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

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Xiongyi; Groves, John T.

Since our initial report in 1976, the oxygen rebound mechanism has become the consensus mechanistic feature for an expanding variety of enzymatic C–H functionalization reactions and small molecule biomimetic catalysts. For both the biotransformations and models, an initial hydrogen atom abstraction from the substrate (R–H) by high-valent iron-oxo species (Fe n=O) generates a substrate radical and a reduced iron hydroxide, [Fe n-1–OH ·R]. This caged radical pair then evolves on a complicated energy landscape through a number of reaction pathways, such as oxygen rebound to form R–OH, rebound to a non-oxygen atom affording R–X, electron transfer of the incipient radicalmore » to yield a carbocation, R +, desaturation to form olefins, and radical cage escape. These various flavors of the rebound process, often in competition with each other, give rise to the wide range of C–H functionalization reactions performed by iron-containing oxygenases. In this review, we first recount the history of radical rebound mechanisms, their general features, and key intermediates involved. We will discuss in detail the factors that affect the behavior of the initial caged radical pair and the lifetimes of the incipient substrate radicals. Several representative examples of enzymatic C–H transformations are selected to illustrate how the behaviors of the radical pair [Fe n-1–OH ·R] determine the eventual reaction outcome. Finally, we discuss the powerful potential of “radical rebound” processes as a general paradigm for developing novel C–H functionalization reactions with synthetic, biomimetic catalysts. We envision that new chemistry will continue to arise by bridging enzymatic “radical rebound” with synthetic organic chemistry.« less

Transient nutation electron spin resonance spectroscopy on spin-correlated radical pairs: A theoretical analysis on hyperfine-induced nuclear modulations

NASA Astrophysics Data System (ADS)

Weber, Stefan; Kothe, Gerd; Norris, James R.

1997-04-01

The influence of anisotropic hyperfine interaction on transient nutation electron paramagnetic resonance (EPR) of light-induced spin-correlated radical pairs is studied theoretically using the density operator formalism. Analytical expressions for the time evolution of the transient EPR signal during selective microwave excitation of single transitions are derived for a model system comprised of a weakly coupled radical pair and one hyperfine-coupled nucleus with I=1/2. Zero-quantum electron coherence and single-quantum nuclear coherence are created as a result of the sudden light-induced generation of the radical pair state from a singlet-state precursor. Depending on the relative sizes of the nuclear Zeeman frequency and the secular and pseudo-secular parts of the hyperfine coupling, transitions between levels with different nuclear spin orientations are predicted to modulate the time-dependent EPR signal. These modulations are in addition to the well-known transient nutations and electron zero-quantum precessions. Our calculations provide insight into the mechanism of recent experimental observations of coherent nuclear modulations in the time-resolved EPR signals of doublets and radical pairs. Two distinct mechanisms of the modulations are presented for various microwave magnetic field strengths. The first modulation scheme arises from electron and nuclear coherences initiated by the laser excitation pulse and is "read out" by the weak microwave magnetic field. While the relative modulation depth of these oscillations with respect to the signal intensity is independent of the Rabi frequency, ω1, the frequencies of this coherence phenomenon are modulated by the effective microwave amplitude and determined by the nuclear Zeeman interaction and hyperfine coupling constants as well as the electron-electron spin exchange and dipolar interactions between the two radical pair halves. In a second mechanism the modulations are both created and detected by the microwave radiation. Here, the laser pulse merely defines the beginning of the microwave-induced coherent time evolution. This second mechanism appears the most consistent with current experimental observations.

Real-time observation of formation and relaxation dynamics of NH4 in (CH3OH)m(NH3)n clusters.

PubMed

Yamada, Yuji; Nishino, Yoko; Fujihara, Akimasa; Ishikawa, Haruki; Fuke, Kiyokazu

2009-03-26

The formation and relaxation dynamics of NH4(CH3OH)m(NH3)n clusters produced by photolysis of ammonia-methanol mixed clusters has been observed by a time-resolved pump-probe method with femtosecond pulse lasers. From the detailed analysis of the time evolutions of the protonated cluster ions, NH4(+)(CH3OH)m(NH3)n, the kinetic model has been constructed, which consists of sequential three-step reaction: ultrafast hydrogen-atom transfer producing the radical pair (NH4-NH2)*, the relaxation process of radical-pair clusters, and dissociation of the solvated NH4 clusters. The initial hydrogen transfer hardly occurs between ammonia and methanol, implying the unfavorable formation of radical pair, (CH3OH2-NH2)*. The remarkable dependence of the time constants in each step on the number and composition of solvents has been explained by the following factors: hydrogen delocalization within the clusters, the internal conversion of the excited-state radical pair, and the stabilization of NH4 by solvation. The dependence of the time profiles on the probe wavelength is attributed to the different ionization efficiency of the NH4(CH3OH)m(NH3)n clusters.

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

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

DNA bases ring-expanded with a cyclopentadiene free radical: a theoretical investigation of building blocks with diradical character.

PubMed

Zhao, Peiwen; Bu, Yuxiang

2016-01-14

In this work, we computationally design radical nucleobases which possess improved electronic properties, especially diradical properties through introducing a cyclopentadiene radical. We predict that the detailed electromagnetic features of base assemblies are based on the orientation of the extra five-membered cyclopentadiene ring. Broken symmetry DFT calculations take into account the relevant structures and properties. Our results reveal that both the radicalized DNA bases and the base pairs formed when they combine with their counterparts remain stable and display larger spin delocalization. The mode of embedding the cyclopentadiene free radical in the structures has some influence on the degree of π-conjugation, which results in various diradical characteristics. Single-layered radical base pairs all have an open-shell singlet ground state, but the energy difference between singlet and triplet is not significant. For two-layered radical base pairs, the situation is more complex. All of them have an open-shell state as their ground state, including an open-shell singlet state and an open-shell triplet state. That is, the majority of radical base pairs possess anti-ferromagnetic or ferromagnetic characteristics. We present here a more in-depth discussion and analyses to study the magnetic characteristics of radical bases and base pairs. As an important factor, two-layered radical base pairs also have been carefully analyzed. We hope that all the measurements and results presented here will stimulate further detailed insights into the related mechanisms in modified DNA bases and the design of better ring-expanded DNA magnetic materials.

Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C–H activation

DOE PAGES

Huang, Xiongyi; Groves, John T.

2016-12-01

Since our initial report in 1976, the oxygen rebound mechanism has become the consensus mechanistic feature for an expanding variety of enzymatic C–H functionalization reactions and small molecule biomimetic catalysts. For both the biotransformations and models, an initial hydrogen atom abