tubulin, a post-translationally modified form of tubulin that accumulates in stable MTs, we localized the stable MTs in mouse 3T3 cells induced to initiate directional migration by experimental wounding of confluent monolayers. Immediately after monolayer wounding, the distribution of stable MTs in cells at the wound edge resembled that in cells in the monolayer interior; most cells either contained randomly distributed stable MTs or lacked them entirely. However, by 20 min after wounding, cells at the wound margin began to generate an asymmetric MT array, with virtually all stable MTs oriented toward the cell edge in contact with the wound. Two hours after monolayer wounding, greater than or equal to 80% of cells at the wound margin had generated this polarized array of stable MTs, and the array was maintained for at least 12 hr. MTs in the polarized array showed enhanced resistance to depolymerization by nocodazole, thus providing an independent test of their stability. Formation of the polar array of stable MTs appeared to precede onset of cell migration and closely paralleled reorientation of the MT-organizing center. These results show that cultured cells can remodel their MT array rapidly in response to an extracellular signal and suggest that selective stabilization of MTs is an early event in the generation of cellular asymmetry. Images PMID:3413068

  18. Direct emission of I2 molecule and IO radical from the heterogeneous reactions of gaseous ozone with aqueous potassium iodide solution.

    PubMed

    Sakamoto, Yosuke; Yabushita, Akihiro; Kawasaki, Masahiro; Enami, Shinichi

    2009-07-09

    Recent studies indicated that gaseous halogens mediate key tropospheric chemical processes. The inclusion of halogen-ozone chemistry in atmospheric box models actually closes the approximately 50% gap between estimated and measured ozone losses in the marine boundary layer. The additional source of gaseous halogens is deemed to involve previously unaccounted for reactions of O(3)(g) with sea surface water and marine aerosols. Here, we report that molecular iodine, I(2)(g), and iodine monoxide radical, IO(g), are released ([I(2)(g)] > 100[IO(g)]) during the heterogeneous reaction of gaseous ozone, O(3)(g), with aqueous potassium iodide, KI(aq). It was found that (1) the amounts of I(2)(g) and IO(g) produced are directly proportional to [KI(aq)] up to 5 mM and (2) IO(g) yields are independent of bulk pH between 2 and 11, whereas I(2)(g) production is markedly enhanced at pH < 4. We propose that O(3)(g) reacts with I(-) at the air/water interface to produce I(2)(g) and IO(g) via HOI and IOOO(-) intermediates, respectively.

  19. Grafting N-Isopropyl Acrylamide) from Poly(vinylidene Fluoride) Mirofiltration, Membranes via Direct Surface-Initiated Atom Transfer Radical Polymerization, and Temperature Sensitivity

    NASA Astrophysics Data System (ADS)

    Chen, Yiwang; Xiao, Jichun; Zhou, Weihua; Deng, Qilan; Nie, Huarong; Wan, Meixiang; Bai, Fenglian

    Well-defined poly(N-isopropyl acrylamide) (PNIPAAm) brushes on commercial hydrophobic poly(vinylidene fluoride) (PVDF) microfiltration membrane surfaces were prepared, via direct atom transfer radical polymerization (ATRP) with the secondary fluorinated site of PVDF as initiator and water as solvent at 80°C. The effect of solvents on the ATRP was studied in detail. The water as reaction solvent was in favor of surface-initiated ATRP of N-isopropyl acrylamide (NIPAAm) from secondary fluoride of PVDF membranes. The chemical composition and structure of the modified PVDF membrane surfaces were determined by attenuated total reflectance (ATR) Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The surface and cross-section morphology of membranes were studied by scanning electron microscopy (SEM). The pore sizes of the pristine PVDF membrane and the PNIPAAm-grafted PVDF membranes were measured using micro-image analysis and process software. The introduction of the well-defined PNIPAAm on the PVDF membrane gave rise to hydrophilicity. Water contact angles of PVDF membranes reduced after the surface grafting of PNIPAAm. Water fluxes and protein solution permeation experiments revealed that the PNIPAAm-grafted PVDF membranes exhibited temperature-responsive permeability. The unique microstructure of PNIPAAm brushes facilitated hydrophilicity below the lower critical solution temperature.

  20. Theoretical investigation of the hydrogen abstraction reaction of the OH radical with CH2FCH2F (HFC-152): a dual-level direct dynamics study.

    PubMed

    Taghikhani, Mahdi; Parsafar, G A

    2007-08-23

    The hydrogen abstraction reaction of the OH radical with CH(2)FCH(2)F (HFC-152) is studied theoretically over the 150-3000 K temperature range. In this study, the two most recently developed hybrid density functional theories, namely, BB1K and MPWB1K, are applied, and their efficiency in reaction dynamics calculation is discussed. The BB1K/6-31+G(d,p) method gives the best result for the potential energy surface (PES) calculations, including barrier heights, reaction path information (the first and second derivatives of PES), geometry of transition state structures, and even weak hydrogen bond orientations. The rate constants were obtained by the dual-level direct dynamics with the interpolated single-point energy method (VTST-ISPE) using the BB1K/MG3S//BB1K/6-31+G(d,p) quantum model. The canonical variational transition state theory (CVT) with the small-curvature tunneling correction methods are used to calculate the rate constants in comparison to the experimental data. The total rate constant and its temperature dependency in the form of a fitted three-parameter Arrhenius expression is k(T) = 5.4 x 10(-13)(T/298)3.13 exp{-322/T} cm3 molecule(-1) s(-1). A significant variational effect, which is not common generally for hydrogen-transfer reactions, is reported and analyzed.

  1. Direct and indirect effects of glomalin, mycorrhizal hyphae, and roots on aggregate stability in rhizosphere of trifoliate orange.

    PubMed

    Wu, Qiang-Sheng; Cao, Ming-Qin; Zou, Ying-Ning; He, Xin-hua

    2014-07-25

    To test direct and indirect effects of glomalin, mycorrhizal hyphae, and roots on aggregate stability, perspex pots separated by 37-μm nylon mesh in the middle were used to form root-free hyphae and root/hyphae chambers, where trifoliate orange (Poncirus trifoliata) seedlings were colonized by Funneliformis mosseae or Paraglomus occultum in the root/hyphae chamber. Both fungal species induced significantly higher plant growth, root total length, easily-extractable glomalin-related soil protein (EE-GRSP) and total GRSP (T-GRSP), and mean weight diameter (an aggregate stability indicator). The Pearson correlation showed that root colonization or soil hyphal length significantly positively correlated with EE-GRSP, difficultly-extractable GRSP (DE-GRSP), T-GRSP, and water-stable aggregates in 2.00-4.00, 0.50-1.00, and 0.25-0.50 mm size fractions. The path analysis indicated that in the root/hyphae chamber, aggregate stability derived from a direct effect of root colonization, EE-GRSP or DE-GRSP. Meanwhile, the direct effect was stronger by EE-GRSP or DE-GRSP than by mycorrhizal colonization. In the root-free hyphae chamber, mycorrhizal-mediated aggregate stability was due to total effect but not direct effect of soil hyphal length, EE-GRSP and T-GRSP. Our results suggest that GRSP among these tested factors may be the primary contributor to aggregate stability in the citrus rhizosphere.

  2. Direct numerical simulation and global stability analysis of three-dimensional instabilities in a lid-driven cavity

    NASA Astrophysics Data System (ADS)

    Chicheportiche, Jérèmie; Merle, Xavier; Gloerfelt, Xavier; Robinet, Jean-Christophe

    2008-07-01

    The first bifurcation in a lid-driven cavity characterized by three-dimensional Taylor-Görtler-Like instabilities is investigated for a cubical cavity with spanwise periodic boundary conditions at Re=1000. The modes predicted by a global linear stability analysis are compared to the results of a direct numerical simulation. The amplification rate, and the shape of the three-dimensional perturbation fields from the direct numerical simulation are in very good agreement with the characteristics of the steady S1 mode from the stability analysis, showing that this mode dominates the other unstable unsteady modes. To cite this article: J. Chicheportiche et al., C. R. Mecanique 336 (2008).

  3. Site directed mutagenesis of StSUT1 reveals target amino acids of regulation and stability.

    PubMed

    Krügel, Undine; Wiederhold, Elena; Pustogowa, Jelena; Hackel, Aleksandra; Grimm, Bernhard; Kühn, Christina

    2013-11-01

    Plant sucrose transporters (SUTs) are functional as sucrose-proton-cotransporters with an optimal transport activity in the acidic pH range. Recently, the pH optimum of the Solanum tuberosum sucrose transporter StSUT1 was experimentally determined to range at an unexpectedly low pH of 3 or even below. Various research groups have confirmed these surprising findings independently and in different organisms. Here we provide further experimental evidence for a pH optimum at physiological extrema. Site directed mutagenesis provides information about functional amino acids, which are highly conserved and responsible for this extraordinary increase in transport capacity under extreme pH conditions. Redox-dependent dimerization of the StSUT1 protein was described earlier. Here the ability of StSUT1 to form homodimers was demonstrated by heterologous expression in Lactococcus lactis and Xenopus leavis using Western blots, and in plants by bimolecular fluorescence complementation. Mutagenesis of highly conserved cysteine residues revealed their importance in protein stability. The accessibility of regulatory amino acid residues in the light of StSUT1's compartmentalization in membrane microdomains is discussed.

  4. LMO2 Oncoprotein Stability in T-Cell Leukemia Requires Direct LDB1 Binding

    PubMed Central

    Layer, Justin H.; Alford, Catherine E.; McDonald, W. Hayes

    2015-01-01

    LMO2 is a component of multisubunit DNA-binding transcription factor complexes that regulate gene expression in hematopoietic stem and progenitor cell development. Enforced expression of LMO2 causes leukemia by inducing hematopoietic stem cell-like features in T-cell progenitor cells, but the biochemical mechanisms of LMO2 function have not been fully elucidated. In this study, we systematically dissected the LMO2/LDB1-binding interface to investigate the role of this interaction in T-cell leukemia. Alanine scanning mutagenesis of the LIM interaction domain of LDB1 revealed a discrete motif, R320LITR, required for LMO2 binding. Most strikingly, coexpression of full-length, wild-type LDB1 increased LMO2 steady-state abundance, whereas coexpression of mutant proteins deficient in LMO2 binding compromised LMO2 stability. These mutant LDB1 proteins also exerted dominant negative effects on growth and transcription in diverse leukemic cell lines. Mass spectrometric analysis of LDB1 binding partners in leukemic lines supports the notion that LMO2/LDB1 function in leukemia occurs in the context of multisubunit complexes, which also protect the LMO2 oncoprotein from degradation. Collectively, these data suggest that the assembly of LMO2 into complexes, via direct LDB1 interaction, is a potential molecular target that could be exploited in LMO2-driven leukemias resistant to existing chemotherapy regimens. PMID:26598604

  5. MOF-5-Polystyrene: Direct Production from Monomer, Improved Hydrolytic Stability, and Unique Guest Adsorption.

    PubMed

    Gamage, Nipuni-Dhanesha H; McDonald, Kyle A; Matzger, Adam J

    2016-09-19

    An unprecedented mode of reactivity of Zn4 O-based metal-organic frameworks (MOFs) offers a straightforward and powerful approach to polymer-hybridized porous solids. The concept is illustrated with the production of MOF-5-polystyrene wherein polystyrene is grafted and uniformly distributed throughout MOF-5 crystals after heating in pure styrene for 4-24 h. The surface area and polystyrene content of the material can be fine-tuned by controlling the duration of heating styrene in the presence of MOF-5. Polystyrene grafting significantly alters the physical and chemical properties of pristine MOF-5, which is evident from the unique guest adsorption properties (solvatochromic dye uptake and improved CO2 capacity) as well as the dramatically improved hydrolytic stability of composite. Based on the fact that MOF-5 is the best studied member of the structure class, and has been produced at scale by industry, these findings can be directly leveraged for a range of current applications.

  6. Formation and stability of gas-phase o-benzoquinone from oxidation of ortho-hydroxyphenyl: A combined neutral and distonic radical study

    DOE PAGES

    Prendergast, Matthew B.; Kirk, Benjamin B.; Savee, John D.; ...

    2015-10-19

    Gas-phase product detection studies of o-hydroxyphenyl radical and O2 are reported at 373, 500, and 600 K, at 4 Torr (533.3 Pa), using VUV time-resolved synchrotron photoionisation mass spectrometry. The dominant products are assigned as o-benzoquinone (C6H4O2, m/z 108) and cyclopentadienone (C5H4O, m/z 80). It is concluded that cyclopentadienone forms as a secondary product from prompt decomposition of o-benzoquinone (and dissociative ionization of o-benzoquinone may contribute to the m/z 80 signal at photon energies ≳9.8 eV). Ion-trap reactions of the distonic o-hydroxyphenyl analogue, the 5-ammonium-2-hydroxyphenyl radical cation, with O2 are also reported and concur with the assignment of o-benzoquinone asmore » the dominant product. In addition, the ion-trap study also provides support for a mechanism where cyclopentadienone is produced by decarbonylation of o-benzoquinone. Kinetic studies compare oxidation of the ammonium-tagged o-hydroxyphenyl and o-methylphenyl radical cations along with trimethylammonium-tagged analogues. Reaction efficiencies are found to be ca. 5% for both charge-tagged o-hydroxyphenyl and o-methylphenyl radicals irrespective of the charged substituent. G3X-K quantum chemical calculations are deployed to rationalise experimental results for o-hydroxyphenyl + O2 and its charge-tagged counterpart. The prevailing reaction mechanism, after O2 addition, involves a facile 1,5-H shift in the peroxyl radical and subsequent elimination of OH to yield o-benzoquinone that is reminiscent of the Waddington mechanism for β-hydroxyperoxyl radicals. These results suggest o-hydroxyphenyl + O2 and decarbonylation of o-benzoquinone serve as plausible OH and CO sources in combustion.« less

  7. Production of sulfate radical from peroxymonosulfate induced by a magnetically separable CuFe2O4 spinel in water: efficiency, stability, and mechanism.

    PubMed

    Zhang, Tao; Zhu, Haibo; Croué, Jean-Philippe

    2013-03-19

    A simple, nonhazardous, efficient and low energy-consuming process is desirable to generate powerful radicals from peroxymonosulfate (PMS) for recalcitrant pollutant removal. In this work, the production of radical species from PMS induced by a magnetic CuFe(2)O(4) spinel was studied. Iopromide, a recalcitrant model pollutant, was used to investigate the efficiency of this process. CuFe(2)O(4) showed higher activity and 30 times lower Cu(2+) leaching (1.5 μg L(-1) per 100 mg L(-1)) than a well-crystallized CuO at the same dosage. CuFe(2)O(4) maintained its activity and crystallinity during repeated batch experiments. In comparison, the activity of CuO declined significantly, which was ascribed to the deterioration in its degree of crystallinity. The efficiency of the PMS/CuFe(2)O(4) was highest at neutral pH and decreased at acidic and alkaline pHs. Sulfate radical was the primary radical species responsible for the iopromide degradation. On the basis of the stoichiometry of oxalate degradation in the PMS/CuFe(2)O(4), the radical production yield from PMS was determined to be near 1 mol/mol. The PMS decomposition involved an inner-sphere complexation with the oxide's surface Cu(II) sites. In situ characterization of the oxide surface with ATR-FTIR and Raman during the PMS decomposition suggested that surface Cu(II)-Cu(III)-Cu(II) redox cycle was responsible for the efficient sulfate radical generation from PMS.

  8. A Stability Study of Ni/Yttria-Stabilized Zirconia Anode for Direct Ammonia Solid Oxide Fuel Cells.

    PubMed

    Yang, Jun; Molouk, Ahmed Fathi Salem; Okanishi, Takeou; Muroyama, Hiroki; Matsui, Toshiaki; Eguchi, Koichi

    2015-12-30

    In recent years, solid oxide fuel cells fueled with ammonia have been attracting intensive attention. In this work, ammonia fuel was supplied to the Ni/yttria-stabilized zirconia (YSZ) cermet anode at 600 and 700 °C, and the change of electrochemical performance and microstructure under the open-circuit state was studied in detail. The influence of ammonia exposure on the microstructure of Ni was also investigated by using Ni/YSZ powder and Ni film deposited on a YSZ disk. The obtained results demonstrated that Ni in the cermet anode was partially nitrided under an ammonia atmosphere, which considerably roughened the Ni surface. Moreover, the destruction of the anode support layer was confirmed for the anode-supported cell upon the temperature cycling test between 600 and 700 °C because of the nitriding phenomenon of Ni, resulting in severe performance degradation.

  9. Thermochemistry of organic, elementorganic and inorganic species. Part XX. Enthalpies of formation for free radicals of main group elements’ halogenides

    NASA Astrophysics Data System (ADS)

    Ponomarev, Dmitry; Takhistov, Viatcheslav; Slayden, Suzanne; Liebman, Joel

    2008-03-01

    General trends in thermochemistry for free radicals as the fragments of halogenated molecules of main group elements were found for the first time applying the series of isodesmic (working) reactions following the Benson's comparison of relative stabilities of free radicals in equations R+RH→ RH+R+Q, where Q is stabilization (destabilization) energy. The enthalpies of formation for parent molecules of main group elements' halogenides necessary for application of this and similar equations were presented earlier [A.V. Golovin, V.V. Takhistov, J. Mol. Struct., 784 (2006) 47.]. For fluorinated free radicals rad EF (E = Be-Ra), rad EF 2 ( rad EHF) (E = B-Tl, N-Bi) and rad EF 3 ( rad EH 2F, rad EHF 2) (E = C-Pb) the gradual decrease in stabilization by fluorine atoms was found when coming down the periodic table. This turned to destabilization for Tl, Sb, and Bi, and IVth group of elements (excluding carbon) with increasing destabilization in the row Si < Ge < Sn < Pb. The destabilization of free radicals by other halogens for IVth group of elements decreased in the row F > Cl > Br > I which was interpreted by involvement of polarizability (PAZ) effect of halogens increasing in this direction. For finding the enthalpies of formation for silicon and germanium-centered free radicals the data on ν ≡ E-H frequencies in IR-spectra were applied. Quite definite tendencies in structure/enthalpy of formation interrelationship were found for chlorinated, brominated and iodinated free radicals of IInd and IIIrd group of elements. In the VIth group the situation with F → Cl → Br → I replacement in stabilization of free radical center appeared completely different compared with II-IV groups. Owing to the high electronegativity of HO-group and low thermodynamic stability of HO rad radical all halogens highly stabilize rad OX radical and perform it in the row F < Cl-Br < I which is explained by increase of PAZ effect in this direction. All halogens are suggested to

  10. Performance, methanol tolerance and stability of Fe-aminobenzimidazole derived catalyst for direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Sebastián, David; Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen; Aricò, Antonino S.; Baglio, Vincenzo

    2016-07-01

    Highly active and durable non-platinum group metals (non-PGM) catalyst based on iron-nitrogen-carbon (Fe-N-C) for the oxygen reduction reaction (ORR) derived from pyrolyzed Fe-aminobenzimidazole (Fe-ABZIM) was synthesized by sacrificial support method (SSM), and characterized by several physical-chemical techniques: scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller method and X-ray photoelectron spectroscopy. In half-cell electrochemical configuration, the Fe-ABZIM catalyst presented a significant improvement of ORR activity with respect to a recently reported non-PGM formulation based on Fe-aminoantipyrine, with an enhancement of half-wave potential of about 85 mV in O2-saturated sulfuric acid solution. To the moment, the gap with respect to a benchmark Pt/C catalyst was about 90 mV. The Fe-ABZIM catalyst showed a remarkably high tolerance to methanol, resulting in superior ORR performance compared to Pt/C at methanol concentrations higher than 0.02 M. In direct methanol fuel cell (DMFC) good performances were also obtained. A durability test (100 h) at 90 °C, feeding 5 M methanol, was carried out. A certain decrease of performance was recorded, amounting to -0.20 mW cm-2 h-1 at the very beginning of test and -0.05 mW cm-2 h-1 at the end. However, the Fe-ABZIM is more adequate than previously reported formulations in terms of both ORR activity and stability.

  11. Theoretical investigation of the hydrogen abstraction reaction of the OH radical with CH3CHF2 (HFC152-a): a dual level direct density functional theory dynamics study.

    PubMed

    Taghikhani, Mahdi; Parsafar, G A; Sabzyan, Hassan

    2005-09-15

    The hydrogen abstraction reaction of the OH radical with CH(3)CHF(2) (HFC152-a) has been studied theoretically over a wide temperature range, 200-3000 K. Two different reactive sites of the molecule, CH(3) and CHF(2) groups have been investigated precisely, and results confirm that CHF(2) position of the molecule is a highly reactive site. In this study, three recently developed hybrid density functional theories, namely, MPWB1K, MPW1B95, and MPW1K, are used. The MPWB1K/6-31+G(d,p) method gives the best result for kinetic calculations, including barrier heights, reaction path information and geometry of transition state structures and other stationary points. To refine the barrier height of each channel, a single point energy calculation was performed in MPWB1K/MG3S method. The obtained rate constants by dual level direct dynamics with the interpolated single point energy method (VTST-ISPE) using DFT quantum computational methods, are consistent with available experimental data. The canonical variational transition state theory (CVT) with the zero-curvature and also the small-curvature tunneling correction methods is used to calculate the rate constants. Over the temperature range 200-3000 K, the variation effect, tunneling contribution, branching ratio of each channel are calculated. The rate constants and their temperature dependency in the form of a fitted three-parameter Arrhenius expression are k(1)(T) = 2.00 x 10(-19)(T)(2.24) exp(-1273/T), k(2)(T) = 1.95 x 10(-19)(T)(2.46) exp(-2374/T), and k(T) = 3.13 x 10(-19)(T)(2.47) exp(- 1694/T) cm(3) molecule(-1) s(-1). For the H abstraction from the CHF(2) group, a nonclassical reflection effect is detected as a dominant quantum effect.

  12. Direct ab initio dynamics studies on the hydrogen-abstraction reactions of OH radicals with HOX (X = F, Cl, and Br).

    PubMed

    Wang, Li; Liu, Jing-Yao; Li, Ze-Sheng; Sun, Chia-Chung

    2004-03-01

    The hydrogen abstract reactions of OH radicals with HOF (R1), HOCl (R2), and HOBr (R3) have been studied systematically by a dual-level direct-dynamics method. The geometries and frequencies of all the stationary points are optimized at the MP2/6-311+G(2d, 2p) level of theory. A hydrogen-bonded complex is located at the product channel for the OH + HOBr reaction. To improve the energetics information along the minimum energy path (MEP), single-point energy calculations are carried out at the CCSD(T)/6-311++G(3df, 3pd) level of theory. Interpolated single-point energy (ISPE) method is employed to correct the energy profiles for the three reactions. It is found that neither the barrier heights (DeltaE) nor the H-O bond dissociation energies [D(H-O)] exhibit any clear-cut linear correlations with the halogen electronegative. The decrease of DeltaE and D(H-O) for the three reactions are in order of HOF > HOBr > HOCl. Rate constants for each reaction are calculated by canonical variational transition-state theory (CVT) with a small-curvature tunneling correction (SCT) within 200-2000 K. The agreement of the rate constants with available experimental values for reactions R2 and R3 at 298 K is good. Our results show that the variational effect is small while the tunneling correction has an important contribution in the calculation of rate constants in the low-temperature range. Due to the lack of the kinetic data of these reactions, the present theoretical results are expected to be useful and reasonable to estimate the dynamical properties of these reactions over a wide temperature range where no experimental value is available.

  13. Near-monodisperse poly(2-(methacryloyloxy)ethyl phosphorylcholine)-based macromonomers prepared by atom transfer radical polymerization and thiol-ene click chemistry: novel reactive steric stabilizers for aqueous emulsion polymerization.

    PubMed

    Warren, Nicholas J; Muise, Carl; Stephens, Alex; Armes, Steven P; Lewis, Andrew L

    2012-02-07

    Poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) macromonomers have been prepared by the atom transfer radical polymerization (ATRP) of 2-(methacryloyloxy)ethyl phosphorylcholine (MPC) using a bifunctional disulfide-based initiator. To attach a terminal polymerizable methacrylate group, the central disulfide bond was cleaved and the resulting thiols were conjugated to 3-(acryloyloxy)-2-hydroxypropyl methacrylate using tris(2-carboxyethyl)phosphine (TCEP) in water. Here TCEP serves as both the disulfide cleavage agent and also the catalyst for the subsequent Michael addition, which is highly selective for the acrylate group. The resulting methacrylate-terminated macromonomers were used as a reactive steric stabilizer for the aqueous emulsion polymerization of styrene, yielding near-monodisperse PMPC-stabilized polystyrene (PS) latexes of around 100-200 nm in diameter. As a comparison, the disulfide-containing PMPC homopolymer precursor and the intermediate thiol-functional PMPC homopolymer (PMPC-SH) were also evaluated as potential steric stabilizers. Interestingly, near-monodisperse latexes were also obtained in each case. These three sterically-stabilized latexes, prepared using either PMPC macromonomer, disulfide-based PMPC homopolymer, or PMPC-SH homopolymer as a reactive steric stabilizer, remained colloidally stable after both freeze-thaw experiments and the addition of an electrolyte, indicating that a coronal layer of PMPC chains prevented flocculation in each case. In contrast, both a charge-stabilized PS latex prepared in the absence of any steric stabilizer and a PS latex prepared in the presence of a nonfunctional PMPC homopolymer exhibited very poor colloidal stability when subjected to a freeze-thaw cycle or the addition of an electrolyte, as expected.

  14. Formation and stability of gas-phase o-benzoquinone from oxidation of ortho-hydroxyphenyl: A combined neutral and distonic radical study

    SciTech Connect

    Prendergast, Matthew B.; Kirk, Benjamin B.; Savee, John D.; Osborn, David L.; Taatjes, Craig A.; Masters, Kye -Simeon; Blanksby, Stephen J.; da Silva, Gabriel; Trevitt, Adam J.

    2015-10-19

    Gas-phase product detection studies of o-hydroxyphenyl radical and O2 are reported at 373, 500, and 600 K, at 4 Torr (533.3 Pa), using VUV time-resolved synchrotron photoionisation mass spectrometry. The dominant products are assigned as o-benzoquinone (C6H4O2, m/z 108) and cyclopentadienone (C5H4O, m/z 80). It is concluded that cyclopentadienone forms as a secondary product from prompt decomposition of o-benzoquinone (and dissociative ionization of o-benzoquinone may contribute to the m/z 80 signal at photon energies ≳9.8 eV). Ion-trap reactions of the distonic o-hydroxyphenyl analogue, the 5-ammonium-2-hydroxyphenyl radical cation, with O2 are also reported and concur with the assignment of o-benzoquinone as the dominant product. In addition, the ion-trap study also provides support for a mechanism where cyclopentadienone is produced by decarbonylation of o-benzoquinone. Kinetic studies compare oxidation of the ammonium-tagged o-hydroxyphenyl and o-methylphenyl radical cations along with trimethylammonium-tagged analogues. Reaction efficiencies are found to be ca. 5% for both charge-tagged o-hydroxyphenyl and o-methylphenyl radicals irrespective of the charged substituent. G3X-K quantum chemical calculations are deployed to rationalise experimental results for o-hydroxyphenyl + O2 and its charge-tagged counterpart. The prevailing reaction mechanism, after O2 addition, involves a facile 1,5-H shift in the peroxyl radical and subsequent elimination of OH to yield o-benzoquinone that is reminiscent of the Waddington mechanism for β-hydroxyperoxyl radicals. These results suggest o-hydroxyphenyl + O2 and decarbonylation of o-benzoquinone serve as plausible OH and CO sources in combustion.

  15. Rapid Screening of Immobilized Amine CO2 Sorbents for Steam Stability by Their Direct Contact with Liquid H2 O.

    PubMed

    Wilfong, Walter Christopher; Kail, Brian W; Gray, McMahan L

    2015-06-22

    Rapid testing of hydrophilic and hydrophobic basic immobilized amine sorbents (BIAS) for CO2 capture stability under practical conditions was achieved by direct contact of the sorbents with flowing liquid water. Losses in both CO2 capture capacity and amine content of sorbents after exposure to 0.5 mL min(-1) of H2 O at 25 °C for 40 min followed similar trends as losses observed after exposure to N2 /steam (105 °C, 7 % H2 O) for 10 h. We also found that hydrophobic TMPED helped stabilize sorbents to H2 O, which was confirmed by DRIFTS and combined TGA-DSC.

  16. Direct and indirect effects of glomalin, mycorrhizal hyphae, and roots on aggregate stability in rhizosphere of trifoliate orange

    PubMed Central

    Wu, Qiang-Sheng; Cao, Ming-Qin; Zou, Ying-Ning; He, Xin-hua

    2014-01-01

    To test direct and indirect effects of glomalin, mycorrhizal hyphae, and roots on aggregate stability, perspex pots separated by 37-μm nylon mesh in the middle were used to form root-free hyphae and root/hyphae chambers, where trifoliate orange (Poncirus trifoliata) seedlings were colonized by Funneliformis mosseae or Paraglomus occultum in the root/hyphae chamber. Both fungal species induced significantly higher plant growth, root total length, easily-extractable glomalin-related soil protein (EE-GRSP) and total GRSP (T-GRSP), and mean weight diameter (an aggregate stability indicator). The Pearson correlation showed that root colonization or soil hyphal length significantly positively correlated with EE-GRSP, difficultly-extractable GRSP (DE-GRSP), T-GRSP, and water-stable aggregates in 2.00–4.00, 0.50–1.00, and 0.25–0.50 mm size fractions. The path analysis indicated that in the root/hyphae chamber, aggregate stability derived from a direct effect of root colonization, EE-GRSP or DE-GRSP. Meanwhile, the direct effect was stronger by EE-GRSP or DE-GRSP than by mycorrhizal colonization. In the root-free hyphae chamber, mycorrhizal-mediated aggregate stability was due to total effect but not direct effect of soil hyphal length, EE-GRSP and T-GRSP. Our results suggest that GRSP among these tested factors may be the primary contributor to aggregate stability in the citrus rhizosphere. PMID:25059396

  17. Calm Water Equilibrium, Directional Stability and Steady Turning Conditions for Recreational Planing Craft

    DTIC Science & Technology

    1975-10-01

    215 6.00 .000 14.a8 el.60 -5.0 .126 -0.3905 -0.3911 A19 R-1851 rABL E A- I 1 (cont’d) MEASURED At.JD FLTTFD LON𔃾GITUDINAL F07RCE RFTA = 5. DLG FLI1...TABLE E-1 STRAIGHT COURSE ELUILIBRILM AND STABILITY RFTA =10. DEC XG= .8 ZG=-0.50 DIRECTIOINAL STABILITY ROOTS CV T CDEL DRAFT ERO REAL IMAG REAL IMAG

  18. Free radical generation and concentration in a plasma polymer: the effect of aromaticity.

    PubMed

    Ershov, Sergey; Khelifa, Farid; Lemaur, Vincent; Cornil, Jérôme; Cossement, Damien; Habibi, Youssef; Dubois, Philippe; Snyders, Rony

    2014-08-13

    Plasma polymer films (PPF) have increasing applications in many fields due to the unique combination of properties of this class of materials. Among notable features arising from the specifics of plasma polymerization synthesis, a high surface reactivity can be advantageously used when exploited carefully. It is related to the presence of free radicals generated during the deposition process through manifold molecular bond scissions in the energetic plasma environment. In ambient atmosphere, these radicals undergo autoxidation reactions resulting in undesired polymer aging. However, when the reactivity of surface radicals is preserved and they are put in direct contact with a chemical group of interest, a specific surface functionalization or grafting of polymeric chains can be achieved. Therefore, the control of the surface free radical density of a plasma polymer is crucially important for a successful grafting. The present investigation focuses on the influence of the hydrocarbon precursor type, aromatic vs aliphatic, on the generation and concentration of free radicals on the surface of the PPF. Benzene and cyclohexane were chosen as model precursors. First, in situ FTIR analysis of the plasma phase supplemented by density functional theory calculations allowed the main fragmentation routes of precursor molecules in the discharge to be identified as a function of energy input. Using nitric oxide (NO) chemical labeling in combination with X-ray photoelectron spectroscopy analysis, a quantitative evaluation of concentration of surface free radicals as a function of input power has been assessed for both precursors. Different evolutions of the surface free radical density for the benzene- and cyclohexane-based PPF, namely, a continuous increase versus stabilization to a plateau, are attributed to different plasma polymerization mechanisms and resulting structures as illustrated by PPF characterization findings. The control of surface free radical density can be

  19. Enhancement of oxidative stability of the subtilisin nattokinase by site-directed mutagenesis expressed in Escherichia coli.

    PubMed

    Weng, MeiZhi; Zheng, ZhongLiang; Bao, Wei; Cai, YongJun; Yin, Yan; Zou, GuoLin; Zou, GouLin

    2009-11-01

    Nattokinase (subtilisin NAT, NK) is a bacterial serine protease with strong fibrinolytic activity and it is a potent cardiovascular drug. In medical and commercial applications, however, it is susceptible to chemical oxidation, and subsequent inactivation or denaturation. Here we show that the oxidative stability of NK was substantially increased by optimizing the amino acid residues Thr(220) and Met(222), which were in the vicinity of the catalytic residue Ser(221) of the enzyme. Two nonoxidative amino acids (Ser and Ala) were introduced at these sites using site-directed mutagenesis. Active enzymes were successfully expressed in Escherichia coli with periplasmic secretion and enzymes were purified to homogeneity. The purified enzymes were analyzed with respect to oxidative stability, kinetic parameters, fibrinolytic activity and thermal stability. M222A mutant was found to have a greatly increased oxidative stability compared with wild-type enzyme and it was resistant to inactivation by more than 1 M H(2)O(2), whereas the wild-type enzyme was inactivated by 0.1 M H(2)O(2) (t(1/2) approximately 11.6 min). The other mutant (T220S) also showed an obvious increase in antioxidative ability. Molecular dynamic simulations on wild-type and T220S mutant proteins suggested that a hydrogen bond was formed between Ser(220) and Asn(155), and the spatial structure of Met(222) was changed compared with the wild-type. The present study demonstrates the feasibility of improving oxidative stability of NK by site-directed mutagenesis and shows successful protein engineering cases to improve stability of NK as a potent therapeutic agent.

  20. Direct laser writing of thermally stabilized channel waveguides with Bragg gratings.

    PubMed

    Nishiyama, Hiroaki; Miyamoto, Isamu; Matsumoto, Shin-Ichi; Saito, Mitsunori; Kintaka, Kenji; Nishii, Junji

    2004-09-20

    Thermally stabilized photo-induced channel waveguides with Bragg gratings were fabricated in Ge-B-SiO2 thin glass films by exposure with KrF excimer laser and successive annealing at 600 degrees C. The annealing reversed the photo-induced refractive index pattern and also enhanced its thermal stability. The stabilized channel waveguide with a Bragg grating showed diffraction efficiency of 18.0 dB and 18.7 dB for TE- and TM-like modes, respectively. The diffraction efficiencies and wavelengths for both modes never changed after heat treatment at 500 degrees C, whereas the conventional photo-induced grating decayed even at 200 degrees C.

  1. Direct laser writing of thermally stabilized channel waveguides with Bragg gratings

    NASA Astrophysics Data System (ADS)

    Nishiyama, Hiroaki; Miyamoto, Isamu; Matsumoto, Shin-Ichi; Saito, Mitsunori; Kintaka, Kenji; Nishii, Junji

    2004-09-01

    Thermally stabilized photo-induced channel waveguides with Bragg gratings were fabricated in Ge-B-SiO2 thin glass films by exposure with KrF excimer laser and successive annealing at 600°C. The annealing reversed the photo-induced refractive index pattern and also enhanced its thermal stability. The stabilized channel waveguide with a Bragg grating showed diffraction efficiency of 18.0 dB and 18.7 dB for TE- and TM-like modes, respectively. The diffraction efficiencies and wavelengths for both modes never changed after heat treatment at 500°C, whereas the conventional photo-induced grating decayed even at 200°C.

  2. Direct Current Electrorheological Stability Determination of Water-in-Crude Oil Emulsions

    NASA Astrophysics Data System (ADS)

    Alvarado, Vladimir; Wang, Xiuyu

    2009-11-01

    Emulsion stability is a fundamental determination for separation technologies. We use the critical electric field (CEF) and viscosity changes in DC eletrorheological (ER) experiments in dynamic mode to determine the stability of water-in-crude oil emulsions, previously studied through bottle tests. The CEF value corresponds to the value of electric field at which the current reaches 95% or larger of the plateau value. The results show that CEF can be consistently obtained through current measurements, resulting from emulsion structure breakdown. Viscosity changes are not good proxies of stability unless a robust emulsion structure is found. Emulsion structure breakdown is explored through rheological characterization before and after voltage sweeps have been performed. When the electric field applied is below the CEF value, the storage and loss moduli responses as well as viscosity as functions of frequency are recovered. However, when the electric field is greater than the CEF value, the emulsion structure breaks down irreversibly.

  3. Homolytic dissociation of the vulcanization accelerator tetramethylthiuram disulfide (TMTD) and structures and stabilities of the related radicals Me2NCSn* (n = 1-4).

    PubMed

    Steudel, Ralf; Steudel, Yana; Mak, Adrian Matthew; Wong, Ming Wah

    2006-12-08

    The homolytic dissociation of the important vulcanization accelerator tetramethylthiuram disulfide (TMTD) has been studied by ab initio calculations according to the G3X(MP2) and G3X(MP2)-RAD theories. Homolytic cleavage of the SS bond requires a low enthalpy of 150.0 kJ mol-1, whereas 268.0 kJ mol-1 is needed for the dissociation of one of the C-S single bonds. To cleave one of the SS bonds of the corresponding trisulfide (TMTT) requires 191.1 kJ mol-1. Me2NCS2* is a particularly stable sulfur radical as reflected in the low S-H bond dissociation enthalpy of the corresponding acid Me2NC(=S)SH (301.7 kJ mol-1). Me2NCS2* (2B2) is a sigma radical characterized by the unpaired spin density shared equally between the two sulfur atoms and by a 4-center (NCS2) delocalized pi system. The ESR g-tensors of the radicals Me2NCSn* (n = 1-3) have been calculated. Both TMTD and the mentioned radicals form stable chelate complexes with a Li+ cation, which here serves as a model for the zinc ions used in accelerated rubber vulcanization. Although the binding energy of the complex [Li(TMTD)]+ is larger than that of the isomeric species [Li(S2CNMe2)2]+ (12), the dissociation enthalpy of TMTD as a ligand is smaller (125.5 kJ mol-1) than that of free TMTD. In other words, the homolytic dissociation of the SS bonds of TMTD is facilitated by the presence of Li+ ions. The sulfurization of TMTD in the presence of Li+ to give the paramagnetic complex [Li(S3CNMe2)2]+ is strongly exothermic. These results suggest that TMTD reacts with naked zinc ions as well as with the surface atoms of solid zinc oxide particles in an analogous manner producing highly reactive complexes, which probably initiate the crosslinking process during vulcanization reactions of natural or synthetic rubber accelerated by TMTD/ZnO.

  4. Locally linearized longitudinal and lateral-directional aerodynamic stability and control derivaties for the X-29A aircraft

    NASA Technical Reports Server (NTRS)

    Budd, G. D.

    1984-01-01

    The locally linearized longitudinal and lateral-directional aerodynamic stability and control derivatives for the X-29A aircraft were calculated for altitudes ranging from sea level to 50,000 ft, Mach numbers from 0.2 to 1.5, and angles of attack from -5 deg to 25 deg. Several other parameters were also calculated, including aerodynamic force and moment coefficients, control face position, normal acceleration, static margin, and reference angle of attack.

  5. Optimizing wind farm layout via LES-calibrated geometric models inclusive of wind direction and atmospheric stability effects

    NASA Astrophysics Data System (ADS)

    Archer, Cristina; Ghaisas, Niranjan

    2015-04-01

    The energy generation at a wind farm is controlled primarily by the average wind speed at hub height. However, two other factors impact wind farm performance: 1) the layout of the wind turbines, in terms of spacing between turbines along and across the prevailing wind direction; staggering or aligning consecutive rows; angles between rows, columns, and prevailing wind direction); and 2) atmospheric stability, which is a measure of whether vertical motion is enhanced (unstable), suppressed (stable), or neither (neutral). Studying both factors and their complex interplay with Large-Eddy Simulation (LES) is a valid approach because it produces high-resolution, 3D, turbulent fields, such as wind velocity, temperature, and momentum and heat fluxes, and it properly accounts for the interactions between wind turbine blades and the surrounding atmospheric and near-surface properties. However, LES are computationally expensive and simulating all the possible combinations of wind directions, atmospheric stabilities, and turbine layouts to identify the optimal wind farm configuration is practically unfeasible today. A new, geometry-based method is proposed that is computationally inexpensive and that combines simple geometric quantities with a minimal number of LES simulations to identify the optimal wind turbine layout, taking into account not only the actual frequency distribution of wind directions (i.e., wind rose) at the site of interest, but also atmospheric stability. The geometry-based method is calibrated with LES of the Lillgrund wind farm conducted with the Software for Offshore/onshore Wind Farm Applications (SOWFA), based on the open-access OpenFOAM libraries. The geometric quantities that offer the best correlations (>0.93) with the LES results are the blockage ratio, defined as the fraction of the swept area of a wind turbine that is blocked by an upstream turbine, and the blockage distance, the weighted distance from a given turbine to all upstream turbines

  6. Temporal Variability and Stability in Infant-Directed Sung Speech: Evidence for Language-Specific Patterns

    ERIC Educational Resources Information Center

    Falk, Simone

    2011-01-01

    In this paper, sung speech is used as a methodological tool to explore temporal variability in the timing of word-internal consonants and vowels. It is hypothesized that temporal variability/stability becomes clearer under the varying rhythmical conditions induced by song. This is explored cross-linguistically in German--a language that exhibits a…

  7. Temporal variability and stability in infant-directed sung speech: evidence for language-specific patterns.

    PubMed

    Falk, Simone

    2011-06-01

    In this paper, sung speech is used as a methodological tool to explore temporal variability in the timing of word-internal consonants and vowels. It is hypothesized that temporal variability/stability becomes clearer under the varying rhythmical conditions induced by song.This is explored crosslinguistically in German - a language that exhibits a potential vocalic quantity distinction - and the non-quantity languages French and Russian. Songs by non-professional singers, i.e. parents that sang to their infants aged 2 to 13 months in a non-laboratory setting, were recorded and analyzed.Vowel and consonant durations at syllable contacts of trochaic word types with CVCV or CV:CV structure were measured under varying rhythmical conditions. Evidence is provided that in German non-professional singing, the two syllable structures can be differentiated by two distinct temporal variability patterns: vocalic variability (and consonantal stability) was found to be dominant in CV:CV structures whereas consonantal variability (and vocalic stability) was characteristic for CVCV structures. In French and Russian, however, only vocalic variability seemed to apply.Additionally, findings suggest that the different temporal patterns found in German were also supported by the stability pattern at the tonal level. These results point to subtle (supra) segmental timing mechanisms in sung speech that affect temporal targets according to the specific prosodic nature of the language in question.

  8. Direct current electrorheological stability determination of water-in-crude oil emulsions.

    PubMed

    Wang, Xiuyu; Alvarado, Vladimir

    2009-10-22

    Emulsion stability is a fundamental determination for separation technologies. We use the critical electric field (CEF) and viscosity changes in DC electrorheological (ER) experiments in dynamic mode to establish the level of stability of water-in-crude oil emulsions previously studied through bottle tests. The CEF value corresponds to the value of electric field at which the current reaches 95% or larger of the plateau value. Our results show that CEF can be obtained through current measurements and viscosity drops resulting from emulsion structure breakdown, although viscosity changes are not always a good proxy of stability. This implies that electrorheology cannot be uncritically used for static stability determination of the CEF value. Emulsion structure breakdown is explored through rheological characterization before and after voltage sweeps have been performed. When the electric field applied is below the CEF value, the storage and loss moduli response, as well as viscosity, as functions of frequency are recovered. However, when the electric field is greater than the CEF value, the emulsion structure breaks down irreversibly.

  9. CROSS-DISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY: The effect of anisotropic surface tension on the morphological stability of planar interface during directional solidification

    NASA Astrophysics Data System (ADS)

    Chen, Ming-Wen; Lan, Man; Yuan, Lin; Wang, Yu-Yan; Wang, Zi-Dong; Xu, Jian-Jun

    2009-04-01

    This paper considers the effect of the anisotropic surface tension on the morphological stability of the planar interface during directional solidification. When the expression exhibiting the four-fold symmetry is included, the modified absolute stability criterion is obtained by employing the multi-variable expansion method. The linear stability analysis reveals that for the given temperature gradient, as the anisotropic surface tension parameter increases, the stability zone tends to decrease.

  10. Dual high-resolution α-glucosidase and radical scavenging profiling combined with HPLC-HRMS-SPE-NMR for identification of minor and major constituents directly from the crude extract of Pueraria lobata.

    PubMed

    Liu, Bingrui; Kongstad, Kenneth T; Qinglei, Sun; Nyberg, Nils T; Jäger, Anna K; Staerk, Dan

    2015-02-27

    The crude methanol extract of Pueraria lobata was investigated by dual high-resolution α-glucosidase inhibition and radical scavenging profiling combined with hyphenated HPLC-HRMS-SPE-NMR. Direct analysis of the crude extract without preceding purification was facilitated by combining chromatograms from two analytical-scale HPLC separations of 120 and 600 μg on-column, respectively. High-resolution α-glucosidase and radical scavenging profiles were obtained after microfractionation of the eluate in 96-well microplates. This allowed full bioactivity profiling of individual peaks in the HPLC chromatogram of the crude methanol extract. Subsequent HPLC-HRMS-SPE-NMR analysis allowed identification of 21 known compounds in addition to two new compounds, i.e., 3'-methoxydaidzein 8-C-[α-D-apiofuranosyl-(1→6)]-β-D-glucopyranoside and 6″-O-malonyl-3'-methoxydaidzin, as well as an unstable compound tentatively identified as 3'-de-O-methylpuerariafuran.

  11. Generalized Solovev equilibrium with sheared flow of arbitrary direction and stability consideration

    SciTech Connect

    Kaltsas, D. A. E-mail: gthroum@cc.uoi.gr; Throumoulopoulos, G. N. E-mail: gthroum@cc.uoi.gr

    2014-08-15

    A Solovev-like solution describing equilibria with field aligned incompressible flows [G. N. Throumoulopoulos and H. Tasso, Phys. Plasmas 19, 014504 (2012)] is extended to non parallel flows. The solution expressed as a superposition of Bessel functions contains an arbitrary number of free parameters which are exploited to construct a variety of configurations including ITER shaped ones. For parallel flows, application of a sufficient condition for linear stability shows that this condition is satisfied in an appreciable part of the plasma region on the high-field side mostly due to the variation of the magnetic field perpendicular to the magnetic surfaces. Also, the results indicate that depending on the shape of the Mach-function profile and the values of the free parameters the flow and flow shear may have either stabilizing or destabilizing effects.

  12. Direct interaction with filamins modulates the stability and plasma membrane expression of CFTR

    PubMed Central

    Thelin, William R.; Chen, Yun; Gentzsch, Martina; Kreda, Silvia M.; Sallee, Jennifer L.; Scarlett, Cameron O.; Borchers, Christoph H.; Jacobson, Ken; Stutts, M. Jackson; Milgram, Sharon L.

    2007-01-01

    The role of the cystic fibrosis transmembrane conductance regulator (CFTR) as a cAMP-dependent chloride channel on the apical membrane of epithelia is well established. However, the processes by which CFTR is regulated on the cell surface are not clear. Here we report the identification of a protein-protein interaction between CFTR and the cytoskeletal filamin proteins. Using proteomic approaches, we identified filamins as proteins that associate with the extreme CFTR N terminus. Furthermore, we identified a disease-causing missense mutation in CFTR, serine 13 to phenylalanine (S13F), which disrupted this interaction. In cells, filamins tethered plasma membrane CFTR to the underlying actin network. This interaction stabilized CFTR at the cell surface and regulated the plasma membrane dynamics and confinement of the channel. In the absence of filamin binding, CFTR was internalized from the cell surface, where it prematurely accumulated in lysosomes and was ultimately degraded. Our data demonstrate what we believe to be a previously unrecognized role for the CFTR N terminus in the regulation of the plasma membrane stability and metabolic stability of CFTR. In addition, we elucidate the molecular defect associated with the S13F mutation. PMID:17235394

  13. Improvement of stability and enzymatic activity by site-directed mutagenesis of E. coli asparaginase II.

    PubMed

    Verma, Shikha; Mehta, Ranjit Kumar; Maiti, Prasanta; Röhm, Klaus-Heinrich; Sonawane, Avinash

    2014-07-01

    Bacterial asparaginases (EC 3.5.1.1) have attracted considerable attention because enzymes of this group are used in the therapy of certain forms of leukemia. Class II asparaginase from Escherichia coli (EcA), a homotetramer with a mass of 138 kDa, is especially effective in cancer therapy. However, the therapeutic potential of EcA is impaired by the limited stability of the enzyme in vivo and by the induction of antibodies in the patients. In an attempt to modify the properties of EcA, several variants with amino acid replacements at subunit interfaces were constructed and characterized. Chemical and thermal denaturation analysis monitored by activity, fluorescence, circular dichroism, and differential scanning calorimetry showed that certain variants with exchanges that weaken dimer-dimer interactions exhibited complex denaturation profiles with active dimeric and/or inactive monomeric intermediates appearing at low denaturant concentrations. By contrast, other EcA variants showed considerably enhanced activity and stability as compared to the wild-type enzyme. Thus, even small changes at a subunit interface may markedly affect EcA stability without impairing its catalytic properties. Variants of this type may have a potential for use in the asparaginase therapy of leukemia.

  14. Improvements in Glucose Sensitivity and Stability of Trichoderma reesei β-Glucosidase Using Site-Directed Mutagenesis

    PubMed Central

    Amano, Yoshihiko

    2016-01-01

    Glucose sensitivity and pH and thermal stabilities of Trichoderma reesei Cel1A (Bgl II) were improved by site-directed mutagenesis of only two amino acid residues (L167W or P172L) at the entrance of the active site. The Cel1A mutant showed high glucose tolerance (50% of inhibitory concentration = 650 mM), glucose stimulation (2.0 fold at 50 mM glucose), and enhanced specific activity (2.4-fold) compared with those of the wild-type Cel1A. Furthermore, the mutant enzyme showed stability at a wide pH range of 4.5–9.0 and possessed high thermal stability up to 50°C with 80% of the residual activities compared with the stability seen at the pH range of 6.5–7.0 and temperatures of up to 40°C in the wild-type Cel1A. Kinetic studies for hydrolysis revealed that the Cel1A mutant was competitively inhibited by glucose at similar levels as the wild-type enzyme. Additionally, the mutant enzyme exhibited substrate inhibition, which gradually disappeared with an increasing glucose concentration. These data suggest that the glucose stimulation was caused by relieve the substrate inhibition in the presence of glucose. To conclude, all the properties improved by the mutagenesis would be great advantages in degradation of cellulosic biomass together with cellulases. PMID:26790148

  15. Reversible light-directed red, green, and blue reflection with thermal stability enabled by a self-organized helical superstructure.

    PubMed

    Li, Yannian; Urbas, Augustine; Li, Quan

    2012-06-13

    Adding external, remote, and dynamic control to self-organized superstructures with desired properties is an important leap necessary in leveraging the fascinating molecular subsystems for employment in applications. Here two novel light-driven dithienylethene chiral molecular switches possessing remarkable changes in helical twisting power during photoisomerization as well as very high helical twisting powers were found to experience photochemically reversible isomerization with thermal stability in both isotropic organic solvents and anisotropic liquid crystal media. When doped into a commercially available achiral liquid crystal host, the chiral switch was able to either immediately induce an optically tunable helical superstructure or retain an achiral photoresponsive liquid crystal phase whose helical superstructure was induced and tuned reversibly upon light irradiation. Moreover, reversible light-directed red, green, and blue reflection colors with thermal stability in a single thin film were demonstrated.

  16. Resistance to antiangiogenic therapy is directed by vascular phenotype, vessel stabilization, and maturation in malignant melanoma

    PubMed Central

    Scheffrahn, Inka; Bartling, Sönke; Weis, Joachim; von Felbert, Verena; Middleton, Mark; Kato, Masahi; Ergün, Süleyman; Augustin, Hellmut G.

    2010-01-01

    Angiogenesis is not only dependent on endothelial cell invasion and proliferation, it also requires pericyte coverage of vascular sprouts for stabilization of vascular walls. Clinical efficacy of angiogenesis inhibitors targeting the vascular endothelial growth factor (VEGF) signaling pathway is still limited to date. We hypothesized that the level of vessel maturation is critically involved in the response to antiangiogenic therapies. To test this hypothesis, we evaluated the vascular network in spontaneously developing melanomas of MT/ret transgenic mice after using PTK787/ZK222584 for anti-VEGF therapy but also analyzed human melanoma metastases taken at clinical relapse in patients undergoing adjuvant treatment using bevacizumab. Both experimental settings showed that tumor vessels, which are resistant to anti-VEGF therapy, are characterized by enhanced vessel diameter and normalization of the vascular bed by coverage of mature pericytes and immunoreactivity for desmin, NG-2, platelet-derived growth factor receptor β, and the late-stage maturity marker α smooth muscle actin. Our findings emphasize that the level of mural cell differentiation and stabilization of the vascular wall significantly contribute to the response toward antiangiogenic therapy in melanoma. This study may be useful in paving the way toward a more rational development of second generation antiangiogenic combination therapies and in providing, for the first time, a murine model to study this. PMID:20194633

  17. Neutral, cationic, and anionic low-spin iron(III) complexes stabilized by amidophenolate and iminobenzosemiquinonate radical in N,N,O ligands.

    PubMed

    Rajput, Amit; Sharma, Anuj K; Barman, Suman K; Koley, Debasis; Steinert, Markus; Mukherjee, Rabindranath

    2014-01-06

    A brownish-black complex [Fe(III)(L)2] (1) (S = 0), supported by two tridentate redox-active azo-appended o-amidophenolates [H2L = 2-(2-phenylazo)-anilino-4,6-di-tert-butylphenol], has been synthesized and structurally characterized. In CH2Cl2 1 displays two oxidative and two reductive 1e(-) redox processes at E1/2 values of 0.48 and 1.06 V and -0.42 and -1.48 V vs SCE, respectively. The one-electron oxidized form [1](+) isolated as a green solid [Fe(III)(L)2][BF4] (2) (S = 1/2) has been structurally characterized. Isolation of a dark ink-blue one-electron reduced form [1](-) has also been achieved [Co(III)(η(5)-C10H15)2][Fe(III)(L)2] (3) (S = 1/2). Mössbauer spectral parameters unequivocally establish that 1 is a low-spin (LS) Fe(III) complex. Careful analysis of Mössbauer spectral data of 2 and 3 at 200 and 80 K reveal that each complex has a major LS Fe(III) and a minor LS Fe(II) component (redox isomers): [Fe(III){(L(ISQ))(-•)}2](+) and [Fe(II){(L(IBQ))(0)}{(L(ISQ))(-•)}](+) (2) and [Fe(III){(L(AP))(2-)}2](-) and [Fe(II){(L(ISQ))(-•)}{(L(AP))(2-)}](-) (3). Notably, for both at 8 K mainly the major component exists. Broken-Symmetry (BS) Density Functional Theory (DFT) calculations at the B3LYP level reveals that in 1 the unpaired electron of LS Fe(III) is strongly antiferromagnetically coupled with a π-radical of o-iminobenzosemiquinonate(1-) (L(ISQ))(-•) form of the ligand, delocalized over two ligands providing 3- charge (X-ray structure). DFT calculations reveal that the unpaired electron in 2 is due to (L(ISQ))(-•) [LS Fe(III) (SFe = 1/2) is strongly antiferromagnetically coupled to one of the (L(ISQ))(-•) radicals (Srad = 1/2)] and 3 is primarily a LS Fe(III) complex, supported by two o-amidophenolate(2-) ligands. Time-Dependent-DFT calculations shed light on the origin of UV-vis-NIR spectral absorptions for 1-3. The collective consideration of Mössbauer, variable-temperature (77-298 K) electron paramagnetic resonance (EPR), and absorption

  18. An experimental study of flame stability in a directly-fueled wall cavity with a supersonic free stream

    NASA Astrophysics Data System (ADS)

    Rasmussen, Chadwick Clifford

    An extensive study of flame stability in a cavity-based fuel injector/flameholder has been performed. Flames were stabilized in cavities with two different aft wall configurations and length to depth ratios of 3 and 4. Fuel was injected directly into the cavity using two injector configurations. Fuel injected from the aft wall of the cavity entered directly into the recirculation zone and provided desirable performance near the lean blowout limit. At high fuel flowrates, the cavity became flooded with fuel and rich blowout occurred. When fuel was injected from the floor of the cavity, excess fuel was directed out of the cavity which allowed for flame stabilization at extremely high fuel flowrates; however, this phenomenon also resulted in suboptimal performance near the lean limit where the blowout point was less predictable. Images of planar laser-induced fluorescence (PLIF) of CH, OH, and formaldehyde give insight into the flameholding mechanisms. CH layers in the cavity are thin and continuous and show structure that is comparable to lifted jet flames, while broad CH zones are sometimes observed in the shear layer. OH PLIF images show that hot recirculated products are always present at the location of flame stabilization, whereas images of formaldehyde indicate that partial premixing takes place in the shear layer portion of the flame. Nonreacting measurements of the boundary layer and the free stream velocity profiles were obtained to provide necessary boundary conditions for computational modeling. Mean and instantaneous velocity profiles were determined for the nonreacting flow using particle image velocimetry (PIV). A correlation of the blowout points for a directly-fueled cavity in a supersonic flow was accomplished using a Damkohler number and an equivalence ratio based upon an effective air mass flowrate. The chemical time was formulated using a generic measure of the reaction rate, tauc ˜ alpha/ S2L , which was found to be adequate for correlating lean

  19. Entry dynamics of space shuttle orbiter with lateral-directional stability and control uncertainties at supersonic and hypersonic speeds

    NASA Technical Reports Server (NTRS)

    Stone, H. W.; Powell, R. W.

    1977-01-01

    A six-degree-of-freedom simulation analysis was conducted to examine the effects of the lateral-directional static aerodynamic stability and control uncertainties on the performance of the automatic (no manual inputs) entry-guidance and control systems of the space shuttle orbiter. To establish the acceptable boundaries of the uncertainties, the static aerodynamic characteristics were varied either by applying a multiplier to the aerodynamic parameter or by adding an increment. Control-system modifications were identified that decrease the sensitivity to off-nominal aerodynamics. With these modifications, the acceptable aerodynamic boundaries were determined.

  20. Sub-kilohertz linewidth narrowing of a mid-infrared optical parametric oscillator idler frequency by direct cavity stabilization.

    PubMed

    Ricciardi, I; Mosca, S; Parisi, M; Maddaloni, P; Santamaria, L; De Natale, P; De Rosa, M

    2015-10-15

    We stabilize the idler frequency of a singly resonant optical parametric oscillator directly to the resonance of a mid-infrared Fabry-Perot reference cavity. This is accomplished by the Pound-Drever-Hall locking scheme, controlling either the pump laser or the resonant signal frequency. A residual relative frequency noise power spectral density below 10(3)  Hz(2)/Hz is reached on average, with a Gaussian linewidth of 920 Hz over 100 ms, which reveals the potential for reaching spectral purity down to the hertz level by locking the optical parametric oscillator against a mid-infrared cavity with state-of-the-art superior performance.

  1. Calculation of lateral-directional stability derivatives of wings by a nonplanar quasi-vortex-lattice method

    NASA Technical Reports Server (NTRS)

    Lan, C. E.

    1981-01-01

    The nonplanar quasi-vortex-lattice method is applied to the calculation of lateral-directional stability derivatives of wings with and without vortex-lift effect. Results for conventional configurations and those with winglets, V-tail, etc. are compared with available data. All rolling moment derivatives are found to be accurately predicted. The prediction of side force and yawing moment derivatives for some configurations is not as accurate. Causes of the discrepancy are discussed. A user's manual for the program and the program listing are also included.

  2. Optimisation of ultrasound-assisted extraction of oil from papaya seed by response surface methodology: oil recovery, radical scavenging antioxidant activity, and oxidation stability.

    PubMed

    Samaram, Shadi; Mirhosseini, Hamed; Tan, Chin Ping; Ghazali, Hasanah Mohd; Bordbar, Sara; Serjouie, Alireza

    2015-04-01

    The present study aimed to investigate the effects of ultrasound-assisted extraction (UAE) condition on the yield, antioxidant activity and stability of the oil from papaya seed. The studied ultrasound variables were time, temperature, ultrasound power and solvent to sample ratio. The main goal was to optimise UAE condition providing the highest recovery of papaya seed oil with the most desirable antioxidant activity and stability. The interaction of ultrasound variables had the most and least significant effects on the antioxidant activity and stability, respectively. Ultrasound-assisted extraction provided a relatively high oil recovery (∼ 73%) from papaya seed. The strongest antioxidant activity was achieved by the extraction at the elevated temperature using low solvent to sample ratio. The optimum ultrasound extraction was set at the elevated temperature (62.5 °C) for 38.5 min at high ultrasound power (700 W) using medium solvent to sample ratio (∼ 7:1 v/w). The optimum point was practically validated.

  3. THERMOCHEMISTRY OF HYDROCARBON RADICALS

    SciTech Connect

    Kent M. Ervin, Principal Investigator

    2004-08-17

    Gas phase negative ion chemistry methods are employed to determine enthalpies of formation of hydrocarbon radicals that are important in combustion processes and to investigate the dynamics of ion-molecule reactions. Using guided ion beam tandem mass spectrometry, we measure collisional threshold energies of endoergic proton transfer and hydrogen atom transfer reactions of hydrocarbon molecules with negative reagent ions. The measured reaction threshold energies for proton transfer yield the relative gas phase acidities. In an alternative methodology, competitive collision-induced dissociation of proton-bound ion-molecule complexes provides accurate gas phase acidities relative to a reference acid. Combined with the electron affinity of the R {center_dot} radical, the gas phase acidity yields the RH bond dissociation energy of the corresponding neutral molecule, or equivalently the enthalpy of formation of the R{center_dot} organic radical, using equation: D(R-H) = {Delta}{sub acid}H(RH) + EA(R) - IE(H). The threshold energy for hydrogen abstraction from a hydrocarbon molecule yields its hydrogen atom affinity relative to the reagent anion, providing the RH bond dissociation energy directly. Electronic structure calculations are used to evaluate the possibility of potential energy barriers or dynamical constrictions along the reaction path, and as input for RRKM and phase space theory calculations. In newer experiments, we have measured the product velocity distributions to obtain additional information on the energetics and dynamics of the reactions.

  4. Direct and indirect effects of unilateral divorce law on marital stability.

    PubMed

    Kneip, Thorsten; Bauer, Gerrit; Reinhold, Steffen

    2014-12-01

    Previous research examining the impact of unilateral divorce law (UDL) on the prevalence of divorce has provided mixed results. Studies based on cross-sectional cross-country/cross-state survey data have received criticism for disregarding unobserved heterogeneity across countries, as have studies using country-level panel data for failing to account for possible mediating mechanisms at the micro level. We seek to overcome both shortcomings by using individual-level event-history data from 11 European countries (SHARELIFE) and controlling for unobserved heterogeneity over countries and cohorts. We find that UDL in total increased the incidence of marital breakdown by about 20 %. This finding, however, neglects potential selection effects into marriage. Accordingly, the estimated effect of unilateral divorce laws becomes much larger when we control for age at marriage, which is used as indicator for match quality. Moreover, we find that UDL particularly affects marital stability in the presence of children.

  5. The direct criterion of Newcomb for the ideal MHD stability of an axisymmetric toroidal plasma

    NASA Astrophysics Data System (ADS)

    Glasser, A. H.

    2016-07-01

    A method is presented for determining the ideal magnetohydrodynamic stability of an axisymmetric toroidal plasma, based on a toroidal generalization of the method developed by Newcomb for fixed-boundary modes in a cylindrical plasma. For toroidal mode number n ≠ 0 , the stability problem is reduced to the numerical integration of a high-order complex system of ordinary differential equations, the Euler-Lagrange equation for extremizing the potential energy, for the coupled amplitudes of poloidal harmonics m as a function of the radial coordinate ψ in a straight-fieldline flux coordinate system. Unlike the cylindrical case, different poloidal harmonics couple to each other, which introduces coupling between adjacent singular intervals. A boundary condition is used at each singular surface, where m = nq and q ( ψ ) is the safety factor, to cross the singular surface and continue the solutions beyond it. Fixed-boundary instability is indicated by the vanishing of a real determinant of a Hermitian complex matrix constructed from the fundamental matrix of solutions, the generalization of Newcomb's crossing criterion. In the absence of fixed-boundary instabilities, an M × M plasma response matrix W P , with M the number of poloidal harmonics used, is constructed from the Euler-Lagrange solutions at the plasma-vacuum boundary. This is added to a vacuum response matrix W V to form a total response matrix W T . The existence of negative eigenvalues of W T indicates the presence of free-boundary instabilities. The method is implemented in the fast and accurate DCON code.

  6. Thermal stability of direct dental esthetic restorative materials at elevated temperatures.

    PubMed

    Robinson, F G; Rueggeberg, F A; Lockwood, P E

    1998-11-01

    With increasing use of direct esthetic restorative materials, the identity of a body may rely upon knowledge of temperature effects on this class of dental restorations. This research examined the effect of atmospheric gas on thermal decomposition and color change of a wide variety of direct esthetic restorative materials. Cured discs (4 x 1 and 8 x 1 mm) were made using manufacturer's directions: traditional glass ionomer (Fuji II), light-curable resonomer (Fuji II LC), compomer (Geristore), and three types of resin composites--highly filled, urethane-based (Occlusin), and two Bis-GMA/TEGDMA resins: hybrid (Herculite XRV) and microfill (Silux Plus). Three replications of each material were heated at 5 degrees C/min in a thermogravimetric analysis unit using either room air or nitrogen purge to simulate different thermal environments. First derivative values of percent weight loss with respect to temperature were obtained to determine temperatures associated with increased decomposition rates. Room-air heating showed greater numbers of decomposition events than did nitrogen-heated discs. The only material decomposing less than 200 degrees C in either atmosphere was traditional glass ionomer. The majority of decomposition occurred between 200 degrees and 500 degrees C for all materials. Only products containing glass ionomer components decomposed between 600 degrees and 800 degrees C. Room-air heating resulted in ash white discs at 800 degrees C and higher. Specimens heated in nitrogen were gray to black at 600 degrees C and higher. Heating atmosphere greatly affected color, and some products demonstrated distinguishing color changes: glass ionomers, in particular, showed characteristic color features. An atlas was constructed from color change of specimens recovered after 200 degrees, 400 degrees, 600 degrees, 800 degrees, and 1000 degrees C compared with non-heated controls.

  7. Doppler modulation and Zeeman modulation: laser frequency stabilization without direct frequency modulation.

    PubMed

    Weis, A; Derler, S

    1988-07-01

    We discuss two methods (Zeeman modulation and Doppler modulation) for locking the frequency of a singlemode cw laser to an atomic absorption line. These methods do not require the laser frequency to be modulated directly. In the first scheme the absorption frequency of the atom is modulated via the Zeeman effect; in the second scheme the laser frequency is modulated indirectly via the Doppler effect in an atomic beam. We used the two methods successfully to lock two dye lasers to the transitions 6S((1/2)) ? 7S((1/2)) and 7S((1/2)) ? 15P(?) in atomic cesium.

  8. VORSTAB: A computer program for calculating lateral-directional stability derivatives with vortex flow effect

    NASA Technical Reports Server (NTRS)

    Lan, C. Edward

    1985-01-01

    A computer program based on the Quasi-Vortex-Lattice Method of Lan is presented for calculating longitudinal and lateral-directional aerodynamic characteristics of nonplanar wing-body combination. The method is based on the assumption of inviscid subsonic flow. Both attached and vortex-separated flows are treated. For the vortex-separated flow, the calculation is based on the method of suction analogy. The effect of vortex breakdown is accounted for by an empirical method. A summary of the theoretical method, program capabilities, input format, output variables and program job control set-up are described. Three test cases are presented as guides for potential users of the code.

  9. Direction-specific impairment of stability limits and falls in children with developmental coordination disorder: Implications for rehabilitation.

    PubMed

    Fong, Shirley S M; Ng, Shamay S M; Chung, Louisa M Y; Ki, W Y; Chow, Lina P Y; Macfarlane, Duncan J

    2016-01-01

    Limit of stability (LOS) is an important yet under-examined postural control ability in children with developmental coordination disorder (DCD). This study aimed to (1) compare the LOS and fall frequencies of children with and without DCD, and (2) explore the relationships between LOS parameters and falls in the DCD population. Thirty primary school-aged children with DCD and twenty age- and sex-matched typically-developing children participated in the study. Postural control ability, specifically LOS in standing, was evaluated using the LOS test. Reaction time, movement velocity, maximum excursion, end point excursion, and directional control were then calculated. Self-reported fall incidents in the previous week were also documented. Multivariate analysis of variance results revealed that children with DCD had shorter LOS maximum excursion in the backward direction compared to the control group (p=0.003). This was associated with a higher number of falls in daily life (rho=-0.556, p=0.001). No significant between-groups differences were found in other LOS-derived outcomes (p>0.05). Children with DCD had direction-specific postural control impairment, specifically, diminished LOS in the backward direction. This is related to their falls in daily life. Therefore, improving LOS should be factored into rehabilitation treatment for children with DCD.

  10. Preparation of Mg(OH)2 hybrid pigment by direct precipitation and graft onto cellulose fiber via surface-initiated atom transfer radical polymerization

    NASA Astrophysics Data System (ADS)

    Wang, Xiao; Zhang, Yue; Lv, Lihua; Cui, Yongzhu; Wei, Chunyan; Pang, Guibing

    2016-02-01

    Mg(OH)2 flame retardant hybrid pigment is synthesized through simultaneous solution precipitation and adsorption of anionic dyes (C.I. Acid Red 6). The Mg(OH)2 hybrid pigment bearing vinyl groups after surface silane modification is immobilized onto the surface of bromo end-functional cellulose fiber by atom transfer radical polymerization (ATRP). The morphology and structure of Mg(OH)2 pigments and cellulose fibers grafted with modified pigments are characterized. The thermal properties, flammability and color fastness of cellulose fibers grafted with modified pigments are measured. The results reveal that anionic dye molecules are adsorbed onto Mg(OH)2 crystals and affect the formation of lamella-like Mg(OH)2 crystals. The cellulose fiber grafted with modified Mg(OH)2 hybrid pigment absorbs about four times heat more than original cellulose fiber with about 4% immobilization ratio of pigment, which shortens nearly half of afterflame time and afterglow time.

  11. Effect of frequency, magnitude and direction of translational and rotational oscillation on the postural stability of standing people

    NASA Astrophysics Data System (ADS)

    Nawayseh, Naser; Griffin, Michael J.

    2006-12-01

    Oscillatory motions can cause injury in transport when standing passengers or crew lose balance and fall. To predict the loss of balance of standing people, a model is required of the relationship between the input motion and the stability of the human body. This experimental study investigated the effect of frequency, magnitude and direction of oscillation on the postural stability of standing subjects and whether response to rotational oscillation can be predicted from knowledge of response to translational oscillation. Twelve male subjects stood on a floor that oscillated in either horizontal (fore-and-aft or lateral) or rotational (pitch or roll) directions. The oscillations were one-third octave bands of random motion centred on five preferred octave centre frequencies (0.125, 0.25, 0.5, 1.0, and 2.0 Hz). The horizontal motions were presented at each of four velocities (0.04, 0.062, 0.099, and 0.16 ms -1 rms) and the rotational motions were presented at each of four rotational angles (0.73, 1.46, 2.92, and 5.85° rms) corresponding to four accelerations (0.125, 0.25, 0.5, and 1.0 ms -2 rms), where the acceleration is that caused by rotation through the gravitational vector. Postural stability was determined by subjective methods and by measuring the displacement of the centre of pressure at the feet during horizontal oscillation. During horizontal oscillation, increases in motion magnitude increased instability and, with the same velocity at all frequencies from 0.125 to 2.0 Hz, most instability occurred in the region of 0.5 Hz. Fore-and-aft oscillation produced more instability than lateral oscillation, although displacements of the centre of pressure were similar in both directions. With the same angular displacement at all frequencies from 0.125 to 2.0 Hz, pitch oscillation caused more instability than roll oscillation, but in both directions instability increased with increased frequency of oscillation. Frequency weightings for acceleration in the plane of

  12. Directed surfaces structures and interfaces for enhanced electrocatalyst activity, selectivity, and stability for energy conversion reactions

    SciTech Connect

    Jaramillo, Thomas F.

    2016-04-20

    IrO3/IrOx catalyst significantly outperforms rutile IrO2 and RuO2, the only other OER catalysts to have reasonable stability and activity in acidic electrolyte, and in fact demonstrates the best activity for any known OER catalyst measured in either acidic or in alkaline electrolyte. For alkaline conditions we have demonstrated that the combined effect of cerium as a dopant and gold as a metal support, significantly enhances the OER activity of electrodeposited NiOx films. This NiCeOx-Au catalyst delivers high OER activity in alkaline media, and is among the most active OER electrocatalysts reported to date (Nature Energy, accepted 2016). These studies of new catalysts for the OER, both in acid and in base, are fundamental to enabling new technologies of interest for the DOE, including the production of sustainable fuels and chemicals. ORR: One method to significantly reduce the Pt loading in fuel cell devices is to increase the ORR activity of Pt based systems. To this end we have synthesized a high surface area supported meso-structured PtxNi alloy thin film with a double gyroid morphology that both exhibits high activity and stability for the ORR (submitted, 2016). We have furthermore developed a Ru-core, Pt-shell system that improves the per Pt site activity by more than a factor of 2 (ChemElectroChem, 2014). Further refinement, optimizing Pt-shell thickness and reducing particle sintering during processing, enabled us to obtain a mass activity that is 2 times higher than commercial Pt/C from TKK. These are important contributions to the DOE goal of reducing Pt loading since an improved understanding of how to increase mass activity and stability helps enable low Pt content fuel cells.

  13. Direct observation of hole shift and characterization of spin states in radical ion pairs generated from photoinduced electron transfer of (phenothiazine)(n)-anthraquinone (n = 1, 3) dyads.

    PubMed

    Karimata, Ayumu; Suzuki, Shuichi; Kozaki, Masatoshi; Kimoto, Kenshi; Nozaki, Koichi; Matsushita, Hironori; Ikeda, Noriaki; Akiyama, Kimio; Kosumi, Daisuke; Hashimoto, Hideki; Okada, Keiji

    2014-11-26

    Photoinduced intramolecular electron transfer of dyad PTZ3-PTZ2-PTZ1-B-AQ consisting of phenothiazine trimer (PTZ3-PTZ2-PTZ1), bicyclo[2.2.2]octane (B), and anthraquinone (AQ) was investigated. After excitation (∼20 ps) of the AQ moiety in THF, a metastable radical ion pair (RIP) PTZ3-PTZ2-PTZ1(+)-B-AQ(-) appeared at ∼620 nm. From 500 ps to 6 ns the spectrum changed to a new absorption (∼950 nm), which was assigned to the hole-shifted stable RIP state PTZ3-PTZ2(+)-PTZ1-B-AQ(-). The time constant of the hole-shift process was determined to be 6.0 ns. The hole-shifted RIP state had a lifetime (τ) of 250 ns and was characterized by spin-polarized signals as a spin-correlated radical pair (SCRP) by means of time-resolved ESR. These results were compared with those for the phenothiazine monomer analog PTZ-B-AQ, which also produced the RIP state PTZ(+)-B-AQ(-) with τ = 1.9 μs. Time-resolved ESR showed an all emission signal pattern showing the triplet mechanism of PTZ-B-(3)AQ* → (3)[PTZ(+)-B-AQ(-)]. The origin of the difference in the lifetimes between the trimer and the monomer RIP states was discussed from various points of view, including free energy difference in the RIP states, reorganization energy difference in the charge recombination process, and the spin-state difference. Of these, the spin-state difference effect provided the most reasonable explanation.

  14. Doppler modulation and Zeeman modulation: laser frequency stabilization without direct frequency modulation

    SciTech Connect

    Weis, A.; Derler, S.

    1988-07-01

    We discuss two methods (Zeeman modulation and Doppler modulation) for locking the frequency of a single-mode cw laser to an atomic absorption line. These methods do not require the laser frequency to be modulated directly. In the first scheme the absorption frequency of the atom is modulated via the Zeeman effect; in the second scheme the laser frequency is modulated indirectly via the Doppler effect in an atomic beam. We used the two methods successfully to lock two dye lasers to the transitions 6S/sub 1/2/..-->..7S/sub 1/2/ and 7S/sub 1/2/..-->..15P/sub 3/2/ in atomic cesium.

  15. Structural Characterization of Hydroxyl Radical Adducts in Aqueous Media

    NASA Astrophysics Data System (ADS)

    Janik, Ireneusz; Tripathi, G. N. R.

    2015-06-01

    The oxidation by the hydroxyl (OH) radical is one of the most widely studied reactions because of its central role in chemistry, biology, organic synthesis, and photocatalysis in aqueous environments, wastewater treatment, and numerous other chemical processes. Although the redox potential of OH is very high, direct electron transfer (ET) is rarely observed. If it happens, it mostly proceeds through the formation of elusive OH adduct intermediate which facilitates ET and formation of hydroxide anion. Using time resolved resonance Raman technique we structurally characterized variety of OH adducts to sulfur containing organic compounds, halide ions as well as some metal cations. The bond between oxygen of OH radical and the atom of oxidized molecule differs depending on the nature of solute that OH radical reacts with. For most of sulfur containing organics, as well as halide and pseudo-halide ions, our observation suggested that this bond has two-center three-electron character. For several metal aqua ions studied, the nature of the bond depends on type of the cation being oxidized. Discussion on spectral parameters of all studied hydroxyl radical adducts as well as the role solvent plays in their stabilization will be presented.

  16. Dynamics of Radical-Mediated Enzyme Catalyses

    NASA Astrophysics Data System (ADS)

    Warncke, Kurt

    1997-11-01

    An emergent class of enzymes harnesses the extreme reactivity of electron-deficient free radical species to perform some of the most difficult reactions in biology. The regio- and stereo-selectivity achieved by these enzymes defies long-held ideas that radical reactions are non-specific. The common primary step in these catalyses is metal- or metallocenter-assisted generation of an electron-deficient organic "initiator radical". The initiator radical abstracts a hydrogen atom from the substrate, opening a new reaction channel for rearrangement to the product. Our aim is to elucidate the detailed molecular mechanisms of the radical pair separation and radical rearrangement steps. Radical pair separation and substrate radical rearrangement are tracked by using time-resolved (10-7 to 10-3 s) techniques of pulsed-electron paramagnetic resonance spectroscopy (FT-EPR, ESEEM). Synchronous time-evolution of the reactions is attained by triggering with a visible laser pulse. Transient non-Boltzmann population of the states of the spin-coupled systems, and resultant electron spin polarization, facilitates study at or near room temperature under conditions where the enzymes are operative. The systems examined include ethanolamine deaminase, a vitamin B12 coenzyme-dependent enzyme, ribonucleotide reductase and photosynthetic reaction centers. The electronic and nuclear structural and kinetic information obtained from the pulsed-EPR studies is used to address how the initiator radicals are stabilized against deleterious recombination with the metal, and to distinguish the participation of concerted versus sequential rearrangement pathways.

  17. Radical Behaviorism and Buddhism: Complementarities and Conflicts

    ERIC Educational Resources Information Center

    Diller, James W.; Lattal, Kennon A.

    2008-01-01

    Comparisons have been made between Buddhism and the philosophy of science in general, but there have been only a few attempts to draw comparisons directly with the philosophy of radical behaviorism. The present review therefore considers heretofore unconsidered points of comparison between Buddhism and radical behaviorism in terms of their…

  18. Direct force measurements reveal that protein Tau confers short-range attractions and isoform-dependent steric stabilization to microtubules

    PubMed Central

    Chung, Peter J.; Choi, Myung Chul; Miller, Herbert P.; Feinstein, H. Eric; Raviv, Uri; Li, Youli; Wilson, Leslie; Feinstein, Stuart C.; Safinya, Cyrus R.

    2015-01-01

    Microtubules (MTs) are hollow cytoskeletal filaments assembled from αβ-tubulin heterodimers. Tau, an unstructured protein found in neuronal axons, binds to MTs and regulates their dynamics. Aberrant Tau behavior is associated with neurodegenerative dementias, including Alzheimer’s. Here, we report on a direct force measurement between paclitaxel-stabilized MTs coated with distinct Tau isoforms by synchrotron small-angle X-ray scattering (SAXS) of MT-Tau mixtures under osmotic pressure (P). In going from bare MTs to MTs with Tau coverage near the physiological submonolayer regime (Tau/tubulin-dimer molar ratio; ΦTau = 1/10), isoforms with longer N-terminal tails (NTTs) sterically stabilized MTs, preventing bundling up to PB ∼ 10,000–20,000 Pa, an order of magnitude larger than bare MTs. Tau with short NTTs showed little additional effect in suppressing the bundling pressure (PB ∼ 1,000–2,000 Pa) over the same range. Remarkably, the abrupt increase in PB observed for longer isoforms suggests a mushroom to brush transition occurring at 1/13 < ΦTau < 1/10, which corresponds to MT-bound Tau with NTTs that are considerably more extended than SAXS data for Tau in solution indicate. Modeling of Tau-mediated MT–MT interactions supports the hypothesis that longer NTTs transition to a polyelectrolyte brush at higher coverages. Higher pressures resulted in isoform-independent irreversible bundling because the polyampholytic nature of Tau leads to short-range attractions. These findings suggest an isoform-dependent biological role for regulation by Tau, with longer isoforms conferring MT steric stabilization against aggregation either with other biomacromolecules or into tight bundles, preventing loss of function in the crowded axon environment. PMID:26542680

  19. Uniformity of spherical shock wave dynamically stabilized by two successive laser profiles in direct-drive inertial confinement fusion implosions

    SciTech Connect

    Temporal, M.; Canaud, B.; Garbett, W. J.; Ramis, R.

    2015-10-15

    The implosion uniformity of a directly driven spherical inertial confinement fusion capsule is considered within the context of the Laser Mégajoule configuration. Two-dimensional (2D) hydrodynamic simulations have been performed assuming irradiation with two laser beam cones located at 49° and 131° with respect to the axis of symmetry. The laser energy deposition causes an inward shock wave whose surface is tracked in time, providing the time evolution of its non-uniformity. The illumination model has been used to optimize the laser intensity profiles used as input in the 2D hydro-calculations. It is found that a single stationary laser profile does not maintain a uniform shock front over time. To overcome this drawback, it is proposed to use two laser profiles acting successively in time, in order to dynamically stabilize the non-uniformity of the shock front.

  20. Charts for Estimating Tail-rotor Contribution to Helicopter Directional Stability and Control in Low-Speed Flight

    NASA Technical Reports Server (NTRS)

    Amer, Kenneth B; Gessow, Alfred

    1955-01-01

    Theoretically derived charts and equations are presented by which tail-rotor design studies of directional trim and control response at low forward speed can be conveniently made. The charts can also be used to obtain the main-rotor stability derivatives of thrust with respect to collective pitch and angle of attack at low forward speeds. The use of the charts and equations for tail-rotor design studies is illustrated. Comparisons between theoretical and experimental results are presented. The charts indicate, and flight tests confirm, that the region of vortex roughness which is familiar for the main rotor is also encountered by the tail rotor and that prolonged operation at the corresponding flight conditions would be difficult.

  1. Contemporary Radical Economics.

    ERIC Educational Resources Information Center

    Sherman, Howard J.

    1984-01-01

    The origins of contemporary radical economics are examined. Applications of radical economics to price and value theory, labor segmentation theory, business cycles, industrial organization, government and business, imperialism and development, and comparative systems are reviewed. (Author/RM)

  2. Slow oscillating transcranial direct current stimulation during sleep has a sleep-stabilizing effect in chronic insomnia: a pilot study.

    PubMed

    Saebipour, Mohammad R; Joghataei, Mohammad T; Yoonessi, Ali; Sadeghniiat-Haghighi, Khosro; Khalighinejad, Nima; Khademi, Soroush

    2015-10-01

    Recent evidence suggests that lack of slow-wave activity may play a fundamental role in the pathogenesis of insomnia. Pharmacological approaches and brain stimulation techniques have recently offered solutions for increasing slow-wave activity during sleep. We used slow (0.75 Hz) oscillatory transcranial direct current stimulation during stage 2 of non-rapid eye movement sleeping insomnia patients for resonating their brain waves to the frequency of sleep slow-wave. Six patients diagnosed with either sleep maintenance or non-restorative sleep insomnia entered the study. After 1 night of adaptation and 1 night of baseline polysomnography, patients randomly received sham or real stimulation on the third and fourth night of the experiment. Our preliminary results show that after termination of stimulations (sham or real), slow oscillatory transcranial direct current stimulation increased the duration of stage 3 of non-rapid eye movement sleep by 33 ± 26 min (P = 0.026), and decreased stage 1 of non-rapid eye movement sleep duration by 22 ± 17.7 min (P = 0.028), compared with sham. Slow oscillatory transcranial direct current stimulation decreased stage 1 of non-rapid eye movement sleep and wake time after sleep-onset durations, together, by 55.4 ± 51 min (P = 0.045). Slow oscillatory transcranial direct current stimulation also increased sleep efficiency by 9 ± 7% (P = 0.026), and probability of transition from stage 2 to stage 3 of non-rapid eye movement sleep by 20 ± 17.8% (P = 0.04). Meanwhile, slow oscillatory transcranial direct current stimulation decreased transitions from stage 2 of non-rapid eye movement sleep to wake by 12 ± 6.7% (P = 0.007). Our preliminary results suggest a sleep-stabilizing role for the intervention, which may mimic the effect of sleep slow-wave-enhancing drugs.

  3. The radical amplifier

    NASA Technical Reports Server (NTRS)

    Hastie, D. R.

    1994-01-01

    The radical amplifier as a method for measuring radical concentrations in the atmosphere has received renewed attention lately. In principle, it can measure the total concentration of HO(x) and RO(x) radicals by reacting ambient air with high concentrations of CO (3-10 percent) and NO (2-6 ppmv), and measuring the NO2 produced.

  4. Enhancement of skin radical scavenging activity and stratum corneum lipids after the application of a hyperforin-rich cream.

    PubMed

    Haag, S F; Tscherch, K; Arndt, S; Kleemann, A; Gersonde, I; Lademann, J; Rohn, S; Meinke, M C

    2014-02-01

    Hyperforin is well-known for its anti-inflammatory, anti-tumor, anti-bacterial, and antioxidant properties. The application of a hyperforin-rich verum cream could strengthen the skin barrier function by reducing radical formation and stabilizing stratum corneum lipids. Here, it was investigated whether topical treatment with a hyperforin-rich cream increases the radical protection of the skin during VIS/NIR irradiation. Skin lipid profile was investigated applying HPTLC on skin lipid extracts. Furthermore, the absorption- and scattering coefficients, which influence radical formation, were determined. 11 volunteers were included in this study. After a single cream application, VIS/NIR-induced radical formation could be completely inhibited by both verum and placebo showing an immediate protection. After an application period of 4weeks, radical formation could be significantly reduced by 45% following placebo application and 78% after verum application showing a long-term protection. Furthermore, the skin lipids in both verum and placebo groups increased directly after a single cream application but only significantly for ceramide [AP], [NP1], and squalene. After long-term cream application, concentration of cholesterol and the ceramides increased, but no significance was observed. These results indicate that regular application of the hyperforin-rich cream can reduce radical formation and can stabilize skin lipids, which are responsible for the barrier function.

  5. Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

    PubMed

    Liao, Zhixiong; Yi, Hong; Li, Zheng; Fan, Chao; Zhang, Xu; Liu, Jie; Deng, Zixin; Lei, Aiwen

    2015-01-01

    A simple copper-catalyzed direct radical carbooxygenation of styrenes is developed utilizing alkyl bromides as radical resources. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of styrenes in one pot. A broad range of styrenes and alcohols are well tolerated in this transformation. The EPR experiment shows that alkyl halides could oxidize Cu(I) to Cu(II) in this transformation.

  6. The tyrosyl free radical in ribonucleotide reductase.

    PubMed Central

    Gräslund, A; Sahlin, M; Sjöberg, B M

    1985-01-01

    The enzyme, ribonucleotide reductase, catalyses the formation of deoxyribonucleotides from ribonucleotides, a reaction essential for DNA synthesis in all living cells. The Escherichia coli ribonucleotide reductase, which is the prototype of all known eukaryotic and virus-coded enzymes, consists of two nonidentical subunits, proteins B1 and B2. The B2 subunit contains an antiferromagnetically coupled pair of ferric ions and a stable tyrosyl free radical. EPR studies show that the tyrosyl radical, formed by loss of ferric ions and a stable tyrosyl free radical. EPR studies show that the tyrosyl radical, formed by loss of an electron, has its unpaired spin density delocalized in the aromatic ring of tyrosine. Effects of iron-radical interaction indicate a relatively close proximity between the iron center and the radical. The EPR signal of the radical can be studied directly in frozen packed cells of E. coli or mammalian origin, if the cells are made to overproduce ribonucleotide reductase. The hypothetic role of the tyrosyl free radical in the enzymatic reaction is not yet elucidated, except in the reaction with the inhibiting substrate analogue 2'-azido-CDP. In this case, the normal tyrosyl radical is destroyed with concomitant appearance of a 2'-azido-CDP-localized radical intermediate. Attempts at spin trapping of radical reaction intermediates have turned out negative. In E. coli the activity of ribonucleotide reductase may be regulated by enzymatic activities that interconvert a nonradical containing form and the fully active protein B2. In synchronized mammalian cells, however, the cell cycle variation of ribonucleotide reductase, studied by EPR, was shown to be due to de novo protein synthesis. Inhibitors of ribonucleotide reductase are of medical interest because of their ability to control DNA synthesis. One example is hydroxyurea, used in cancer therapy, which selectively destroys the tyrosyl free radical. PMID:3007085

  7. Bacterial Fucose-Rich Polysaccharide Stabilizes MAPK-Mediated Nrf2/Keap1 Signaling by Directly Scavenging Reactive Oxygen Species during Hydrogen Peroxide-Induced Apoptosis of Human Lung Fibroblast Cells

    PubMed Central

    Roy Chowdhury, Sougata; Sinha, Tridib Kumar; Sen, Ramkrishna; Basak, Ratan Kumar; Adhikari, Basudam; Bhattacharyya, Arindam

    2014-01-01

    Continuous free radical assault upsets cellular homeostasis and dysregulates associated signaling pathways to promote stress-induced cell death. In spite of the continuous development and implementation of effective therapeutic strategies, limitations in treatments for stress-induced toxicities remain. The purpose of the present study was to determine the potential therapeutic efficacy of bacterial fucose polysaccharides against hydrogen peroxide (H2O2)-induced stress in human lung fibroblast (WI38) cells and to understand the associated molecular mechanisms. In two different fermentation processes, Bacillus megaterium RB-05 biosynthesized two non-identical fucose polysaccharides; of these, the polysaccharide having a high-fucose content (∼42%) conferred the maximum free radical scavenging efficiency in vitro. Structural characterizations of the purified polysaccharides were performed using HPLC, GC-MS, and 1H/13C/2D-COSY NMR. H2O2 (300 µM) insult to WI38 cells showed anti-proliferative effects by inducing intracellular reactive oxygen species (ROS) and by disrupting mitochondrial membrane permeability, followed by apoptosis. The polysaccharide (250 µg/mL) attenuated the cell death process by directly scavenging intracellular ROS rather than activating endogenous antioxidant enzymes. This process encompasses inhibition of caspase-9/3/7, a decrease in the ratio of Bax/Bcl2, relocalization of translocated Bax and cytochrome c, upregulation of anti-apoptotic members of the Bcl2 family and a decrease in the phosphorylation of MAPKs (mitogen activated protein kinases). Furthermore, cellular homeostasis was re-established via stabilization of MAPK-mediated Nrf2/Keap1 signaling and transcription of downstream cytoprotective genes. This molecular study uniquely introduces a fucose-rich bacterial polysaccharide as a potential inhibitor of H2O2-induced stress and toxicities. PMID:25412177

  8. Bacterial fucose-rich polysaccharide stabilizes MAPK-mediated Nrf2/Keap1 signaling by directly scavenging reactive oxygen species during hydrogen peroxide-induced apoptosis of human lung fibroblast cells.

    PubMed

    Roy Chowdhury, Sougata; Sengupta, Suman; Biswas, Subir; Sinha, Tridib Kumar; Sen, Ramkrishna; Basak, Ratan Kumar; Adhikari, Basudam; Bhattacharyya, Arindam

    2014-01-01

    Continuous free radical assault upsets cellular homeostasis and dysregulates associated signaling pathways to promote stress-induced cell death. In spite of the continuous development and implementation of effective therapeutic strategies, limitations in treatments for stress-induced toxicities remain. The purpose of the present study was to determine the potential therapeutic efficacy of bacterial fucose polysaccharides against hydrogen peroxide (H2O2)-induced stress in human lung fibroblast (WI38) cells and to understand the associated molecular mechanisms. In two different fermentation processes, Bacillus megaterium RB-05 biosynthesized two non-identical fucose polysaccharides; of these, the polysaccharide having a high-fucose content (∼ 42%) conferred the maximum free radical scavenging efficiency in vitro. Structural characterizations of the purified polysaccharides were performed using HPLC, GC-MS, and (1)H/(13)C/2D-COSY NMR. H2O2 (300 µM) insult to WI38 cells showed anti-proliferative effects by inducing intracellular reactive oxygen species (ROS) and by disrupting mitochondrial membrane permeability, followed by apoptosis. The polysaccharide (250 µg/mL) attenuated the cell death process by directly scavenging intracellular ROS rather than activating endogenous antioxidant enzymes. This process encompasses inhibition of caspase-9/3/7, a decrease in the ratio of Bax/Bcl2, relocalization of translocated Bax and cytochrome c, upregulation of anti-apoptotic members of the Bcl2 family and a decrease in the phosphorylation of MAPKs (mitogen activated protein kinases). Furthermore, cellular homeostasis was re-established via stabilization of MAPK-mediated Nrf2/Keap1 signaling and transcription of downstream cytoprotective genes. This molecular study uniquely introduces a fucose-rich bacterial polysaccharide as a potential inhibitor of H2O2-induced stress and toxicities.

  9. [Lavoisier and radicals].

    PubMed

    Lafont, Olivier

    2007-01-01

    Lavoisier and his co-workers (Guyton de Morveau, Bertholet, Fourcroy) considered that acids were constituted of oxygen and of something else that they called radicals. These radicals were known in some cases, i.e. nitrogen for nitrous acid, carbon for carbonic acid, phosphorus for phosphoric acid. In the case of sulfur, the sulfuric radical could be associated with different quantities of oxigen leading to sulfuric or sulfurous acids. In other cases radicals remained unknown at the time i.e. muriatic radical for muriatic acid, or benzoyl radical for benzoic acid. It is interesting to notice that Lavoisier evoked the case of compound radicals constituted of different substances such as carbon and hydrogen.

  10. Radical Nature of C-Lignin

    SciTech Connect

    Berstis, Laura; Elder, Thomas; Crowley, Michael; Beckham, Gregg T.

    2016-05-17

    The recently discovered lignin composed of caffeoyl alcohol monolignols or C-lignin is particularly intriguing given its homogeneous, linear polymeric structure and exclusive benzodioxane linkage between monomers. By virtue of this simplified chemistry, the potential emerges for improved valorization strategies with C-lignin relative to other natural heterogeneous lignins. To better understand caffeoyl alcohol polymers, we characterize the thermodynamics of the radical recombination dimerization reactions forming the benzodioxane linkage and the bond dissociation into radical monolignol products. These properties are also predicted for the cross-coupling of caffeoyl alcohol with the natural monolignols, coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol, in anticipation of polymers potentially enabled by genetic modification. The average BDEs for the C-lignin benzodioxane $\\alpha$- and β-bonds are 56.5 and 63.4 kcal/mol, respectively, with similar enthalpies for heterodimers. The BDE of the $\\alpha$-bond within the benzodioxane linkage is consistently greater than that of the β-bond in all dimers of each stereochemical arrangement, explained by the ability the $\\alpha$-carbon radical generated to delocalize onto the adjacent phenyl ring. Relative thermodynamics of the heterodimers demonstrates that the substituents on the phenyl ring directly neighboring the bond coupling the monolignols more strongly impact the dimer bond strengths and product stability, compared to the substituents present on the terminal phenyl ring. Enthalpy comparisons furthermore demonstrate that the erythro stereochemical configurations of the benzodioxane bond are slightly less thermodynamically stable than the threo configurations. The overall differences in strength of bonds and reaction enthalpies between stereoisomers are generally found to be insignificant, supporting that postcoupling rearomatization is under kinetic control. Projecting the lowest-energy stereoisomer

  11. Radical Nature of C-Lignin

    DOE PAGES

    Berstis, Laura; Elder, Thomas; Crowley, Michael; ...

    2016-05-17

    The recently discovered lignin composed of caffeoyl alcohol monolignols or C-lignin is particularly intriguing given its homogeneous, linear polymeric structure and exclusive benzodioxane linkage between monomers. By virtue of this simplified chemistry, the potential emerges for improved valorization strategies with C-lignin relative to other natural heterogeneous lignins. To better understand caffeoyl alcohol polymers, we characterize the thermodynamics of the radical recombination dimerization reactions forming the benzodioxane linkage and the bond dissociation into radical monolignol products. These properties are also predicted for the cross-coupling of caffeoyl alcohol with the natural monolignols, coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol, in anticipation of polymers potentially enabled by genetic modification. The average BDEs for the C-lignin benzodioxanemore » $$\\alpha$$- and β-bonds are 56.5 and 63.4 kcal/mol, respectively, with similar enthalpies for heterodimers. The BDE of the $$\\alpha$$-bond within the benzodioxane linkage is consistently greater than that of the β-bond in all dimers of each stereochemical arrangement, explained by the ability the $$\\alpha$$-carbon radical generated to delocalize onto the adjacent phenyl ring. Relative thermodynamics of the heterodimers demonstrates that the substituents on the phenyl ring directly neighboring the bond coupling the monolignols more strongly impact the dimer bond strengths and product stability, compared to the substituents present on the terminal phenyl ring. Enthalpy comparisons furthermore demonstrate that the erythro stereochemical configurations of the benzodioxane bond are slightly less thermodynamically stable than the threo configurations. The overall differences in strength of bonds and reaction enthalpies between stereoisomers are generally found to be insignificant, supporting that postcoupling rearomatization is under kinetic control. Projecting the lowest

  12. A computer program for calculating symmetrical aerodynamic characteristics and lateral-directional stability derivatives of wing-body combinations with blowing jets

    NASA Technical Reports Server (NTRS)

    Lan, C. E.; Mehrotra, S. C.; Fox, C. H., Jr.

    1978-01-01

    The necessary information for using a computer program to calculate the aerodynamic characteristics under symmetrical flight conditions and the lateral-directional stability derivatives of wing-body combinations with upper-surface-blowing (USB) or over-wing-blowing (OWB) jets are described. The following new features were added to the program: (1) a fuselage of arbitrary body of revolution has been included. The effect of wing-body interference can now be investigated, and (2) all nine lateral-directional stability derivatives can be calculated. The program is written in FORTRAN language and runs on CDC Cyber 175 and Honeywell 66/60 computers.

  13. Measurement of Flying Qualities of a Dehavilland Mosquito F-8 Airplane (AAF No. 43-334960) I: Lateral and Directional Stability and Control Characteristics

    NASA Technical Reports Server (NTRS)

    Gray, W.E.; Talmage, D.B.; Crane, H.L.

    1945-01-01

    The data presented have no bearing on performance characteristics of airplane, which were considered exceptionally good in previous tests. Some of the undesirable features of lateral and directional stability and control characteristics of the F-8 are listed. Directional stability, with rudder fixed, did not sufficiently restrict aileron yaw; rudder control was inadequate during take-off and landing, and was insufficient to fly airplane with one engine; in clean condition, power of ailerons was slightly below minimum value specified; it was difficult to trim airplane in rough air.

  14. Extraction of Lateral-Directional Stability and Control Derivatives for the Basic F-18 Aircraft at High Angles of Attack

    NASA Technical Reports Server (NTRS)

    Iliff, Kenneth W.; Wang, Kon-Sheng Charles

    1997-01-01

    The results of parameter identification to determine the lateral-directional stability and control derivatives of an F-18 research aircraft in its basic hardware and software configuration are presented. The derivatives are estimated from dynamic flight data using a specialized identification program developed at NASA Dryden Flight Research Center. The formulation uses the linearized aircraft equations of motions in their continuous/discrete form and a maximum likelihood estimator that accounts for both state and measurement noise. State noise is used to model the uncommanded forcing function caused by unsteady aerodynamics, such as separated and vortical flows, over the aircraft. The derivatives are plotted as functions of angle of attack between 3 deg and 47 deg and compared with wind-tunnel predictions. The quality of the derivative estimates obtained by parameter identification is somewhat degraded because the maneuvers were flown with the aircraft's control augmentation system engaged, which introduced relatively high correlations between the control variables and response variables as a result of control motions from the feedback control system.

  15. X-29A Lateral-Directional Stability and Control Derivatives Extracted From High-Angle-of-Attack Flight Data

    NASA Technical Reports Server (NTRS)

    Iliff, Kenneth W.; Wang, Kon-Sheng Charles Wang

    1996-01-01

    The lateral-directional stability and control derivatives of the X-29A number 2 are extracted from flight data over an angle-of-attack range of 4 degrees to 53 degrees using a parameter identification algorithm. The algorithm uses the linearized aircraft equations of motion and a maximum likelihood estimator in the presence of state and measurement noise. State noise is used to model the uncommanded forcing function caused by unsteady aerodynamics over the aircraft at angles of attack above 15 degrees. The results supported the flight-envelope-expansion phase of the X-29A number 2 by helping to update the aerodynamic mathematical model, to improve the real-time simulator, and to revise flight control system laws. Effects of the aircraft high gain flight control system on maneuver quality and the estimated derivatives are also discussed. The derivatives are plotted as functions of angle of attack and compared with the predicted aerodynamic database. Agreement between predicted and flight values is quite good for some derivatives such as the lateral force due to sideslip, the lateral force due to rudder deflection, and the rolling moment due to roll rate. The results also show significant differences in several important derivatives such as the rolling moment due to sideslip, the yawing moment due to sideslip, the yawing moment due to aileron deflection, and the yawing moment due to rudder deflection.

  16. Quantitative measurement of hydroxyl radical (OH) concentration in premixed flat flame by combining laser-induced fluorescence and direct absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, Shuang; Su, Tie; Li, Zhong-Shan; Bai, Han-Chen; Yan, Bo; Yang, Fu-Rong

    2016-10-01

    An accurate and reasonable technique combining direct absorption spectroscopy and laser-induced fluorescence (LIF) methods is developed to quantitatively measure the concentrations of hydroxyl in CH4/air flat laminar flame. In our approach, particular attention is paid to the linear laser-induced fluorescence and absorption processes, and experimental details as well. Through measuring the temperature, LIF signal distribution and integrated absorption, spatially absolute OH concentrations profiles are successfully resolved. These experimental results are then compared with the numerical simulation. It is proved that the good quality of the results implies that this method is suitable for calibrating the OH-PLIF measurement in a practical combustor. Project supported by the National Natural Science Foundation of China (Grant No. 11272338), the Science and Technology on Scramjet Key Laboratory Funding, China (Grant No. STSKFKT 2013004), and the China Scholarship Council.

  17. Forgotten Radicals in Biology

    PubMed Central

    Luc, Rochette; Vergely, Catherine

    2008-01-01

    Redox reactions play key roles in intra- and inter-cellular signaling, and in adaptative processes of tissues towards stress. Among the major free radicals with essential functions in cells are reactive oxygen species (ROS) including superoxide anion (O2•-), hydroxyl radical (•OH) and reactive nitrogen species (RNS) such as nitric oxide (•NO). In this article, we review the forgotten and new radicals with potential relevance to cardiovascular pathophysiology. Approximately 0.3% of O2•- present in cytosol exists in its protonated form: hydroperoxyl radical (HO2•). Water (H2O) can be split into two free radicals: •OH and hydrogen radical (H•). Several free radicals, including thiyl radicals (RS•) and nitrogen dioxide (NO2•) are known to isomerize double bonds. In the omega-6 series of poly-unsaturated fatty acids (PUFAs), cis-trans isomerization of γ-linolenate and arachidonate catalyzed by RS• has been investigated. Evidence is emerging that hydrogen disulphide (H2S) is a signaling molecule in vivo which can be a source of free radicals. The Cu-Zn superoxide dismutase (SOD) enzyme can oxidize the ionized form of H2S to hydro-sulphide radical: HS•. Recent studies suggest that H2S plays an important function in cardiovascular functions. Carbonate radical, which can be formed when •OH reacts with carbonate or bicarbonate ions, is also involved in the activity of Cu-Zn-SOD. Recently, it has been reported that carbonate anion were potentially relevant oxidants of nucleic acids in physiological environments. In conclusion, there is solid evidence supporting the formation of many free radicals by cells leading which may play an important role in their homeostasis. PMID:23675099

  18. Cathodal transcranial direct current stimulation can stabilize perception of movement: Evidence from the two-thirds power law illusion.

    PubMed

    Scocchia, Lisa; Bolognini, Nadia; Convento, Silvia; Stucchi, Natale

    2015-11-16

    Human movements conform to specific kinematic laws of motion. One of such laws, the "two-thirds power law", describes the systematic co-variation between curvature and velocity of body movements. Noticeably, the same law also influences the perception of moving stimuli: the velocity of a dot moving along a curvilinear trajectory is perceived as uniform when the dot kinematics complies with the two-thirds power law. Instead, if the dot moves at constant speed, its velocity is perceived as highly non-uniform. This dynamic visual illusion points to a strong coupling between action and perception; however, how this coupling is implemented in the brain remains elusive. In this study, we tested whether the premotor cortex (PM) and the primary visual cortex (V1) play a role in the illusion by means of transcranial Direct Current Stimulation (tDCS). All participants underwent three tDCS sessions during which they received active or sham cathodal tDCS (1.5mA) over PM or V1 of the left hemisphere. During tDCS, participants were required to adjust the velocity of a dot moving along an elliptical trajectory until it looked uniform across the whole trajectory. Results show that occipital tDCS decreases the illusion variability both within and across participants, as compared to sham tDCS. This means that V1 stimulation increases individual sensitivity to the illusory motion and also increases coherence across different observers. Conversely, the illusion seems resistant to tDCS in terms of its magnitude, with cathodal stimulation of V1 or PM not affecting the amount of the illusory effect. Our results provide evidence for strong visuo-motor coupling in visual perception: the velocity of a dot moving along an elliptical trajectory is perceived as uniform only when its kinematics closely complies to the same law of motion that constrains human movement production. Occipital stimulation by cathodal tDCS can stabilize such illusory percept.

  19. Formation and Fragmentation of Unsaturated Fatty Acid [M - 2H + Na]- Ions: Stabilized Carbanions for Charge-Directed Fragmentation

    NASA Astrophysics Data System (ADS)

    Thomas, Michael C.; Kirk, Benjamin B.; Altvater, Jens; Blanksby, Stephen J.; Nette, Geoffrey W.

    2013-12-01

    Fatty acids are long-chain carboxylic acids that readily produce [M - H]- ions upon negative ion electrospray ionization (ESI) and cationic complexes with alkali, alkaline earth, and transition metals in positive ion ESI. In contrast, only one anionic monomeric fatty acid-metal ion complex has been reported in the literature, namely [M - 2H + FeIICl]-. In this manuscript, we present two methods to form anionic unsaturated fatty acid-sodium ion complexes (i.e., [M - 2H + Na]-). We find that these ions may be generated efficiently by two distinct methods: (1) negative ion ESI of a methanolic solution containing the fatty acid and sodium fluoride forming an [M - H + NaF]- ion. Subsequent collision-induced dissociation (CID) results in the desired [M - 2H + Na]- ion via the neutral loss of HF. (2) Direct formation of the [M - 2H + Na]- ion by negative ion ESI of a methanolic solution containing the fatty acid and sodium hydroxide or bicarbonate. In addition to deprotonation of the carboxylic acid moiety, formation of [M - 2H + Na]- ions requires the removal of a proton from the fatty acid acyl chain. We propose that this deprotonation occurs at the bis-allylic position(s) of polyunsaturated fatty acids resulting in the formation of a resonance-stabilized carbanion. This proposal is supported by ab initio calculations, which reveal that removal of a proton from the bis-allylic position, followed by neutral loss of HX (where X = F- and -OH), is the lowest energy dissociation pathway.

  20. Radical prostatectomy - discharge

    MedlinePlus

    ... prostatectomy - discharge; Laparoscopic radical prostatectomy - discharge; LRP - discharge; Robotic-assisted laparoscopic prostatectomy - discharge ; RALP - discharge; Pelvic lymphadenectomy - discharge; Prostate cancer - prostatectomy

  1. Pyrimidine nucleobase radical reactivity in DNA and RNA

    NASA Astrophysics Data System (ADS)

    Greenberg, Marc M.

    2016-11-01

    Nucleobase radicals are major products of the reactions between nucleic acids and hydroxyl radical, which is produced via the indirect effect of ionizing radiation. The nucleobase radicals also result from hydration of cation radicals that are produced via the direct effect of ionizing radiation. The role that nucleobase radicals play in strand scission has been investigated indirectly using ionizing radiation to generate them. More recently, the reactivity of nucleobase radicals resulting from formal hydrogen atom or hydroxyl radical addition to pyrimidines has been studied by independently generating the reactive intermediates via UV-photolysis of synthetic precursors. This approach has provided control over where the reactive intermediates are produced within biopolymers and facilitated studying their reactivity. The contributions to our understanding of pyrimidine nucleobase radical reactivity by this approach are summarized.

  2. Radical [1,3]-Rearrangements of Breslow Intermediates

    PubMed Central

    Alwarsh, Sefat; Xu, Yi; Qian, Steven

    2015-01-01

    Breslow intermediates that bear radical stabilizing N-substituents including benzyl, cinnamyl, and diarylmethyl undergo facile homolytic C-N bond scission under mild conditions to give products of formal [1,3]-rearrangement rather than benzoin condensation. EPR experiments and computational analysis support a radical mechanism. Implications for thiamine based enzymes are discussed. PMID:26553753

  3. Radical behaviorism and buddhism: complementarities and conflicts.

    PubMed

    Diller, James W; Lattal, Kennon A

    2008-01-01

    Comparisons have been made between Buddhism and the philosophy of science in general, but there have been only a few attempts to draw comparisons directly with the philosophy of radical behaviorism. The present review therefore considers heretofore unconsidered points of comparison between Buddhism and radical behaviorism in terms of their respective goals, conceptualization of human beings, and the outcomes of following either philosophy. From these comparisons it is concluded that the commonalities discerned between these two philosophies may enhance both philosophical systems.

  4. Hydroxyl Radical-Mediated Novel Modification of Peptides: N-Terminal Cyclization through the Formation of α-Ketoamide.

    PubMed

    Lee, Seon Hwa; Kyung, Hyunsook; Yokota, Ryo; Goto, Takaaki; Oe, Tomoyuki

    2015-01-20

    The hydroxyl radical-mediated oxidation of peptides and proteins constitutes a large group of post-translational modifications that can result in structural and functional changes. These oxidations can lead to hydroxylation, sulfoxidation, or carbonylation of certain amino acid residues and cleavage of peptide bonds. In addition, hydroxyl radicals can convert the N-terminus of peptides to an α-ketoamide via abstraction of the N-terminal α-hydrogen and hydrolysis of the ketimine intermediate. In the present study, we identified N-terminal cyclization as a novel modification mediated by a hydroxyl radical. The reaction of angiotensin (Ang) II (DRVYIHPF) and the hydroxyl radical generated by the Cu(II)/ascorbic acid (AA) system or UV/hydrogen peroxide system produced N-terminal cyclized-Ang II (Ang C) and pyruvamide-Ang II (Ang P, CH3COCONH-RVYIHPF). The structure of Ang C was confirmed by mass spectrometry and comparison to an authentic standard. The subsequent incubation of isolated Ang P in the presence of Cu(II)/AA revealed that Ang P was the direct precursor of Ang C. The proposed mechanism involves the formation of a nitrogen-centered (aminyl) radical, which cyclizes to form a five-membered ring containing the alkoxy radical. The subsequent β-scission reaction of the alkoxyl radical results in the cleavage of the terminal CH3CO group. The initial aminyl radical can be stabilized by chelation to the Cu(II) ions. The affinity of Ang C toward the Ang II type 1 receptor was significantly lower than that of Ang II or Ang P. Ang C was not further metabolized by aminopeptidase A, which converts Ang II to Ang III. Hydroxyl radical-mediated N-terminal cyclization was also observed in other Ang peptides containing N-terminal alanine, arginine, valine, and amyloid β 1-11 (DAEFRHDSGYE).

  5. Stability properties of the steady state solutions of a non-neutral plasma diode when there is a uniform magnetic field along transverse direction

    NASA Astrophysics Data System (ADS)

    Kuznetsov, V. I.; Pramanik, Sourav; Gerasimenko, A. B.; Chakrabarti, Nikhil

    2017-02-01

    The stability properties of a non-neutral plasma diode [Pramanik et al., Phys. Plasmas 23, 103105 (2016)] have been investigated for the stationary states taking arbitrary value of the neutralization parameter. A constant magnetic field is also assumed to be applied externally along the transverse direction. The (η, ɛ)-diagram technique is used to study the stability features of all types of solutions with respect to small aperiodic perturbations. Employing the first order perturbation theory, a relevant dispersion relation has been derived and analyzed for the regimes when electrons are not turned around by the magnetic field. These regimes of solutions belong to the "Normal C branch" and "C-overlap branch" of the "emitter field strength vs. diode gap"-diagrams. With the help of this dispersion relation, both aperiodic and oscillatory stability properties of such solutions have been presented.

  6. Formation of stable radicals in the radiolysis of fluoroorganic compounds

    NASA Astrophysics Data System (ADS)

    Goldanskii, V. I.; Barkalov, I. M.

    The existence of anomally long-living radicals (life time in liquid more than 100 days at 300 K) which arise in the process of radiolysis has been discovered in liquid perfluorocarbons. The ESR spectra analysis has allowed the singling out of two types of radical: (1) the perfluoroalkyl radical in which the unpaired electron stabilization is thought to be connected with the steric isolation of the surrounding perfluoromethyl groups and (2) the perfluoroalkyl radical whose stabilization is connected with the delocalization of the unpaired electron conjugated with the double CC bond. These stable radicals may be employed in the synthesis and modification of fluoropolymers as initiators and regulators, in the dosimetry of reactor irradiation, as well as in medico-biological investigations as spin-labelled compounds.

  7. Stability of Large Direct-Current Power Systems That Use Switching Converters and the Application of Switching Converters to the International Space Station

    NASA Technical Reports Server (NTRS)

    Manners, Bruce A.; Gholdston, E. W.; Karimi, K.; Lee, F. C.; Rajagopalan, J.; Panov, Y.

    1997-01-01

    As direct-current space power systems continue to grow in size, switching power converters are playing an ever larger role in power conditioning and control. When a large direct-current system that uses power converters of this type is being designed, special attention must be placed on the electrical stability of the system and of the individual loads on the system. The impedance specification approach for system stability was accomplished as a result of cooperative work of the International Space Station program team, which consists of the NASA Lewis Research Center, the Boeing Company, and Rocketdyne Division/Rockwell International. In addition, major contributions were provided by the Virginia Polytechnic Institute and State University working under a grant to NASA Lewis.

  8. Intensity-Stabilized Fast-Scanned Direct Absorption Spectroscopy Instrumentation Based on a Distributed Feedback Laser with Detection Sensitivity down to 4 × 10−6

    PubMed Central

    Zhao, Gang; Tan, Wei; Jia, Mengyuan; Hou, Jiajuan; Ma, Weiguang; Dong, Lei; Zhang, Lei; Feng, Xiaoxia; Wu, Xuechun; Yin, Wangbao; Xiao, Liantuan; Axner, Ove; Jia, Suotang

    2016-01-01

    A novel, intensity-stabilized, fast-scanned, direct absorption spectroscopy (IS-FS-DAS) instrumentation, based on a distributed feedback (DFB) diode laser, is developed. A fiber-coupled polarization rotator and a fiber-coupled polarizer are used to stabilize the intensity of the laser, which significantly reduces its relative intensity noise (RIN). The influence of white noise is reduced by fast scanning over the spectral feature (at 1 kHz), followed by averaging. By combining these two noise-reducing techniques, it is demonstrated that direct absorption spectroscopy (DAS) can be swiftly performed down to a limit of detection (LOD) (1σ) of 4 × 10−6, which opens up a number of new applications. PMID:27657082

  9. Radical chemistry of artemisinin

    NASA Astrophysics Data System (ADS)

    Denisov, Evgenii T.; Solodova, S. L.; Denisova, Taisa G.

    2010-12-01

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  10. Direct Epoxidation of Propylene over Stabilized Cu+ Surface Sites on Ti Modified Cu2O

    SciTech Connect

    Yang, X.; Kattel, S.; Xiong, K.; Mudiyanselage, K.; Rykov, S.; Senanayake, S. D.; Rodriguez, J. A.; Liu, P.; Stacchiola, D. J.; Chen, J. G.

    2015-07-17

    Direct propylene epoxidation by O2 is a challenging reaction because of the strong tendency for complete combustion. Results from the current study demonstrate the feasibility to tune the epoxidation selectivity by generating highly dispersed and stabilized Cu+ active sites in a TiCuOx mixed oxide. The TiCuOx surface anchors the key surface intermediate, oxametallacycle, leading to higher selectivity for epoxidation of propylene.

  11. Computational Study of the Thermodynamics of Atmospheric Nitration of PAHs via OH-Radical-Initiated Reaction

    NASA Astrophysics Data System (ADS)

    Jariyasopit, N.; Cheong, P.; Simonich, S. L.

    2011-12-01

    Nitrated polycyclic aromatic hydrocarbons (NPAHs) are an important class of PAH derivatives that are more toxic than their parent PAHs (1) and are emitted from direct emission and secondary emission to the atmosphere. The secondary emissions, particularly the OH-radical initiated and NO3-radical-initiated reactions, have been shown to influence the NPAH concentrations in the atmosphere. Gas-phase reactions are thought to be the major sources of NPAHs containing four or fewer rings (2). Besides NPAHs, PAHs lead to a number of other products including oxygenated, hydroxy substituted and ring-opened PAH derivatives (3). For some PAHs, the OH-initiated and NO3-initiated reactions result in the formation of different NPAH isomers, allowing the ratio of these isomers to be used in the determination of direct or secondary emission sources. Previous studies have shown that the PAH gas-phase reactions with OH radical is initiated by the addition of OH radical to the aromatic ring to form hydroxycyclohexadienyl radicals (4). In the presence of NO2, these reactive intermediates readily nitrate with the elimination of water (4). The hydroxycyclohexadienyl-type radical intermediates are also prone to react with other species in the atmosphere or revert back to the original compound (3). The objective of this study was to investigate the thermodynamics of PAH nitration through day-time OH-radical-initiated reactions. The theoretical investigation were carried out using Density Functioanl Theory (B3LYP) and the 6-31G(d) basis set, as implemented in Gaussian03. A number of different PAHs were studied including fluoranthene, pyrene, as well as the molecular weight 302 PAHs such as dibenzo[a,l]pyrene. Computations were also used to predict unknown NPAHs formed by OH-radical-initiated reaction. All intermediates for the OH-radical addition and the following nitration were computed. We have discovered that the thermodynamic stability of the intermediates involved in the PAH

  12. OVERVIEW OF THE HISTORY, PRESENT STATUS, AND FUTURE DIRECTION OF SOLIDIFICATION/STABILIZATION TECHNOLOGIES FOR HAZARDOUS WASTE TREATMENT

    EPA Science Inventory

    Solidification/stabilization (S/S) technology processes are currently being utilized in the United States to treat inorganic and organic hazardous waste and radioactive waste. These wastes are generated from operating industry or have resulted from the uncontrolled management of ...

  13. Direct Measurement of Electric-Field-Induced Birefringence in a Polymer-Stabilized Blue-Phase Liquid Crystal Composite

    DTIC Science & Technology

    2010-05-01

    Wu, “Low voltage and high transmittance blue-phase liquid crystal displays with corrugated electrodes,” Appl. Phys. Lett. 96(1), 011102 (2010). 7. K...Cloud, Optical Methods of Engineering Analysis (Cambridge, New York, 1998). 1.Introduction Polymer-stabilized blue phase liquid crystal (PS-BPLC...with a large induced birefringence for lowering the operation voltage of display devices. 2. Experiment and theoretical analysis The PS-BPLC employed

  14. 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…

  15. Vibronic Spectroscopy of the Phenylcyanomethyl Radical

    NASA Astrophysics Data System (ADS)

    Mehta, Deepali N.; Kidwell, Nathanael M.; Zwier, Timothy S.

    2011-06-01

    Resonance stabilized radicals (RSRs) are thought to be key intermediates in the formation of larger molecules in planetary atmospheres. Given the nitrogen-rich atmosphere of Titan, and the prevalence of nitriles there, it is likely that nitrile and isonitrile RSRs could be especially important in pathways leading to the formation of more complex nitrogen-containing compounds and the aerosols ("tholins") that are ultimately produced. In this talk, the results of a gas phase, jet-cooled vibronic spectroscopy study of the phenylcyanomethyl radical (C_6H_5.{C}HCN), the nitrogen-containing analog of the 1-phenylpropargyl radical, will be presented. A resonant two color photon ionization spectrum over the range 21,350-22,200 Cm-1 (450.0-468.0 nm) has been recorded, and the D_0-D_1 origin band has been tentatively identified at 21,400 Cm-1. Studies identifying the ionization threshold, and characterizing the vibronic structure will also be presented. An analogous study of the phenylisocyanomethyl radical, C_6H_5.{C}HNC, is currently being pursued for comparison with that of phenylcyanomethyl radical.

  16. Carbon-Centered Free Radicals in Particulate Matter Emissions from Wood and Coal Combustion

    PubMed Central

    2009-01-01

    Electron paramagnetic resonance (EPR) spectroscopy was used to measure the free radicals in the particulate matter (PM) emissions from wood and coal combustion. The intensity of radicals in PM dropped linearly within two months of sample storage and stabilized after that. This factor of storage time was adjusted when comparing radical intensities among different PM samples. An inverse relationship between coal rank and free radical intensities in PM emissions was observed, which was in contrast with the pattern of radical intensities in the source coals. The strong correlation between intensities of free radical and elemental carbon in PM emissions suggests that the radical species may be carbon-centered. The increased g-factors, 2.0029−2.0039, over that of purely carbon-centered radicals may indicate the presence of vicinal oxygen heteroatom. The redox and biology activities of these carbon-centered radicals are worthy of evaluation. PMID:19551161

  17. Spectroscopic detection, reactivity, and acid-base behavior of ring-dimethoxylated phenylethanoic acid radical cations and radical zwitterions in aqueous solution.

    PubMed

    Bietti, Massimo; Capone, Alberto

    2004-01-23

    A product and time-resolved kinetic study of the one-electron oxidation of ring-dimethoxylated phenylethanoic acids has been carried out at different pH values. Oxidation leads to the formation of aromatic radical cations or radical zwitterions depending on pH, and pK(a) values for the corresponding acid-base equilibria have been measured. The radical cations undergo decarboxylation with first-order rate constants (k(dec)) ranging from <10(2) to 5.6 x 10(4) s(-1) depending on radical cation stability. A significant increase in k(dec) (between 10 and 40 times) is observed on going from the radical cations to the corresponding radical zwitterions. The results are discussed in terms of the ease of intramolecular side chain to ring electron transfer required for decarboxylation, in both the radical cations and radical zwitterions.

  18. Hydroxyl radical generation by red tide algae.

    PubMed

    Oda, T; Akaike, T; Sato, K; Ishimatsu, A; Takeshita, S; Muramatsu, T; Maeda, H

    1992-04-01

    The unicellular marine phytoplankton Chattonella marina is known to have toxic effects against various living marine organisms, especially fishes. However, details of the mechanism of the toxicity of this plankton remain obscure. Here we demonstrate the generation of superoxide and hydroxyl radicals from a red tide unicellular organism, C. marina, by using ESR spectroscopy with the spin traps 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and N-t-butyl-alpha-phenylnitrone (PBN), and by using the luminol-enhanced chemiluminescence response. The spin-trapping assay revealed productions of spin adduct of superoxide anion (O2-) (DMPO-OOH) and that of hydroxyl radical (.OH) (DMPO-OH) in the algal suspension, which was not observed in the ultrasonic-ruptured suspension. The addition of superoxide dismutase (500 U/ml) almost completely inhibited the formation of both DMPO-OOH and DMPO-OH, and carbon-centered radicals were generated with the disappearance of DMPO-OH after addition of 5% dimethyl sulfoxide (Me2SO) and 5% ethanol. Furthermore, the generation of methyl and methoxyl radicals, which are thought to be produced by the reaction of hydroxyl radical and Me2SO under aerobic condition, was identified using spin trapping with a combination of PBN and Me2SO. Luminol-enhanced chemiluminescence assay also supported the above observations. These results clearly indicate that C. marina generates and releases the superoxide radical followed by the production of hydroxyl radical to the surrounding environment. The velocity of superoxide generation by C. marina was about 100 times faster than that by mammalian phagocytes per cell basis. The generation of oxygen radical is suggested to be a pathogenic principle in the toxication of red tide to susceptible aquaculture fishes and may be directly correlated with the coastal pollution by red tide.

  19. Chemistry of ascorbic acid radicals

    SciTech Connect

    Bielski, B.H.J.

    1982-01-01

    The chemistry of ascorbic acid free radicals is reviewed. Particular emphasis is placed on identification and characterization of ascorbate radicals by spectrophotometric and electron paramagnetic resonance techniques, the kinetics of formation and disappearance of ascorbate free radicals in enzymatic and nonenzymatic reactions, the effect of pH upon the spectral and kinetic properties of ascorbate anion radical, and chemical reactivity of ascorbate free radicals.

  20. Site-directed mutagenesis reveals regions implicated in the stability and fiber formation of human λ3r light chains.

    PubMed

    Villalba, Miryam I; Canul-Tec, Juan C; Luna-Martínez, Oscar D; Sánchez-Alcalá, Rosalba; Olamendi-Portugal, Timoteo; Rudiño-Piñera, Enrique; Rojas, Sonia; Sánchez-López, Rosana; Fernández-Velasco, Daniel A; Becerril, Baltazar

    2015-01-30

    Light chain amyloidosis (AL) is a disease that affects vital organs by the fibrillar aggregation of monoclonal light chains. λ3r germ line is significantly implicated in this disease. In this work, we contrasted the thermodynamic stability and aggregation propensity of 3mJL2 (nonamyloidogenic) and 3rJL2 (amyloidogenic) λ3 germ lines. Because of an inherent limitation (extremely low expression), Cys at position 34 of the 3r germ line was replaced by Tyr reaching a good expression yield. A second substitution (W91A) was introduced in 3r to obtain a better template to incorporate additional mutations. Although the single mutant (C34Y) was not fibrillogenic, the second mutation located at CDR3 (W91A) induced fibrillogenesis. We propose, for the first time, that CDR3 (position 91) affects the stability and fiber formation of human λ3r light chains. Using the double mutant (3rJL2/YA) as template, other variants were constructed to evaluate the importance of those substitutions into the stability and aggregation propensity of λ3 light chains. A change in position 7 (P7D) boosted 3rJL2/YA fibrillogenic properties. Modification of position 48 (I48M) partially reverted 3rJL2/YA fibril aggregation. Finally, changes at positions 8 (P8S) or 40 (P40S) completely reverted fibril formation. These results confirm the influential roles of N-terminal region (positions 7 and 8) and the loop 40-60 (positions 40 and 48) on AL. X-ray crystallography revealed that the three-dimensional topology of the single and double λ3r mutants was not significantly altered. This mutagenic approach helped to identify key regions implicated in λ3 AL.

  1. Site-directed Mutagenesis Reveals Regions Implicated in the Stability and Fiber Formation of Human λ3r Light Chains

    SciTech Connect

    Villalba, Miryam I.; Canul-Tec, Juan C.; Luna-Martínez, Oscar D.; Sánchez-Alcalá, Rosalba; Olamendi-Portugal, Timoteo; Rudiño-Piñera, Enrique; Rojas, Sonia; Sánchez-López, Rosana; Fernández-Velasco, Daniel A.; Becerril, Baltazar

    2014-12-11

    Light chain amyloidosis (AL) is a disease that affects vital organs by the fibrillar aggregation of monoclonal light chains. λ3r germ line is significantly implicated in this disease. In this paper, we contrasted the thermodynamic stability and aggregation propensity of 3mJL2 (nonamyloidogenic) and 3rJL2 (amyloidogenic) λ3 germ lines. Because of an inherent limitation (extremely low expression), Cys at position 34 of the 3r germ line was replaced by Tyr reaching a good expression yield. A second substitution (W91A) was introduced in 3r to obtain a better template to incorporate additional mutations. Although the single mutant (C34Y) was not fibrillogenic, the second mutation located at CDR3 (W91A) induced fibrillogenesis. We propose, for the first time, that CDR3 (position 91) affects the stability and fiber formation of human λ3r light chains. Using the double mutant (3rJL2/YA) as template, other variants were constructed to evaluate the importance of those substitutions into the stability and aggregation propensity of λ3 light chains. A change in position 7 (P7D) boosted 3rJL2/YA fibrillogenic properties. Modification of position 48 (I48M) partially reverted 3rJL2/YA fibril aggregation. Finally, changes at positions 8 (P8S) or 40 (P40S) completely reverted fibril formation. These results confirm the influential roles of N-terminal region (positions 7 and 8) and the loop 40–60 (positions 40 and 48) on AL. X-ray crystallography revealed that the three-dimensional topology of the single and double λ3r mutants was not significantly altered. Finally, this mutagenic approach helped to identify key regions implicated in λ3 AL.

  2. Site-directed Mutagenesis Reveals Regions Implicated in the Stability and Fiber Formation of Human λ3r Light Chains

    DOE PAGES

    Villalba, Miryam I.; Canul-Tec, Juan C.; Luna-Martínez, Oscar D.; ...

    2014-12-11

    Light chain amyloidosis (AL) is a disease that affects vital organs by the fibrillar aggregation of monoclonal light chains. λ3r germ line is significantly implicated in this disease. In this paper, we contrasted the thermodynamic stability and aggregation propensity of 3mJL2 (nonamyloidogenic) and 3rJL2 (amyloidogenic) λ3 germ lines. Because of an inherent limitation (extremely low expression), Cys at position 34 of the 3r germ line was replaced by Tyr reaching a good expression yield. A second substitution (W91A) was introduced in 3r to obtain a better template to incorporate additional mutations. Although the single mutant (C34Y) was not fibrillogenic, themore » second mutation located at CDR3 (W91A) induced fibrillogenesis. We propose, for the first time, that CDR3 (position 91) affects the stability and fiber formation of human λ3r light chains. Using the double mutant (3rJL2/YA) as template, other variants were constructed to evaluate the importance of those substitutions into the stability and aggregation propensity of λ3 light chains. A change in position 7 (P7D) boosted 3rJL2/YA fibrillogenic properties. Modification of position 48 (I48M) partially reverted 3rJL2/YA fibril aggregation. Finally, changes at positions 8 (P8S) or 40 (P40S) completely reverted fibril formation. These results confirm the influential roles of N-terminal region (positions 7 and 8) and the loop 40–60 (positions 40 and 48) on AL. X-ray crystallography revealed that the three-dimensional topology of the single and double λ3r mutants was not significantly altered. Finally, this mutagenic approach helped to identify key regions implicated in λ3 AL.« less

  3. Site-directed Mutagenesis Reveals Regions Implicated in the Stability and Fiber Formation of Human λ3r Light Chains*

    PubMed Central

    Villalba, Miryam I.; Canul-Tec, Juan C.; Luna-Martínez, Oscar D.; Sánchez-Alcalá, Rosalba; Olamendi-Portugal, Timoteo; Rudiño-Piñera, Enrique; Rojas, Sonia; Sánchez-López, Rosana; Fernández-Velasco, Daniel A.; Becerril, Baltazar

    2015-01-01

    Light chain amyloidosis (AL) is a disease that affects vital organs by the fibrillar aggregation of monoclonal light chains. λ3r germ line is significantly implicated in this disease. In this work, we contrasted the thermodynamic stability and aggregation propensity of 3mJL2 (nonamyloidogenic) and 3rJL2 (amyloidogenic) λ3 germ lines. Because of an inherent limitation (extremely low expression), Cys at position 34 of the 3r germ line was replaced by Tyr reaching a good expression yield. A second substitution (W91A) was introduced in 3r to obtain a better template to incorporate additional mutations. Although the single mutant (C34Y) was not fibrillogenic, the second mutation located at CDR3 (W91A) induced fibrillogenesis. We propose, for the first time, that CDR3 (position 91) affects the stability and fiber formation of human λ3r light chains. Using the double mutant (3rJL2/YA) as template, other variants were constructed to evaluate the importance of those substitutions into the stability and aggregation propensity of λ3 light chains. A change in position 7 (P7D) boosted 3rJL2/YA fibrillogenic properties. Modification of position 48 (I48M) partially reverted 3rJL2/YA fibril aggregation. Finally, changes at positions 8 (P8S) or 40 (P40S) completely reverted fibril formation. These results confirm the influential roles of N-terminal region (positions 7 and 8) and the loop 40–60 (positions 40 and 48) on AL. X-ray crystallography revealed that the three-dimensional topology of the single and double λ3r mutants was not significantly altered. This mutagenic approach helped to identify key regions implicated in λ3 AL. PMID:25505244

  4. Calculation of the Lateral Stability of a Directly Coupled Tandem-Towed Fighter Airplane and Correlation with Experimental Data

    NASA Technical Reports Server (NTRS)

    Shanks, Robert E.

    1958-01-01

    A theoretical method is presented for predicting the dynamic lateral stability characteristics of an airplane towed in tandem by a much larger airplane. Values of period and time to damp to one-half amplitude and rolling motions calculated by an analog computer have been correlated with results of two experimental investigations conducted in the Langley free-flight tunnel which were part of a U.S. Air Force program (Project FICON) to develop a satisfactory arrangement by which a bomber could tow a parasite fighter. In general, the theoretical results agree with the experimental results.

  5. Radicals in ionic liquids.

    PubMed

    Strehmel, Veronika

    2012-05-14

    Stable radicals and recombination of photogenerated lophyl radicals are investigated in ionic liquids. The 2,2,6,6-tetramethylpiperidine-1-yloxyl derivatives contain various substituents at the 4-position to the nitroxyl group, including hydrogen-bond-forming or ionic substituents that undergo additional interactions with the individual ions of the ionic liquids. Some of these spin probes contain similar ions to ionic liquids to avoid counter-ion exchange with the ionic liquid. Depending on the ionic liquid anion, the Stokes-Einstein theory or the Spernol-Gierer-Wirtz theory can be applied to describe the temperature dependence of the average rotational correlation time of the spin probe in the ionic liquids. Furthermore, the spin probes give information about the micropolarity of the ionic liquids. In this context the substituent at the 4-position to the nitroxyl group plays a significant role. Covalent bonding of a spin probe to the imidazolium ion results in bulky spin probes that are strongly immobilized in the ionic liquid. Furthermore, lophyl radical recombination in the dark, which is chosen to understand the dynamics of bimolecular reactions in ionic liquids, shows a slow process at longer timescale and a rise time at a shorter timescale. Although various reactions may contribute to the slower process during lophyl radical recombination, it follows a second-order kinetics that does not clearly show solvent viscosity dependence. However, the rise time, which may be attributed to radical pair formation, increases with increasing solvent viscosity.

  6. The application of parameter estimation to flight measurements to obtain lateral-directional stability derivatives of an augmented jet-flap STOL airplane

    NASA Technical Reports Server (NTRS)

    Stephenson, J. D.

    1983-01-01

    Flight experiments with an augmented jet flap STOL aircraft provided data from which the lateral directional stability and control derivatives were calculated by applying a linear regression parameter estimation procedure. The tests, which were conducted with the jet flaps set at a 65 deg deflection, covered a large range of angles of attack and engine power settings. The effect of changing the angle of the jet thrust vector was also investigated. Test results are compared with stability derivatives that had been predicted. The roll damping derived from the tests was significantly larger than had been predicted, whereas the other derivatives were generally in agreement with the predictions. Results obtained using a maximum likelihood estimation procedure are compared with those from the linear regression solutions.

  7. Effects of Dynamic Multi-directional Loading on the Microstructural Evolution and Thermal Stability of Pure Aluminum

    NASA Astrophysics Data System (ADS)

    Yang, Yang; Zhang, Hua; Chen, Yadong

    2016-09-01

    Microstructural evolution and thermal stability of 1050 commercial pure aluminum processed by means of split Hopkinson pressure bar and Instron-3369 mechanical testing machine to an accumulated strain of 3.6 were investigated. The nominal strain rates reached up to 3.0 × 103 and 1 × 10-3/s, respectively. Samples in the deformed state and annealed in the temperature interval 423-523 K for 1 h were characterized by transmission electron microscopy (TEM). TEM observations reveal that the initial coarse grains are refined significantly, and the deformed structures mainly consist of equiaxed subgrains and dislocation cells with a high density of interior dislocation. In addition, the average subgrain/cell sizes of these two kinds of deformed samples are nearly the same. As to recovery behavior, recovered subgrains are observed at 473 (dynamic) versus 523 K (quasi-static), that is to say, recovery is fairly slow in the quasi-static deformed samples. It is therefore to be expected that thermal stability of this dynamic deformed aluminum is weaker than that of the quasi-static compressed one, which is due to the higher density of dislocation and nonequilibrium dislocation configurations produced during dynamic loading.

  8. Enhancement of thermal stability of chondroitinase ABC I by site-directed mutagenesis: an insight from Ramachandran plot.

    PubMed

    Nazari-Robati, Mahdieh; Khajeh, Khosro; Aminian, Mahdi; Mollania, Nasrin; Golestani, Abolfazl

    2013-02-01

    The application of chondroitinase ABC I (cABC I) in damaged nervous tissue is believed to prune glycosaminoglycan chains of proteoglycans, thereby facilitates axon regeneration. However, the utilization of cABC I as therapeutics is notably restricted due to its thermal instability. In the present study, we have explored the possibility of thermostabilization of cABC I through release of its conformational strain using Ramachandran plot information. In this regard, Gln140 with non-optimal φ and ψ values were replaced with Gly, Ala and Asn. The results indicated that Q140G and Q140A mutants were able to improve both activity and thermal stability of the enzyme while Q140N variant reduced the enzyme activity and destabilized it. Moreover, the two former variants displayed a remarkable resistance to trypsin degradation. Structural analysis of all mutants showed an increase in intrinsic fluorescence intensity and secondary structure content of Q140G and Q140A compared to the wild type which indicated more compact structure upon mutation. This investigation demonstrated that relief of conformational tension can be considered as a possible approach to increase the stability of the protein.

  9. Antioxidant effects of water- and lipid-soluble nitroxide radicals in liposomes.

    PubMed

    Cimato, Alejandra N; Piehl, Lidia L; Facorro, Graciela B; Torti, Horacio B; Hager, Alfredo A

    2004-12-15

    Liposomes are today useful tools in different fields of science and technology. A lack of stability due to lipid peroxidation is the main problem in the extension of the use of these formulations. Recent investigative works have reported the protective effects of stable nitroxide radicals against oxidative processes in different media and under different stress conditions. Our group has focused its attention on the natural aging of liposomes and the protection provided by the water- and lipid-soluble nitroxide radicals 2,2,6,6-tetramethylpiperdine-1-oxyl (TEMPO) and doxylstearic acids (5-DSA, 12-DSA, and 16-DSA), respectively. Unilamellar liposomes were incubated under air atmosphere at 37 degrees C, both in the absence and in the presence of these radicals. Conjugated dienes, lipid hydroperoxides, TBARS, membrane fluidity, and nitroxide ESR signal intensity were followed as a function of time. Our results demonstrated that doxylstearic acids were more efficient than TEMPO in retarding lipid peroxidation at all the concentrations tested. The inhibition percentages, depending on the total nitroxide concentration, were not proportional to the lipid-water partition coefficient. Furthermore, time-course ESR signals showed a slower decrease for doxylstearic acids than for TEMPO. No significant differences were found among 5-DSA, 12-DSA, and 16-DSA. We concluded that the nitroxide radical efficiency as antioxidant directly depends on both nitroxide concentration and lipophilicity.

  10. Radical addition-initiated domino reactions of conjugated oxime ethers.

    PubMed

    Ueda, Masafumi

    2014-01-01

    The application of conjugated oxime ethers to the synthesis of complex chemical scaffolds using domino radical reactions has been described in detail. The triethylborane-mediated hydroxysulfenylation reaction allows for the regioselective construction of a carbon-sulfur bond and a carbon-oxygen bond in a single operation for the formation of β-hydroxy sulfides. This reaction proceeds via a radical pathway involving regioselective thiyl addition and the subsequent trapping of the resulting α-imino radical with O₂, where the imino group enhances the stability of the intermediate radical. Hydroxyalkylation reactions that occur via a carbon radical addition reaction followed by the hydroxylation of the resulting N-borylenamine with O₂ have also been developed. We investigated sequential radical addition aldol-type reactions in detail to explore the novel domino reactions that occur via the generation of N-borylenamine. The radical reaction of a conjugated oxime ether with triethylborane in the presence of an aldehyde affords γ-butyrolactone via sequential processes including ethyl radical addition, the generation of N-borylenamine, an aldol-type reaction with an aldehyde, and a lactonization reaction. A novel domino reaction has also been developed involving the [3,3]-sigmatropic rearrangement of N-boryl-N-phenoxyenamine. The triethylborane-mediated domino reactions of O-phenyl-conjugated oxime ethers afforded the corresponding benzofuro[2,3-b]pyrrol-2-ones via a radical addition/[3,3]-sigmatropic rearrangement/cyclization/lactamization cascade.

  11. Experimental evidence for efficient hydroxyl radical regeneration in isoprene oxidation

    NASA Astrophysics Data System (ADS)

    Fuchs, H.; Hofzumahaus, A.; Rohrer, F.; Bohn, B.; Brauers, T.; Dorn, H.-P.; Häseler, R.; Holland, F.; Kaminski, M.; Li, X.; Lu, K.; Nehr, S.; Tillmann, R.; Wegener, R.; Wahner, A.

    2013-12-01

    Most pollutants in the Earth's atmosphere are removed by oxidation with highly reactive hydroxyl radicals. Field measurements have revealed much higher concentrations of hydroxyl radicals than expected in regions with high loads of the biogenic volatile organic compound isoprene. Different isoprene degradation mechanisms have been proposed to explain the high levels of hydroxyl radicals observed. Whether one or more of these mechanisms actually operates in the natural environment, and the potential impact on climate and air quality, has remained uncertain. Here, we present a complete set of measurements of hydroxyl and peroxy radicals collected during isoprene-oxidation experiments carried out in an atmospheric simulation chamber, under controlled atmospheric conditions. We detected significantly higher concentrations of hydroxyl radicals than expected based on model calculations, providing direct evidence for a strong hydroxyl radical enhancement due to the additional recycling of radicals in the presence of isoprene. Specifically, our findings are consistent with the unimolecular reactions of isoprene-derived peroxy radicals postulated by quantum chemical calculations. Our experiments suggest that more than half of the hydroxyl radicals consumed in isoprene-rich regions, such as forests, are recycled by these unimolecular reactions with isoprene. Although such recycling is not sufficient to explain the high concentrations of hydroxyl radicals observed in the field, we conclude that it contributes significantly to the oxidizing capacity of the atmosphere in isoprene-rich regions.

  12. The nighttime production of OH radicals in the continental troposphere

    NASA Astrophysics Data System (ADS)

    Bey, Isabelle; Aumont, Bernard; Toupance, Gérard

    1997-05-01

    Chemical pathways involved in the nocturnal production of hydroxyl radical (OH) and associated peroxy radicals (HO2 and RO2) are quantified for various environmental situations of the continental troposphere by means of numerical simulations. In the nocturnal stable layer, most of the OH radicals are directly produced by VOC+O3 reactions in rural and semipolluted environments while in urban environments, they result mainly from the radical chain propagation from RO2 and HO2. The radical propagation is mainly driven by NO: the nitrate radical (NO3) plays no role in such processes but is significantly involved in the direct formation of RO2 radicals. Above the nocturnal stable layer, whatever the environmental situation, OH radicals are mainly due to radical chain propagation in which NO3 plays a significant role. The nighttime simulated OH concentrations are 3 × 104 to 5 × 105 and 1 × 104 to 5 × 104 molec cm-3 for the nocturnal stable and residual layers respectively.

  13. Structure and thermal cycling stability of a hafnium monocarbide reinforced directionally solidified cobalt-base eutectic alloy

    NASA Technical Reports Server (NTRS)

    Kim, Y. G.

    1975-01-01

    A nominal composition of Co-15Cr-2ONi-10.5 Hf-0.7 C (NASA-HAFCO-11) was directionally solidified at 0.8 cm/hr growth rate to produce aligned HfC in a cobalt matrix alloy. The aligned HfC fibers were present as rod and plate types. The diameter of the aligned fibers was about 1 micron, with volume fraction in the range of 11 to 15 percent. The growth direction of the fibers was parallel to the 100. The NASA-HAFCO-11 alloy was subjected to thermal cycling between 425 deg and 1100 C, using a 2.5 minute cycle. No microstructural degradation of the HfC fibers in the alloy was observed after 2500 cycles.

  14. Radical Behaviorism and Buddhism: Complementarities and Conflicts

    PubMed Central

    Diller, James W; Lattal, Kennon A

    2008-01-01

    Comparisons have been made between Buddhism and the philosophy of science in general, but there have been only a few attempts to draw comparisons directly with the philosophy of radical behaviorism. The present review therefore considers heretofore unconsidered points of comparison between Buddhism and radical behaviorism in terms of their respective goals, conceptualization of human beings, and the outcomes of following either philosophy. From these comparisons it is concluded that the commonalities discerned between these two philosophies may enhance both philosophical systems. PMID:22478509

  15. Radical Socioeducational Analysis.

    ERIC Educational Resources Information Center

    Sigmon, Scott B.

    This book describes an interactive-interdisciplinary way of looking at the social conditions which impinge upon schooling, and which impact upon the social facts of life. It examines current schooling problems from the perspective of radical social democratic thought. The book is organized into four major sections. Part 1 provides an overview and…

  16. Against Radical Multiculturalism.

    ERIC Educational Resources Information Center

    Zorn, Jeff

    This essay presents two strands of arguments against radical or critical emancipatory multiculturalism. In strand 1, "'Culture' is...whatever..." the looseness of the core concept of "culture," which can refer to anything at all concerning a social group that itself may exist only theoretically, is shown. In strand 2, "From ideology to leveling,…

  17. Beyond Radical Educational Cynicism.

    ERIC Educational Resources Information Center

    Wood, George H.

    1982-01-01

    An alternative is presented to counter current radical arguments that the schools cannot bring about social change because they are instruments of capitalism. The works of Samuel Bowles, Herbert Gintis, and Louis Althusser are discussed. Henry Giroux's "Ideology, Culture and the Process of Schooling" provides an alternative to cynicism.…

  18. Radically enhanced molecular recognition

    NASA Astrophysics Data System (ADS)

    Trabolsi, Ali; Khashab, Niveen; Fahrenbach, Albert C.; Friedman, Douglas C.; Colvin, Michael T.; Cotí, Karla K.; Benítez, Diego; Tkatchouk, Ekaterina; Olsen, John-Carl; Belowich, Matthew E.; Carmielli, Raanan; Khatib, Hussam A.; Goddard, William A.; Wasielewski, Michael R.; Stoddart, J. Fraser

    2010-01-01

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication.

  19. Radical School Reform.

    ERIC Educational Resources Information Center

    Gross, Beatrice, Ed.; Gross, Ronald, Ed.

    This book provides a comprehensive examination of the nature of the school crisis and the ways in which radical thinkers and educators are dealing with it. Excerpts from the writings of Jonathan Kozol, John Holt, Kenneth Clark, and others are concerned with the realities of education in ghettos and suburbs. Paul Goodman, Marshall McLuhan, Sylvia…

  20. Validation of three-dimensional incompressible spatial direct numerical simulation code: A comparison with linear stability and parabolic stability equation theories for boundary-layer transition on a flat plate

    NASA Technical Reports Server (NTRS)

    Joslin, Ronald D.; Streett, Craig L.; Chang, Chau-Lyan

    1992-01-01

    Spatially evolving instabilities in a boundary layer on a flat plate are computed by direct numerical simulation (DNS) of the incompressible Navier-Stokes equations. In a truncated physical domain, a nonstaggered mesh is used for the grid. A Chebyshev-collocation method is used normal to the wall; finite difference and compact difference methods are used in the streamwise direction; and a Fourier series is used in the spanwise direction. For time stepping, implicit Crank-Nicolson and explicit Runge-Kutta schemes are used to the time-splitting method. The influence-matrix technique is used to solve the pressure equation. At the outflow boundary, the buffer-domain technique is used to prevent convective wave reflection or upstream propagation of information from the boundary. Results of the DNS are compared with those from both linear stability theory (LST) and parabolized stability equation (PSE) theory. Computed disturbance amplitudes and phases are in very good agreement with those of LST (for small inflow disturbance amplitudes). A measure of the sensitivity of the inflow condition is demonstrated with both LST and PSE theory used to approximate inflows. Although the DNS numerics are very different than those of PSE theory, the results are in good agreement. A small discrepancy in the results that does occur is likely a result of the variation in PSE boundary condition treatment in the far field. Finally, a small-amplitude wave triad is forced at the inflow, and simulation results are compared with those of LST. Again, very good agreement is found between DNS and LST results for the 3-D simulations, the implication being that the disturbance amplitudes are sufficiently small that nonlinear interactions are negligible.

  1. Direct comparison of gluco-oligosaccharide oxidase variants and glucose oxidase: substrate range and H2O2 stability

    PubMed Central

    Vuong, Thu V.; Foumani, Maryam; MacCormick, Benjamin; Kwan, Rachel; Master, Emma R.

    2016-01-01

    Glucose oxidase (GO) activity is generally restricted to glucose and is susceptible to inactivation by H2O2. By comparison, the Y300A variant of gluco-oligosaccharide oxidase (GOOX) from Sarocladium strictum showed broader substrate range and higher H2O2 stability. Specifically, Y300A exhibited up to 40 times higher activity on all tested sugars except glucose, compared to GO. Moreover, fusion of the Y300A variant to a family 22 carbohydrate binding module from Clostridium thermocellum (CtCBM22A) nearly doubled its catalytic efficiency on glucose, while retaining significant activity on oligosaccharides. In the presence of 200 mM of H2O2, the recombinant CtCBM22A_Y300A retained 80% of activity on glucose and 100% of activity on cellobiose, the preferred substrate for this enzyme. By contrast, a commercial glucose oxidase reported to contain ≤0.1 units catalase/ mg protein, retained 60% activity on glucose under the same conditions. GOOX variants appear to undergo a different mechanism of inactivation, as a loss of histidine instead of methionine was observed after H2O2 incubation. The addition of CtCBM22A also promoted functional binding of the fusion enzyme to xylan, facilitating its simultaneous purification and immobilization using edible oat spelt xylan, which might benefit the usage of this enzyme preparation in food and baking applications. PMID:27869125

  2. Direct comparison of gluco-oligosaccharide oxidase variants and glucose oxidase: substrate range and H2O2 stability.

    PubMed

    Vuong, Thu V; Foumani, Maryam; MacCormick, Benjamin; Kwan, Rachel; Master, Emma R

    2016-11-21

    Glucose oxidase (GO) activity is generally restricted to glucose and is susceptible to inactivation by H2O2. By comparison, the Y300A variant of gluco-oligosaccharide oxidase (GOOX) from Sarocladium strictum showed broader substrate range and higher H2O2 stability. Specifically, Y300A exhibited up to 40 times higher activity on all tested sugars except glucose, compared to GO. Moreover, fusion of the Y300A variant to a family 22 carbohydrate binding module from Clostridium thermocellum (CtCBM22A) nearly doubled its catalytic efficiency on glucose, while retaining significant activity on oligosaccharides. In the presence of 200 mM of H2O2, the recombinant CtCBM22A_Y300A retained 80% of activity on glucose and 100% of activity on cellobiose, the preferred substrate for this enzyme. By contrast, a commercial glucose oxidase reported to contain ≤0.1 units catalase/ mg protein, retained 60% activity on glucose under the same conditions. GOOX variants appear to undergo a different mechanism of inactivation, as a loss of histidine instead of methionine was observed after H2O2 incubation. The addition of CtCBM22A also promoted functional binding of the fusion enzyme to xylan, facilitating its simultaneous purification and immobilization using edible oat spelt xylan, which might benefit the usage of this enzyme preparation in food and baking applications.

  3. Expanded sodalite-type metal-organic frameworks: increased stability and H(2) adsorption through ligand-directed catenation.

    PubMed

    Dinca, Mircea; Dailly, Anne; Tsay, Charlene; Long, Jeffrey R

    2008-01-07

    The torsion between the central benzene ring and the outer aromatic rings in 1,3,5-tri-p-(tetrazol-5-yl)phenylbenzene (H3TPB-3tz) and the absence of such strain in 2,4,6-tri-p-(tetrazol-5-yl)phenyl-s-triazine (H3TPT-3tz) are shown to allow the selective synthesis of noncatenated and catenated versions of expanded sodalite-type metal-organic frameworks. The reaction of H3TPB-3tz with CuCl2.2H2O affords the noncatenated compound Cu3[(Cu4Cl)3(TPB-3tz)8]2.11CuCl2.8H2O.120DMF (2), while the reaction of H3TPT-3tz with MnCl2.4H2O or CuCl2.2H2O generates the catenated compounds Mn3[(Mn4Cl)3(TPT-3tz)8]2.25H2O.15CH3OH.95DMF (3) and Cu3[(Cu4Cl)3(TPT-3tz)8]2.xsolvent (4). Significantly, catenation helps to stabilize the framework toward collapse upon desolvation, leading to an increase in the surface area from 1120 to 1580 m2/g and an increase in the hydrogen storage capacity from 2.8 to 3.7 excess wt % at 77 K for 2 and 3, respectively. The total hydrogen uptake in desolvated 3 reaches 4.5 wt % and 37 g/L at 80 bar and 77 K, demonstrating that control of catenation can be an important factor in the generation of hydrogen storage materials.

  4. Tropospheric aqueous-phase free-radical chemistry: radical sources, spectra, reaction kinetics and prediction tools.

    PubMed

    Herrmann, Hartmut; Hoffmann, Dirk; Schaefer, Thomas; Bräuer, Peter; Tilgner, Andreas

    2010-12-17

    The most important radicals which need to be considered for the description of chemical conversion processes in tropospheric aqueous systems are the hydroxyl radical (OH), the nitrate radical (NO(3)) and sulphur-containing radicals such as the sulphate radical (SO(4)(-)). For each of the three radicals their generation and their properties are discussed first in the corresponding sections. The main focus herein is to summarize newly published aqueous-phase kinetic data on OH, NO(3) and SO(4)(-) radical reactions relevant for the description of multiphase tropospheric chemistry. The data compilation builds up on earlier datasets published in the literature. Since the last review in 2003 (H. Herrmann, Chem. Rev. 2003, 103, 4691-4716) more than hundred new rate constants are available from literature. In case of larger discrepancies between novel and already published rate constants the available kinetic data for these reactions are discussed and recommendations are provided when possible. As many OH kinetic data are obtained by means of the thiocyanate (SCN(-)) system in competition kinetic measurements of OH radical reactions this system is reviewed in a subchapter of this review. Available rate constants for the reaction sequence following the reaction of OH+SCN(-) are summarized. Newly published data since 2003 have been considered and averaged rate constants are calculated. Applying competition kinetics measurements usually the formation of the radical anion (SCN)(2)(-) is monitored directly by absorption measurements. Within this subchapter available absorption spectra of the (SCN)(2)(-) radical anion from the last five decades are presented. Based on these spectra an averaged (SCN)(2)(-) spectrum was calculated. In the last years different estimation methods for aqueous phase kinetic data of radical reactions have been developed and published. Such methods are often essential to estimate kinetic data which are not accessible from the literature. Approaches for

  5. Interaction between alkyl radicals and single wall carbon nanotubes.

    PubMed

    Denis, Pablo A

    2012-06-30

    The addition of primary, secondary, and tertiary alkyl radicals to single wall carbon nanotubes (SWCNTs) was studied by means of dispersion corrected density functional theory. The PBE, B97-D, M06-L, and M06-2X functionals were used. Consideration of Van der Waals interactions is essential to obtain accurate addition energies. In effect, the enthalpy changes at 298 K, for the addition of methyl, ethyl, isopropyl, and tert-butyl radicals onto a (5,5) SWCNT are: -25.7, -25.1, -22.4, and -16.6 kcal/mol, at the M06-2X level, respectively, whereas at PBE/6-31G* level they are significantly lower: -25.0, -19.0, -16.7, and -5.0 kcal/mol respectively. Although the binding energies are small, the attached alkyl radicals are expected to be stable because of the large desorption barriers. The importance of nonbonded interactions was more noticeable as we moved from primary to tertiary alkyl radicals. Indeed, for the tert-butyl radical, physisorption onto the (11,0) SWCNT is preferred rather than chemisorption. The bond dissociation energies determined for alkyl radicals and SWCNT follow the trend suggested by the consideration of radical stabilization energies. However, they are in disagreement with some degrees of functionalization observed in recent experiments. This discrepancy would stem from the fact that for some HiPco nanotubes, nonbonded interactions with alkyl radicals are stronger than covalent bonds.

  6. Direct observation of pH-induced coalescence of latex-stabilized bubbles using high-speed video imaging.

    PubMed

    Ata, Seher; Davis, Elizabeth S; Dupin, Damien; Armes, Steven P; Wanless, Erica J

    2010-06-01

    The coalescence of pairs of 2 mm air bubbles grown in a dilute electrolyte solution containing a lightly cross-linked 380 nm diameter PEGMA-stabilized poly(2-vinylpyridine) (P2VP) latex was monitored using a high-speed video camera. The air bubbles were highly stable at pH 10 when coated with this latex, although coalescence could be induced by increasing the bubble volume when in contact. Conversely, coalescence was rapid when the bubbles were equilibrated at pH 2, since the latex undergoes a latex-to-microgel transition and the swollen microgel particles are no longer adsorbed at the air-water interface. Rapid coalescence was also observed for latex-coated bubbles equilibrated at pH 10 and then abruptly adjusted to pH 2. Time-dependent postrupture oscillations in the projected surface area of coalescing P2VP-coated bubble pairs were studied using a high-speed video camera in order to reinvestigate the rapid acid-induced catastrophic foam collapse previously reported [Dupin, D.; et al. J. Mater. Chem. 2008, 18, 545]. At pH 10, the P2VP latex particles adsorbed at the surface of coalescing bubbles reduce the oscillation frequency significantly. This is attributed to a close-packed latex monolayer, which increases the bubble stiffness and hence restricts surface deformation. The swollen P2VP microgel particles that are formed in acid also affected the coalescence dynamics. It was concluded that there was a high concentration of swollen microgel at the air-water interface, which created a localized, viscous surface gel layer that inhibited at least the first period of the surface area oscillation. Close comparison between latex-coated bubbles at pH 10 and those coated with 66 microm spherical glass beads indicated that the former system exhibits more elastic behavior. This was attributed to the compressibility of the latex monolayer on the bubble surface during coalescence. A comparable elastic response was observed for similar sized titania particles, suggesting

  7. Toward Radicalizing Community Service Learning

    ERIC Educational Resources Information Center

    Sheffield, Eric C.

    2015-01-01

    This article advocates a radicalized theoretical construction of community service learning. To accomplish this radicalization, I initially take up a discussion of traditional understandings of CSL rooted in pragmatic/progressive thought. I then suggest that this traditional structural foundation can be radicalized by incorporating Deborah…

  8. EPR study of radiation-induced radicals in glutaric and amino acid derivatives in solid state

    NASA Astrophysics Data System (ADS)

    Yeşim Dicle, Işık

    2015-05-01

    Gamma radiation-induced radicals of 2-methylglutaric acid (2MG), diethyl amino malonate hydrochloride (DEAMHCl), ethyl malonate monoamide have been investigated at room temperature by the electron paramagnetic resonance technique. The type of radicals formed and their room temperature stability were evaluated. Three different radicals have been detected. The free radicals formed in compounds were attributed to the HOOCCH3ĊCH2CH2 COOH, CH3ĊHCO2CHNH2COCH2CH3 HCl and NH2COCH2COOĊHCH3 radicals, respectively. The results were found to be in good agreement with the existing literature data and theoretical predictions conformation.

  9. Methylation of 2'-deoxyguanosine by a free radical mechanism.

    PubMed

    Crean, Conor; Geacintov, Nicholas E; Shafirovich, Vladimir

    2009-09-24

    The mechanistic aspects of the methylation of guanine in DNA initiated by methyl radicals that are derived from the metabolic oxidation of some chemical carcinogens remain poorly understood. In this work, we investigated the kinetics and the formation of methylated guanine products by two methods: (i) the combination of *CH3 radicals and guanine neutral radicals, G(-H)*, and (ii) the direct addition of *CH3 radicals to guanine bases. The simultaneous generation of *CH3 and dG(-H)* radicals was triggered by the competitive one-electron oxidation of dimethyl sulfoxide (DMSO) and 2'-deoxyguanosine (dG) by photochemically generated sulfate radicals in deoxygenated aqueous buffer solutions (pH 7.5). The photolysis of methylcob(III)alamin to form *CH3 radicals was used to investigate the direct addition of these radicals to guanine bases. The major end products of the radical combination reactions are the 8-methyl-dG and N2-methyl-dG products formed in a ratio of 1:0.7. In contrast, the methylation of dG by *CH3 radicals generates mostly the 8-methyl-dG adduct and only minor quantities of N2-methyl-dG (1:0.13 ratio). The methylation of the self-complementary 5'-d(AACGCGAATTCGCGTT) duplexes was achieved by the selective oxidation of the guanines with carbonate radical anions in the presence of DMSO as the precursor of *CH3 radicals. The methyl-G lesions formed were excised by the enzymatic digestion and identified by LC-MS/MS methods using uniformly 15N-labeled 8-methyl-dG and N2-methyl-dG adducts as internal standards. The ratios of 8-methyl-G/N2-methyl-G lesions derived from the combination of methyl radicals with G(-H)* radicals positioned in double-stranded DNA or that with the free nucleoside dG(-H)* radicals were found to be similar. Utilizing the photochemical method and dipropyl or dibutyl sulfoxides as sources of alkyl radicals, the corresponding 8-alkyl-dG and N2-alkyl-dG adducts were also generated in ratios similar to those obtained with DMSO.

  10. Direct frequency comb measurement of OD + CO → DOCO kinetics.

    PubMed

    Bjork, B J; Bui, T Q; Heckl, O H; Changala, P B; Spaun, B; Heu, P; Follman, D; Deutsch, C; Cole, G D; Aspelmeyer, M; Okumura, M; Ye, J

    2016-10-28

    The kinetics of the hydroxyl radical (OH) + carbon monoxide (CO) reaction, which is fundamental to both atmospheric and combustion chemistry, are complex because of the formation of the hydrocarboxyl radical (HOCO) intermediate. Despite extensive studies of this reaction, HOCO has not been observed under thermal reaction conditions. Exploiting the sensitive, broadband, and high-resolution capabilities of time-resolved cavity-enhanced direct frequency comb spectroscopy, we observed deuteroxyl radical (OD) + CO reaction kinetics and detected stabilized trans-DOCO, the deuterated analog of trans-HOCO. By simultaneously measuring the time-dependent concentrations of the trans-DOCO and OD species, we observed unambiguous low-pressure termolecular dependence of the reaction rate coefficients for N2 and CO bath gases. These results confirm the HOCO formation mechanism and quantify its yield.

  11. Radicals in melanin biochemistry.

    PubMed

    Riley, P A

    1988-01-01

    Melanins are light-absorbant polymeric pigments found widely dispersed in nature. They possess many interesting physicochemical properties. One of these is the expression in the polymer of stable free radicals which appear to have a protective action in cells, probably by acting as a sink for diffusible free-radical species. Polymer formation is thought to occur by a free-radical process in which semiquinones are added to the chain. Semiquinones are formed by redox equilibration interactions between metabolic intermediates formed during the tyrosinase-catalyzed oxidation process. In the continued presence of substrate, steady-state concentrations of reactive species are predicted in the reaction system, and the melanogenic pathway may be considered as potentially hazardous for pigment-generating cells. This feature has been exploited by the use of analogue substrates to generate cytotoxic species as a possible rational approach to the treatment of malignant melanoma. One such substance is 4-hydroxyanisole, the oxidation of which gives rise to semiquinone radical species. The possibility that the anisyl semiquinone initiates a mechanism leading to cell damage has not been excluded. However, the current view is that the major cytotoxicity due to the oxidation products of this compound is the result of the action of the corresponding orthoquinone. A number of mechanisms exist for detoxifying quinones if they reach the cytosol such as O-methylation and the formation of thiol adducts with cysteine or glutathione, and these can be used as markers of melanogenesis. In general, however, only small amounts of reactive intermediates of melanogenesis escape from the confines of the melanosome, probably because of their limited lipid solubility. The selective toxic action of anisyl quinone in the treatment of melanoma may, in part, be due to membrane defects in the melanosomes of malignant melanocytes.

  12. Free radical explosive composition

    DOEpatents

    Walker, Franklin E.; Wasley, Richard J.

    1979-01-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a getter additive comprising a compound or mixture of compounds capable of capturing or deactivating free radicals or ions under mechanical or electrical shock conditions and which is not an explosive. Exemplary getter additives are isocyanates, olefins and iodine.

  13. Probability and radical behaviorism

    PubMed Central

    Espinosa, James M.

    1992-01-01

    The concept of probability appears to be very important in the radical behaviorism of Skinner. Yet, it seems that this probability has not been accurately defined and is still ambiguous. I give a strict, relative frequency interpretation of probability and its applicability to the data from the science of behavior as supplied by cumulative records. Two examples of stochastic processes are given that may model the data from cumulative records that result under conditions of continuous reinforcement and extinction, respectively. PMID:22478114

  14. Free radical propulsion concept

    NASA Technical Reports Server (NTRS)

    Hawkins, C. E.; Nakanishi, S.

    1981-01-01

    The concept of a free radical propulsion system, utilizing the recombination energy of dissociated low molecular weight gases to produce thrust, is analyzed. The system, operating at a theoretical impulse with hydrogen, as high as 2200 seconds at high thrust to power ratio, is hypothesized to bridge the gap between chemical and electrostatic propulsion capabilities. A comparative methodology is outlined by which characteristics of chemical and electric propulsion for orbit raising mission can be investigated. It is noted that free radicals proposed in rockets previously met with difficulty and complexity in terms of storage requirements; the present study proposes to eliminate the storage requirements by using electric energy to achieve a continuous-flow product of free radicals which are recombined to produce a high velocity propellant. Microwave energy used to dissociate a continuously flowing gas is transferred to the propellant via three-body-recombination for conversion to propellant kinetic energy. Microwave plasma discharge was found in excess of 90 percent over a broad range of pressure in preliminary experiments, and microwave heating compared to electrothermal heating showed much higher temperatures in gasdynamic equations.

  15. Types of radical hysterectomies

    PubMed Central

    Marin, F; Plesca, M; Bordea, CI; Moga, MA; Blidaru, A

    2014-01-01

    Abstract The treatment for cervical cancer is a complex, multidisciplinary issue, which applies according to the stage of the disease. The surgical elective treatment of cervical cancer is represented by the radical abdominal hysterectomy. In time, many surgeons perfected this surgical technique; the ones who stood up for this idea were Thoma Ionescu and Ernst Wertheim. There are many varieties of radical hysterectomies performed by using the abdominal method and some of them through vaginal and mixed way. Each method employed has advantages and disadvantages. At present, there are three classifications of radical hysterectomies which are used for the simplification of the surgical protocols: Piver-Rutledge-Smith classification which is the oldest, GCG-EORTC classification and Querlow and Morrow classification. The last is the most evolved and recent classification; its techniques can be adapted for conservative operations and for different types of surgical approaches: abdominal, vaginal, laparoscopic or robotic. Abbreviations: GCG-EORTC = Gynecologic Cancer Group of the European Organization of Research and Treatment of Cancer; LEEP = loop electrosurgical excision procedure; I.O.B. = Institute of Oncology Bucharest; PRS = Piver-Rutledge-Smith PMID:25408722

  16. [Radical prostatectomy - pro robotic].

    PubMed

    Gillitzer, R

    2012-05-01

    Anatomical radical prostatectomy was introduced in the early 1980s by Walsh and Donker. Elucidation of key anatomical structures led to a significant reduction in the morbidity of this procedure. The strive to achieve similar oncological and functional results to this gold standard open procedure but with further reduction of morbidity through a minimally invasive access led to the establishment of laparoscopic prostatectomy. However, this procedure is complex and difficult and is associated with a long learning curve. The technical advantages of robotically assisted surgery coupled with the intuitive handling of the device led to increased precision and shortening of the learning curve. These main advantages, together with a massive internet presence and aggressive marketing, have resulted in a rapid dissemination of robotic radical prostatectomy and an increasing patient demand. However, superiority of robotic radical prostatectomy in comparison to the other surgical therapeutic options has not yet been proven on a scientific basis. Currently robotic-assisted surgery is an established technique and future technical improvements will certainly further define its role in urological surgery. In the end this technical innovation will have to be balanced against the very high purchase and running costs, which remain the main limitation of this technology.

  17. Alternative radical pairs for cryptochrome-based magnetoreception

    PubMed Central

    Lee, Alpha A.; Lau, Jason C. S.; Hogben, Hannah J.; Biskup, Till; Kattnig, Daniel R.; Hore, P. J.

    2014-01-01

    There is growing evidence that the remarkable ability of animals, in particular birds, to sense the direction of the Earth's magnetic field relies on magnetically sensitive photochemical reactions of the protein cryptochrome. It is generally assumed that the magnetic field acts on the radical pair [FAD•− TrpH•+] formed by the transfer of an electron from a group of three tryptophan residues to the photo-excited flavin adenine dinucleotide cofactor within the protein. Here, we examine the suitability of an [FAD•− Z•] radical pair as a compass magnetoreceptor, where Z• is a radical in which the electron spin has no hyperfine interactions with magnetic nuclei, such as hydrogen and nitrogen. Quantum spin dynamics simulations of the reactivity of [FAD•− Z•] show that it is two orders of magnitude more sensitive to the direction of the geomagnetic field than is [FAD•− TrpH•+] under the same conditions (50 µT magnetic field, 1 µs radical lifetime). The favourable magnetic properties of [FAD•− Z•] arise from the asymmetric distribution of hyperfine interactions among the two radicals and the near-optimal magnetic properties of the flavin radical. We close by discussing the identity of Z• and possible routes for its formation as part of a spin-correlated radical pair with an FAD radical in cryptochrome. PMID:24671932

  18. miR-181b-3p promotes epithelial-mesenchymal transition in breast cancer cells through Snail stabilization by directly targeting YWHAG.

    PubMed

    Yoo, Je-Ok; Kwak, Seo-Young; An, Hyun-Ju; Bae, In-Hwa; Park, Myung-Jin; Han, Young-Hoon

    2016-07-01

    Epithelial-mesenchymal transition (EMT) is essential for increased invasion and metastasis during cancer progression. Among the candidate EMT-regulating microRNAs that we previously identified, miR-181b-3p was found to induce EMT in MCF7 breast cancer cells, as indicated by an EMT-characteristic morphological change, increased invasiveness, and altered expression of an EMT marker. Transfection with a miR-181b-3p inhibitor reduced the expression of mesenchymal markers and the migration and invasion of highly invasive breast cancer cells. miR-181b-3p induced the upregulation of Snail, a master EMT inducer and transcriptional repressor of E-cadherin, through protein stabilization. YWHAG was identified as a direct target of miR-181b-3p, downregulation of which induced Snail stabilization and EMT phenotypes. Ectopic expression of YWHAG abrogated the effect of miR-181b-3p, including Snail stabilization and the promotion of invasion. In situ hybridization and immunohistochemical analyses indicated that YWHAG expression was inversely correlated with the expression of miR-181b-3p and Snail in human breast cancer tissues. Furthermore, transfection with miR-181b-3p increased the frequency of metastatic nodule formation in the lungs of mice in experimental metastasis assays using MDA-MB-231 cells. Taken together, our data suggest that miR-181b-3p functions as a metastasis activator by promoting Snail-induced EMT, and may therefore be a therapeutic target in metastatic cancers.

  19. Incorporation of HVDC and SVC models in the Northern State Power Co. (NSP) network for on-line implementation of direct transient stability assessment

    SciTech Connect

    Jing, C.; Vittal, V.; Ejebe, G.C.; Irisarri, G.D.

    1995-05-01

    In this paper the authors discuss the incorporation of the 4 dc systems and 2 SVCs in the NSP network for on-line implementation of direct transient stability assessment. The dc and SVC models used are more complicated than those used in the existing AC-DC-SVC Transient Energy Function (TEF) literature. In this new approach, the commutation failure of the HVDC is also considered. It is necessary to use these complicated dc and SVC models because in the NSP network they are located in an area where the transient stability is of great concern. The dc and SVC systems are treated as part of the ac network and their effect on the transient energy function is included. The effect of dc and SVC on the calculation of the potential energy is reflected in the ac network solution. The equivalent models and the proposed procedure developed is tested on a NSP equivalent network of 273 generators and 2,217 buses. The result obtained are in excellent agreement with those obtained by time domain simulation using EPRI ETMSP V3.0.

  20. Highly Enhanced Electromechanical Stability of Large-Area Graphene with Increased Interfacial Adhesion Energy by Electrothermal-Direct Transfer for Transparent Electrodes.

    PubMed

    Kim, Jangheon; Kim, Gi Gyu; Kim, Soohyun; Jung, Wonsuk

    2016-09-07

    Graphene, a two-dimensional sheet of carbon atoms in a hexagonal lattice structure, has been extensively investigated for research and industrial applications as a promising material with outstanding electrical, mechanical, and chemical properties. To fabricate graphene-based devices, graphene transfer to the target substrate with a clean and minimally defective surface is the first step. However, graphene transfer technologies require improvement in terms of uniform transfer with a clean, nonfolded and nontorn area, amount of defects, and electromechanical reliability of the transferred graphene. More specifically, uniform transfer of a large area is a key challenge when graphene is repetitively transferred onto pretransferred layers because the adhesion energy between graphene layers is too low to ensure uniform transfer, although uniform multilayers of graphene have exhibited enhanced electrical and optical properties. In this work, we developed a newly suggested electrothermal-direct (ETD) transfer method for large-area high quality monolayer graphene with less defects and an absence of folding or tearing of the area at the surface. This method delivers uniform multilayer transfer of graphene by repetitive monolayer transfer steps based on high adhesion energy between graphene layers and the target substrate. To investigate the highly enhanced electromechanical stability, we conducted mechanical elastic bending experiments and reliability tests in a highly humid environment. This ETD-transferred graphene is expected to replace commercial transparent electrodes with ETD graphene-based transparent electrodes and devices such as a touch panels with outstanding electromechanical stability.

  1. A strategic approach for direct recovery and stabilization of Fusarium sp. ICT SAC1 cutinase from solid state fermented broth by carrier free cross-linked enzyme aggregates.

    PubMed

    Chaudhari, Sandeep A; Singhal, Rekha S

    2017-05-01

    The major hurdles in commercial exploitation of cutinase (having both esterolytic and lipolytic activities) with potent industrial applications are its high production cost, operational instability and reusability. Although commercially available in immobilized form, its immobilization process (synthesis of support/carrier) makes it expensive. Herein we tried to address multiple issues of production cost, stability, and reusability, associated with cutinase. Waste watermelon rinds, an agroindustrial waste was considered as a cheap support for solid state fermentation (SSF) for cutinase production by newly isolated Fusarium sp. ICT SAC1. Subsequently, carrier free cross-linked enzyme aggregates of cutinase (cut-CLEA) directly from the SSF crude broth were developed. All the process variables affecting CLEA formation along with the different additives were evaluated. It was found that 50% (w/v) of ammonium sulphate, 125μmol of glutaraldehyde, cross-linking for 1h at 30°C and broth pH of 7.0, yielded 58.12% activity recovery. All other additives (hexane, butyric acid, sodium dodecyl sulphate, Trition-X 100, Tween-20, BSA) evaluated presented negative results to our hypothesis. Kinetics and morphology studies confirmed the diffusive nature of cut-CLEA and BSA cut-CLEA. Developed CLEA showed better thermal, solvent, detergent and storage stability, making it more elegant and efficient for industrial biocatalytic process.

  2. Bioequivalence studies and sugar-based excipients effects on the properties of new generic ketoconazole tablets formulations and stability evaluation by using direct compression method.

    PubMed

    Viçosa, Alessandra L; Chatah, Eliane N; Santos, Tereza C; Jones, Luiz F; Dantas, Cide B; Dornelas, Camila B; Rodrigues, Carlos R; Castro, Helena C; Sousa, Valéria P; Dias, Luiza R S; Cabral, Lúcio M

    2009-01-01

    In this work we described the development of a new solid oral formulation of ketoconazole, a broad-spectrum antifungal agent that belongs to the class II of Biopharmaceutics Classification System (BCS). The ketoconazole raw material supplier was selected to present a best flow and compactation. In addition we used direct compression and superdisintegrants associated to polyols to enhance the dissolution of the ketoconazole tablets. The dissolution was evaluated based in level C in vivo/in vitro correlation established. The best formulation was obtained with croscarmellose/maltose association that in the accelerated stability assays presented no differences on quality specifications and no drug-excipients interaction by DSC analyses. In this work it was possible to confirm the use of sugar-based excipients as suitable dissolution enhancers in pharmaceutical technology and real processes conditions.

  3. Direct growth of NiCo2O4 nanostructures on conductive substrates with enhanced electrocatalytic activity and stability for methanol oxidation

    NASA Astrophysics Data System (ADS)

    Qian, Lei; Gu, Li; Yang, Li; Yuan, Hongyan; Xiao, Dan

    2013-07-01

    In this report, NiCo2O4 nanostructures with different morphologies were directly grown on conductive substrates (stainless steel and ITO) by a facile electrodeposition method in addition to a post-annealing process. The morphology changes on different conductive substrates are discussed in detail. The NiCo2O4 on stainless steel (SS) had a high surface area (119 m2 g-1) and was successfully used in the electrocatalytic oxidation of methanol. The electrocatalytic performance was investigated by cyclic voltammetry (CV), chronoamperometry and electrochemical impedance spectroscopy (EIS) measurements. Impressively, the NiCo2O4 showed much higher electrocatalytic activity, lower overpotential and greater stability compared to that of only NiO or Co3O4 synthesized by the same method. The higher electrocatalytic activity is due to the high electron conductivity, large surface area of NiCo2O4 and the fast ion/electron transport in the electrode and at the electrolyte-electrode interface. This is important for further development of high performance non-platinum electrocatalysts for application in direct methanol fuel cells.In this report, NiCo2O4 nanostructures with different morphologies were directly grown on conductive substrates (stainless steel and ITO) by a facile electrodeposition method in addition to a post-annealing process. The morphology changes on different conductive substrates are discussed in detail. The NiCo2O4 on stainless steel (SS) had a high surface area (119 m2 g-1) and was successfully used in the electrocatalytic oxidation of methanol. The electrocatalytic performance was investigated by cyclic voltammetry (CV), chronoamperometry and electrochemical impedance spectroscopy (EIS) measurements. Impressively, the NiCo2O4 showed much higher electrocatalytic activity, lower overpotential and greater stability compared to that of only NiO or Co3O4 synthesized by the same method. The higher electrocatalytic activity is due to the high electron conductivity

  4. Cfr and RlmN contain a single [4Fe-4S] cluster, which directs two distinct reactivities for S-adenosylmethionine: methyl transfer by SN2 displacement and radical generation.

    PubMed

    Grove, Tyler L; Radle, Matthew I; Krebs, Carsten; Booker, Squire J

    2011-12-14

    The radical SAM (RS) proteins RlmN and Cfr catalyze methylation of carbons 2 and 8, respectively, of adenosine 2503 in 23S rRNA. Both reactions are similar in scope, entailing the synthesis of a methyl group partially derived from S-adenosylmethionine (SAM) onto electrophilic sp(2)-hybridized carbon atoms via the intermediacy of a protein S-methylcysteinyl (mCys) residue. Both proteins contain five conserved Cys residues, each required for turnover. Three cysteines lie in a canonical RS CxxxCxxC motif and coordinate a [4Fe-4S]-cluster cofactor; the remaining two are at opposite ends of the polypeptide. Here we show that each protein contains only the one "radical SAM" [4Fe-4S] cluster and the two remaining conserved cysteines do not coordinate additional iron-containing species. In addition, we show that, while wild-type RlmN bears the C355 mCys residue in its as-isolated state, RlmN that is either engineered to lack the [4Fe-4S] cluster by substitution of the coordinating cysteines or isolated from Escherichia coli cultured under iron-limiting conditions does not bear a C355 mCys residue. Reconstitution of the [4Fe-4S] cluster on wild-type apo RlmN followed by addition of SAM results in rapid production of S-adenosylhomocysteine (SAH) and the mCys residue, while treatment of apo RlmN with SAM affords no observable reaction. These results indicate that in Cfr and RlmN, SAM bound to the unique iron of the [4Fe-4S] cluster displays two reactivities. It serves to methylate C355 of RlmN (C338 of Cfr), or to generate the 5'-deoxyadenosyl 5'-radical, required for substrate-dependent methyl synthase activity.

  5. Cfr and RlmN Contain a Single [4Fe-4S] Cluster, which Directs Two Distinct Reactivities for S-Adenosylmethionine: Methyl Transfer by SN2 Displacement and Radical Generation

    PubMed Central

    Grove, Tyler L.; Radle, Matthew I.; Krebs, Carsten; Booker, Squire J.

    2012-01-01

    The radical SAM (RS) proteins RlmN and Cfr catalyze methylation of carbons 2 and 8, respectively, of adenosine 2503 in 23S rRNA. Both reactions are similar in scope, entailing the synthesis of a methyl group partially derived from S-adenosylmethionine (SAM) onto electrophilic sp2-hybridized carbon atoms via the intermediacy of a protein S-methylcysteinyl (mCys) residue. Both proteins contain five conserved Cys residues, each of which is required for turnover. Three cysteines lie in a canonical RS CxxxCxxC motif and coordinate a [4Fe–4S]-cluster cofactor. The remaining two cysteines are at opposite ends of the polypeptide. Herein we show that each protein contains only the one “radical SAM” [4Fe–4S] cluster, and that the two remaining conserved cysteines do not coordinate additional iron-containing species. In addition, we show that while wild-type RlmN bears the C355 mCys residue in its as-isolated state, RlmN that is either engineered to lack the [4Fe–4S] cluster by substitution of the coordinating cysteines, or isolated from Escherichia coli cultured under iron-limiting conditions, does not bear a C355 mCys residue. Reconstitution of the [4Fe–4S] cluster on wild-type apo RlmN followed by addition of SAM results in rapid production of S-adenosylhomocysteine (SAH) and the mCys residue, while treatment of apo RlmN with SAM affords no observable reaction. These results indicate that in Cfr and RlmN, SAM bound to the unique iron of the [4Fe–4S] cluster displays two reactivities. It serves to methylate C355 of RlmN (C338 of Cfr), or it serves to generate the 5’-deoxyadenosyl 5’-radical, required for substrate-dependent methyl synthase activity. PMID:21916495

  6. Low-Dose Lithium Stabilizes Human Endothelial Barrier by Decreasing MLC Phosphorylation and Universally Augments Cholinergic Vasorelaxation Capacity in a Direct Manner

    PubMed Central

    Bosche, Bert; Molcanyi, Marek; Rej, Soham; Doeppner, Thorsten R.; Obermann, Mark; Müller, Daniel J.; Das, Anupam; Hescheler, Jürgen; Macdonald, R. Loch; Noll, Thomas; Härtel, Frauke V.

    2016-01-01

    Lithium at serum concentrations up to 1 mmol/L has been used in patients suffering from bipolar disorder for decades and has recently been shown to reduce the risk for ischemic stroke in these patients. The risk for stroke and thromboembolism depend not only on cerebral but also on general endothelial function and health; the entire endothelium as an organ is therefore pathophysiologically relevant. Regardless, the knowledge about the direct impact of lithium on endothelial function remains poor. We conducted an experimental study using lithium as pharmacologic pretreatment for murine, porcine and human vascular endothelium. We predominantly investigated endothelial vasorelaxation capacities in addition to human basal and dynamic (thrombin-/PAR-1 receptor agonist-impaired) barrier functioning including myosin light chain (MLC) phosphorylation (MLC-P). Low-dose therapeutic lithium concentrations (0.4 mmol/L) significantly augment the cholinergic endothelium-dependent vasorelaxation capacities of cerebral and thoracic arteries, independently of central and autonomic nerve system influences. Similar concentrations of lithium (0.2–0.4 mmol/L) significantly stabilized the dynamic thrombin-induced and PAR-1 receptor agonist-induced permeability of human endothelium, while even the basal permeability appeared to be stabilized. The lithium-attenuated dynamic permeability was mediated by a reduced endothelial MLC-P known to be followed by a lessening of endothelial cell contraction and paracellular gap formation. The well-known lithium-associated inhibition of inositol monophosphatase/glycogen synthase kinase-3-β signaling-pathways involving intracellular calcium concentrations in neurons seems to similarly occur in endothelial cells, too, but with different down-stream effects such as MLC-P reduction. This is the first study discovering low-dose lithium as a drug directly stabilizing human endothelium and ubiquitously augmenting cholinergic endothelium

  7. Formation of ions and radicals from icy grains in comets

    NASA Technical Reports Server (NTRS)

    Jackson, William M.; Gerth, Christopher; Hendricks, Charles

    1991-01-01

    Ion and radical formation in comets are thought to occur primarily by photodissociation of gas phase molecules. Experimental evidence and theoretical calculations are presented that show that some of the radical and ions can come directly from ice grains. The experimental evidence suggest that if the frozen molecules on the surface of grains undergo direct dissociation then they may be able to release radicals directly in the gas phase. If the molecules undergo predissociation it is unlikely that they will release radicals in the gas phase since they should be quenched. Calculations of this direct photodissociation mechanism further indicate that even if the parent molecule undergoes direct dissociation, the yield will not be high enough to explain the rays structure in comets unless the radicals are stored in the grains and then released when the grain evaporates. Calculations were also performed to determine the maximum number of ions that can be stored in an icy grain's radius. This number is compared with the ratio of the ion to neutral molecular density. The comparison suggests that some of the ions observed near the nucleus of the comet could have originally been present in the cometary nucleus. It is also pointed out that the presence of these ions in icy grains could lead to radical formation via electron recombination. Finally, an avalanche process was evaluated as another means of producing ions in comets.

  8. Energy and Entropy Effects in Dissociation of Peptide Radical Anions

    SciTech Connect

    Laskin, Julia; Yang, Zhibo; Lam, Corey; Chu, Ivan K.

    2012-04-15

    Time- and collision energy-resolved surface-induced dissociation (SID) of peptide radical anions was studied for the first time using a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) configured for SID experiments. Peptide radical cations and anions were produced by gas-phase fragmentation of CoIII(salen)-peptide complexes. The effect of the charge, radical, and the presence of a basic residue on the energetics and dynamics of dissociation of peptide ions was examined using RVYIHPF (1) and HVYIHPF (2) as model systems. Comparison of the survival curves for of [M+H]{sup +}, [M-H]{sup -}, M{sup +{sm_bullet}}, and [M-2H]{sup -{sm_bullet}} ions of these precursors demonstrated that even-electron ions are more stable towards fragmentation than their odd-electron counterparts. RRKM modeling of the experimental data demonstrated that the lower stability of the positive radicals is mainly attributed to lower dissociation thresholds while entropy effects are responsible the relative instability of the negative radicals. Substitution of arginine with less basic histidine residue has a strong destabilizing effect on the [M+H]{sup +} ions and a measurable stabilizing effect on the odd-electron ions. Lower threshold energies for dissociation of both positive and negative radicals of 1 are attributed to the presence of lower-energy dissociation pathways that are most likely promoted by the presence of the basic residue.

  9. Catalysis of Radical Reactions: A Radical Chemistry Perspective.

    PubMed

    Studer, Armido; Curran, Dennis P

    2016-01-04

    The area of catalysis of radical reactions has recently flourished. Various reaction conditions have been discovered and explained in terms of catalytic cycles. These cycles rarely stand alone as unique paths from substrates to products. Instead, most radical reactions have innate chains which form products without any catalyst. How do we know if a species added in "catalytic amounts" is a catalyst, an initiator, or something else? Herein we critically address both catalyst-free and catalytic radical reactions through the lens of radical chemistry. Basic principles of kinetics and thermodynamics are used to address problems of initiation, propagation, and inhibition of radical chains. The catalysis of radical reactions differs from other areas of catalysis. Whereas efficient innate chain reactions are difficult to catalyze because individual steps are fast, both inefficient chain processes and non-chain processes afford diverse opportunities for catalysis, as illustrated with selected examples.

  10. Comparative evaluation of effects of bleaching on color stability and marginal adaptation of discolored direct and indirect composite laminate veneers under in vivo conditions

    PubMed Central

    Jain, Veena; Das, Taposh K.; Pruthi, Gunjan; Shah, Naseem; Rajendiran, Suresh

    2015-01-01

    CLV's showed significant color change at CE and IE regions when ΔE was compared at 180 days and 284 days (CE 10 vs. CE 30, P = 0.008, IE 10 vs. IE 30, P = 0.003). No significant differences were found when within group comparison was made for indirect laminates. Intergroup comparison between the groups showed significant difference in marginal adaptation at CE margin at all.time points (at baseline, P = 0.005; at 180 days, P = 0.007; 194 days, P = 0.025; at 284 days, P = 0.067). Conclusion: After bleaching, indirect CLVs performed better in terms of color stability whereas direct CLVs performed better in terms of marginal adaptation. Clinical Significance: Indirect composites should be preferred to direct composites as veneering materials as they have better color stability. Special attention should be given to their marginal adaptation especially in the CE region. Bleaching should be avoided in patients with composite restorations in the mouth. PMID:26929486

  11. Consciousness: the radical plasticity thesis.

    PubMed

    Cleeremans, Axel

    2008-01-01

    In this chapter, I sketch a conceptual framework which takes it as a starting point that conscious and unconscious cognition are rooted in the same set of interacting learning mechanisms and representational systems. On this view, the extent to which a representation is conscious depends in a graded manner on properties such as its stability in time or its strength. Crucially, these properties are accrued as a result of learning, which is in turn viewed as a mandatory process that always accompanies information processing. From this perspective, consciousness is best characterized as involving (1) a graded continuum defined over "quality of representation", such that availability to consciousness and to cognitive control correlates with quality, and (2) the implication of systems of metarepresentations. A first implication of these ideas is that the main function of consciousness is to make flexible, adaptive control over behavior possible. A second, much more speculative implication, is that we learn to be conscious. This I call the "radical plasticity thesis"--the hypothesis that consciousness emerges in systems capable not only of learning about their environment, but also about their own internal representations of it.

  12. Direct growth of NiCo2O4 nanostructures on conductive substrates with enhanced electrocatalytic activity and stability for methanol oxidation.

    PubMed

    Qian, Lei; Gu, Li; Yang, Li; Yuan, Hongyan; Xiao, Dan

    2013-08-21

    In this report, NiCo2O4 nanostructures with different morphologies were directly grown on conductive substrates (stainless steel and ITO) by a facile electrodeposition method in addition to a post-annealing process. The morphology changes on different conductive substrates are discussed in detail. The NiCo2O4 on stainless steel (SS) had a high surface area (119 m(2) g(-1)) and was successfully used in the electrocatalytic oxidation of methanol. The electrocatalytic performance was investigated by cyclic voltammetry (CV), chronoamperometry and electrochemical impedance spectroscopy (EIS) measurements. Impressively, the NiCo2O4 showed much higher electrocatalytic activity, lower overpotential and greater stability compared to that of only NiO or Co3O4 synthesized by the same method. The higher electrocatalytic activity is due to the high electron conductivity, large surface area of NiCo2O4 and the fast ion/electron transport in the electrode and at the electrolyte-electrode interface. This is important for further development of high performance non-platinum electrocatalysts for application in direct methanol fuel cells.

  13. Human papillomavirus 16 E2 stability and transcriptional activation is enhanced by E1 via a direct protein-protein interaction

    SciTech Connect

    King, Lauren E.; Dornan, Edward S.; Donaldson, Mary M.; Morgan, Iain M.

    2011-05-25

    Human papillomavirus 16 E1 and E2 interact with cellular factors to replicate the viral genome. E2 forms homodimers and binds to 12 bp palindromic sequences adjacent to the viral origin and recruits E1 to the origin. E1 forms a di-hexameric helicase complex that replicates the viral genome. This manuscript demonstrates that E1 stabilises the E2 protein, increasing the half life in both C33a and 293 T cells respectively. This stabilisation requires a direct protein--protein interaction. In addition, the E1 protein enhances E2 transcription function in a manner that suggests the E1 protein itself can contribute to transcriptional regulation not simply by E2 stabilisation but by direct stimulation of transcription. This activation of E2 transcription is again dependent upon an interaction with E1. Overall the results suggest that in the viral life cycle, co-expression of E1 with E2 can increase E2 stability and enhance E2 function.

  14. Maclurin protects against hydroxyl radical-induced damages to mesenchymal stem cells: antioxidant evaluation and mechanistic insight.

    PubMed

    Li, Xican; Gao, Yaoxiang; Li, Fei; Liang, Aifeng; Xu, Zhiming; Bai, Ye; Mai, Wenqiong; Han, Lu; Chen, Dongfeng

    2014-08-05

    Maclurin, an exceptional member of phytophenol family, was found to effectively protect against mesenchymal stem cells (MSCs) oxidative damage induced by hydroxyl radical (OH) at 62.1-310.5 μM. Antioxidant assays indicated that maclurin could efficiently protect DNA from OH-induced damage at 114.6-382.2 μM, and scavenge OH, DPPH (1,1-diphenyl-2-picrylhydrazyl radical), ABTS(+) (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid radical), and bind Cu(2+) (IC50 values were respectively 122.87 ± 10.14, 10.15 ± 0.85, 0.97 ± 0.07, and 133.95 ± 11.92 μM). HPLC-DAD and HPLC-ESI-MS/MS analyses of the end-product of maclurin reaction with DPPH clearly suggested that maclurin (m/z = 261.12 [M-H](-)) donated two hydrogen atoms to DPPH (m/z = 394.06 [M](+)) to form ortho-benzoquinone moiety (λmax = 364 nm; m/z = 259.06 [M-H](-), loss of m/z = 28) and DPPH2 molecule (m/z = 395.03, 396.01), via hydrogen atom transfer (HAT) or sequential electron (e) proton transfer (SEPT), not radical adduct formation (RAF) mechanisms. Therefore, we concluded that: (i) maclurin can effectively protect against OH-induced damages to DNA and MSCs, thereby it may have a therapeutic potential in prevention of many diseases or MSCs transplantation; (ii) a possible mechanism for maclurin to protect against oxidative damages is OH radical-scavenging; (iii) maclurin scavenges OH possibly through metal-chelating, and direct radical-scavenging which is mainly via HAT or SEPT mechanisms; and (iv) the protective and antioxidant effects of maclurin can be primarily attributed to ortho-dihydroxyl groups, and ultimately to the relative stability of the ortho-benzoquinone form.

  15. Oligorotaxane Radicals under Orders.

    PubMed

    Wang, Yuping; Frasconi, Marco; Liu, Wei-Guang; Sun, Junling; Wu, Yilei; Nassar, Majed S; Botros, Youssry Y; Goddard, William A; Wasielewski, Michael R; Stoddart, J Fraser

    2016-02-24

    A strategy for creating foldameric oligorotaxanes composed of only positively charged components is reported. Threadlike components-namely oligoviologens-in which different numbers of 4,4'-bipyridinium (BIPY(2+)) subunits are linked by p-xylylene bridges, are shown to be capable of being threaded by cyclobis(paraquat-p-phenylene) (CBPQT(4+)) rings following the introduction of radical-pairing interactions under reducing conditions. UV/vis/NIR spectroscopic and electrochemical investigations suggest that the reduced oligopseudorotaxanes fold into highly ordered secondary structures as a result of the formation of BIPY(•+) radical cation pairs. Furthermore, by installing bulky stoppers at each end of the oligopseudorotaxanes by means of Cu-free alkyne-azide cycloadditions, their analogous oligorotaxanes, which retain the same stoichiometries as their progenitors, can be prepared. Solution-state studies of the oligorotaxanes indicate that their mechanically interlocked structures lead to the enforced interactions between the dumbbell and ring components, allowing them to fold (contract) in their reduced states and unfold (expand) in their fully oxidized states as a result of Coulombic repulsions. This electrochemically controlled reversible folding and unfolding process, during which the oligorotaxanes experience length contractions and expansions, is reminiscent of the mechanisms of actuation associated with muscle fibers.

  16. Oligorotaxane Radicals under Orders

    PubMed Central

    2016-01-01

    A strategy for creating foldameric oligorotaxanes composed of only positively charged components is reported. Threadlike components—namely oligoviologens—in which different numbers of 4,4′-bipyridinium (BIPY2+) subunits are linked by p-xylylene bridges, are shown to be capable of being threaded by cyclobis(paraquat-p-phenylene) (CBPQT4+) rings following the introduction of radical-pairing interactions under reducing conditions. UV/vis/NIR spectroscopic and electrochemical investigations suggest that the reduced oligopseudorotaxanes fold into highly ordered secondary structures as a result of the formation of BIPY•+ radical cation pairs. Furthermore, by installing bulky stoppers at each end of the oligopseudorotaxanes by means of Cu-free alkyne–azide cycloadditions, their analogous oligorotaxanes, which retain the same stoichiometries as their progenitors, can be prepared. Solution-state studies of the oligorotaxanes indicate that their mechanically interlocked structures lead to the enforced interactions between the dumbbell and ring components, allowing them to fold (contract) in their reduced states and unfold (expand) in their fully oxidized states as a result of Coulombic repulsions. This electrochemically controlled reversible folding and unfolding process, during which the oligorotaxanes experience length contractions and expansions, is reminiscent of the mechanisms of actuation associated with muscle fibers. PMID:27163033

  17. Radically innovative steelmaking technologies

    NASA Astrophysics Data System (ADS)

    Szekely, Julian

    1980-09-01

    The steel industry is faced with serious problems caused by the increasing cost of energy, labor and capital and by tough overseas competition, employing new highly efficient process plants. The very high cost of capital and of capital equipment renders the construction of new green field site plants, exemplifying the best available technology economically unattractive. For this reason, over the long term the development radically innovative steelmaking technologies appears to be the only satisfactory resolution of this dilemma. The purpose of this article is to present a critical review of some of the radically innovative steelmaking technologies that have been proposed during the past few years and to develop the argument that these indeed do deserve serious consideration at the present time. It should be stressed, however, that these innovative technologies can be implemented only as part of a carefully conceived long range plan, which contains as a subset short term solutions, such as trigger prices improved investment credits, and so forth and intermediate term solutions, such as more extensive use of continuous casting, external desulfurization and selective modernization in general.

  18. Pyrolysis of Tropyl Radical (C7H7) and Benzyl Radical (C6H5CH2) in a Heated Micro-Reactor

    NASA Astrophysics Data System (ADS)

    Buckingham, Grant; Ellison, Barney; Porterfield, Jessica P.; Daily, John W.; Ahmed, Musahid; Robichaud, David; Nimlos, Mark R.

    2016-06-01

    Benzyl radical (C6H5CH2) is a crucial intermediate in the combustion and pyrolysis of substituted aromatic species that are common both in modern gasoline and potential future biofuels. The decomposition of benzyl radical is complicated and has been shown by isotopic labeling to require interesting isomerizations pathways. To better understand these pathways, a set of C7H7 radicals has been studied in a heated micro-reactor. Through multiple experiments, it has be shown that benzyl radical and cycloheptatrienyl (tropyl) radical (c-C7H7) do not interconvert, even at temperatures where both have completely thermally decomposed. To confirm this, tropyl radical has been studied directly and its pyrolysis is quite simple, only cyclopentadienyl radical (c-C5H5) and acetylene (HCCH) are formed. Cyclopentadienyl radical then decomposes to acetylene and propargyl radical (HCCCH2). These products have all been identified through use of tunable synchrotron radiation by confirming their respective photoionization spectra. Matrix isolation infrared (IR) spectroscopy has also been used to identity these products. A previously unanswered question in benzyl radical decomposition has been addressed by studying the pyrolysis of 2,5-norbornadiene, which indicates benzyl radical may decompose through a norbornadiene-like bicyclic radical intermediate. This pathways successfully predicts the correct isotopically labeled products observed previously during 13C labeled benzyl pyrolysis.

  19. Superoxide Radical Lifetime on the Martian Surface

    NASA Astrophysics Data System (ADS)

    Zent, A. P.; Ichimura, A.; Quinn, R. C.

    2005-08-01

    We have examined the formation and stability of the superoxide radical O2-, which has been hypothesized as a potential Mars oxidant. Rutile (TiO2) was heated to ˜ 400 degrees C under vacuum. The samples were tipped off in ampules under 8-9 torr O2, photolyzed with a Hg lamp for 30 minutes; EPR spectra were immediately obtained at 77K. The signature of O2- was clearly observed in the rutile. The sealed ampules were stored at room temperature for up to 2 weeks without any decrease in the number of spins. The same process, applied to rutile that was not baked out yielded superoxide signals that could not be detected once the photolyzing flux was cut off. To examine the effects of partial dehydration, we carried out the same series of experiments on rutile that was baked out at 200 degrees C. This material showed decay of superoxide spins to zero in less than 10 minutes. This qualitative pattern is also observed in experiments on anatase (Attwood, et al., , 2003). We hypothesize that O2- can be stabilized against reaction with H2O and OH by crystalline surface defects. On hydrated surfaces, O2- must compete for stabilizing sites, and the population is quickly extinguished; in dehydrated samples, it can migrate to stabilizing defects. Once sorbed, the O2- radical is stable in the presence of H2O. OMEGA Mars Express data (Poullet et al, 2005) suggest one to several percent adsorbed H2O across the Martian surface, which will significantly decrease O2- lifetime. One possibility for subsurface stabilization of O2- can be postulated based on EPR spectra of anatase, exposed to H2O2 in our lab in 1996, and which in 2005 shows the signature of O2-. Evidently, H2O2 can convert to stable O2- on some surfaces. This hypothesis might allow subsurface diffusion of H2O2, followed by conversion to O2-.

  20. Free radicals in adolescent varicocele testis.

    PubMed

    Romeo, Carmelo; Santoro, Giuseppe

    2014-01-01

    We examine the relationship between the structure and function of the testis and the oxidative and nitrosative stress, determined by an excessive production of free radicals and/or decreased availability of antioxidant defenses, which occur in the testis of adolescents affected by varicocele. Moreover, the effects of surgical treatment on oxidative stress were provided. We conducted a PubMed and Medline search between 1980 and 2014 using "adolescent," "varicocele," "free radicals," "oxidative and nitrosative stress," "testis," and "seminiferous tubules" as keywords. Cross-references were checked in each of the studies, and relevant articles were retrieved. We conclude that increased concentration of free radicals, generated by conditions of hypoxia, hyperthermia, and hormonal dysfunction observed in adolescent affected by varicocele, can harm germ cells directly or indirectly by influencing nonspermatogenic cells and basal lamina. With regard to few available data in current literature, further clinical trials on the pre- and postoperative ROS and RNS levels together with morphological studies of the cellular component of the testis are fundamental for complete comprehension of the role played by free radicals in the pathogenesis of adolescent varicocele and could justify its pharmacological treatment with antioxidants.

  1. Free Radicals in Adolescent Varicocele Testis

    PubMed Central

    Romeo, Carmelo; Santoro, Giuseppe

    2014-01-01

    We examine the relationship between the structure and function of the testis and the oxidative and nitrosative stress, determined by an excessive production of free radicals and/or decreased availability of antioxidant defenses, which occur in the testis of adolescents affected by varicocele. Moreover, the effects of surgical treatment on oxidative stress were provided. We conducted a PubMed and Medline search between 1980 and 2014 using “adolescent,” “varicocele,” “free radicals,” “oxidative and nitrosative stress,” “testis,” and “seminiferous tubules” as keywords. Cross-references were checked in each of the studies, and relevant articles were retrieved. We conclude that increased concentration of free radicals, generated by conditions of hypoxia, hyperthermia, and hormonal dysfunction observed in adolescent affected by varicocele, can harm germ cells directly or indirectly by influencing nonspermatogenic cells and basal lamina. With regard to few available data in current literature, further clinical trials on the pre- and postoperative ROS and RNS levels together with morphological studies of the cellular component of the testis are fundamental for complete comprehension of the role played by free radicals in the pathogenesis of adolescent varicocele and could justify its pharmacological treatment with antioxidants. PMID:25580183

  2. Carotenoid cation radicals: electrochemical, optical, and EPR study

    SciTech Connect

    Grant, J.L.; Kramer, V.J.; Ding, R.; Kispert, L.D.

    1988-03-30

    The general aim of this investigation is to determine whether carotenoid cation radicals can be produced, and stabilized, electrochemically. Hence, the authors have undertaken a detailed study of the electrooxidation of various carotenoids (..beta..-carotene (I), ..beta..-apo-8'-carotenal (II), and canthaxanthin (III) using the techniques of cyclic voltammetry, controlled-potential electrolysis (cpe) in conjunction with optical spectroscopy, and EPR spectroscopy coupled with in situ electrolysis. They report the successful generation of carotenoid cation radicals via electrochemical oxidation and, furthermore, the stabilization of these radicals for several minutes in CH/sub 2/Cl/sub 2/ and C/sub 2/H/sub 4/Cl/sub 2/ solvents.

  3. Understanding the Influence of the Electronic Structure on the Crystal Structure of a TTF-PTM Radical Dyad.

    PubMed

    Vela, Sergi; Souto, Manuel; Ratera, Imma; Rovira, Concepció; Veciana, Jaume

    2016-12-29

    The understanding of the crystal structure of organic compounds, and its relationship to their physical properties, have become essential to design new advanced molecular materials. In this context, we present a computational study devoted to rationalize the different crystal packing displayed by two closely related organic systems based on the TTF-PTM dyad (TTF = tetrathiafulvalene, PTM = polychlorotriphenylmethane) with almost the same molecular structure but a different electronic one. The radical species (1), with an enhanced electronic donor-acceptor character, exhibits a herringbone packing, whereas the nonradical protonated analogue (2) is organized forming dimers. The stability of the possible polymorphs is analyzed in terms of the cohesion energy of the unit cell, intermolecular interactions between pairs, and molecular flexibility of the dyad molecules. It is observed that the higher electron delocalization in radical compound 1 has a direct influence on the geometry of the molecule, which seems to dictate its preferential crystal structure.

  4. Austenite stabilization and high strength-elongation product of a low silicon aluminum-free hot-rolled directly quenched and dynamically partitioned steel

    SciTech Connect

    Tan, Xiao-Dong; Xu, Yun-Bo; Yang, Xiao-Long; Hu, Zhi-Ping; Peng, Fei; Ju, Xiao-Wei; Wu, Di

    2015-06-15

    Microstructures composed of lath martensite and retained austenite with volume fraction between 8.0 vol.% and 12.0 vol.% were obtained in a low-C low-Si Al-free steel through hot-rolling direct quenching and dynamical partitioning (HDQ&DP) processes. The austenite stabilization mechanism in the low-C low-Si Al-free steel under the special dynamical partitioning processes is investigated by analyzing the carbon partition behavior from martensite to austenite and the carbide precipitation-coarsening behavior in martensite laths combining with the possible hot rolling deformation inheritance. Results show that the satisfying retained austenite amount in currently studied low-Si Al-free HDQ&DP steel is caused by the high-efficiency carbon enrichment in the 30–80 nm thick regions of austenite near the interfaces in the hot-rolled ultra-fast cooled structure and the avoidance of serious carbides coarsening during the continuous cooling procedures. The excellent strength-elongation product reaching up to 26,000 MPa% shows that the involved HDQ&DP process is a promising method to develop a new generation of advanced high strength steel. - Highlights: • HDQ&DP processes were applied to a low-C low-Si Al-free steel. • Effective partitioning time during the continuous cooling processes is 1–220 s. • Retained austenite with volume fraction between 8.0 vol. % and 12.0 vol. % has been obtained. • The special austenite stabilization mechanism has been expounded.

  5. Density functional theory study of the interaction of vinyl radical, ethyne, and ethene with benzene, aimed to define an affordable computational level to investigate stability trends in large van der Waals complexes.

    PubMed

    Maranzana, Andrea; Giordana, Anna; Indarto, Antonius; Tonachini, Glauco; Barone, Vincenzo; Causà, Mauro; Pavone, Michele

    2013-12-28

    Our purpose is to identify a computational level sufficiently dependable and affordable to assess trends in the interaction of a variety of radical or closed shell unsaturated hydro-carbons A adsorbed on soot platelet models B. These systems, of environmental interest, would unavoidably have rather large sizes, thus prompting to explore in this paper the performances of relatively low-level computational methods and compare them with higher-level reference results. To this end, the interaction of three complexes between non-polar species, vinyl radical, ethyne, or ethene (A) with benzene (B) is studied, since these species, involved themselves in growth processes of polycyclic aromatic hydrocarbons (PAHs) and soot particles, are small enough to allow high-level reference calculations of the interaction energy ΔEAB. Counterpoise-corrected interaction energies ΔEAB are used at all stages. (1) Density Functional Theory (DFT) unconstrained optimizations of the A-B complexes are carried out, using the B3LYP-D, ωB97X-D, and M06-2X functionals, with six basis sets: 6-31G(d), 6-311 (2d,p), and 6-311++G(3df,3pd); aug-cc-pVDZ and aug-cc-pVTZ; N07T. (2) Then, unconstrained optimizations by Møller-Plesset second order Perturbation Theory (MP2), with each basis set, allow subsequent single point Coupled Cluster Singles Doubles and perturbative estimate of the Triples energy computations with the same basis sets [CCSD(T)//MP2]. (3) Based on an additivity assumption of (i) the estimated MP2 energy at the complete basis set limit [EMP2/CBS] and (ii) the higher-order correlation energy effects in passing from MP2 to CCSD(T) at the aug-cc-pVTZ basis set, ΔECC-MP, a CCSD(T)/CBS estimate is obtained and taken as a computational energy reference. At DFT, variations in ΔEAB with basis set are not large for the title molecules, and the three functionals perform rather satisfactorily even with rather small basis sets [6-31G(d) and N07T], exhibiting deviation from the computational

  6. Density functional theory study of the interaction of vinyl radical, ethyne, and ethene with benzene, aimed to define an affordable computational level to investigate stability trends in large van der Waals complexes

    SciTech Connect

    Maranzana, Andrea E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it Giordana, Anna E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it Indarto, Antonius Tonachini, Glauco; Barone, Vincenzo E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it; Causà, Mauro E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it; Pavone, Michele E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it

    2013-12-28

    Our purpose is to identify a computational level sufficiently dependable and affordable to assess trends in the interaction of a variety of radical or closed shell unsaturated hydro-carbons A adsorbed on soot platelet models B. These systems, of environmental interest, would unavoidably have rather large sizes, thus prompting to explore in this paper the performances of relatively low-level computational methods and compare them with higher-level reference results. To this end, the interaction of three complexes between non-polar species, vinyl radical, ethyne, or ethene (A) with benzene (B) is studied, since these species, involved themselves in growth processes of polycyclic aromatic hydrocarbons (PAHs) and soot particles, are small enough to allow high-level reference calculations of the interaction energy ΔE{sub AB}. Counterpoise-corrected interaction energies ΔE{sub AB} are used at all stages. (1) Density Functional Theory (DFT) unconstrained optimizations of the A−B complexes are carried out, using the B3LYP-D, ωB97X-D, and M06-2X functionals, with six basis sets: 6-31G(d), 6-311 (2d,p), and 6-311++G(3df,3pd); aug-cc-pVDZ and aug-cc-pVTZ; N07T. (2) Then, unconstrained optimizations by Møller-Plesset second order Perturbation Theory (MP2), with each basis set, allow subsequent single point Coupled Cluster Singles Doubles and perturbative estimate of the Triples energy computations with the same basis sets [CCSD(T)//MP2]. (3) Based on an additivity assumption of (i) the estimated MP2 energy at the complete basis set limit [E{sub MP2/CBS}] and (ii) the higher-order correlation energy effects in passing from MP2 to CCSD(T) at the aug-cc-pVTZ basis set, ΔE{sub CC-MP}, a CCSD(T)/CBS estimate is obtained and taken as a computational energy reference. At DFT, variations in ΔE{sub AB} with basis set are not large for the title molecules, and the three functionals perform rather satisfactorily even with rather small basis sets [6-31G(d) and N07T], exhibiting

  7. ESR measurement of radical clearance in lung of whole mouse

    SciTech Connect

    Takeshita, K.; Utsumi, H.; Hamada, A. )

    1991-06-14

    Clearance of the nitroxide radicals, hydroxy-TEMPO and carboxy-PROxYL, in whole-mouse lung was directly measured by in vivo ESR. After injecting a nitroxide radical, distribution of the nitroxide radical all over the lung was confirmed by ESR imaging. The ESR signal of hydroxy-TEMPO was reduced in the lung and the clearance obeyed first-order kinetics, whereas the signal of carboxy-PROxYL remained constant. Comparison of the clearance rates of live and dead mice indicated the presence of 2 different clearance systems in the lung: loss of its paramagnetism in the lung, and transfer from alveolar to the blood circulation system.

  8. Lidocaine: an inhibitor in the free-radical-induced hemolysis of erythrocytes.

    PubMed

    Tang, You-Zhi; Liu, Zai-Qun; Wu, Di

    2009-01-01

    Lidocaine was reported to protect erythrocytes from hemolysis induced by 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH). Since AAPH-induced hemolysis was a convenient in vitro experimental system to mimic erythrocytes undergoing peroxyl radicals attack, the aim of this work was to investigate the antioxidant effect of lidocaine on AAPH-induced hemolysis by chemical kinetics. As a result, one molecule of lidocaine can only trap 0.37 radical, much lower than melatonin. Meanwhile, lidocaine cannot protect erythrocytes from hemolysis induced by hemin, which the mechanism of hemolysis was due to the erythrocyte membrane destroyed by hemin. Accordingly, lidocaine protected erythrocytes by scavenging radicals preferentially rather than by stabilizing membrane. Moreover, the interactions of lidocaine with two radical species, including 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) radical cation (ABTS(+*)) and 2,2'-diphenyl-1-picrylhydrazyl (DPPH), indicated that lidocaine can reduce ABTS(+*) with 260 microM as the 50% inhibition concentration (IC(50)) and cannot react with DPPH. Thus, lidocaine served as a reductant rather than a hydrogen donor to interact with radicals. Finally, the quantum calculation proved that, compared with the melatonin radical, the stabilization of N-centered radical of lidocaine was higher than the amide-type N-centered radical but lower than the indole-type N-centered radical in melatonin. These results provided basic information for lidocaine to be an antiradical drug.

  9. Radicals in Berkeley?

    PubMed Central

    Linn, Stuart

    2015-01-01

    In a previous autobiographical sketch for DNA Repair (Linn, S. (2012) Life in the serendipitous lane: excitement and gratification in studying DNA repair. DNA Repair 11, 595–605), I wrote about my involvement in research on mechanisms of DNA repair. In this Reflections, I look back at how I became interested in free radical chemistry and biology and outline some of our bizarre (at the time) observations. Of course, these studies could never have succeeded without the exceptional aid of my mentors: my teachers; the undergraduate and graduate students, postdoctoral fellows, and senior lab visitors in my laboratory; and my faculty and staff colleagues here at Berkeley. I am so indebted to each and every one of these individuals for their efforts to overcome my ignorance and set me on the straight and narrow path to success in research. I regret that I cannot mention and thank each of these mentors individually. PMID:25713083

  10. Radicals in Berkeley?

    PubMed

    Linn, Stuart

    2015-04-03

    In a previous autobiographical sketch for DNA Repair (Linn, S. (2012) Life in the serendipitous lane: excitement and gratification in studying DNA repair. DNA Repair 11, 595-605), I wrote about my involvement in research on mechanisms of DNA repair. In this Reflections, I look back at how I became interested in free radical chemistry and biology and outline some of our bizarre (at the time) observations. Of course, these studies could never have succeeded without the exceptional aid of my mentors: my teachers; the undergraduate and graduate students, postdoctoral fellows, and senior lab visitors in my laboratory; and my faculty and staff colleagues here at Berkeley. I am so indebted to each and every one of these individuals for their efforts to overcome my ignorance and set me on the straight and narrow path to success in research. I regret that I cannot mention and thank each of these mentors individually.

  11. Free radical propulsion concept

    NASA Technical Reports Server (NTRS)

    Hawkins, C. E.; Nakanishi, S.

    1981-01-01

    A free radical propulsion concept utilizing the recombination energy of dissociated low molecular weight gases to produce thrust was examined. The concept offered promise of a propulsion system operating at a theoretical impulse, with hydrogen, as high as 2200 seconds at high thrust to power ratio, thus filling the gas existing between chemical and electrostatic propulsion capabilities. Microwave energy used to dissociate a continuously flowing gas was transferred to the propellant via three body recombination for conversion to propellant kinetic energy. Power absorption by the microwave plasma discharge was in excess of 90 percent over a broad range of pressures. Gas temperatures inferred from gas dynamic equations showed much higher temperatures from microwave heating than from electrothermal heating. Spectroscopic analysis appeared to corroborate the inferred temperatures of one of the gases tested.

  12. Radical Change by Entrepreneurial Design

    DTIC Science & Technology

    1998-01-01

    This article offers a conceptual framework to understand radical change. It opens with a typology that defines change in terms of its pace and scope...known entrepreneurs who have been successful in molding and shaping the radical change process. The implications of this conceptual framework to

  13. Directed evolution of anti-HER2 DARPins by SNAP display reveals stability/function trade-offs in the selection process.

    PubMed

    Houlihan, Gillian; Gatti-Lafranconi, Pietro; Lowe, David; Hollfelder, Florian

    2015-09-01

    In vitro display technologies have proved to be powerful tools for obtaining high-affinity protein binders. We recently described SNAP display, an entirely in vitro DNA display system that uses the SNAP-tag to link protein with its encoding DNA in water-in-oil emulsions. Here, we apply SNAP display for the affinity maturation of a designed ankyrin repeat proteins (DARPin) that binds to the extracellular domain of HER2 previously isolated by ribosome display. After four SNAP display selection cycles, proteins that bound specifically to HER2 in vitro, with dissociation constants in the low- to sub-nanomolar range, were isolated. In vitro affinities of the panel of evolved DARPins directly correlated with the fluorescence intensities of evolved DARPins bound to HER2 on a breast cancer cell line. A stability trade-off is observed as the most improved DARPins have decreased thermostability, when compared with the parent DARPin used as a starting point for affinity maturation. Dissection of the framework mutations of the highest affinity variant, DARPin F1, shows that functionally destabilising and compensatory mutations accumulated throughout the four rounds of evolution.

  14. Unstructured Grid Euler Method Assessment for Longitudinal and Lateral/Directional Stability Analysis of the HSR Reference H Configuration at Transonic Speeds

    NASA Technical Reports Server (NTRS)

    Ghaffari, Farhad

    1999-01-01

    Transonic Euler computations, based on unstructured grid methodology, are performed for a proposed High Speed Civil Transport (HSCT) configuration, designated as the Reference H configuration within the High Speed Research (HSR) Program. The predicted results are correlated with appropriate experimental wind-tunnel data for the baseline configuration with and without control surface deflections for a range of angle of attack at M(sub infinity) = 0.95. Good correlations between the predictions and measured data have been obtained for the longitudinal aerodynamic characteristics of the baseline configuration. The incremental effects in the longitudinal aerodynamic characteristics due to horizontal rail deflections as well as wing leading-edge and trailing-edge flap deflections have also been predicted reasonably well. Computational results and correlations with data are also presented for the lateral and directional stability characteristics for a range of angle of attack at a constant sideslip angle as well as a range of sideslip angles at a constant angle of attack. In addition, the results are presented to assess the computational method performance and convergence characteristics.

  15. Phage phi 29 regulatory protein p4 stabilizes the binding of the RNA polymerase to the late promoter in a process involving direct protein-protein contacts.

    PubMed

    Nuez, B; Rojo, F; Salas, M

    1992-12-01

    Transcription from the late promoter, PA3, of Bacillus subtilis phage phi 29 is activated by the viral regulatory protein p4. A kinetic analysis of the activation process has revealed that the role of protein p4 is to stabilize the binding of RNA polymerase to the promoter as a closed complex without significantly affecting further steps of the initiation process. Electrophoretic band-shift assays performed with a DNA fragment spanning only the protein p4 binding site showed that RNA polymerase could efficiently retard the complex formed by protein p4 bound to the DNA. Similarly, when a DNA fragment containing only the RNA polymerase-binding region of PA3 was used, p4 greatly stimulated the binding of RNA polymerase to the DNA. These results strongly suggest that p4 and RNA polymerase contact each other at the PA3 promoter. In the light of current knowledge of the p4 activation mechanism, we propose that direct contacts between the two proteins participate in the activation process.

  16. Electron paramagnetic resonance measurements of free radicals in the intact beating heart: a technique for detection and characterization of free radicals in whole biological tissues.

    PubMed Central

    Zweier, J L; Kuppusamy, P

    1988-01-01

    Free radicals have been hypothesized to be important mediators of disease in a variety of organs and tissues. Electron paramagnetic resonance (EPR) spectroscopy can be applied to directly measure free radicals; however, it has not been possible to measure important biological radicals in situ because conventional spectrometer designs are not suitable for the performance of measurements on whole organs or tissues. We report the development of an EPR spectrometer designed for optimum performance in measuring free radicals in intact biological organs or tissues. This spectrometer consists of a 1- to 2-GHz microwave bridge with the source locked to the resonant frequency of a recessed gap loop-gap resonator. With this spectrometer, radical concentrations as low as 0.4 microM can be measured. Isolated beating hearts were studied in which simultaneous real time measurements of free radicals and cardiac contractile function were performed. This in vivo EPR technique was applied to study the kinetics of free radical uptake and metabolism in normally perfused and globally ischemic hearts. In addition, we show that this technique can be used to noninvasively measure tissue oxygen consumption. Thus, it is demonstrated that EPR spectroscopy can be applied to directly measure in vivo free radical metabolism and tissue oxygen consumption. This technique offers great promise in the study of in vivo free radical generation and the effects of this radical generation on whole biological tissues. PMID:2840672

  17. Studies of radiation-produced radicals and radical ions

    SciTech Connect

    Williams, T.F.

    1991-01-01

    The radiolytic oxidation of anti-5-methylbicyclo(2.1.0)pentane gives the 1-methylcyclopentene radical cation as the sole rearrangement product H migration whereas oxidation of its syn isomer results in the highly selective formation of the 3-methylcyclopentene radical cation by methyl group migration. Since exactly the same stereoselectivity of olefin formation was observed in corresponding PET (photosensitized electron transfer) studies in the liquid phase, it is concluded that the rearrangement in this case also occurs through the intermediacy of radical cations. Clearly, the radical cation rearrangement must occur very rapidly (10{sup {minus}8}--10{sup {minus}9}s) under liquid-phase conditions at room temperature to compete with back electron transfer, and therefore the hydrogen (or methyl) migration is a fast process under these conditions. An intramolecular cycloaddition reaction was demonstrated in the radical cation rearrangement of 4-vinylcyclohexene to bicyclo(3.2.1)oct-2-ene. ESR studies show that the radiolytic oxidation of quadricyclane in Freon matrices under conditions of high substrate dilution leads to the bicyclo(3.2.0)hepta-2,6-diene radical cation as well as the previously reported norbornadiene radical cation, the former species predominating at sufficiently low concentrations.

  18. Are free radicals involved in thiol-based redox signaling?

    PubMed

    Winterbourn, Christine C

    2015-03-01

    Cells respond to many stimuli by transmitting signals through redox-regulated pathways. It is generally accepted that in many instances signal transduction is via reversible oxidation of thiol proteins, although there is uncertainty about the specific redox transformations involved. The prevailing view is that thiol oxidation occurs by a two electron mechanism, most commonly involving hydrogen peroxide. Free radicals, on the other hand, are considered as damaging species and not generally regarded as important in cell signaling. This paper examines whether it is justified to dismiss radicals or whether they could have a signaling role. Although there is no direct evidence that radicals are involved in transmitting thiol-based redox signals, evidence is presented that they are generated in cells when these signaling pathways are activated. Radicals produce the same thiol oxidation products as two electron oxidants, although by a different mechanism, and at this point radical-mediated pathways should not be dismissed. There are unresolved issues about how radical mechanisms could achieve sufficient selectivity, but this could be possible through colocalization of radical-generating and signal-transducing proteins. Colocalization is also likely to be important for nonradical signaling mechanisms and identification of such associations should be a priority for advancing the field.

  19. Fluorescence probes to detect lipid-derived radicals.

    PubMed

    Yamada, Ken-Ichi; Mito, Fumiya; Matsuoka, Yuta; Ide, Satsuki; Shikimachi, Kazushige; Fujiki, Ayano; Kusakabe, Daiki; Ishida, Yuma; Enoki, Masataka; Tada, Arisa; Ariyoshi, Miyuki; Yamasaki, Toshihide; Yamato, Mayumi

    2016-08-01

    Lipids and their metabolites are easily oxidized in chain reactions initiated by lipid radicals, forming lipid peroxidation products that include the electrophiles 4-hydroxynonenal and malondialdehyde. These markers can bind cellular macromolecules, causing inflammation, apoptosis and other damage. Methods to detect and neutralize the initiating radicals would provide insights into disease mechanisms and new therapeutic approaches. We describe the first high-sensitivity, specific fluorescence probe for lipid radicals, 2,2,6-trimethyl-4-(4-nitrobenzo[1,2,5]oxadiazol-7-ylamino)-6-pentylpiperidine-1-oxyl (NBD-Pen). NBD-Pen directly detected lipid radicals in living cells by turn-on fluorescence. In a rat model of hepatic carcinoma induced by diethylnitrosamine (DEN), NBD-Pen detected lipid radical generation within 1 h of DEN administration. The lipid radical scavenging moiety of NBD-Pen decreased inflammation, apoptosis and oxidative stress markers at 24 h after DEN, and liver tumor development at 12 weeks. Thus, we have developed a novel fluorescence probe that provides imaging information about lipid radical generation and potential therapeutic benefits in vivo.

  20. Tar balls from Deep Water Horizon oil spill: environmentally persistent free radicals (EPFR) formation during crude weathering.

    PubMed

    Kiruri, Lucy W; Dellinger, Barry; Lomnicki, Slawo

    2013-05-07

    Tar balls collected from the Gulf of Mexico shores of Louisiana and Florida after the BP oil spill have shown the presence of electron paramagnetic resonance (EPR) spectra characteristic of organic free radicals as well as transition metal ions, predominantly iron(III) and manganese(II). Two types of organic radicals were distinguished: an asphaltene radical species typically found in crude oil (g = 2.0035) and a new type of radical resulting from the environmental transformations of crude (g = 2.0041-47). Pure asphaltene radicals are resonance stabilized over a polyaromatic structure and are stable in air and unreactive. The new radicals were identified as products of partial oxidation of crude components and result from the interaction of the oxidized aromatics with metal ion centers. These radicals are similar to semiquinone-type, environmentally persistent free radicals (EPFRs) previously observed in combustion-generated particulate and contaminated soils.

  1. Tar Balls from Deep Water Horizon Oil Spill: Environmentally Persistent Free Radicals (EPFR) Formation During Crude Weathering

    PubMed Central

    Kiruri, Lucy W.; Dellinger, Barry; Lomnicki, Slawo

    2014-01-01

    Tar balls collected from the Gulf of Mexico shores of Louisiana and Florida after the BP oil spill have shown the presence of electron paramagnetic resonance (EPR) spectra characteristic of organic free radicals as well as transition metal ions, predominantly iron(III) and manganese(II). Two types of organic radicals were distinguished: an asphaltene radical species typically found in crude oil (g = 2.0035) and a new type of radical resulting from the environmental transformations of crude (g = 2.0041−47). Pure asphaltene radicals are resonance stabilized over a polyaromatic structure and are stable in air and unreactive. The new radicals were identified as products of partial oxidation of crude components and result from the interaction of the oxidized aromatics with metal ion centers. These radicals are similar to semiquinone-type, environmentally persistent free radicals (EPFRs) previously observed in combustion-generated particulate and contaminated soils. PMID:23510127

  2. Free radicals and male reproduction.

    PubMed

    Agarwal, Ashok; Allamaneni, Shyam S R

    2011-03-01

    Male factor accounts for almost 50% cases of infertility. The exact mechanism of sperm dysfunction is not known in many cases. Extensive research in the last decade has led to the identification of free radicals (reactive oxygen species) as mediators of sperm dysfunction in both specific diagnoses and idiopathic cases of male infertility. Elevated levels of reactive oxygen species are seen in up to 30-80% of men with male infertility. The role of free radicals has been studied extensively in the process of human reproduction. We know now that a certain level of free radicals is necessary for normal sperm function, whereas an excessive level of free radicals can cause detrimental effect on sperm function and subsequent fertilisation and offspring health. Oxidative stress develops when there is an imbalance between generation of free radicals and scavenging capacity of anti-oxidants in reproductive tract. Oxidative stress has been shown to affect both standard semen parameters and fertilising capacity. In addition, high levels of free radicals have been associated with lack of or poor fertility outcome after natural conception or assisted reproduction. Diagnostic techniques to quantify free radicals in infertile patients can assist physicians treating patients with infertility to plan for proper treatment strategies. In vivo anti-oxidants can be used against oxidative stress in male reproductive tract. Supplementation of in vitro anti-oxidants can help prevent the oxidative stress during sperm preparation techniques in assisted reproduction.

  3. Inhomogeneous ensembles of radical pairs in chemical compasses

    NASA Astrophysics Data System (ADS)

    Procopio, Maria; Ritz, Thorsten

    2016-11-01

    The biophysical basis for the ability of animals to detect the geomagnetic field and to use it for finding directions remains a mystery of sensory biology. One much debated hypothesis suggests that an ensemble of specialized light-induced radical pair reactions can provide the primary signal for a magnetic compass sensor. The question arises what features of such a radical pair ensemble could be optimized by evolution so as to improve the detection of the direction of weak magnetic fields. Here, we focus on the overlooked aspect of the noise arising from inhomogeneity of copies of biomolecules in a realistic biological environment. Such inhomogeneity leads to variations of the radical pair parameters, thereby deteriorating the signal arising from an ensemble and providing a source of noise. We investigate the effect of variations in hyperfine interactions between different copies of simple radical pairs on the directional response of a compass system. We find that the choice of radical pair parameters greatly influences how strongly the directional response of an ensemble is affected by inhomogeneity.

  4. Inhomogeneous ensembles of radical pairs in chemical compasses

    PubMed Central

    Procopio, Maria; Ritz, Thorsten

    2016-01-01

    The biophysical basis for the ability of animals to detect the geomagnetic field and to use it for finding directions remains a mystery of sensory biology. One much debated hypothesis suggests that an ensemble of specialized light-induced radical pair reactions can provide the primary signal for a magnetic compass sensor. The question arises what features of such a radical pair ensemble could be optimized by evolution so as to improve the detection of the direction of weak magnetic fields. Here, we focus on the overlooked aspect of the noise arising from inhomogeneity of copies of biomolecules in a realistic biological environment. Such inhomogeneity leads to variations of the radical pair parameters, thereby deteriorating the signal arising from an ensemble and providing a source of noise. We investigate the effect of variations in hyperfine interactions between different copies of simple radical pairs on the directional response of a compass system. We find that the choice of radical pair parameters greatly influences how strongly the directional response of an ensemble is affected by inhomogeneity. PMID:27804956

  5. Radical formation in the coma from photodissociation of ice grains

    NASA Technical Reports Server (NTRS)

    Jackson, William M.; Gerth, Christopher

    1990-01-01

    Long ago visual observations of comets suggested that there are jets in comets but it has only been recently that A'Hearn et al. have proven that some of these jets are due to emission from the CN radical. Recent studies in the lab have shown that CN radicals can be ejected directly into the gas phase from the photolysis of frozen vapors if the parent molecular has been excited to repulsive excited state. This later observation suggests that the jets that have been observed may be due to photodissociation of icy grains in the coma. A theory of radical formation from icy grains is presented. It is shown that direct formation of free radicals in the coma is an effective way to produce radicals from icy grains in the coma. The model predicts that icy grains could produce from 6 to 800,000 OH radicals/s per grain depending upon whether the radius of the grain is 0.3 to 100 micron.

  6. Evidence of the direct involvement of the substrate TCP radical in functional switching from oxyferrous O2 carrier to ferric peroxidase in the dual-function hemoglobin/dehaloperoxidase from Amphitrite ornata.

    PubMed

    Sun, Shengfang; Sono, Masanori; Du, Jing; Dawson, John H

    2014-08-05

    The coelomic O2-binding hemoglobin dehaloperoxidase (DHP) from the sea worm Amphitrite ornata is a dual-function heme protein that also possesses a peroxidase activity. Two different starting oxidation states are required for reversible O2 binding (ferrous) and peroxidase (ferric) activity, bringing into question how DHP manages the two functions. In our previous study, the copresence of substrate 2,4,6-trichlorophenol (TCP) and H2O2 was found to be essential for the conversion of oxy-DHP to enzymatically active ferric DHP. On the basis of that study, a functional switching mechanism involving substrate radicals (TCP(•)) was proposed. To further support this mechanism, herein we report details of our investigations into the H2O2-mediated conversion of oxy-DHP to the ferric or ferryl ([TCP] < [H2O2]) state triggered by both biologically relevant [TCP and 4-bromophenol (4-BP)] and nonrelevant (ferrocyanide) compounds. At <50 μM H2O2, all of these conversion reactions are completely inhibited by ferric heme ligands (KCN and imidazole), indicating the involvement of ferric DHP. Furthermore, the spin-trapping reagent 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) effectively inhibits the TCP/4-BP (but not ferrocyanide)-triggered conversion of oxy-DHP to ferric DHP. These results and O2 concentration-dependent conversion rates observed in this study demonstrate that substrate TCP triggers the conversion of oxy-DHP to a peroxidase by TCP(•) oxidation of the deoxyferrous state. TCP(•) is progressively generated, by increasingly produced amounts of ferric DHP, upon H2O2 oxidation of TCP catalyzed initially by trace amounts of ferric enzyme present in the oxy-DHP sample. The data presented herein further address the mechanism of how the halophenolic substrate triggers the conversion of hemoglobin DHP into a peroxidase.

  7. ACAT inhibitor pactimibe sulfate (CS-505) reduces and stabilizes atherosclerotic lesions by cholesterol-lowering and direct effects in apolipoprotein E-deficient mice.

    PubMed

    Terasaka, Naoki; Miyazaki, Atsuhiro; Kasanuki, Naomi; Ito, Kayoko; Ubukata, Naoko; Koieyama, Tadashi; Kitayama, Ken; Tanimoto, Tatsuo; Maeda, Naoyuki; Inaba, Toshimori

    2007-02-01

    The objective of the present study was to determine whether a novel acyl-CoA:cholesterol acyltransferase (ACAT) inhibitor, pactimibe sulfate (CS-505), could reduce atherosclerotic lesions beyond and independent of the reduction achieved by cholesterol lowering alone from two different types of lesions. (1) Early lesion model. Twelve-week-old apolipoprotein E (apoE)(-/-) mice were treated with 0.03 or 0.1% (w/w) CS-505, 0.1 or 0.3% avasimibe (CI-1011), or 3% cholestyramine for 12 weeks. Each treatment significantly reduced plasma cholesterol by a similar degree (43-48%). The antiatherosclerotic activity of 0.1% CS-505, however, was more efficacious than the effects of the other treatments (90% versus 40-50%). (2) Advanced lesion model. Twenty-four-week-old apoE(-/-) mice were treated with 0.03 or 0.1% CS-505 or 0.1% CI-1011 for 12 weeks. CS-505 at 0.1% revealed enhanced lesion reduction compared with 0.1% CI-1011 (77% versus 54%), whereas the plasma cholesterol-lowering effect of 0.1% CS-505 was almost the same as that of 0.1% CI-1011. Furthermore, immunohistochemical analysis demonstrated that CS-505 significantly reduced the number of macrophages and expression of matrix metalloproteinase (MMP)-2, MMP-9, and MMP-13. These data indicate that CS-505 can reduce and stabilize atherosclerotic lesions. This antiatherosclerotic activity is exerted via both cholesterol lowering and direct ACAT inhibition in plaque macrophages.

  8. Pathogens and fecal indicators in waste stabilization pond systems with direct reuse for irrigation: Fate and transport in water, soil and crops.

    PubMed

    Verbyla, M E; Iriarte, M M; Mercado Guzmán, A; Coronado, O; Almanza, M; Mihelcic, J R

    2016-05-01

    Wastewater use for irrigation is expanding globally, and information about the fate and transport of pathogens in wastewater systems is needed to complete microbial risk assessments and develop policies to protect public health. The lack of maintenance for wastewater treatment facilities in low-income areas and developing countries results in sludge accumulation and compromised performance over time, creating uncertainty about the contamination of soil and crops. The fate and transport of pathogens and fecal indicators was evaluated in waste stabilization ponds with direct reuse for irrigation, using two systems in Bolivia as case studies. Results were compared with models from the literature that have been recommended for design. The removal of Escherichia coli in both systems was adequately predicted by a previously-published dispersed flow model, despite more than 10years of sludge accumulation. However, a design equation for helminth egg removal overestimated the observed removal, suggesting that this equation may not be appropriate for systems with accumulated sludge. To assess the contamination of soil and crops, ratios were calculated of the pathogen and fecal indicator concentrations in soil or on crops to their respective concentrations in irrigation water (termed soil-water and crop-water ratios). Ratios were similar within each group of microorganisms but differed between microorganism groups, and were generally below 0.1mLg(-1) for coliphage, between 1 and 100mLg(-1) for Giardia and Cryptosporidium, and between 100 and 1000mLg(-1) for helminth eggs. This information can be used for microbial risk assessments to develop safe water reuse policies in support of the United Nations' 2030 Sustainable Development Agenda.

  9. The influence of stabilizers on the production of gold nanoparticles by direct current atmospheric pressure glow microdischarge generated in contact with liquid flowing cathode

    NASA Astrophysics Data System (ADS)

    Dzimitrowicz, Anna; Jamroz, Piotr; Greda, Krzysztof; Nowak, Piotr; Nyk, Marcin; Pohl, Pawel

    2015-04-01

    Gold nanoparticles (Au NPs) were prepared by direct current atmospheric pressure glow microdischarge (dc-μAPGD) generated between a miniature argon flow microjet and a flowing liquid cathode. The applied discharge system was operated in a continuous flow liquid mode. The influence of various stabilizers added to the solution of the liquid cathode, i.e., gelatin (GEL), polyvinylpyrrolidone (PVP), or polyvinyl alcohol (PVA), as well as the concentration of the Au precursor (chloroauric acid, HAuCl4) in the solution on the production growth of Au NPs was investigated. Changes in the intensity of the localized surface plasmon resonance (LSPR) band in UV/Vis absorption spectra of solutions treated by dc-μAPGD and their color were observed. The position and the intensity of the LSPR band indicated that relatively small nanoparticles were formed in solutions containing GEL as a capping agent. In these conditions, the maximum of the absorption LSPR band was at 531, 534, and 535 nm, respectively, for 50, 100, and 200 mg L-1 of Au. Additionally, scanning electron microscopy (SEM) and dynamic light scattering (DLS) were used to analyze the structure and the morphology of obtained Au NPs. The shape of Au NPs was spherical and uniform. Their mean size was ca. 27, 73, and 92 nm, while the polydispersity index was 0.296, 0.348, and 0.456 for Au present in the solution of the flowing liquid cathode at a concentration of 50, 100, and 200 mg L-1, respectively. The production rate of synthesized Au NPs depended on the precursor concentration with mean values of 2.9, 3.5, and 5.7 mg h-1, respectively.

  10. Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products

    SciTech Connect

    Fang, Yi; Liu, Fang; Barber, Victoria P.; Klippenstein, Stephen J.; McCoy, Anne B.; Lester, Marsha I.

    2016-02-14

    In the atmosphere, a dominant loss process for carbonyl oxide intermediates produced from alkene ozonolysis is also an important source of hydroxyl radicals. The rate of appearance of OH radicals is revealed through direct time-domain measurements following vibrational activation of prototypical methyl-substituted Criegee intermediates under collision-free conditions. Complementary theoretical calculations predict the unimolecular decay rate for the Criegee intermediates in the vicinity of the barrier for 1,4 hydrogen transfer that leads to OH products. Both experiment and theory yield unimolecular decay rates of ca. 10(8) and 10(7) s(-1) for syn-CH3CHOO and (CH3)(2)COO, respectively, at energies near the barrier. Tunneling through the barrier, computed from high level electronic structure theory and experimentally validated, makes a significant contribution to the decay rate. Extension to thermally averaged unimolecular decay of stabilized Criegee intermediates under atmospheric conditions yields rates that are six orders of magnitude slower than those evaluated directly in the barrier region.

  11. Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products

    NASA Astrophysics Data System (ADS)

    Fang, Yi; Liu, Fang; Barber, Victoria P.; Klippenstein, Stephen J.; McCoy, Anne B.; Lester, Marsha I.

    2016-02-01

    In the atmosphere, a dominant loss process for carbonyl oxide intermediates produced from alkene ozonolysis is also an important source of hydroxyl radicals. The rate of appearance of OH radicals is revealed through direct time-domain measurements following vibrational activation of prototypical methyl-substituted Criegee intermediates under collision-free conditions. Complementary theoretical calculations predict the unimolecular decay rate for the Criegee intermediates in the vicinity of the barrier for 1,4 hydrogen transfer that leads to OH products. Both experiment and theory yield unimolecular decay rates of ca. 108 and 107 s-1 for syn-CH3CHOO and (CH3)2COO, respectively, at energies near the barrier. Tunneling through the barrier, computed from high level electronic structure theory and experimentally validated, makes a significant contribution to the decay rate. Extension to thermally averaged unimolecular decay of stabilized Criegee intermediates under atmospheric conditions yields rates that are six orders of magnitude slower than those evaluated directly in the barrier region.

  12. Probing RNA folding by hydroxyl radical footprinting.

    PubMed

    Costa, Maria; Monachello, Dario

    2014-01-01

    In recent years RNA molecules have emerged as central players in the regulation of gene expression. Many of these noncoding RNAs possess well-defined, complex, three-dimensional structures which are essential for their biological function. In this context, much effort has been devoted to develop computational and experimental techniques for RNA structure determination. Among available experimental tools to investigate the higher-order folding of structured RNAs, hydroxyl radical probing stands as one of the most informative and reliable ones. Hydroxyl radicals are oxidative species that cleave the nucleic acid backbone solely according to the solvent accessibility of individual phosphodiester bonds, with no sequence or secondary structure specificity. Therefore, the cleavage pattern obtained directly reflects the degree of protection/exposure to the solvent of each section of the molecule under inspection, providing valuable information about how these different sections interact together to form the final three-dimensional architecture. In this chapter we describe a robust, accurate and very sensitive hydroxyl radical probing method that can be applied to any structured RNA molecule and is suitable to investigate RNA folding and RNA conformational changes induced by binding of a ligand.

  13. Redox Properties of Free Radicals.

    ERIC Educational Resources Information Center

    Neta, P.

    1981-01-01

    Describes pulse radiolysis as a useful means in studing one-electron redox potentials. This method allows the production of radicals and the determination of their concentration and rates of reaction. (CS)

  14. [Simultaneous radical retropubic prostatectomy, diverticulectomy].

    PubMed

    Loran, O B; Sokolov, A E; Guspanov, R I; Polegen'kiĭ, V V

    2014-01-01

    Presented clinical case demonstrates a combination of rare congenital abnormality - giant true diverticula of the bladder - and high-risk prostate cancer, as well as a successful result of simultaneous operation - a radical prostatectomy with diverticulectomy.

  15. Free radical inactivation of pepsin

    NASA Astrophysics Data System (ADS)

    Josimović, Lj; Ruvarac, I.; Janković, I.; Jovanović, S. V.

    1994-06-01

    Alkylperoxy radicals containing one, two or three chlorine atoms, CO -2, O 2 - were reacted with pepsin in aqueous solutions. It was found that only Cl 3COO and CO -2 inactive pepsin, attacking preferentially the disulfide bridge. Transient spectra obtained upon completion of the Cl 3COO + pepsin reaction at pH 5 indicate that 20% of initially produced Cl 3COO radicals oxidizes tryptophan residues, and 40% disulfide bridges. The inactivation induced by the Cl 3COO radical increases at lower pH, and the maximal inactivation, Gin = 5.8, was observed at pH 1.5. The inactivation of pepsin by CO -2 radicals depends on the absorbed dose. The maximal inactivation, Gin = 4.5, was determined in the dose range from 38 to 53 Gy.

  16. Antioxidant capacity of betacyanins as radical scavengers for peroxyl radical and nitric oxide.

    PubMed

    Taira, Junsei; Tsuchida, Eito; Katoh, Megumi C; Uehara, Masatsugu; Ogi, Takayuki

    2015-01-01

    This study was designed to assess the antioxidant capacity of betacyanins as indole derived plant pigments, such as betanin, phyllocactin and betanidin. The antioxidant capacity of the betacyanins was evaluated as an index of radical scavenging ability using the peroxyl radical generating system in the presence of AAPH and NO generating system using NOR3 as an NO donor. The peroxyl radical scavenging capacity was dose-dependent in the low concentration range (25-100 nM). The mol-Trolox equivalent activity/mol compound (mol-TEA/mol-compound) as an index of the antioxidant capacity indicated the following order at 10.70 ± 0.01, 3.31 ± 0.14 and 2.83 ± 0.01 mol-TEA/mol-compound for betanidin, betanin and phyllocactin, respectively. In addition, betacyanins reduced the nitrite-level in the low concentration range of 2.5-20 μM. The IC₅₀ values (μM) of nitrogen radical scavenging activity were 24.48, 17.51 and 6.81 for betanin, phyllocactin and betanidin. ESR studies provided evidence that the compounds directly scavenged NO. These results indicated that betacyanins have a strong antioxidant capacity, particularly betanidin with a catechol group had higher activity than those of the glycoside of betacyanins. This study demonstrated that the betacyanins will be useful as natural pigments to provide defence against oxidative stress.

  17. Flight Investigation of Effect of Various Vertical-Tail Modifications on the Directional Stability and Control Characteristics of the P-63A-1 Airplane (AAF No. 42-68889)

    NASA Technical Reports Server (NTRS)

    Johnson, Harold I.

    1946-01-01

    Because the results of preliminary flight tests had indicated. the P-63A-1 airplane possessed insufficient directional stability, the NACA and the manufacturer (Bell Aircraft Corporation) suggested three vertical-tail modifications to remedy the deficiencies in the directional characteristics. These modifications included an enlarged vertical tail formed by adding a tip extension to the original vertical tail, a large sharp-edge ventral fin, and a small dorsal fin. The enlarged vertical tail involved only a slight increase in total vertical-tail area from 23.73 to 26.58 square feet but a relatively much larger increase in geometric aspect ratio from 1.24 to 1.73 based on height and area above the horizontal tail. At the request of the Air Material Command, Army Air Forces, flight tests were made to determine the effect of these modifications and of some combinations of these modifications on the directional stability and control characteristics of the airplane, In all, six different vertical-tail. configurations were investigated to determine the lateral and directional oscillation characteristics of the airplane, the sideslip characteristics, the yaw due to ailerons in rudder-fixed rolls from turns and pull-outs, the trim changes due to speed changes; and the trim changes due to power changes. Results of the tests showed that the enlarged vertical tail approximately doubled the directional stability of the airplane and that the pilots considered the directional stability provided by the enlarged vertical tail to be satisfactory. Calculations based on sideslip data obtained at an indicated airspeed of 300 miles per hour showed that the directional stability of the airplane with the original vertical tail corresponded to a value of 0(sub n beta) of -0.00056 whereas for the enlarged vertical tail the estimated va1ue of C(sub n beta) was -0.00130, The ventral fin was found to increase by a moderate amount the directional stability of the airplane with the original

  18. Stabilization of Penicillin G Acylase from Escherichia coli: Site-Directed Mutagenesis of the Protein Surface To Increase Multipoint Covalent Attachment

    PubMed Central

    Abian, Olga; Grazú, Valeria; Hermoso, Juan; González, Ramón; García, José Luis; Fernández-Lafuente, Roberto; Guisán, José Manuel

    2004-01-01

    Three mutations on the penicillin acylase surface (increasing the number of Lys in a defined area) were performed. They did not alter the enzyme's stability and kinetic properties; however, after immobilization on glyoxyl-agarose, the mutant enzyme showed improved stability under all tested conditions (e.g., pH 2.5 at 4°C, pH 5 at 60°C, pH 7 at 55°C, or 60% dimethylformamide), with stabilization factors ranging from 4 to 11 compared with the native enzyme immobilized on glyoxyl-agarose. PMID:14766616

  19. Fragmentation Pathways in the Uracil Radical Cation

    SciTech Connect

    Zhou, Congyi; Matsika, Spiridoula; Kotur, Marija; Weinacht, Thomas C.

    2012-08-24

    We investigate pathways for fragmentation in the uracil radical cation using ab initio electronic structure calculations. We focus on the main fragments produced in pump–probe dissociative ionization experiments. These are fragments with mass to charge ratios (m/z) of 69, 28, 41, and 42. Barriers to dissociation along the ground ionic surface are reported, which provide an estimate of the energetic requirements for the production of the main fragments. Finally, direct and sequential fragmentation mechanisms have been analyzed, and it is concluded that sequential fragmentation after production of fragment with m/z 69 is the dominant mechanism for the production of the smaller fragments.

  20. π-Radical to σ-Radical Tautomerization in One-Electron-Oxidized 1-Methylcytosine and Its Analogs.

    PubMed

    Adhikary, Amitava; Kumar, Anil; Bishop, Casandra T; Wiegand, Tyler J; Hindi, Ragda M; Adhikary, Ananya; Sevilla, Michael D

    2015-09-03

    In this work, iminyl σ-radical formation in several one-electron-oxidized cytosine analogs, including 1-MeC, cidofovir, 2'-deoxycytidine (dCyd), and 2'-deoxycytidine 5'-monophosphate (5'-dCMP), were investigated in homogeneous, aqueous (D2O or H2O) glassy solutions at low temperatures by employing electron spin resonance (ESR) spectroscopy. Upon employing density functional theory (DFT) (DFT/B3LYP/6-31G* method), the calculated hyperfine coupling constant (HFCC) values of iminyl σ-radical agree quite well with the experimentally observed ones, thus confirming its assignment. ESR and DFT studies show that the cytosine iminyl σ-radical is a tautomer of the deprotonated cytosine π-cation radical [cytosine π-aminyl radical, C(N4-H)(•)]. Employing 1-MeC samples at various pHs ranging from ca. 8 to 11, ESR studies show that the tautomeric equilibrium between C(N4-H)(•) and the iminyl σ-radical at low temperature is too slow to be established without added base. ESR and DFT studies agree that, in the iminyl σ-radical, the unpaired spin is localized on the exocyclic nitrogen (N4) in an in-plane pure p-orbital. This gives rise to an anisotropic nitrogen hyperfine coupling (Azz = 40 G) from N4 and a near isotropic β-nitrogen coupling of 9.7 G from the cytosine ring nitrogen at N3. Iminyl σ-radical should exist in its N3-protonated form, as the N3-protonated iminyl σ-radical is stabilized in solution by over 30 kcal/mol (ΔG = -32 kcal/mol) over its conjugate base, the N3-deprotonated form. This is the first observation of an isotropic β-hyperfine ring nitrogen coupling in an N-centered DNA radical. Our theoretical calculations predict that the cytosine iminyl σ-radical can be formed in double-stranded DNA by a radiation-induced ionization-deprotonation process that is only 10 kcal/mol above the lowest energy path.

  1. Spectroscopy of Organometallic Radicals

    SciTech Connect

    Morse, Michael D.

    2015-12-14

    In this grant, we have been mainly concerned with characterization of the chemical bond between transition metals and carbon, although some work has also been directed toward understanding the bonding between transition metals and other main group elements. We have also undertaken some studies on the actinide metals, U and Th.

  2. Crystalline bipyridinium radical complexes and uses thereof

    DOEpatents

    Fahrenbach, Albert C.; Barnes, Jonathan C.; Li, Hao; Stoddart, J. Fraser; Basuray, Ashish Neil; Sampath, Srinivasan

    2015-09-01

    Described herein are methods of generating 4,4'-bipyridinium radical cations (BIPY.sup..cndot.+), and methods for utilizing the radical-radical interactions between two or more BIPY.sup..cndot.+ radical cations that ensue for the creation of novel materials for applications in nanotechnology. Synthetic methodologies, crystallographic engineering techniques, methods of physical characterization, and end uses are described.

  3. Adenine oxidation by pyrite-generated hydroxyl radicals.

    PubMed

    Cohn, Corey A; Fisher, Shawn C; Brownawell, Bruce J; Schoonen, Martin Aa

    2010-04-26

    Cellular exposure to particulate matter with concomitant formation of reactive oxygen species (ROS) and oxidization of biomolecules may lead to negative health outcomes. Evaluating the particle-induced formation of ROS and the oxidation products from reaction of ROS with biomolecules is useful for gaining a mechanistic understanding of particle-induced oxidative stress. Aqueous suspensions of pyrite particles have been shown to form hydroxyl radicals and degrade nucleic acids. Reactions between pyrite-induced hydroxyl radicals and nucleic acid bases, however, remain to be determined. Here, we compared the oxidation of adenine by Fenton-generated (i.e., ferrous iron and hydrogen peroxide) hydroxyl radicals to adenine oxidation by hydroxyl radicals generated in pyrite aqueous suspensions. Results show that adenine oxidizes in the presence of pyrite (without the addition of hydrogen peroxide) and that the rate of oxidation is dependent on the pyrite loading. Adenine oxidation was prevented by addition of either catalase or ethanol to the pyrite/adenine suspensions, which implies that hydrogen peroxide and hydroxyl radicals are causing the adenine oxidation. The adenine oxidation products, 8-oxoadenine and 2-hydroxyadenine, were the same whether hydroxyl radicals were generated by Fenton or pyrite-initiated reactions. Although nucleic acid bases are unlikely to be directly exposed to pyrite particles, the formation of ROS in the vicinity of cells may lead to oxidative stress.

  4. Formation and Dissociation of Phosphorylated Peptide Radical Cations

    NASA Astrophysics Data System (ADS)

    Kong, Ricky P. W.; Quan, Quan; Hao, Qiang; Lai, Cheuk-Kuen; Siu, Chi-Kit; Chu, Ivan K.

    2012-12-01

    In this study, we generated phosphoserine- and phosphothreonine-containing peptide radical cations through low-energy collision-induced dissociation (CID) of the ternary metal-ligand phosphorylated peptide complexes [CuII(terpy) p M]·2+ and [CoIII(salen) p M]·+ [ p M: phosphorylated angiotensin III derivative; terpy: 2,2':6',2''-terpyridine; salen: N, N '-ethylenebis(salicylideneiminato)]. Subsequent CID of the phosphorylated peptide radical cations ( p M·+) revealed fascinating gas-phase radical chemistry, yielding (1) charge-directed b- and y-type product ions, (2) radical-driven product ions through cleavages of peptide backbones and side chains, and (3) different degrees of formation of [M - H3PO4]·+ species through phosphate ester bond cleavage. The CID spectra of the p M·+ species and their non-phosphorylated analogues featured fragment ions of similar sequence, suggesting that the phosphoryl group did not play a significant role in the fragmentation of the peptide backbone or side chain. The extent of neutral H3PO4 loss was influenced by the peptide sequence and the initial sites of the charge and radical. A preliminary density functional theory study, at the B3LYP 6-311++G(d,p) level of theory, of the neutral loss of H3PO4 from a prototypical model— N-acetylphosphorylserine methylamide—revealed several factors governing the elimination of neutral phosphoryl groups through charge- and radical-induced mechanisms.

  5. Free radical destruction of beta-blockers in aqueous solution.

    PubMed

    Song, Weihua; Cooper, William J; Mezyk, Stephen P; Greaves, John; Peake, Barrie M

    2008-02-15

    Many pharmaceutical compounds and metabolites are currently found in surface and ground waters which indicates their ineffective removal by conventional water treatment technologies. Advanced oxidation/reduction processes (AO/ RPs) are alternatives to traditional water treatment, which utilize free radical reactions to directly degrade chemical contaminants. This study reports the absolute rate constants for reaction of three beta-blockers (atenolol, metoprolol, and propranolol) with the two major AO/RP radicals; the hydroxyl radical (*OH) and hydrated electron ((e-)aq). The bimolecular reaction rate constants for *OH are (7.05 +/- 0.27) x 10(9), (8.39 +/- 0.06) x 10(9), and (1.07 +/- 0.02) x 10(10), and for (e-)aq they are (5.91 +/- 0.21) x 10(8), (1.73 +/- 0.03) x 10(8), and (1.26 +/- 0.02) x 10(10), respectively. Transient spectra were observed for the intermediate radicals produced by hydroxyl radical reactions. In addition, preliminary degradation mechanisms and major products were elucidated using 60Co gamma-irradiation and LC-MS. These data are required for both evaluating the potential use of AO/RPs for the destruction of these compounds and for studies of their fate and transport in surface waters where radical chemistry may be important in assessing their lifetime.

  6. Methods for determining the efficacy of radical-trapping antioxidants.

    PubMed

    Li, Bo; Pratt, Derek A

    2015-05-01

    Hydrocarbon autoxidation is the free radical chain reaction primarily responsible for the oxidative degradation of organic materials, including those that make up cells, tissues, and organs. The identification of compounds that slow this process (antioxidants) and the quantitation of their efficacies have long been goals of academic and industrial researchers. Antioxidants are generally divided into two types: preventive and radical-trapping (also commonly referred to as chain-breaking). Preventive antioxidants slow the rate of initiation of autoxidation, whereas radical-trapping antioxidants slow the rate of propagation by reacting with chain-propagating peroxyl radicals. The purpose of this review is to provide a comprehensive overview of different approaches to measure the kinetics of the reactions of radical-trapping antioxidants with peroxyl radicals, and their use to study the inhibition of hydrocarbon (lipid) autoxidation in homogeneous solution, as well as biphasic media (lipid bilayers) and cell culture. Direct and indirect approaches are presented and advantages and disadvantages of each are discussed in order to facilitate method selection for investigators seeking to address particular questions in this immensely popular field.

  7. Floquet theory of radical pairs in radiofrequency magnetic fields

    NASA Astrophysics Data System (ADS)

    Hiscock, Hamish G.; Kattnig, Daniel R.; Manolopoulos, David E.; Hore, P. J.

    2016-09-01

    We present a new method for calculating the product yield of a radical pair recombination reaction in the presence of a weak time-dependent magnetic field. This method successfully circumvents the computational difficulties presented by a direct solution of the Liouville-von Neumann equation for a long-lived radical pair containing many hyperfine-coupled nuclear spins. Using a modified formulation of Floquet theory, treating the time-dependent magnetic field as a perturbation, and exploiting the slow radical pair recombination, we show that one can obtain a good approximation to the product yield by considering only nearly degenerate sub-spaces of the Floquet space. Within a significant parameter range, the resulting method is found to give product yields in good agreement with exact quantum mechanical results for a variety of simple model radical pairs. Moreover it is considerably more efficient than the exact calculation, and it can be applied to radical pairs containing significantly more nuclear spins. This promises to open the door to realistic theoretical investigations of the effect of radiofrequency electromagnetic radiation on the photochemically induced radical pair recombination reactions in the avian retina which are believed to be responsible for the magnetic compass sense of migratory birds.

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

    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).

  9. Standard Electrode Potentials Involving Radicals in Aqueous Solution: Inorganic Radicals

    SciTech Connect

    Armstrong, David A.; Huie, Robert E.; Koppenol, Willem H.; Lymar, Sergei V.; Merenyi, Gabor; Neta, Pedatsur; Ruscic, Branko; Stanbury, David M.; Steenken, Steen; Wardman, Peter

    2015-12-01

    Recommendations are made for standard potentials involving select inorganic radicals in aqueous solution at 25 °C. These recommendations are based on a critical and thorough literature review and also by performing derivations from various literature reports. The recommended data are summarized in tables of standard potentials, Gibbs energies of formation, radical pKa’s, and hemicolligation equilibrium constants. In all cases, current best estimates of the uncertainties are provided. An extensive set of Data Sheets is appended that provide original literature references, summarize the experimental results, and describe the decisions and procedures leading to each of the recommendations

  10. Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery.

    PubMed

    Wei, Xiaoliang; Xu, Wu; Huang, Jinhua; Zhang, Lu; Walter, Eric; Lawrence, Chad; Vijayakumar, M; Henderson, Wesley A; Liu, Tianbiao; Cosimbescu, Lelia; Li, Bin; Sprenkle, Vincent; Wang, Wei

    2015-07-20

    Nonaqueous redox flow batteries hold the promise of achieving higher energy density because of the broader voltage window than aqueous systems, but their current performance is limited by low redox material concentration, cell efficiency, cycling stability, and current density. We report a new nonaqueous all-organic flow battery based on high concentrations of redox materials, which shows significant, comprehensive improvement in flow battery performance. A mechanistic electron spin resonance study reveals that the choice of supporting electrolytes greatly affects the chemical stability of the charged radical species especially the negative side radical anion, which dominates the cycling stability of these flow cells. This finding not only increases our fundamental understanding of performance degradation in flow batteries using radical-based redox species, but also offers insights toward rational electrolyte optimization for improving the cycling stability of these flow batteries.

  11. Stable radical content and anti-radical activity of roasted Arabica coffee: from in-tact bean to coffee brew.

    PubMed

    Troup, Gordon J; Navarini, Luciano; Suggi Liverani, Furio; Drew, Simon C

    2015-01-01

    The roasting of coffee beans generates stable radicals within melanoidins produced by non-enzymatic browning. Roasting coffee beans has further been suggested to increase the antioxidant (AO) capacity of coffee brews. Herein, we have characterized the radical content and AO capacity of brews prepared from Coffea arabica beans sourced directly from an industrial roasting plant. In-tact beans exhibited electron paramagnetic resonance signals arising from Fe3+, Mn2+ and at least three distinct stable radicals as a function of roasting time, whose intensity changed upon grinding and ageing. In coffee brews, the roasting-induced radicals were harboured within the high molecular weight (> 3 kD) melanoidin-containing fraction at a concentration of 15 nM and was associated with aromatic groups within the melanoidins. The low molecular weight (< 3 kD) fraction exhibited the highest AO capacity using DPPH as an oxidant. The AO activity was not mediated by the stable radicals or by metal complexes within the brew. While other non-AO functions of the roasting-induced radical and metal complexes may be possible in vivo, we confirm that the in vitro antiradical activity of brewed coffee is dominated by low molecular weight phenolic compounds.

  12. Stable Radical Content and Anti-Radical Activity of Roasted Arabica Coffee: From In-Tact Bean to Coffee Brew

    PubMed Central

    Troup, Gordon J.; Navarini, Luciano; Liverani, Furio Suggi; Drew, Simon C.

    2015-01-01

    The roasting of coffee beans generates stable radicals within melanoidins produced by non-enzymatic browning. Roasting coffee beans has further been suggested to increase the antioxidant (AO) capacity of coffee brews. Herein, we have characterized the radical content and AO capacity of brews prepared from Coffea arabica beans sourced directly from an industrial roasting plant. In-tact beans exhibited electron paramagnetic resonance signals arising from Fe3+, Mn2+ and at least three distinct stable radicals as a function of roasting time, whose intensity changed upon grinding and ageing. In coffee brews, the roasting-induced radicals were harboured within the high molecular weight (> 3 kD) melanoidin-containing fraction at a concentration of 15 nM and was associated with aromatic groups within the melanoidins. The low molecular weight (< 3 kD) fraction exhibited the highest AO capacity using DPPH as an oxidant. The AO activity was not mediated by the stable radicals or by metal complexes within the brew. While other non-AO functions of the roasting-induced radical and metal complexes may be possible in vivo, we confirm that the in vitro antiradical activity of brewed coffee is dominated by low molecular weight phenolic compounds. PMID:25856192

  13. The role of free radicals in traumatic brain injury.

    PubMed

    O'Connell, Karen M; Littleton-Kearney, Marguerite T

    2013-07-01

    Traumatic brain injury (TBI) is a significant cause of death and disability in both the civilian and the military populations. The primary impact causes initial tissue damage, which initiates biochemical cascades, known as secondary injury, that expand the damage. Free radicals are implicated as major contributors to the secondary injury. Our review of recent rodent and human research reveals the prominent role of the free radicals superoxide anion, nitric oxide, and peroxynitrite in secondary brain injury. Much of our current knowledge is based on rodent studies, and the authors identified a gap in the translation of findings from rodent to human TBI. Rodent models are an effective method for elucidating specific mechanisms of free radical-induced injury at the cellular level in a well-controlled environment. However, human TBI does not occur in a vacuum, and variables controlled in the laboratory may affect the injury progression. Additionally, multiple experimental TBI models are accepted in rodent research, and no one model fully reproduces the heterogeneous injury seen in humans. Free radical levels are measured indirectly in human studies based on assumptions from the findings from rodent studies that use direct free radical measurements. Further study in humans should be directed toward large samples to validate the findings in rodent studies. Data obtained from these studies may lead to more targeted treatment to interrupt the secondary injury cascades.

  14. Radical-Mediated Enzymatic Polymerizations

    PubMed Central

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  15. Epistemological barriers to radical behaviorism.

    PubMed

    O'Donohue, W T; Callaghan, G M; Ruckstuhl, L E

    1998-01-01

    The historian and philosopher of science Gaston Bachelard proposed the concept of epistemological barriers to describe the intellectual challenges encountered by scientists in their work. In order to embrace novel ways of approaching a problem in science, scientists must overcome barriers or obstacles posed by their prior views. For example, Einsteinian physics presents scientists with claims that space is curved and that time and space are on the same continuum. We utilize Bachelard's concept of epistemological barriers to describe the differences between the intellectual journeys students pursuing advanced studies face when attempting to accept cognitive psychology or radical behaviorism. We contend that the folk psychological beliefs that students typically hold when entering these studies pose less challenge to cognitive psychology than to radical behaviorism. We also suggest that these barriers may also partly be involved in the problematic exegesis that has plagued radical behaviorism. In close, we offer some suggestions for dealing with these epistemological barriers.

  16. Epistemological barriers to radical behaviorism

    PubMed Central

    O'Donohue, William T.; Callaghan, Glenn M.; Ruckstuhl, L. E.

    1998-01-01

    The historian and philosopher of science Gaston Bachelard proposed the concept of epistemological barriers to describe the intellectual challenges encountered by scientists in their work. In order to embrace novel ways of approaching a problem in science, scientists must overcome barriers or obstacles posed by their prior views. For example, Einsteinian physics presents scientists with claims that space is curved and that time and space are on the same continuum. We utilize Bachelard's concept of epistemological barriers to describe the differences between the intellectual journeys students pursuing advanced studies face when attempting to accept cognitive psychology or radical behaviorism. We contend that the folk psychological beliefs that students typically hold when entering these studies pose less challenge to cognitive psychology than to radical behaviorism. We also suggest that these barriers may also partly be involved in the problematic exegesis that has plagued radical behaviorism. In close, we offer some suggestions for dealing with these epistemological barriers. PMID:22478314

  17. Stabilization of hydrocarbon fuel combustion by non-stationary electric field

    NASA Astrophysics Data System (ADS)

    Kozulin, V. S.; Tretyakov, P. K.; Tupikin, A. V.

    2016-10-01

    The research results of a non-stationary weak electric field effect on diffusion combustion of gas hydrocarbons are presented in the paper. The main attention was focused on the study of electric field parameters effect on a flame stabilization. The two field types were considered: pulse-periodic and with variable direction of an electric vector. In the experiments the direct photography and the video shooting were used, as well as the spectrozonal photography of the own flame luminescence (at the wavelengths of excited OH* and CH* radicals emission). It was shown that the stabilization zone tends to the place of the largest electric field strength. The rotation of the electric vector leads to the flame stabilization in the electrodes plane and the local intensification of combustion.

  18. VUV Photoionisation of hydrocarbon radicals

    NASA Astrophysics Data System (ADS)

    Alcaraz, C.; Noller, Bastian; Hemberger, Patrick; Fischer, Ingo; Gans, Bérenger; Boyé-Peronne, Séverine; Douin, Stéphane; Gauyacq, Dolorès; Soldi-Lose, Héloïse; Garcia, Gustavo

    2008-09-01

    Hydrocarbon radicals CxHy are constituents of various planetary atmospheres, in particular Titan, as a result of the methane photochemistry induced by the solar radiation. They contribute to the neutral chemistry, but are also important for the ionosphere through their photoionisation leading to their cations CxHy +. These cations are also produced by ion-molecule reactions starting from the reaction of the primary ions CH4 + and CH3 + which are created in the non-dissociative and dissociative photoionisation of CH4. This work aims at caracterizing the VUV photoionisation of small hydrocarbon radicals as a function of photon energy. The objective is to provide laboratory data for modelers on the spectroscopy, the thermochemistry, and the reactivity of the radicals and their cations. The hydrocarbon radicals are much less caracterized than stable molecules since they have to be produced in situ in the laboratory experiment. We have adapted at Orsay [1-3] a pyrolysis source (Figure 1) well suited to produce cold beams of hydrocarbon radicals to our experimental setups. Available now at Orsay, we have two new sources of VUV radiation, complementary in terms of tunability and resolution, that can be used for these studies. The first one is the DESIRS beamline [4] at the new french synchrotron, SOLEIL. The second one is the VUV laser developped at the Centre Laser de l'Université Paris-Sud (CLUPS) [5]. At SOLEIL, a photoelectron-photoion coincidence spectrometer is used to monitor the photoionisation on a large photon energy range. At the CLUPS, a pulsedfield ionisation (PFI-ZEKE) spectrometer allows studies at higher resolution on selected photon energies. The first results obtained with these new setups will be presented. References [1] Fischer, I., Schussler, T., Deyerl, H.J., Elhanine, M. & Alcaraz, C., Photoionization and dissociative photoionization of the allyl radical, C3H5. Int. J. Mass Spectrom., 261 (2-3), 227-233 (2007) [2] Schüßler, T., Roth, W., Gerber

  19. Donor free radical explosive composition

    DOEpatents

    Walker, Franklin E. [15 Way Points Rd., Danville, CA 94526; Wasley, Richard J. [4290 Colgate Way, Livermore, CA 94550

    1980-04-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a donor additive comprising an organic compound or mixture of organic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and which is not an explosive, or an inorganic compound or mixture of inorganic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and selected from ammonium or alkali metal persulfates.

  20. Laparoscopic radical and partial cystectomy

    PubMed Central

    Challacombe, Ben J.; Rose, Kristen; Dasgupta, Prokar

    2005-01-01

    Radical cystectomy remains the standard treatment for muscle invasive organ confined bladder carcinoma. Laparoscopic radical cystoprostatectomy (LRC) is an advanced laparoscopic procedure that places significant demands on the patient and the surgeon alike. It is a prolonged procedure which includes several technical steps and requires highly developed laparoscopic skills including intra-corporeal suturing. Here we review the development of the technique, the indications, complications and outcomes. We also examine the potential benefits of robotic-assisted LRC and explore the indications and technique of laparoscopic partial cystectomy. PMID:21206662

  1. 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.

  2. Hexamethylenetetramine directed synthesis and properties of a new family of alpha-nickel hydroxide organic-inorganic hybrid materials with high chemical stability.

    PubMed

    Liu, Bian-Hua; Yu, Shu-Hong; Chen, Shao-Feng; Wu, Chun-Yan

    2006-03-09

    A new family of organic-inorganic hybrid material of alpha-nickel hydroxide formulated as Ni(OH)2-x(An-)x/n-(C6H12N4)y.zH2O (A=Cl-, CH3COO-, SO4(2-), NO3-; x=0.05-0.18, y=0.09-0.11, z=0.36-0.43) with high stability and adjustable interlayer spacing ranging from 7.21 to 15.12 A has been successfully prepared by a simple hydrothermal method. The effects of various anions and hexamethylenetetramine (HMT) on the d values of alpha-nickel hydroxide have been systematically investigated. This family of hybrid materials is of such high stability that they can stand more than 40 days in 6 M KOH. The product with a formula Ni(OH)1.95(C6H12N4)0.11(Cl-)0.05(H2O)0.36 has a high surface area of about 299.26 m2/g and an average pore diameter of about 45.1 A. The coercivity (Hc) value is ca. 2000 Oe for the sample with a d spacing of 13.14 A. Moreover, the prepared alpha-Ni(OH)2 in our experiment is of high stability in strong alkali solution. Such high stability could be derived from strong chelating interactions between the Ni ions and HMT molecules with the interlayers. This high chemical stability could make this material more suitable for the applications.

  3. Transformation of γ-Ray-Formed Methyl Radicals in Methane Hydrate at 10 MPa

    NASA Astrophysics Data System (ADS)

    Ishikawa, Kenji; Tani, Atsushi; Otsuka, Takahiro; Nakashima, Satoru

    2007-01-01

    The stability of methyl radicals formed in synthetic methane hydrate by γ-ray irradiation at 77 K was studied at 200-273 K and 10 MPa. The methyl radicals decayed under these conditions, despite the stability of methane hydrate, and changed into other molecules that could not be detected by electron spin resonance (ESR). Decay products were investigated by gas cell infrared (IR) spectroscopy by measuring the decomposed gas from the γ-irradiated methane hydrate. Only ethane molecules were detected from the irradiated sample, while these were absent in an unirradiated sample. The molar ratio of ethane to methane (C2H6/CH4) was 12± 1 ppm, which did not contradict with that of methyl radical to methane (CH3{}\\bullet/CH4) in the literature. Hence, most of the methyl radicals generated by irradiation were supposed to be transformed to ethane in methane hydrate.

  4. Oxygen Radicals in Influenza-Induced Pathogenesis and Treatment with Pyran Polymer-Conjugated SOD

    NASA Astrophysics Data System (ADS)

    Oda, Tatsuya; Akaike, Takaaki; Hamamoto, Takayoshi; Suzuki, Fujio; Hirano, Takashi; Maeda, Hiroshi

    1989-05-01

    The pathogenicity of influenza virus infection in the mice involves, at least in part, overreaction of the immune responses of the host rather than a direct effect of virus multiplication. Xanthine oxidase, which is responsible for the generation of oxygen free radicals, was elevated in serum and lung tissue of mice infected with influenza virus. To test the theory that oxygen-free radicals are involved in pathogenesis, free radicals were removed by injecting superoxide dismutase (SOD), a specific superoxide radical scavenger, which was conjugated with a pyran copolymer. The conjugate protected mice against a potentially lethal influenza virus infection if administered 5 to 8 days after infection. These findings indicate that oxygen radicals are important in the pathogenesis of influenza virus infection, and that a polymer-conjugated SOD has therapeutic potential for this virus infection and other diseases associated with free radicals.

  5. Infrared absorption spectroscopy and chemical kinetics of free radicals

    SciTech Connect

    Curl, R.F.; Glass, G.P.

    1993-12-01

    This research is directed at the detection, monitoring, and study of chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. During the last year, infrared kinetic spectroscopy using excimer laser flash photolysis and color-center laser probing has been employed to study the high resolution spectrum of HCCN, the rate constant of the reaction between ethynyl (C{sub 2}H) radical and H{sub 2} in the temperature region between 295 and 875 K, and the recombination rate of propargyl (CH{sub 2}CCH) at room temperature.

  6. Vascular effects of free radicals generated by electrical stimulation

    SciTech Connect

    Lamb, F.S.; Webb, R.C.

    1984-11-01

    Electrical field stimulation (9 V, 1.0 ms, 4 Hz) of isolated segments of rat tail arteries and dog coronary arteries inhibits contractile response to exogenous norephinephrine and elevated potassium concentration. This inhibitory effect of electrical stimulation is blocked by various agents that alter oxygen metabolism: superoxide dismutase, catalase, glutathione, ascorbate, and dimethyl sulfoxide. The observations suggest that the inhibitory effect is due to an action of oxygen free radical metabolites that are generated by the electrical stimulation of the oxygen-rich buffer. These free radical metabolites have two actions: 1) they oxidize drugs in the experimental system, and 2) they exert a direct inhbitory action on vascular smooth muscle.

  7. International Robotic Radical Cystectomy Consortium: A way forward.

    PubMed

    Raza, Syed Johar; Field, Erinn; Kibel, Adam S; Mottrie, Alex; Weizer, Alon Z; Wagner, Andrew; Hemal, Ashok K; Scherr, Douglas S; Schanne, Francis; Gaboardi, Franco; Wu, Guan; Peabody, James O; Koauk, Jihad; Redorta, Joan Palou; Pattaras, John G; Rha, Koon-Ho; Richstone, Lee; Balbay, M Derya; Menon, Mani; Hayn, Mathew; Stoeckle, Micheal; Wiklund, Peter; Dasgupta, Prokar; Pruthi, Raj; Ghavamian, Reza; Khan, Shamim; Siemer, Stephan; Maatman, Thomas; Wilson, Timothy; Poulakis, Vassilis; Wilding, Greg; Guru, Khurshid A

    2014-07-01

    Robot-assisted radical cystectomy (RARC) is an emerging operative alternative to open surgery for the management of invasive bladder cancer. Studies from single institutions provide limited data due to the small number of patients. In order to better understand the related outcomes, a world-wide consortium was established in 2006 of patients undergoing RARC, called the International Robotic Cystectomy Consortium (IRCC). Thus far, the IRCC has reported its findings on various areas of operative interest and continues to expand its capacity to include other operative modalities and transform it into the International Radical Cystectomy Consortium. This article summarizes the findings of the IRCC and highlights the future direction of the consortium.

  8. The microwave spectrum of the AlO radical

    NASA Technical Reports Server (NTRS)

    Yamada, Chikashi; Fujitake, Masaharu; Hirota, Eizi; Cohen, Edward A.

    1990-01-01

    The rotational spectrum of the aluminum monoxide radical in the ground electronic state X 2Sigma(+) was observed in the millimeter- and submillimeter-wave region. Aluminum monoxide radicals were generated directly in a flow reactor absorption cell by the reaction of N2O with aluminum vaporized from a high-temperature crucible. The observed spectrum was analyzed to yield molecular constants including the rotational constant, centrifugal distortion constant, spin-rotation interaction constant, magnetic hyperfine interaction constants, and nuclear quadrupole coupling constant.

  9. Students' Ideas and Radical Constructivism

    ERIC Educational Resources Information Center

    Sánchez Gómez, Pedro J.

    2016-01-01

    In this article, I study, from the point of view of the analytic philosophy of mind, the compatibility of students' ideas studies (SIS) with radical constructivism (RC). I demonstrate that RC is based on a psychology of "narrow mental states"; that is, the idea that the mental content of an individual can be fully characterised without…

  10. The Other Women: Radicalizing Feminism.

    ERIC Educational Resources Information Center

    Puigvert, Lidia; Darder, Antonia; Merrill, Barbara; de los Reyes, Eileen; Stromquist, Nelly

    A recent international symposium on radicalizing feminism explored ways of developing a dialogic feminism that emphasizes working in different settings under the common goal of including women who have been invisible in the dominant feminist literature by furthering theories and practices based on the principles of dialogic feminism. The seminar…

  11. Mitigating Radicalism in Northern Nigeria

    DTIC Science & Technology

    2013-08-01

    radicalization in northern Nigeria. u Active engagement of youth and communities in peacebuilding programs that facilitate interactions among individuals...leaders, sustained development investments in marginalized communities , promotion of values of inclusivity to mitigate the spread of extremist ideology...claiming to have repelled Boko Haram, the militants return, regroup, and seek revenge. As a result, social and economic activities in the northern

  12. Chemical stabilization of the coumarin 1 dye laser

    SciTech Connect

    von Trebra, R.J.; Koch, T.H.

    1983-01-15

    The chemical stabilization of coumarin 1, 7-diethylamino-4-methylcoumarin, in a nitrogen laser pumped dye laser and coumarin 311, 7-dimethylamino-4-methylcoumarin, under cw conditions with sulfur-free radical chain transfer agents, are described. The mechanism for stabilization involves encounter of triplet coumarin and ground state coumarin with subsequent radical formation and radical disproportionation catalyzed by the chain transfer agents. The output of the coumarin 1 dye laser decreased 10% when the dye solution was stabilized with cysteine hydrochloride over a 12-h period. The output of the unstabilized dye laser decreased 50% during a similar period of operation.

  13. Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere

    NASA Technical Reports Server (NTRS)

    Wennberg, P. O.; Hanisco, T. F.; Jaegle, L.; Jacob, D. J.; Hintsa, E. J.; Lanzendorf, E. J.; Anderson, J. G.; Gao, R.-S.; Keim, E. R.; Donnelly, S. G.; DelNegro, L. A.; Fahey, D. W.; McKeen, S. A.; Salawitch, R. J.; Webster, C. R.; May, R. D.; Herman, R. L.; Proffitt, M. H.; Margitan, J. J.; Atlas, E. L.

    1998-01-01

    The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3, in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HO(x) required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of 03 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day.This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more 03 than expected.

  14. Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere

    NASA Technical Reports Server (NTRS)

    Wennberg, P. O.; Hanisco, T. F.; Jaegle, L.; Jacob, D. J.; Hintsa, E. J.; Lanzendorf, E. J.; Anderson, J. G.; Gao, R.-S.; Keim, E. R.; Donnelly, S. G.; DelNegro, L. A.; Fahey, D. W.; McKeen, S. A.; Salawitch, R. J.; Webster, C. R.; May, R. D.; Herman, R. L.; Profitt, M. H.; Margitan, J. J.; Atlas, E. L.

    1998-01-01

    The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HO(sub x) required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more O3 than expected.

  15. Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere

    NASA Technical Reports Server (NTRS)

    Wennberg, P. O.; Hanisco, T. F.; Jaegle, L.; Jacob, D. J.; Hintsa, E. J.; Lanzendorf, E. J.; Anderson, J. G.; Gao, R.-S.; Keim, E. R.; Donnelly, S. G.; DelNegro, L. A.; Fahey, D. W.; McKeen, S. A.; Salawitch, R. J.; Webster, C. R.; May, R. D.; Herman, R. L.; Proffitt, M. H.; Margitan, J. J.; Atlas, E. L.; Schauffler, S. M.; Flocke, F.; McElroy, C. T.; Bui, T.P.

    1998-01-01

    The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HO, required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production Of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about I part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more 03 than expected.

  16. Hydrogen radicals, nitrogen radicals, and the production of O3 in the upper troposphere

    PubMed

    Wennberg; Hanisco; Jaegle; Jacob; Hintsa; Lanzendorf; Anderson; Gao; Keim; Donnelly; Negro; Fahey; McKeen; Salawitch; Webster; May; Herman; Proffitt; Margitan; Atlas; Schauffler; Flocke; McElroy; Bui

    1998-01-02

    The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HOx required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more O3 than expected.

  17. Halogen radicals contribute to photooxidation in coastal and estuarine waters

    NASA Astrophysics Data System (ADS)

    Parker, Kimberly M.; Mitch, William A.

    2016-05-01

    Although halogen radicals are recognized to form as products of hydroxyl radical (•OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM (3DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater •OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark •OH generation by gamma radiolysis demonstrates that halogen radical production via •OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl- and Br- by 3DOM*, an •OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters.

  18. Halogen radicals contribute to photooxidation in coastal and estuarine waters

    PubMed Central

    Parker, Kimberly M.; Mitch, William A.

    2016-01-01

    Although halogen radicals are recognized to form as products of hydroxyl radical (•OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM (3DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater •OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark •OH generation by gamma radiolysis demonstrates that halogen radical production via •OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl− and Br− by 3DOM*, an •OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters. PMID:27162335

  19. Effect of plasma and carboxylesterase on the stability, mutagenicity, and DNA cross-linking activity of some direct-acting N-nitroso compounds.

    PubMed

    Aukerman, S L; Brundrett, R B; Hilton, J; Hartman, P E

    1983-01-01

    The effects of mouse plasma, human plasma, and purified porcine liver carboxylesterase on nitrosourea, nitrosamide, and nitrosocarbamate chemical stability, mutagenicity, and DNA cross-linking activity were compared. These three classes of N-nitroso compounds are chemically similar but displayed different biological activities and were affected differently by plasma and carboxylesterase. Nitrosourea stability as well as mutagenicity and DNA cross-linking activity were affected negligibly by esterase or plasma. In contrast, nitrosamide and nitrosocarbamate stability, mutagenicity, and DNA cross-linking activity were rapidly decreased in the presence of plasma or carboxylesterase. For example, chemical half-lives were from 10- to 20-fold shorter for the nitrosamides and nitrosocarbamates in the presence of 5% mouse plasma. Similar decreases were seen for mutagenicity and DNA cross-linking activity. Preliminary studies indicated one active plasma component to be an enzyme, possibly an esterase. Additional factors such as sulfhydryls may also participate. Whereas some nitrosoureas are active antitumor agents, the lack of antitumor activity for analogous nitrosamides and nitrosocarbamates may reside predominantly in their rapid in vivo inactivation. These results may help to account for the high in vitro mutagenicity as compared with the low in vivo activities of nitrosamides and nitrosocarbamates.

  20. Kinetics for Tautomerizations and Dissociations of Triglycine Radical Cations

    SciTech Connect

    Siu, Chi-Kit; Zhao, Junfang; Laskin, Julia; Chu, Ivan K.; Hopkinson, Alan C.; Siu , K W Michael

    2009-06-01

    Fragmentations of tautomers of the α-centered radical triglycine radical cation, [GGG*]+, [GG*G]+, and [G*GG]+, are charge-driven, giving b-type ions; these are processes that are facilitated by a mobile proton, as in the fragmentation of protonated triglycine (Rodriquez, C.F. et al. J. Am. Chem. Soc. 2001, 123, 3006 - 3012). By contrast, radical centers are less mobile. Two mechanisms have been examined theoretically utilizing density functional theory and Rice-Ramsperger-Kassel-Marcus modeling: (1) a direct hydrogen-atom migration between two α-carbons, and (2) a two-step proton migration involving a canonical [GGG]*+ as an intermediate. Predictions employing the latter mechanism are in good agreement with results of recent CID experiments (Chu, I.K. et al. J. Am. Chem. Soc. 2008, 130, 7862 - 7872).

  1. Carbohydrates and their free radical scavenging capability: a theoretical study.

    PubMed

    Hernandez-Marin, Elizabeth; Martínez, Ana

    2012-08-16

    A density functional theory (DFT) study on the free radical (OH(•) and OOH(•)) scavenging properties of some mono- and polysaccharides is presented. Two mechanisms, single electron transfer (SET) and hydrogen atom transfer (HAT), are considered. The former mechanism is studied by making use of the vertical ionization energy and vertical electron affinity of the radicals and carbohydrates. It is confirmed that the SET mechanism is not plausible to occur. With respect to the HAT, not only does the OH(•) radical react preferably with one hydrogen atom bonded to one carbon atom, but also the reaction with a hydrogen atom bonded to an oxygen is possible. Finally, it is suggested that the carbohydrates are not able to directly scavenge OOH(•).

  2. Unexpectedly high indoor hydroxyl radical concentrations associated with nitrous acid.

    PubMed

    Gómez Alvarez, Elena; Amedro, Damien; Afif, Charbel; Gligorovski, Sasho; Schoemaecker, Coralie; Schoemacker, Coralie; Fittschen, Christa; Doussin, Jean-Francois; Wortham, Henri

    2013-08-13

    The hydroxyl (OH) radical is the most important oxidant in the atmosphere since it controls its self-oxidizing capacity. The main sources of OH radicals are the photolysis of ozone and the photolysis of nitrous acid (HONO). Due to the attenuation of solar radiation in the indoor environment, the possibility of OH formation through photolytic pathways indoors has been ignored up to now. In the indoor air, the ozonolysis of alkenes has been suggested as an alternative route of OH formation. Models and indirect measurements performed up to now according to this hypothesis suggest concentrations of OH radicals on the order of 10(4)-10(5) molecules per cubic centimeter. Here, we present direct measurements of significant amounts of OH radicals of up to 1.8⋅10(6) molecules per cubic centimeter during an experimental campaign carried out in a school classroom in Marseille. This concentration is on the same order of magnitude of outdoor OH levels in the urban scenario. We also show that photolysis of HONO is an important source of OH radicals indoors under certain conditions (i.e., direct solar irradiation inside the room). Additionally, the OH concentrations were found to follow a linear dependence with the product J(HONO)⋅[HONO]. This was also supported by using a simple quasiphotostationary state model on the OH radical budget. These findings force a change in our understanding of indoor air quality because the reactivity linked to OH would involve formation of secondary species through chemical reactions that are potentially more hazardous than the primary pollutants in the indoor air.

  3. Unexpectedly high indoor hydroxyl radical concentrations associated with nitrous acid

    PubMed Central

    Gómez Alvarez, Elena; Amedro, Damien; Afif, Charbel; Gligorovski, Sasho; Schoemaecker, Coralie; Fittschen, Christa; Doussin, Jean-Francois; Wortham, Henri

    2013-01-01

    The hydroxyl (OH) radical is the most important oxidant in the atmosphere since it controls its self-oxidizing capacity. The main sources of OH radicals are the photolysis of ozone and the photolysis of nitrous acid (HONO). Due to the attenuation of solar radiation in the indoor environment, the possibility of OH formation through photolytic pathways indoors has been ignored up to now. In the indoor air, the ozonolysis of alkenes has been suggested as an alternative route of OH formation. Models and indirect measurements performed up to now according to this hypothesis suggest concentrations of OH radicals on the order of 104–105 molecules per cubic centimeter. Here, we present direct measurements of significant amounts of OH radicals of up to 1.8⋅106 molecules per cubic centimeter during an experimental campaign carried out in a school classroom in Marseille. This concentration is on the same order of magnitude of outdoor OH levels in the urban scenario. We also show that photolysis of HONO is an important source of OH radicals indoors under certain conditions (i.e., direct solar irradiation inside the room). Additionally, the OH concentrations were found to follow a linear dependence with the product J(HONO)⋅[HONO]. This was also supported by using a simple quasiphotostationary state model on the OH radical budget. These findings force a change in our understanding of indoor air quality because the reactivity linked to OH would involve formation of secondary species through chemical reactions that are potentially more hazardous than the primary pollutants in the indoor air. PMID:23898188

  4. Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery

    SciTech Connect

    Wei, Xiaoliang; Xu, Wu; Huang, Jinhua; Zhang, Lu; Walter, Eric D.; Lawrence, Chad W.; Vijayakumar, M.; Henderson, Wesley A.; Liu, Tianbiao L.; Cosimbescu, Lelia; Li, Bin; Sprenkle, Vincent L.; Wang, Wei

    2015-07-20

    Nonaqueous redox flow batteries hold the promise to achieve higher energy density ascribed to the broader voltage window than their aqueous counterparts, but their current performance is limited by low redox material concentration, poor cell efficiency, and inferior cycling stability. We report a new nonaqueous total-organic flow battery based on high concentrations of 9-fluorenone as negative and 2,5-di-tert-butyl-1-methoxy-4-[2’-methoxyethoxy]benzene as positive redox materials. The supporting electrolytes are found to greatly affect the cycling stability of flow cells through varying chemical stabilities of the charged radical species, especially the 9-fluorenone radical anions, as confirmed by electron spin resonance. Such an electrolyte optimization sheds light on mechanistic understandings of capacity fading in flow batteries employing organic radical-based redox materials and demonstrates that rational design of supporting electrolyte is vital for stable cyclability.

  5. Imaging free radicals in organelles, cells, tissue, and in vivo with immuno-spin trapping.

    PubMed

    Mason, Ronald Paul

    2016-08-01

    The accurate and sensitive detection of biological free radicals in a reliable manner is required to define the mechanistic roles of such species in biochemistry, medicine and toxicology. Most of the techniques currently available are either not appropriate to detect free radicals in cells and tissues due to sensitivity limitations (electron spin resonance, ESR) or subject to artifacts that make the validity of the results questionable (fluorescent probe-based analysis). The development of the immuno-spin trapping technique overcomes all these difficulties. This technique is based on the reaction of amino acid- and DNA base-derived radicals with the spin trap 5, 5-dimethyl-1-pyrroline N-oxide (DMPO) to form protein- and DNA-DMPO nitroxide radical adducts, respectively. These adducts have limited stability and decay to produce the very stable macromolecule-DMPO-nitrone product. This stable product can be detected by mass spectrometry, NMR or immunochemistry by the use of anti-DMPO nitrone antibodies. The formation of macromolecule-DMPO-nitrone adducts is based on the selective reaction of free radical addition to the spin trap and is thus not subject to artifacts frequently encountered with other methods for free radical detection. The selectivity of spin trapping for free radicals in biological systems has been proven by ESR. Immuno-spin trapping is proving to be a potent, sensitive (a million times higher sensitivity than ESR), and easy (not quantum mechanical) method to detect low levels of macromolecule-derived radicals produced in vitro and in vivo. Anti-DMPO antibodies have been used to determine the distribution of free radicals in cells and tissues and even in living animals. In summary, the invention of the immuno-spin trapping technique has had a major impact on the ability to accurately and sensitively detect biological free radicals and, subsequently, on our understanding of the role of free radicals in biochemistry, medicine and toxicology.

  6. Quantum chemical and master equation simulations of the oxidation and isomerization of vinoxy radicals.

    PubMed

    Kuwata, Keith T; Hasson, Alam S; Dickinson, Ray V; Petersen, Erin B; Valin, Lukas C

    2005-03-24

    The vinoxy radical, a common intermediate in gas-phase alkene ozonolysis, reacts with O2 to form a chemically activated alpha-oxoperoxy species. We report CBS-QB3 energetics for O2 addition to the parent (*CH2CHO, 1a), 1-methylvinoxy (*CH2COCH3, 1b), and 2-methylvinoxy (CH3*CHCHO, 1c) radicals. CBS-QB3 predictions for peroxy radical formation agree with experimental data, while the G2 method systematically overestimates peroxy radical stability. RRKM/master equation simulations based on CBS-QB3 data are used to estimate the competition between prompt isomerization and thermalization for the peroxy radicals derived from 1a, 1b, and 1c. The lowest energy isomerization pathway for radicals 4a and 4c (derived from 1a and 1c, respectively) is a 1,4-shift of the acyl hydrogen requiring 19-20 kcal/mol. The resulting hydroperoxyacyl radical decomposes quantitatively to form *OH. The lowest energy isomerization pathway for radical 4b (derived from 1b) is a 1,5-shift of a methyl hydrogen requiring 26 kcal/mol. About 25% of 4a, but only approximately 5% of 4c, isomerizes promptly at 1 atm pressure. Isomerization of 4b is negligible at all pressures studied.

  7. Novel active stabilization technology in highly crosslinked UHMWPEs for superior stability

    NASA Astrophysics Data System (ADS)

    Oral, Ebru; Neils, Andrew L.; Wannomae, Keith K.; Muratoglu, Orhun K.

    2014-12-01

    Radiation cross-linked ultrahigh molecular weight polyethylene (UHMWPE) is the bearing of choice in joint arthroplasty. The demands on the longevity of this polymer are likely to increase with the recently advancing deterioration of the performance of alternative metal-on-metal implants. Vitamin E-stabilized, cross-linked UHMWPEs are considered the next generation of improved UHMWPE bearing surfaces for improving the oxidation resistance of the polymer. It was recently discovered that in the absence of radiation-induced free radicals, lipids absorbed into UHMWPE from the synovial fluid can initiate oxidation and result in new free radical-mediated oxidation mechanisms. In the presence of radiation-induced free radicals, it is possible for the polymer to oxidize through both existing free radicals at the time of implantation and through newly formed free radicals in vivo. Thus, we showed that reducing the radiation-induced free radicals in vitamin E-stabilized UHMWPE would increase its oxidative stability and presumably lead to improved longevity. We describe mechanical annealing and warm irradiation of irradiated vitamin E blends as novel methods to eliminate 99% of radiation-induced free radicals without sacrificing crystallinity. These are significant improvements in the processing of highly cross-linked UHMWPE for joint implants with improved longevity.

  8. The Radical Axis: A Motion Study

    ERIC Educational Resources Information Center

    McGivney, Ray; McKim, Jim

    2006-01-01

    Interesting problems sometimes have surprising sources. In this paper we take an innocent looking problem from a calculus book and rediscover the radical axis of classical geometry. For intersecting circles the radical axis is the line through the two points of intersection. For nonintersecting, nonconcentric circles, the radical axis still…

  9. Free-radical chemistry of sulfite.

    PubMed Central

    Neta, P; Huie, R E

    1985-01-01

    The free-radical chemistry of sulfite oxidation is reviewed. Chemical transformations of organic and biological molecules induced by sulfite oxidation are summarized. The kinetics of the free-radical oxidations of sulfite are discussed, as are the kinetics of the reactions of the sulfite-derived radicals SO3 and the peroxy derivative SO5 with organic compounds. PMID:3830699

  10. REACTIONS OF FREE RADICALS CONTAINING NITROGEN.

    DTIC Science & Technology

    deduced. The reactions of methyl and ethyl radicals with a variety of amino compounds were studied. The reactions of difluoroamino radicals in the...Hydrazines, Anilines and Cyanides were pyrolysed and the heats of formation of the resultant radicals and the strengths of the bonds formed by them

  11. Mutagenicity of Oxygen Free Radicals

    NASA Astrophysics Data System (ADS)

    Moody, Carmella S.; Hassan, Hosni M.

    1982-05-01

    Paraquat 1,1'-dimethyl-4,4'-bipyridinium dichloride) was used as an intracellular generator of oxygen free radicals and was found to be highly mutagenic for Salmonella typhimurium. It caused both base-pair substitution and frameshift mutations. Paraquat was much more toxic and mutagenic in a simple nutritionally restricted medium than in a rich complex medium. The mutagenicity of paraquat was dependent upon the presence of a supply of both electrons and oxygen. Cells containing high levels of superoxide dismutase (superoxide:superoxide oxidoreductase, EC 1.15.1.1) were more resistant to the toxicity and the mutagenicity of paraquat than were cells containing normal levels of this enzyme. The mutagenicity of paraquat thus appears to be due to its ability to exacerbate the intracellular production of superoxide radicals.

  12. Highly durable photochromic radical complexes having no steric protections of radicals.

    PubMed

    Kobayashi, Yoichi; Mishima, Yasuhiro; Mutoh, Katsuya; Abe, Jiro

    2017-04-21

    Steric protection groups are usually necessary for stable radicals. However, here, we developed novel photochromic radical complexes which generate sterically unprotected imidazolyl and phenoxyl radicals upon UV light irradiation based on the phenoxyl-imidazolyl radical complex (PIC) framework. These photochromic compounds show excellent durability against repeated irradiation of intense nanosecond laser pulses even in polar protic solvents, such as ethanol.

  13. Rovibronic Variational Calculations of the Nitrate Radical

    NASA Astrophysics Data System (ADS)

    Changala, Bryan; Baraban, Joshua H.; Stanton, John F.

    2015-06-01

    In recent years, sophisticated diabatic Hamiltonians have been developed in order to understand the low-energy vibronic level structure of the nitrate radical (NO_3), which exhibits strong coupling between the ~X and doubly degenerate ~B states. Previous studies have reproduced the observed vibronic level positions up to 2000 wn~above the zero-point level, yet the rotational structure has remained uninvestigated with ab initio methods. In this talk, we present calculations of the N≥0 rovibronic structure of low-lying vibronic states of NO_3, in which complicated rovibrational and Coriolis interactions have been observed. Our results include calculations using both adiabatic and diabatic Hamiltonians, enabling a direct comparison between the two. We discuss extensions of our treatment to include spin-orbit and spin-rotation effects.

  14. Spectroscopy, Kinetics, and Dynamics of Combustion Radicals

    SciTech Connect

    Nesbitt, David J.

    2013-08-06

    Spectroscopy, kinetics and dynamics of jet cooled hydrocarbon transients relevant to the DOE combustion mission have been explored, exploiting i) high resolution IR lasers, ii) slit discharge sources for formation of jet cooled radicals, and iii) high sensitivity detection with direct laser absorption methods and near the quantum shot noise limit. What makes this combination powerful is that such transients can be made under high concentrations and pressures characteristic of actual combustion conditions, and yet with the resulting species rapidly cooled (T ≈10-15K) in the slit supersonic expansion. Combined with the power of IR laser absorption methods, this provides novel access to spectral detection and study of many critical combustion species.

  15. Geoscientists and the Radical Middle

    NASA Astrophysics Data System (ADS)

    Tinker, S. W.

    2015-12-01

    Addressing the great challenges facing society requires industry, government, and academia to work together. I call this overlap space, where compromises are made and real solutions determined, the Radical Middle. Radical because it can appear at times as if the loudest and most publicly influential voices lie outside of the actual solution space, content to provoke but not problem-solve. One key area where geoscientists can play a lead role in the Radical Middle is in the overlap between energy, the environment, and the economy. Globally, fossil fuels still represent 85% of the aggregate energy mix. As existing conventional oil and natural-gas reservoir production continues to slowly decline, unconventional reservoirs, led today by shale and other more expensive resources, will represent a growing part of the oil and gas production mix. Many of these unconventional reservoirs require hydraulic fracturing. The positive economic impact of hydraulic fracturing and associated natural gas and oil production on the United States economy is well documented and undeniable. Yet there are environmental concerns about fracking, and some states and nations have imposed moratoria. This energy-environment-economy space is ideal for leadership from the geosciences. Another such overlap space is the potential for geoscience leadership in relations with China, whose economy and global presence continue to expand. Although China is building major hydropower and natural-gas power plants, as well as nuclear reactors, coal is still king—with the associated environmental impacts. Carbon sequestration—onshore in brine and to enhance oil recovery, as well as offshore—could prove viable. It is vital that educated and objective geoscientists from industry, government, and academia leave their corners and work together in the Radical Middle to educate the public and develop and deliver balanced, economically sensible energy and environmental strategies.

  16. Radical Islam in East Africa

    DTIC Science & Technology

    2009-01-01

    track may not be feasible because of lack of political will on either side, but an effort should be made to detach the moderate (or less radical...Director, Sub-Saharan African Orientation Course, U.S. Air Force Special Operations School, February 15, 2008. 12 Among those arrested were the party’s...Sudan is the Tijaniyya Niassiyya, which has grown rapidly since 1950.7 The Sudanese Niassiyya is a millennial movement that preaches the imminence

  17. Comparison of fluorescence-based techniques for the quantification of particle-induced hydroxyl radicals

    PubMed Central

    Cohn, Corey A; Simon, Sanford R; Schoonen, Martin AA

    2008-01-01

    Background Reactive oxygen species including hydroxyl radicals can cause oxidative stress and mutations. Inhaled particulate matter can trigger formation of hydroxyl radicals, which have been implicated as one of the causes of particulate-induced lung disease. The extreme reactivity of hydroxyl radicals presents challenges to their detection and quantification. Here, three fluorescein derivatives [aminophenyl fluorescamine (APF), amplex ultrared, and dichlorofluorescein (DCFH)] and two radical species, proxyl fluorescamine and tempo-9-ac have been compared for their usefulness to measure hydroxyl radicals generated in two different systems: a solution containing ferrous iron and a suspension of pyrite particles. Results APF, amplex ultrared, and DCFH react similarly to the presence of hydroxyl radicals. Proxyl fluorescamine and tempo-9-ac do not react with hydroxyl radicals directly, which reduces their sensitivity. Since both DCFH and amplex ultrared will react with reactive oxygen species other than hydroxyl radicals and another highly reactive species, peroxynitite, they lack specificity. Conclusion The most useful probe evaluated here for hydroxyl radicals formed from cell-free particle suspensions is APF due to its sensitivity and selectivity. PMID:18307787

  18. Are the Radical Centers in Peptide Radical Cations Mobile? The Generation, Tautomerism, and Dissociation of Isomeric α-Carbon-Centered Triglycine Radical Cations in the Gas Phase

    SciTech Connect

    Chu, Ivan K.; Zhao, Junfang; Xu, Minjie; Siu, Shiu On; Hopkinson, Alan C.; Siu , K W Michael

    2008-05-31

    The mobility of the radical center in three isomeric triglycine radical cationss[G•GG]+, [GG•G]+, and [GGG•]+shas been investigated theoretically via density functional theory (DFT) and experimentally via tandem mass spectrometry. These radical cations were generated by collision-induced dissociations (CIDs) of Cu(II)-containing ternary complexes that contain the tripeptides YGG, GYG, and GGY, respectively (G and Y are the glycine and tyrosine residues, respectively). Dissociative electron transfer within the complexes led to observation of [Y•GG]+, [GY•G]+, and [GGY•]+; CID resulted in cleavage of the tyrosine side chain as p-quinomethide, yielding [G•GG]+, [GG•G]+, and [GGG•]+, respectively. Interconversions between these isomeric triglycine radical cations have relatively high barriers (g44.7 kcal/mol), in support of the thesis that isomerically pure [G•GG]+, [GG•G]+, and [GGG•]+ can be experimentally produced. This is to be contrasted with barriers < 17 kcal/mol that were encountered in the tautomerism of protonated triglycine [Rodriquez C. F. et al. J. Am. Chem. Soc. 2001, 123, 3006-3012]. The CID spectra of [G•GG]+, [GG•G]+, and [GGG•]+ were substantially different, providing experimental proof that initially these ions have distinct structures. DFT calculations showed that direct dissociations are competitive with interconversions followed by dissociation.

  19. Radical scavengers from heavy hydrocarbons

    SciTech Connect

    Kubo, Junichi

    1996-10-01

    The hydrogen-donating properties of some hydrocarbons form the basis for processes such as coal liquefaction and heavy oil upgrading. However, these hydrocarbons have seldom been used for other purposes, because their potential applications have not been well recognized. Research has indicated that these hydrogen-donating hydrocarbons can be used in important reactions as radical scavengers and have properties particular to those of pure hydrocarbons without functional groups containing heteroatoms. Over years of study researchers have found that pure hydrocarbons with radical-scavenging effects nearly as high as those in conventional hindered phenolic antioxidants can be produced from petroleum, and these hydrogen-donating hydrocarbons exhibit such effects even in oxidative atmospheres (i.e., they function as antioxidants). He has also shown that these mixtures have some properties particular to pure hydrocarbons without functional groups containing heteroatoms, and they`ve seen that a mechanism based on the steric effects appears when these hydrocarbons are used in heavy oil hydroprocessing. Hydrogen-donating hydrocarbons should be a viable resource in many applications. In this article, he presents radical-scavenging abilities, characteristics as pure hydrocarbons, and applications on the basis of the studies.

  20. Mechanistic aspects of hydration of guanine radical cations in DNA.

    PubMed

    Rokhlenko, Yekaterina; Cadet, Jean; Geacintov, Nicholas E; Shafirovich, Vladimir

    2014-04-23

    The mechanistic aspects of hydration of guanine radical cations, G(•+) in double- and single-stranded oligonucleotides were investigated by direct time-resolved spectroscopic monitoring methods. The G(•+) radical one-electron oxidation products were generated by SO4(•-) radical anions derived from the photolysis of S2O8(2-) anions by 308 nm laser pulses. In neutral aqueous solutions (pH 7.0), after the complete decay of SO4(•-) radicals (∼5 μs after the actinic laser flash) the transient absorbance of neutral guanine radicals, G(-H)(•) with maximum at 312 nm, is dominant. The kinetics of decay of G(-H)(•) radicals depend strongly on the DNA secondary structure. In double-stranded DNA, the G(-H)(•) decay is biphasic with one component decaying with a lifetime of ∼2.2 ms and the other with a lifetime of ∼0.18 s. By contrast, in single-stranded DNA the G(-H)(•) radicals decay monophasically with a ∼ 0.28 s lifetime. The ms decay component in double-stranded DNA is correlated with the enhancement of 8-oxo-7,8-dihydroguanine (8-oxoG) yields which are ∼7 greater than in single-stranded DNA. In double-stranded DNA, it is proposed that the G(-H)(•) radicals retain radical cation character by sharing the N1-proton with the N3-site of C in the [G(•+):C] base pair. This [G(-H)(•):H(+)C ⇆ G(•+):C] equilibrium allows for the hydration of G(•+) followed by formation of 8-oxoG. By contrast, in single-stranded DNA, deprotonation of G(•+) and the irreversible escape of the proton into the aqueous phase competes more effectively with the hydration mechanism, thus diminishing the yield of 8-oxoG, as observed experimentally.

  1. Educating Our Black Children: New Directions and Radical Approaches.

    ERIC Educational Resources Information Center

    Majors, Richard, Ed.

    This collection of papers from U.S. and British contributors focuses on positive social inclusion policy and practice for black students. There are 15 chapters in five parts. Part 1, "Tackling Historical and Contemporary Education Problems," includes: (1) "Racism, Policy and the (Mis)Education of Black Children" (David…

  2. Detection of radicals produced by reaction of hydroperoxides with rat liver microsomal fractions.

    PubMed

    Greenley, T L; Davies, M J

    1992-04-22

    EPR spin trapping using the spin traps 5,5-dimethyl-1-pyrroline N-oxide (DMPO) and 3,5-dibromo-4-nitrosobenzene sulphonic acid (DBNBS) has been employed to examine the generation of radicals produced on reaction of a number of primary, secondary and lipid hydroperoxides with rat liver microsomal fractions in both the presence and absence of reducing equivalents. Two major mechanisms of radical generation have been elucidated. In the absence of NADPH or NADH, oxidative degradation of the hydroperoxide occurs to give initially a peroxyl radical which in the majority of cases can be detected as a spin adduct to DMPO; these radicals can undergo further reactions which result in the generation of alkoxyl and carbon-centered radicals. In the presence of NADPH (and to a lesser extent NADH) alkoxyl radicals are generated directly via reductive cleavage of the hydroperoxide. These alkoxyl radicals undergo further fragmentation and rearrangement reactions to give carbon-centered species which can be identified by trapping with DBNBS. The type of transformation that occurs is highly dependent on the structure of the alkoxyl radical with species arising from beta-scission, 1,2-hydrogen shifts and ring closure reactions being identified; these processes are in accord with previous chemical studies and are characteristic of alkoxyl radicals present in free solution. Studies using specific enzyme inhibitors and metal-ion chelators suggest that most of the radical generation occurs via a catalytic process involving haem proteins and in particular cytochrome P-450. An unusual species (an acyl radical) is observed with lipid hydroperoxides; this is believed to arise via a cage reaction after beta-scission of an initial alkoxyl radical.

  3. Tryptophan tryptophylquinone biosynthesis: a radical approach to posttranslational modification.

    PubMed

    Davidson, Victor L; Liu, Aimin

    2012-11-01

    Protein-derived cofactors are formed by irreversible covalent posttranslational modification of amino acid residues. An example is tryptophan tryptophylquinone (TTQ) found in the enzyme methylamine dehydrogenase (MADH). TTQ biosynthesis requires the cross-linking of the indole rings of two Trp residues and the insertion of two oxygen atoms onto adjacent carbons of one of the indole rings. The diheme enzyme MauG catalyzes the completion of TTQ within a precursor protein of MADH. The preMADH substrate contains a single hydroxyl group on one of the tryptophans and no crosslink. MauG catalyzes a six-electron oxidation that completes TTQ assembly and generates fully active MADH. These oxidation reactions proceed via a high valent bis-Fe(IV) state in which one heme is present as Fe(IV)=O and the other is Fe(IV) with both axial heme ligands provided by amino acid side chains. The crystal structure of MauG in complex with preMADH revealed that catalysis does not involve direct contact between the hemes of MauG and the protein substrate. Rather it is accomplished through long-range electron transfer, which presumably generates radical intermediates. Kinetic, spectrophotometric, and site-directed mutagenesis studies are beginning to elucidate how the MauG protein controls the reactivity of the hemes and mediates the long range electron/radical transfer required for catalysis. This article is part of a Special Issue entitled: Radical SAM enzymes and Radical Enzymology.

  4. Direct observation of vinyl hydroperoxide.

    PubMed

    Liu, Fang; Fang, Yi; Kumar, Manoj; Thompson, Ward H; Lester, Marsha I

    2015-08-28

    Many alkyl-substituted Criegee intermediates are predicted to undergo an intramolecular 1,4-hydrogen transfer to form isomeric vinyl hydroperoxide species (C[double bond, length as m-dash]COOH moiety), which break apart to release OH and vinoxy radicals. We report direct detection of stabilized vinyl hydroperoxides formed via carboxylic acid-catalyzed tautomerization of Criegee intermediates. A doubly hydrogen-bonded interaction between the Criegee intermediate and carboxylic acid facilitates efficient hydrogen transfer through a double hydrogen shift. Deuteration of formic or acetic acid permits migration of a D atom to yield partially deuterated vinyl hydroperoxides, which are distinguished from the CH3CHOO, (CH3)2COO, and CH3CH2CHOO Criegee intermediates by mass. Using 10.5 eV photoionization, three prototypical vinyl hydroperoxides, CH2[double bond, length as m-dash]CHOOD, CH2[double bond, length as m-dash]C(CH3)OOD, and CH3CH[double bond, length as m-dash]CHOOD, are detected directly. Complementary electronic structure calculations reveal several reaction pathways, including the barrierless acid-catalyzed tautomerization reaction predicted previously and a barrierless addition reaction that yields hydroperoxy alkyl formate.

  5. Free-radical-mediated DNA binding.

    PubMed Central

    O'Brien, P J

    1985-01-01

    Free-radical metabolites can be generated metabolically by a one-electron reductase-catalyzed reaction or a "peroxidase" catalyzed oxidation or by photoactivation of a wide variety of aromatic xenobiotics. Radicals may also be generated during lipid peroxidation. Some radicals can react with DNA or bind covalently or noncovalently as a dismutation product or as a dimer, trimer or polymeric product. Modification to the DNA can result in single-strand breaks, loss of template activity, and crosslinking. The binding can prevent enzymic digestion. In some cases, the radicals react with oxygen, resulting before conversion to DNA reactive oxygen species. Most radicals probably do not interact with DNA. PMID:3007090

  6. Direct identification of interstitial Mn in heavily p-type doped GaAs and evidence of its high thermal stability

    SciTech Connect

    Pereira, L. M. C.; Wahl, U.; Correia, J. G.; Decoster, S.; Vantomme, A.; Silva, M. R. da; Araujo, J. P.

    2011-05-16

    We report on the lattice location of Mn in heavily p-type doped GaAs by means of {beta}{sup -} emission channeling from the decay of {sup 56}Mn. The majority of the Mn atoms substitute for Ga and up to 31% occupy the tetrahedral interstitial site with As nearest neighbors. Contrary to the general belief, we find that interstitial Mn is immobile up to 400 deg. C, with an activation energy for diffusion of 1.7-2.3 eV. Such high thermal stability of interstitial Mn has significant implications on the strategies and prospects for achieving room temperature ferromagnetism in Ga{sub 1-x}Mn{sub x}As.

  7. Powering up the future: radical polymers for battery applications.

    PubMed

    Janoschka, Tobias; Hager, Martin D; Schubert, Ulrich S

    2012-12-18

    Our society's dependency on portable electric energy, i.e., rechargeable batteries, which permit power consumption at any place and in any time, will eventually culminate in resource wars on limited commodities like lithium, cobalt, and rare earth metals. The substitution of conventional metals as means of electric charge storage by organic and polymeric materials, which may ultimately be derived from renewable resources, appears to be the only feasible way out. In this context, the novel class of organic radical batteries (ORBs) excelling in rate capability (i.e., charging speed) and cycling stability (>1000 cycles) sets new standards in battery research. This review examines stable nitroxide radical bearing polymers, their processing to battery systems, and their promising performance.

  8. Oxidative stress, free radicals and protein peroxides.

    PubMed

    Gebicki, Janusz M

    2016-04-01

    Primary free radicals generated under oxidative stress in cells and tissues produce a cascade of reactive secondary radicals, which attack biomolecules with efficiency determined by the reaction rate constants and target concentration. Proteins are prominent targets because they constitute the bulk of the organic content of cells and tissues and react readily with many of the secondary radicals. The reactions commonly lead to the formation of carbon-centered radicals, which generally convert in vivo to peroxyl radicals and finally to semistable hydroperoxides. All of these intermediates can initiate biological damage. This article outlines the advantages of the application of ionizing radiations to studies of radicals, with particular reference to the generation of desired radicals, studies of the kinetics of their reactions and correlating the results with events in biological systems. In one such application, formation of protein hydroperoxides in irradiated cells was inhibited by the intracellular ascorbate and glutathione.

  9. Applying Human ADAR1p110 and ADAR1p150 for Site-Directed RNA Editing—G/C Substitution Stabilizes GuideRNAs against Editing

    PubMed Central

    Heep, Madeleine; Mach, Pia; Reautschnig, Philipp; Wettengel, Jacqueline; Stafforst, Thorsten

    2017-01-01

    Site-directed RNA editing is an approach to reprogram genetic information at the RNA level. We recently introduced a novel guideRNA that allows for the recruitment of human ADAR2 to manipulate genetic information. Here, we show that the current guideRNA design is already able to recruit another human deaminase, ADAR1, in both isoforms, p110 and p150. However, further optimization seems necessary as the current design is less efficient for ADAR1 isoforms. Furthermore, we describe hotspots at which the guideRNA itself is edited and show a way to circumvent this auto-editing without losing editing efficiency at the target. Both findings are important for the advancement of site-directed RNA editing as a tool in basic biology or as a platform for therapeutic editing. PMID:28098820

  10. 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

  11. Free radical generation induced by ultrasound in red wine and model wine: An EPR spin-trapping study.

    PubMed

    Zhang, Qing-An; Shen, Yuan; Fan, Xue-hui; Martín, Juan Francisco García; Wang, Xi; Song, Yun

    2015-11-01

    Direct evidence for the formation of 1-hydroxylethyl radicals by ultrasound in red wine and air-saturated model wine is presented in this paper. Free radicals are thought to be the key intermediates in the ultrasound processing of wine, but their nature has not been established yet. Electron paramagnetic resonance (EPR) spin trapping with 5,5-dimethyl-l-pyrrolin N-oxide (DMPO) was used for the detection of hydroxyl free radicals and 1-hydroxylethyl free radicals. Spin adducts of hydroxyl free radicals were detected in DMPO aqueous solution after sonication while 1-hydroxylethyl free radical adducts were observed in ultrasound-processed red wine and model wine. The latter radical arose from ethanol oxidation via the hydroxyl radical generated by ultrasound in water, thus providing the first direct evidence of the formation of 1-hydroxylethyl free radical in red wine exposed to ultrasound. Finally, the effects of ultrasound frequency, ultrasound power, temperature and ultrasound exposure time were assessed on the intensity of 1-hydroxylethyl radical spin adducts in model wine.

  12. Anodic electrogenerated chemiluminescence of quantum dots: size and stabilizer matter

    NASA Astrophysics Data System (ADS)

    Hu, Tao; Li, Tangsong; Yuan, Lang; Liu, Shaoqin; Wang, Zhenlong

    2012-08-01

    The electrogenerated chemiluminescence (ECL) of semiconductor quantum dots (QDs) is generally believed to be independent of particle sizes or the capping agents used. Herein, we demonstrate that CdTe QDs with different sizes and stabilizers evidently exhibit different ECL behavior in aqueous solution. The ECL of CdTe QDs stabilized by 3-mercaptopropionic acid (MPA) displays two waves at potentials of about +1.17 V and +1.74 V vs. Ag/AgCl, respectively. ECL spectra confirm that the ECL of QDs is attributed to their band gap luminescence, in which the peak positions are changed with QD sizes. The ECL mechanism of CdTe QDs involves superoxide radical generation by reduction of dissolved oxygen at lower potential or water splitting at higher potential. Direct evidence for superoxide radicals in this medium was obtained via electron spin resonance (ESR) experiments. In comparison, the 2-mercaptoethylamine (MEA)-capped CdTe QDs did not exhibit any ECL in air-saturated pH 7.4 PBS. Both ESR and X-ray photon spectroscopy (XPS) experiments revealed that amine groups in MEA-capped QDs were responsible for the absence of ECL. The reaction of an amine group with a superoxide radical leads to the quenching of ECL. The ECL quenching of MPA-capped CdTe QDs was further used to detect melamine. Under the optimum conditions, the inhibited ECL was linear with the logarithm of concentration of melamine within the concentration range of 10-9 to 10-5 M and the detection limit was found to be 6.74 × 10-10 M, which was 100-100 000 times lower than that of the most previous methods.The electrogenerated chemiluminescence (ECL) of semiconductor quantum dots (QDs) is generally believed to be independent of particle sizes or the capping agents used. Herein, we demonstrate that CdTe QDs with different sizes and stabilizers evidently exhibit different ECL behavior in aqueous solution. The ECL of CdTe QDs stabilized by 3-mercaptopropionic acid (MPA) displays two waves at potentials of about +1

  13. ESR study on radiation-induced radicals in carboxymethyl cellulose aqueous solution

    NASA Astrophysics Data System (ADS)

    Saiki, Seiichi; Nagasawa, Naotsugu; Hiroki, Akihiro; Morishita, Norio; Tamada, Masao; Kudo, Hisaaki; Katsumura, Yosuke

    2011-02-01

    Carboxymethyl cellulose (CMC) at highly concentrated aqueous solution undergoes radiation crosslinking reaction by ionizing irradiation. It is assumed that this radiation-induced reaction takes place by the indirect effect of water radiolysis, especially through the OH radical. However, the reaction mechanism is not well known. In this topic, ESR spectra of CMC radicals formed by reaction with OH radicals were measured directly in aqueous solution to identify the initially formed radical site. The ESR spectra were observed successfully and were interpreted as the overlapping of two spectra; a Triplet×Doublet spectrum and a Doublet spectrum. Each spectrum was assigned to radicals located on carboxymethyl groups linked to C6 and C2/C3.

  14. Micromachined silicon acoustic delay line with 3D-printed micro linkers and tapered input for improved structural stability and acoustic directivity

    NASA Astrophysics Data System (ADS)

    Cho, Y.; Kumar, A.; Xu, S.; Zou, J.

    2016-10-01

    Recent studies have shown that micromachined silicon acoustic delay lines can provide a promising solution to achieve real-time photoacoustic tomography without the need for complex transducer arrays and data acquisition electronics. To achieve deeper imaging depth and wider field of view, a longer delay time and therefore delay length are required. However, as the length of the delay line increases, it becomes more vulnerable to structural instability due to reduced mechanical stiffness. In this paper, we report the design, fabrication, and testing of a new silicon acoustic delay line enhanced with 3D printed polymer micro linker structures. First, mechanical deformation of the silicon acoustic delay line (with and without linker structures) under gravity was simulated by using finite element method. Second, the acoustic crosstalk and acoustic attenuation caused by the polymer micro linker structures were evaluated with both numerical simulation and ultrasound transmission testing. The result shows that the use of the polymer micro linker structures significantly improves the structural stability of the silicon acoustic delay lines without creating additional acoustic attenuation and crosstalk. In addition, the improvement of the acoustic acceptance angle of the silicon acoustic delay lines was also investigated to better suppress the reception of unwanted ultrasound signals outside of the imaging plane. These two improvements are expected to provide an effective solution to eliminate current limitations on the achievable acoustic delay time and out-of-plane imaging resolution of micromachined silicon acoustic delay line arrays.

  15. Highly stable tetrathiafulvalene radical dimers in [3]catenanes

    SciTech Connect

    Spruell, Jason M.; Coskun, Ali; Friedman, Douglas C.; Forgan, Ross S.; Sarjeant, Amy A.; Trabolsi, Ali; Fahrenbach, Albert C.; Barin, Gokhan; Paxton, Walter F.; Dey, Sanjeev K.; Olson, Mark A.; Benítez, Diego; Tkatchouk, Ekaterina; Colvin, Michael T.; Carmielli, Raanan; Caldwell, Stuart T.; Rosair, Georgina M.; Hewage, Shanika Gunatilaka; Duclairoir, Florence; Seymour, Jennifer L.; Slawin, Alexandra M.Z.; Goddard, III, William A.; Wasielewski, Michael R.; Cooke, Graeme; Stoddart, J. Fraser

    2010-12-03

    Two [3]catenane 'molecular flasks' have been designed to create stabilized, redox-controlled tetrathiafulvalene (TTF) dimers, enabling their spectrophotometric and structural properties to be probed in detail. The mechanically interlocked framework of the [3]catenanes creates the ideal arrangement and ultrahigh local concentration for the encircled TTF units to form stable dimers associated with their discrete oxidation states. These dimerization events represent an affinity umpolung, wherein the inversion in electronic affinity replaces the traditional TTF-bipyridinium interaction, which is over-ridden by stabilizing mixed-valence (TTF){sub 2}{sup {sm_bullet}+} and radical-cation (TTF{sup {sm_bullet}+}){sub 2} states inside the 'molecular flasks.' The experimental data, collected in the solid state as well as in solution under ambient conditions, together with supporting quantum mechanical calculations, are consistent with the formation of stabilized paramagnetic mixed-valence dimers, and then diamagnetic radical-cation dimers following subsequent one-electron oxidations of the [3]catenanes.

  16. Laser spectroscopy of hydrocarbon radicals

    SciTech Connect

    Chen, P.

    1993-12-01

    The author reports the application of supersonic jet flash pyrolysis to the specific preparation of a range of organic radicals, biradicals, and carbenes in a skimmed molecular beam. Each species was produced cleanly and specifically, with little or no secondary reactions by the thermal dissociation of appropriately designed and synthesized organic precursors. Photoelectron spectra of the three isomeric C{sub 3}H{sub 2} carbenes, ortho-benzyne, and the {alpha},3-dehydrotoluene biradical, were used to establish adiabatic ionization potentials for use in thermochemical determinations.

  17. Aromatic-radical oxidation chemistry

    SciTech Connect

    Glassman, I.; Brezinsky, K.

    1993-12-01

    The research effort has focussed on discovering an explanation for the anomalously high CO{sub 2} concentrations observed early in the reaction sequence of the oxidation of cyclopentadiene. To explain this observation, a number of plausible mechanisms have been developed which now await experimental verification. One experimental technique for verifying mechanisms is to probe the reacting system by perturbing the radical concentrations. Two forms of chemical perturbation of the oxidation of cyclopentadiene were begun during this past year--the addition of NO{sub 2} and CO to the reacting mixture.

  18. Neuroprotective strategies in radical prostatectomy.

    PubMed

    Schiff, Jonathan D; Mulhall, John P

    2005-01-01

    In this section, authors from New York give their views on the various neuroprotective strategies for patients having a radical prostatectomy, such as the use of nerve grafts and other approaches. A joint study from Korea, the USA, Canada and the UK is presented in a paper on the importance of patient perception in the clinical assessment and management of BPH. There is also a review of robotic urological surgery. Finally, authors from New York give a review on the life of Isaac Newton. This is a new historical review in the journal, but one that will be of general interest.

  19. Iron and iron derived radicals

    SciTech Connect

    Borg, D.C.; Schaich, K.M.

    1987-04-01

    We have discussed some reactions of iron and iron-derived oxygen radicals that may be important in the production or treatment of tissue injury. Our conclusions challenge, to some extent, the usual lines of thought in this field of research. Insofar as they are born out by subsequent developments, the lessons they teach are two: Think fastexclamation Think smallexclamation In other words, think of the many fast reactions that can rapidly alter the production and fate of highly reactive intermediates, and when considering the impact of competitive reactions on such species, think how they affect the microenvironment (on the molecular scale) ''seen'' by each reactive molecule. 21 refs., 3 figs., 1 tab.

  20. Transition-Metal Hydride Radical Cations.

    PubMed

    Hu, Yue; Shaw, Anthony P; Estes, Deven P; Norton, Jack R

    2016-08-10

    Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described.

  1. An investigation of color stability and fluorescence behavior of ubiquinone solutions

    NASA Astrophysics Data System (ADS)

    Timofeeva, Elvira O.; Gorbunova, Elena V.; Chertov, Aleksandr N.; Korotaev, Valery V.

    2016-04-01

    Antioxidants, reactive oxygen species and other radicals are involved in oxidative stress phenomena. There are many available methods to quantify the progress of the process and evidence its existence for each stage of oxidative damage process which can be classified into direct and indirect approaches. The technic of experimental determination of optical characteristics stability of antioxidant solutions with spectroscopic method was offered in this work as a direct method for investigation of color stability in time and fluorescence behavior of antioxidant solutions. Coenzyme Q10, or ubiquinone, in the form of oil and alcohol solutions was chosen as an antioxidant of research. The experimental results connected with the optical density and color characteristics confirm the possibility of applying the clinical diagnosis method of estimation redox potential. Also, future prospects, including application of this technic in pharmaceutical analysis for quality control, were discussed.

  2. Observation of nocturnal atmospheric NO3 radical over Beijing by Cavity Ring Down spectroscopy

    NASA Astrophysics Data System (ADS)

    Hu, Renzhi; Wang, Dan; Xie, Pinhua; Liu, Jianguo; Liu, Wenqing

    2016-04-01

    A cavity ring-down spectroscopy (CRDS) instrument is applied for measuring atmospheric NO3 radical. Light from a red laser diode (661.85nm) is coupled on-axis into an optical cavity formed by a pair of high-reflectivity mirrors (R≥99.9985%) to achieve an effective absorption path length of approximately 20 km. Considering its loss of the NO3 radical in the inlet system, two kinds of direct and indirect methods are applied for calibrating its transmission efficiency. The experimental results show the overall transmission efficiency of the NO3 radical in the system is approximately 75±5% .The detection limit of the NO3 radical determined by Allan variance is approximately 3.2 pptv (2 σ, 10s). Moreover, the measurement of NO3 radical was performed at a suburb site in Beijing from October 29 to November 15, 2014. During the observation, the concentration of NO3 radical is relatively low, the maximum of NO3 radical concentration is 50pptv and the average of its concentration is approximately10pptv. Combining of NO2, O3 and NO data, the NO3 radical production rates were calculated ranging from 0.04pptv/s to 1.03pptv/s, and NO3 radical lifetime is averaged at 68s. The NO3 radical loss process in the atmosphere is further analyzed. Combining of related auxiliary data, the influence of different humidity as well as particulate matter concentration on the atmospheric NO3 radical removal is researched.

  3. Reaction Of Single-Wall Carbon Nanotubes With Radicals

    NASA Astrophysics Data System (ADS)

    Lobach, A. S.; Solomentsev, V. V.; Obraztsova, E. D.; Shchegolikhin, A. N.; Sokolov, V. I.

    2004-09-01

    A method for functionalizing the sidewalls of HiPco SWNT via interaction with carbon- and metal-centered radicals is presented. A number of methods: UV-vis-NIR spectroscopy, thermogravimetric analysis, TEM and Raman spectroscopy provided a direct evidence of a chemical attachment of functional groups to the tubes. Functionalization was shown to be reversible: a thermal treatment led to the recovering of pristine structure of SWNT.

  4. Control of surface charges by radicals as a principle of antistatic polymers protecting electronic circuitry.

    PubMed

    Baytekin, H Tarik; Baytekin, Bilge; Hermans, Thomas M; Kowalczyk, Bartlomiej; Grzybowski, Bartosz A

    2013-09-20

    Even minute quantities of electric charge accumulating on polymer surfaces can cause shocks, explosions, and multibillion-dollar losses to electronic circuitry. This paper demonstrates that to remove static electricity, it is not at all necessary to "target" the charges themselves. Instead, the way to discharge a polymer is to remove radicals from its surface. These radicals colocalize with and stabilize the charges; when they are scavenged, the surfaces discharge rapidly. This radical-charge interplay allows for controlling static electricity by doping common polymers with small amounts of radical-scavenging molecules, including the familiar vitamin E. The effectiveness of this approach is demonstrated by rendering common polymers dust-mitigating and also by using them as coatings that prevent the failure of electronic circuitry.

  5. Electron spin resonance studies on reduction process of nitroxyl spin radicals used in molecular imaging

    SciTech Connect

    Dhas, M. Kumara; Benial, A. Milton Franklin; Jawahar, A.

    2014-04-24

    The Electron spin resonance studies on the reduction process of nitroxyl spin probes were carried out for 1mM {sup 14}N labeled nitroxyl radicals in pure water and 1 mM concentration of ascorbic acid as a function of time. The electron spin resonance parameters such as signal intensity ratio, line width, g-value, hyperfine coupling constant and rotational correlation time were determined. The half life time was estimated for 1mM {sup 14}N labeled nitroxyl radicals in 1 mM concentration of ascorbic acid. The ESR study reveals that the TEMPONE has narrowest line width and fast tumbling motion compared with TEMPO and TEMPOL. From the results, TEMPONE has long half life time and high stability compared with TEMPO and TEMPOL radical. Therefore, this study reveals that the TEMPONE radical can act as a good redox sensitive spin probe for molecular imaging.

  6. Microsegregation during directional solidification

    NASA Technical Reports Server (NTRS)

    Coriell, S. R.; Mcfadden, G. B.

    1984-01-01

    During the directional solidification of alloys, solute inhomogeneities transverse to the growth direction arise due to morphological instabilities (leading to cellular or dendritic growth) and/or due to convection in the melt. In the absence of convection, the conditions for the onset of morphological instability are given by the linear stability analysis of Mullins and Sekerka. For ordinary solidification rates, the predictions of linear stability analysis are similar to the constitutional supercooling criterion. However, at very rapid solidification rates, linear stability analysis predicts a vast increase in stabilization in comparison to constitutional supercooling.

  7. On radicalizing behaviorism: A call for cultural analysis

    PubMed Central

    Malagodi, E. F.

    1986-01-01

    Our culture at large continues many practices that work against the well-being of its members and its chances for survival. Our discipline has failed to realize its potential for contributing to the understanding of these practices and to the generation of solutions. This failure of realization is in part a consequence of the general failure of behavior analysts to view social and cultural analysis as a fundamental component of radical behaviorism. This omission is related to three prevailing practices of our discipline. First, radical behaviorism is characteristically defined as a “philosophy of science,” and its concerns are ordinarily restricted to certain epistemological issues. Second, theoretical extensions to social and cultural phenomena too often depend solely upon principles derived from the analysis of behavior. Third, little attention has been directed at examining the relationships that do, or that should, exist between our discipline and related sciences. These practices themselves are attributed to certain features of the history of our field. Two general remedies for this situation are suggested: first, that radical behaviorism be treated as a comprehensive world view in which epistemological, psychological, and cultural analyses constitute interdependent components; second, that principles derived from compatible social-science disciplines be incorporated into radical behaviorism. PMID:22478643

  8. On radicalizing behaviorism: A call for cultural analysis.

    PubMed

    Malagodi, E F

    1986-01-01

    Our culture at large continues many practices that work against the well-being of its members and its chances for survival. Our discipline has failed to realize its potential for contributing to the understanding of these practices and to the generation of solutions. This failure of realization is in part a consequence of the general failure of behavior analysts to view social and cultural analysis as a fundamental component of radical behaviorism. This omission is related to three prevailing practices of our discipline. First, radical behaviorism is characteristically defined as a "philosophy of science," and its concerns are ordinarily restricted to certain epistemological issues. Second, theoretical extensions to social and cultural phenomena too often depend solely upon principles derived from the analysis of behavior. Third, little attention has been directed at examining the relationships that do, or that should, exist between our discipline and related sciences. These practices themselves are attributed to certain features of the history of our field. Two general remedies for this situation are suggested: first, that radical behaviorism be treated as a comprehensive world view in which epistemological, psychological, and cultural analyses constitute interdependent components; second, that principles derived from compatible social-science disciplines be incorporated into radical behaviorism.

  9. OH-PLIF visualisation of radical farming supersonic combustion flows

    NASA Astrophysics Data System (ADS)

    Boyce, R. R.; Mudford, N. R.; McGuire, J. R.

    2012-01-01

    Experimental investigations employing Planar Laser-induced fluorescence visualisation of the qualitative distribution of the OH radical (OH-PLIF), coupled with surface pressure measurements, have been made of flow in a generic, nominally two-dimensional inlet-injection radical farming supersonic combustion scramjet engine model. The test flows were provided by a hypersonic shock tunnel, and covered total enthalpies corresponding to the flight Mach number range 8.7-11.8 and approximately 150 kPa dynamic pressure. The surface pressure measurements displayed radical farming behaviour, that is a series of adjacent high and low pressure regions corresponding to successive shock/expansion structures, with no significant combustion-induced pressure rise until the second structure. OH-PLIF imaging between the first two structures provides the first direct experimental evidence of significant OH radical concentrations upstream of the ignition point in this mode of scramjet operation and shows that combustion reactions were occurring in highly localised regions in a complex turbulent and poorly micromixed fuel/air mixing layer confined to the fuel injection side of the combustor.

  10. Free radicals in the stratosphere - A new observational technique

    NASA Technical Reports Server (NTRS)

    Anderson, J. G.; Hazen, N. L.; Mclaren, B. E.; Rowe, S. P.; Schiller, C. M.; Schwab, M. J.; Solomon, L.; Thompson, E. E.; Weinstock, E. M.

    1985-01-01

    A new approach to in situ observations of trace reactive species in the stratosphere is described. A balloon-borne system, floating 40 kilometers above the earth's surface, successfully lowered and then retracted a cluster of instruments a distance of 12 kilometers on a filament of Kevlar. This instrument cluster is capable of detecting gas-phase free radicals at the part-per-trillion level. The suspended instrument array has excellent stability and has been used to measured atomic oxygen concentrations in the stratosphere.

  11. Free radicals in the stratosphere: a new observational technique.

    PubMed

    Anderson, J G; Hazen, N L; McLaren, B E; Rowe, S P; Schiller, C M; Schwab, M J; Solomon, L; Thompson, E E; Weinstock, E M

    1985-06-14

    A new approach to in situ observations of trace reactive species in the stratosphere is described. A balloon-borne system, floating 40 kilometers above the earth's surface, successfully lowered and then retracted a cluster of instruments a distance of 12 kilometers on a filament of Kevlar. This instrument cluster is capable of detecting gas-phase free radicals at the part-per-trillion level. The suspended instrument array has excellent stability and has been used to measure atomic oxygen concentrations in the stratosphere.

  12. Electro-optical Properties of Neutral and Radical Ion Thienosquaraines.

    PubMed

    Maltese, Vito; Cospito, Sante; Beneduci, Amerigo; De Simone, Bruna Clara; Russo, Nino; Chidichimo, Giuseppe; Janssen, René A J

    2016-07-11

    Thienosquaraines are an interesting class of electroactive dyes that are useful for applications in organic electronics. Herein, the redox chemistry and electrochromic response of a few newly synthesized thienosquaraines are presented. These properties are compared to those of the commercial 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl]squaraine. The stability of the radical ions formed in electrochemical processes strongly affects these properties, as shown by cyclic voltammetry, in situ spectroelectrochemistry, and quantum chemical calculations. Furthermore, all of the dyes show aggregation tendency resulting in panchromatic absorption covering the whole UV/Vis spectral range.

  13. Preventive and therapeutic application of molecular hydrogen in situations with excessive production of free radicals.

    PubMed

    Slezák, J; Kura, B; Frimmel, K; Zálešák, M; Ravingerová, T; Viczenczová, C; Okruhlicová, Ľ; Tribulová, N

    2016-09-19

    Excessive production of oxygen free radicals has been regarded as a causative common denominator of many pathological processes in the animal kingdom. Hydroxyl and nitrosyl radicals represent the major cause of the destruction of biomolecules either by a direct reaction or by triggering a chain reaction of free radicals. Scavenging of free radicals may act preventively or therapeutically. A number of substances that preferentially react with free radicals can serve as scavengers, thus increasing the internal capacity/activity of endogenous antioxidants and protecting cells and tissues against oxidative damage. Molecular hydrogen (H(2)) reacts with strong oxidants, such as hydroxyl and nitrosyl radicals, in the cells, that enables utilization of its potential for preventive and therapeutic applications. H(2) rapidly diffuses into tissues and cells without affecting metabolic redox reactions and signaling reactive species. H(2) reduces oxidative stress also by regulating gene expression, and functions as an anti-inflammatory and anti-apoptotic agent. There is a growing body of evidence based on the results of animal experiments and clinical observations that H(2) may represent an effective antioxidant for the prevention of oxidative stress-related diseases. Application of molecular hydrogen in situations with excessive production of free radicals, in particular, hydroxyl and nitrosyl radicals is relatively simple and effective, therefore, it deserves special attention.

  14. Protein, lipid, and DNA radicals to measure skin UVA damage and modulation by melanin.

    PubMed

    Haywood, Rachel; Rogge, Fabrice; Lee, Martin

    2008-03-15

    Afro-Caribbeans have a lower incidence of skin cancer than Caucasians, but the effectiveness of melanin as a photoprotective pigment is debated. We investigated the UVA and solar irradiation of ex vivo human skin and DMPO using electron spin resonance spectroscopy, to determine whether pigmented skin is protected by melanin against free radical damage. Initial ascorbate radicals in Caucasian skin were superseded by lipid and/or protein radical adducts with isotropic (a(H)=1.8 mT) and anisotropic spectra comparable to spectra in irradiated pig fat (a(H)=1.9 mT) and BSA. DNA carbon-centered radical adducts (a(H)=2.3 mT) and a broad singlet were detected in genomic DNA/melanin but were not distinguishable in irradiated Caucasian skin. Protein and lipid radicals (n=6 in Caucasian skin) were minimal in Afro-Caribbean skin (n=4) and intermediate skin pigmentations were variable (n=3). In irradiated Afro-Caribbean skin a shoulder to the melanin radical (also in UVA-irradiated pigmented melanoma cells and genomic DNA/melanin and intrinsic to pheomelanin) was detected. In this sample group, protein (but not lipid) radical adducts decreased directly with pigmentation. ESR/spin trapping methodology has potential for screening skin susceptibility to aging and cancer-related radical damage and for measuring protection afforded by melanin, sunscreens, and antiaging creams.

  15. Biotin synthase: insights into radical-mediated carbon-sulfur bond formation.

    PubMed

    Fugate, Corey J; Jarrett, Joseph T

    2012-11-01

    The enzyme cofactor and essential vitamin biotin is biosynthesized in bacteria, fungi, and plants through a pathway that culminates with the addition of a sulfur atom to generate the five-membered thiophane ring. The immediate precursor, dethiobiotin, has methylene and methyl groups at the C6 and C9 positions, respectively, and formation of a thioether bridging these carbon atoms requires cleavage of unactivated CH bonds. Biotin synthase is an S-adenosyl-l-methionine (SAM or AdoMet) radical enzyme that catalyzes reduction of the AdoMet sulfonium to produce 5'-deoxyadenosyl radicals, high-energy carbon radicals that can directly abstract hydrogen atoms from dethiobiotin. The available experimental and structural data suggest that a [2Fe-2S](2+) cluster bound deep within biotin synthase provides a sulfur atom that is added to dethiobiotin in a stepwise reaction, first at the C9 position to generate 9-mercaptodethiobiotin, and then at the C6 position to close the thiophane ring. The formation of sulfur-containing biomolecules through a radical reaction involving an iron-sulfur cluster is an unprecedented reaction in biochemistry; however, recent enzyme discoveries suggest that radical sulfur insertion reactions may be a distinct subgroup within the burgeoning Radical SAM superfamily. This article is part of a Special Issue entitled: Radical SAM enzymes and Radical Enzymology.

  16. Stability considerations of aspartame in the direct analysis of artificial sweeteners in water samples using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS).

    PubMed

    Berset, Jean-Daniel; Ochsenbein, Nicole

    2012-07-01

    A HPLC-MS/MS method is presented for the simultaneous determination of frequently used artificial sweeteners (ASs) and the main metabolite of aspartame (ASP), diketopiperazine (DKP), in environmental water samples using the direct-injection (DI) technique, thereby achieving limits of quantification (LOQ) of 10 ng L(-1). For a reliable quantification of ASP pH should be adjusted to 4.3 to prevent formation of the metabolite. Acesulfame (ACE), saccharin (SAC), cyclamate (CYC) and sucralose (SUC) were ubiquitously found in water samples. Highest concentrations up to 61 μg L(-1) of ACE were found in wastewater effluents, followed by surface water with concentrations up to 7 μg L(-1), lakes up to 600 ng L(-1) and groundwater and tap water up to 70 ng L(-1). The metabolite DKP was only detected in wastewater up to 200 ng L(-1) and at low detection frequencies.

  17. Drugs with susceptible sites for free radical induced oxidative transformations: the case of a penicillin.

    PubMed

    Szabó, László; Tóth, Tünde; Rácz, Gergely; Takács, Erzsébet; Wojnárovits, László

    2016-01-01

    Penicillins, as bactericidal antibiotics, have been widely used to treat infections for several decades. Their structure contains both aromatic and thioether moieties susceptible to free radical oxidation. The (•)OH induced oxidation mechanism of amoxicillin was investigated by pulse radiolysis techniques and by final product analysis performed after steady-state γ-irradiation. The predominant sites of the (•)OH attack are suggested to be the thioether group, initially yielding an (•)OH adduct to the sulfur, and the aromatic ring. This adduct to the sulfur converts to sulfur radical cation, which has three competitive reaction paths: (1) by deprotonation at the adjacent carbon α-(alkylthio)alkyl radicals form, which undergo disproportionation leading presumably to sulfoxide as main product; (2) via the pseudo-Kolbe mechanism it may transform to α-aminoalkyl radicals; (3) the radical cation can be stabilized through intramolecular S.˙.O bond formation. The reaction mechanism suggests the presence of a short-living and a stabilized (via hydrogen bonding) long-living (•)OH adduct to the sulfur. The three-electron bonded dimers of amoxicillin were not formed owing to steric hindrance. Thiyl radicals were also present in equilibrium with α-aminoalkyl radicals. In the presence of dissolved oxygen, aromatic ring hydroxylation occurred along with complex reactions resulting in e.g. oxidation of the methyl groups. The formation of the sulfoxide is especially effective in the presence of dissolved oxygen, under anaerobic condition, however, it is also generated owing to H2O2 and α-(alkylthio)alkyl radicals. The thioether moiety appears to be more sensitive to oxidation compared to the aromatic ring in case of amoxicillin.

  18. The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol

    NASA Astrophysics Data System (ADS)

    Müller, Jean-François; Liu, Zhen; Nguyen, Vinh Son; Stavrakou, Trissevgeni; Harvey, Jeremy N.; Peeters, Jozef

    2016-10-01

    Methyl peroxy, a key radical in tropospheric chemistry, was recently shown to react with the hydroxyl radical at an unexpectedly high rate. Here, the molecular reaction mechanisms are elucidated using high-level quantum chemical methodologies and statistical rate theory. Formation of activated methylhydrotrioxide, followed by dissociation into methoxy and hydroperoxy radicals, is found to be the main reaction pathway, whereas methylhydrotrioxide stabilization and methanol formation (from activated and stabilized methylhydrotrioxide) are viable minor channels. Criegee intermediate formation is found to be negligible. Given the theoretical uncertainties, useful constraints on the yields are provided by atmospheric methanol measurements. Using a global chemistry-transport model, we show that the only explanation for the high observed methanol abundances over remote oceans is the title reaction with an overall methanol yield of ~30%, consistent with the theoretical estimates given their uncertainties. This makes the title reaction a major methanol source (115 Tg per year), comparable to global terrestrial emissions.

  19. The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol.

    PubMed

    Müller, Jean-François; Liu, Zhen; Nguyen, Vinh Son; Stavrakou, Trissevgeni; Harvey, Jeremy N; Peeters, Jozef

    2016-10-17

    Methyl peroxy, a key radical in tropospheric chemistry, was recently shown to react with the hydroxyl radical at an unexpectedly high rate. Here, the molecular reaction mechanisms are elucidated using high-level quantum chemical methodologies and statistical rate theory. Formation of activated methylhydrotrioxide, followed by dissociation into methoxy and hydroperoxy radicals, is found to be the main reaction pathway, whereas methylhydrotrioxide stabilization and methanol formation (from activated and stabilized methylhydrotrioxide) are viable minor channels. Criegee intermediate formation is found to be negligible. Given the theoretical uncertainties, useful constraints on the yields are provided by atmospheric methanol measurements. Using a global chemistry-transport model, we show that the only explanation for the high observed methanol abundances over remote oceans is the title reaction with an overall methanol yield of ∼30%, consistent with the theoretical estimates given their uncertainties. This makes the title reaction a major methanol source (115 Tg per year), comparable to global terrestrial emissions.

  20. The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol

    PubMed Central

    Müller, Jean-François; Liu, Zhen; Nguyen, Vinh Son; Stavrakou, Trissevgeni; Harvey, Jeremy N.; Peeters, Jozef

    2016-01-01

    Methyl peroxy, a key radical in tropospheric chemistry, was recently shown to react with the hydroxyl radical at an unexpectedly high rate. Here, the molecular reaction mechanisms are elucidated using high-level quantum chemical methodologies and statistical rate theory. Formation of activated methylhydrotrioxide, followed by dissociation into methoxy and hydroperoxy radicals, is found to be the main reaction pathway, whereas methylhydrotrioxide stabilization and methanol formation (from activated and stabilized methylhydrotrioxide) are viable minor channels. Criegee intermediate formation is found to be negligible. Given the theoretical uncertainties, useful constraints on the yields are provided by atmospheric methanol measurements. Using a global chemistry-transport model, we show that the only explanation for the high observed methanol abundances over remote oceans is the title reaction with an overall methanol yield of ∼30%, consistent with the theoretical estimates given their uncertainties. This makes the title reaction a major methanol source (115 Tg per year), comparable to global terrestrial emissions. PMID:27748363

  1. In vitro antioxidant and radical-scavenging capacities of Citrullus colocynthes (L) and Artemisia absinthium extracts using promethazine hydrochloride radical cation and contemporary assays.

    PubMed

    Asghar, M Nadeem; Khan, I Ullah; Bano, N

    2011-10-01

    A new, quick and economical decolorization assay based upon the generation of a radical cation made from promethazine hydrochloride (PMZH) is described for screening of antioxidant activity of plants/herbal extracts. PMZH radical cations, produced through a reaction between PMZH and potassium persulfate (K(2)S(2)O(8)) in phosphoric acid medium, have maximum absorption at 515 nm in their first-order derivative spectrum. Theconcentrations of chromagen and K(2)S(2)O(8) were optimized (final concentration of PMZH and K₂S₂O₈ were 0.166 mM and 0.11 mM, respectively) for better stability and sensitivity of the radical cation produced. Agood linear correlation was found between the percentage inhibition and the increasing amounts of standard antioxidants, with correlation coefficients ranging from 0.989 to 0.999. The newly developed assay was employed to evaluate the antioxidant capacity of Citrullus colocynthes L. and Artemisia absinthium extracts. The proposed assay involved a more stable radical cation and required only 1 h for preparation of a working solution in comparison to the 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical cation decolorizaion assay, which was reported to be less sensitive at low pH and almost 12-16 h were required for preparation of a working ABTS solution. Other assays employed to evaluate the antioxidant potential andradical-scavenging capacities of the extracts were the ferric-reducing antioxidant power, 2,2'-diphenyl-1-picrylhydrazyl radical scavenging, total phenolic contents assay, total flavonoid contents and metal-chelating activity assays, and the lipid peroxidation value in linoleic acid emulsion systems. The results indicate that boththe plants have potent free radical-scavenging activity and the ability to prevent lipid peroxidation and radical chain reactions.

  2. Quantitative determination of atmospheric hydroperoxyl radical

    DOEpatents

    Springston, Stephen R.; Lloyd, Judith; Zheng, Jun

    2007-10-23

    A method for the quantitative determination of atmospheric hydroperoxyl radical comprising: (a) contacting a liquid phase atmospheric sample with a chemiluminescent compound which luminesces on contact with hydroperoxyl radical; (b) determining luminescence intensity from the liquid phase atmospheric sample; and (c) comparing said luminescence intensity from the liquid phase atmospheric sample to a standard luminescence intensity for hydroperoxyl radical. An apparatus for automating the method is also included.

  3. Bioinspired terpene synthesis: a radical approach.

    PubMed

    Justicia, José; Álvarez de Cienfuegos, Luis; Campaña, Araceli G; Miguel, Delia; Jakoby, Verena; Gansäuer, Andreas; Cuerva, Juan M

    2011-07-01

    This tutorial review highlights the development of radical-based bioinspired synthesis of terpenes from the initial proposal to the development of modern catalytic methods for performing such processes. The power of the radical approach is demonstrated by the straightforward syntheses of many natural products from readily available starting materials. The efficiency of these processes nicely complements the described cationic polyolefin cyclisations and even suggests that modern radical methods provide means to improve upon nature's synthetic pathways.

  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. 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

  6. Formation of free radicals during phacoemulsification.

    PubMed

    Holst, A; Rolfsen, W; Svensson, B; Ollinger, K; Lundgren, B

    1993-04-01

    During phacoemulsification cavitation bubbles are formed. These bubbles are believed to be one source of damage to corneal endothelium seen after phacoemulsification. Free radicals are induced whenever cavitation bubbles implode. The aim of this study was to confirm the initiation of free radicals by phacoemulsification and to correlate the power of ultrasound in the phacoemulsification process to the amount of free radicals formed, using both in vitro and in vivo techniques. The formation of free radicals was determined by adding luminol to a buffer and measuring the chemoluminescence in vitro and in rabbit eyes (Lumacounter 2080 or a single-photon-counting apparatus) during phacoemulsification. The data obtained show that free radicals are formed during phacoemulsification and that the amount of free radicals correlates with the power of ultrasound. Furthermore, the radical formation could be inhibited by the radical scavengers SOD, Healon and Healon GV. These results were achieved both in vitro in the test tube and in vivo in rabbit eyes. By showing that the addition of SOD to the irrigation buffer during phacoemulsification decreases the corneal endothelial cell damage, we show that free radicals could have a role in postoperative complications seen clinically.

  7. Influence of electronic and steric effects on stability constants and electrochemical reversibility of divalent ion complexes with glycine and sarcosine. A glass electrode potentiometric, sampled direct current polarographic, virtual potentiometric, and molecular modelling study.

    PubMed

    Cukrowski, Ignacy; Marques, Helder M; Mkwizu, Tumaini S; Magampa, Philemon P; Serge, Claudette

    2007-05-08

    Cd(II) complexes with glycine (gly) and sarcosine (sar) were studied by glass electrode potentiometry, direct current polarography, virtual potentiometry, and molecular modelling. The electrochemically reversible Cd(II)-glycine-OH labile system was best described by a model consisting of M(HL), ML, ML2, ML3, ML(OH) and ML2(OH) (M = Cd(II), L = gly) with the overall stability constants, as log beta, determined to be 10.30+/-0.05, 4.21+/-0.03, 7.30+/-0.05, 9.84+/-0.04, 8.9+/-0.1, and 10.75+/-0.10, respectively. In case of the electrochemically quasi-reversible Cd(II)-sarcosine-OH labile system, only ML, ML2 and ML3 (M = Cd(II), L = sar) were found and their stability constants, as log beta, were determined to be 3.80+/-0.03, 6.91+/-0.07, and 8.9+/-0.4, respectively. Stability constants for the ML complexes, the prime focus of this work, were thus established with an uncertainty smaller than 0.05 log units. The observed departure from electrochemical reversibility for the Cd-sarcosine-OH system was attributed mainly to the decrease in the transfer coefficient alpha. The MM2 force field, supplemented by additional parameters, reproduced the reported crystal structures of diaqua-bis(glycinato-O,N)nickel(II) and fac-tri(glycinato)-nickelate(II) very well. These parameters were used to predict structures of all possible isomers of (i) [Ni(H2O)4(gly)]+ and [Ni(H2O)4(sar)]+; and (ii) [Ni(H2O)3(IDA)] and [Ni(H2O)3(MIDA)] (IDA = iminodiacetic acid, MIDA = N-methyl iminodiacetic acid) by molecular mechanics/simulated annealing methods. The change in strain energy, deltaU(str), that accompanies the substitution of one ligand by another (ML + L' --> ML' + L), was computed and a strain energy deltaU(str) = +0.28 kcal mol(-1) for the reaction [Ni(H2O)4(gly)]+ + sar --> [Ni(H2O)4(sar)]+ + gly was found. This predicts the monoglycine complex to be marginally more stable. By contrast, for the reaction [Ni(H2O)3IDA] + MIDA --> [Ni(H2O)3MIDA] + IDA, deltaU(str) = -0.64 kcal mol(-1

  8. Cost analysis of open radical cystectomy versus robot-assisted radical cystectomy.

    PubMed

    Mmeje, Chinedu O; Martin, Aaron D; Nunez-Nateras, Rafael; Parker, Alexander S; Thiel, David D; Castle, Erik P

    2013-02-01

    Bladder cancer is the fourth and ninth most common malignancy in males and females, respectively, in the U.S. and one of the most costly cancers to manage. With the current economic condition, physicians will need to become more aware of cost-effective therapies for the treatment of various malignancies. Robot-assisted radical cystectomy (RARC) is the latest minimally invasive surgical option for muscle-invasive bladder cancer. Current reports have shown less blood loss, a shorter hospital stay, and a lower morbidity with RARC, as compared with the traditional open radical cystectomy (ORC), although long-term oncologic results of RARC are still maturing. There are few studies that have assessed the cost outcomes of RARC as compared with ORC. Currently, ORC appears to offer a direct cost advantage due to the high purchase and maintenance cost of the robotic platform, although when the indirect costs of complications and extended hospital stay with ORC are considered, RARC may be less expensive than the traditional open procedure. In order to accurately evaluate the cost effectiveness of RARC versus ORC, prospective randomized trials between the two surgical techniques with long-term oncologic efficacy are needed.

  9. Entanglement and Sources of Magnetic Anisotropy in Radical Pair-Based Avian Magnetoreceptors

    NASA Astrophysics Data System (ADS)

    Hogben, Hannah J.; Biskup, Till; Hore, P. J.

    2012-11-01

    One of the principal models of magnetic sensing in migratory birds rests on the quantum spin dynamics of transient radical pairs created photochemically in ocular cryptochrome proteins. We consider here the role of electron spin entanglement and coherence in determining the sensitivity of a radical pair-based geomagnetic compass and the origins of the directional response. It emerges that the anisotropy of radical pairs formed from spin-polarized molecular triplets could form the basis of a more sensitive compass sensor than one founded on the conventional hyperfine-anisotropy model. This property offers new and more flexible opportunities for the design of biologically inspired magnetic compass sensors.

  10. Insight into the free-radical-scavenging mechanism of hydroxyl-substituent Schiff bases in the free-radical-induced hemolysis of erythrocytes.

    PubMed

    Tang, You-Zhi; Liu, Zai-Qun

    2007-01-01

    This work aimed to explore the mechanism by which hydroxyl-substituent Schiff bases scavenge free-radicals. Thus, four Schiff bases, that is benzylidene aniline (BAN), 2-(phenyliminomethyl)phenol (BAH), 4-benzimidoylphenol (PBH) and 2-benzimidoylphenol (OBH), were applied to protect human erythrocytes against 2,2'-azobis(2-amidinopropane hydrochloride) (AAPH)-induced hemolysis. The results revealed that the --OH attached to the ortho-position of methylene in Schiff base scavenges 1.46 radicals per molecule, the --OH attached to the para-position of the N atom scavenges 2.94 radicals and the --OH attached to the ortho-position of the N atom scavenges 3.63 radicals. In addition, four Schiff bases were used together with some familiar antioxidants, such as 6-hydroxyl-2,5,7,8-tetramethyl chroman-2-carboxylic acid (Trolox), L-ascorbic acid (VC), alpha-tocopherol (TOH) and L-ascorbyl-6-laurate (VC-12) in AAPH-induced hemolysis of erythrocytes. It was found that, except for BAN+VC-12, BAH + VC-12, OBH + VC-12 and PBH+TOH, all the other combinations protected erythrocytes more perfectly than when used individually. This result demonstrated that a promotive protection existed between Schiff base and other antioxidants and this improved their ability to scavenge free-radicals. Finally, IC(50) values of the aforementioned Schiff bases together with 2-((o-hydroxylphenylimino) methyl)phenol (OSAP) and 2-((p-hydroxylphenylimino)methyl)phenol (PSAP) were determined by reaction with two radical species, that is, 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) radical (ABTS(+.)) and 2,2'-diphenyl-1-picrylhydrazyl (DPPH). The results implied that the molecular framework of a Schiff base and an --OH attached to the ortho-position of methylene were apt to reduce radicals, but the --OH attached to the aniline ring in a Schiff base was prone to scavenge radicals directly.

  11. The lightest organic radical cation for charge storage in redox flow batteries

    SciTech Connect

    Huang, Jinhua; Pan, Baofei; Duan, Wentao; Wei, Xiaoliang; Assary, Rajeev S.; Su, Liang; Brushett, Fikile; Cheng, Lei; Liao, Chen; Ferrandon, Magali S.; Wang, Wei; Zhang, Zhengcheng; Burrell, Anthony K.; Curtiss, Larry A.; Shkrob, Ilya A.; Moore, Jeffrey S.; Zhang, Lu

    2016-08-25

    Electrochemically reversible fluids of high energy density are promising materials for capturing the electrical energy generated from intermittent sources like solar and wind. To meet this technological challenge there is a need to understand the fundamental limits and interplay of electrochemical potential, stability and solubility in “lean” derivatives of redox-active molecules. Here we describe the process of molecular pruning, illustrated for 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene, a molecule known to produce a persistently stable, high-potential radical cation. By systematically shedding molecular fragments considered important for radical cation steric stabilization, we discovered a minimalistic structure that retains long-term stability in its oxidized form. Interestingly, we find the tert-butyl groups are unnecessary; high stability of the radical cation and high solubility are both realized in derivatives having appropriately positioned arene methyl groups. These stability trends are rationalized by mechanistic considerations of the postulated decomposition pathways. We suggest that the molecular pruning approach will uncover lean redox active derivatives for electrochemical energy storage leading to materials with long-term stability and high intrinsic capacity.

  12. Tuning aryl, hydrazine radical cation electronic interactions using substituent effects.

    PubMed

    Valverde-Aguilar, Guadalupe; Wang, Xianghuai; Plummer, Edward; Lockard, Jenny V; Zink, Jeffrey I; Luo, Yun; Weaver, Michael N; Nelsen, Stephen F

    2008-08-14

    Absorption spectra for 2,3-diaryl-2,3-diazabicyclo[2.2.2]octane radical cations (2(X)(*+)) and for their monoaryl analogues 2-tert-butyl-3-aryl-2,3-diazabicyclo[2.2.2]octane radical cations (1(X)(*+)) having para chloro, bromo, iodo, cyano, phenyl, and nitro substituents are reported and compared with those for the previously reported 1- and 2(H)(*+) and 1- and 2(OMe)(*+). The calculated geometries and optical absorption spectra for 2(Cl)(*+) demonstrate that p-C6H4Cl lies between p-C6H4OMe and C6H5 in its ability to stabilize the lowest energy optical transition of the radical cation, which involves electron donation from the aryl groups toward the pi*(NN)(+)-centered singly occupied molecular orbital of 2(X)(*+). Resonance Raman spectral determination of the reorganization energy for their lowest energy transitions (lambda(v)(sym)) increase in the same order, having values of 1420, 5300, and 6000 cm(-1) for X = H, Cl, and OMe, respectively. A neighboring orbital analysis using Koopmans-based calculations of relative orbital energies indicates that the diabatic aryl pi-centered molecular orbital that interacts with the dinitrogen pi system lies closest in energy to the bonding pi(NN)-centered orbital and has an electronic coupling with it of about 9200 +/- 600 cm(-1), which does not vary regularly with electron donating power of the X substituent.

  13. The Influence of Zeolites on Radical Formation During Lignin Pyrolysis.

    PubMed

    Bährle, Christian; Custodis, Victoria; Jeschke, Gunnar; van Bokhoven, Jeroen A; Vogel, Frédéric

    2016-09-08

    Lignin from lignocellulosic biomass is a promising source of energy, fuels, and chemicals. The conversion of the polymeric lignin to fuels and chemicals can be achieved by catalytic and noncatalytic pyrolysis. The influence of nonporous silica and zeolite catalysts, such as silicalite, HZSM5, and HUSY, on the radical and volatile product formation during lignin pyrolysis was studied by in situ high-temperature electron paramagnetic resonance spectroscopy (HTEPR) as well as GC-MS. Higher radical concentrations were observed in the samples containing zeolite compared to the sample containing only lignin, which suggests that there is a stabilizing effect by the inorganic surfaces on the formed radical fragments. This effect was observed for nonporous silica as well as for HUSY, HZSM5, and silicalite zeolite catalysts. However, the effect is far larger for the zeolites owing to their higher specific surface area. The zeolites also showed an effect on the volatile product yield and the product distribution within the volatile phase. Although silicalite showed no effect on the product selectivity, the acidic zeolites such as HZSM5 or HUSY increased the formation of deoxygenated products such as benzene, toluene, xylene (BTX), and naphthalene.

  14. Hammett correlations in the chemistry of 3-phenylpropyl radicals.

    PubMed

    Modglin, James D; Erdely, Victoria K; Lin, Ching Yeh; Coote, Michelle L; Poole, James S

    2011-12-29

    The energetics and kinetics of the reaction of variously substituted benzyl radicals with a model alkene were calculated at the G3(MP2)-RAD//B3-LYP/6-31G(d) level of theory to determine whether such reactions are amenable to Hammett analysis. The reactions were studied both in the gas phase and in toluene solution in the temperature range 298-353 K; calculations include 1D-hindered rotor corrections for low frequency torsional modes, and the solvation energies were calculated using COSMO-RS at the BP/TZP level of theory. The addition reaction was found to be dominated by radical stabilization effects, but under circumstances where olefin substituent effects were decoupled from aryl substituent effects, a modest polar effect comes into play, which is enhanced by solvation. Reasonable correlations with empirical substituent parameters such as Hammett σ and σ(•) are observed for the enthalpy of activation, but additional entropic factors act to decrease the degree of correlation with respect to free energies and rate coefficients, confirming hypotheses from earlier experimental work. Substituent effects on the reverse β-fragmentation reaction, and potential cyclization of the 3-phenylpropyl radicals formed by addition are also discussed.

  15. Activation energy of methyl radical decay in methane hydrate.

    PubMed

    Takeya, Kei; Nango, Kouhei; Sugahara, Takeshi; Ohgaki, Kazunari; Tani, Atsushi

    2005-11-10

    The thermal stability of gamma-ray-induced methyl radicals in methane hydrate was studied using the ESR method at atmospheric pressure and 210-260 K. The methyl radical decay proceeded with the second-order reaction, and ethane molecules were generated from the dimerization process. The methyl radical decay proceeds by two different temperature-dependent processes, that is, the respective activation energies of these processes are 20.0 +/- 1.6 kJ/mol for the lower temperature region of 210-230 K and 54.8 +/- 5.7 kJ/mol for the higher temperature region of 235-260 K. The former agrees well with the enthalpy change of methane hydrate dissociation into ice and gaseous methane, while the latter agrees well with the enthalpy change into liquid water and gaseous methane. The present findings reveal that methane hydrates dissociate into liquid (supercooled) water and gaseous methane in the temperature range of 235-260 K.

  16. Kinetics Studies of Radical-Radical Reactions: The NO2 + N2H3 System

    DTIC Science & Technology

    2013-10-01

    investigating the kinetics of this elementary reaction . 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT 18. NUMBER OF PAGES...Viewgraph 3. DATES COVERED (From - To) September 2013- October 2013 4. TITLE AND SUBTITLE Kinetics Studies of Radical-Radical Reactions (I): The NO2...characteristics in relevant operating environments. Here we report theoretical results obtained on the prototypical radical- radical reaction : NO2 + N2H3

  17. Shell stability and conditions analyzed using a new method of extracting shell areal density maps from spectrally resolved images of direct-drive inertial confinement fusion implosions

    DOE PAGES

    Johns, H. M.; Mancini, R. C.; Nagayama, T.; ...

    2016-01-25

    In warm target direct-drive ICF implosion experiments performed at the OMEGA laser facility, plastic microballoons doped with a titanium tracer layer in the shell and filled with deuterium gas were imploded using a low-adiabat shaped laser pulse. Continuum radiation emitted in the core is transmitted through the tracer layer and the resulting spectrum recorded with a gated multi-monochromatic x-ray imager (MMI). Titanium K-shell line absorption spectra observed in the data are due to transitions in L-shell titanium ions driven by the backlighting continuum. The MMI data consist of an array of spectrally resolved images of the implosion. These 2-D space-resolvedmore » titanium spectral features constrain the plasma conditions and areal density of the titanium doped region of the shell. The MMI data were processed to obtain narrow-band images and space resolved spectra of titanium spectral features. Shell areal density maps, ρL(x,y), extracted using a new method using both narrow-band images and space resolved spectra are confirmed to be consistent within uncertainties. We report plasma conditions in the titanium-doped region of electron temperature (Te) = 400±28eV, electron number density (Ne) = 8.5x1024±2.5x1024 cm-3, and average areal density <ρR> = 86±7mg/cm2. Fourier analysis of areal density maps reveals shell modulations caused by hydrodynamic instability growth near the fuel-shell interface in the deceleration phase. We observe significant structure in modes l = 2-9, dominated by l = 2. We extract a target breakup fraction of 7.1±1.5% from our Fourier analysis. A new method for estimating mix width is evaluated against existing literature and our target breakup fraction. We estimate a mix width of 10.5±1μm.« less

  18. Free radical generation from an aniline derivative in HepG2 cells: a possible captodative effect.

    PubMed

    Horinouchi, Yuya; Summers, Fiona A; Ehrenshaft, Marilyn; Mason, Ronald P

    2015-01-01

    Xenobiotic metabolism can induce the generation of protein radicals, which are believed to play an important role in the toxicity of chemicals and drugs. It is therefore important to identify chemical structures capable of inducing macromolecular free radical formation in living cells. In this study, we evaluated the ability of four structurally related environmental chemicals, aniline, nitrosobenzene, N,N-dimethylaniline, and N,N-dimethyl-4-nitrosoaniline (DMNA), to induce free radicals and cellular damage in the hepatoma cell line HepG2. Cytotoxicity was assessed using lactate dehydrogenase assays, and morphological changes were observed using phase contrast microscopy. Protein free radicals were detected by immuno-spin trapping using in-cell western experiments and confocal microscopy to determine the subcellular locale of free radical generation. DMNA induced free radical generation, lactate dehydrogenase release, and morphological changes in HepG2 cells, whereas aniline, nitrosobenzene, N,N-dimethylaniline did not. Confocal microscopy showed that DMNA induced free radical generation mainly in the cytosol. Preincubation of HepG2 cells with N-acetylcysteine and 2,2'-dipyridyl significantly prevented free radical generation on subsequent incubation with DMNA, whereas preincubation with apocynin and dimethyl sulfoxide had no effect. These results suggest that DMNA is metabolized to reactive free radicals capable of generating protein radicals which may play a critical role in DMNA toxicity. We propose that the captodative effect, the combined action of the electron-releasing dimethylamine substituent, and the electron-withdrawing nitroso substituent, leads to a thermodynamically stabilized radical, facilitating enhanced protein radical formation by DMNA.

  19. Students' Ideas and Radical Constructivism

    NASA Astrophysics Data System (ADS)

    Sánchez Gómez, Pedro J.

    2016-08-01

    In this article, I study, from the point of view of the analytic philosophy of mind, the compatibility of students' ideas studies (SIS) with radical constructivism (RC). I demonstrate that RC is based on a psychology of narrow mental states; that is, the idea that the mental content of an individual can be fully characterised without any reference external to her or him. I show that this fact imposes some severe restrictions to SIS to be incorporated into RC. In particular, I argue that only qualitative studies can comply with the requirement of narrowness. Nevertheless, I propose that quantitative works can be employed as sources of types in order to study token actual students. I use this type-token dichotomy to put forward an outline of a theory of the relation between school contents and mental contents. In this view, token mental contents regarding a given topic can be defined, and probed, only by resorting to typical school contents.

  20. X-Ray Crystal Structure Analysis of Radical Bisphthalocyaninatoneodymium(III).

    DTIC Science & Technology

    1980-06-01

    prepared.7 Recently, intense attention has been also directed toward electrochromism of the bisphthalocyaninato- 8 lanthanide (III) complexes for color...uaercyclic planes. From E1 see surements, the title complex was found to contain an organic-free radical (S " 2.0029). Magnetic susceptibility muasuremente...also denonstrated that the titi complex contains one organic-free radical which could have an exchange Inter- action with f-electrens of the central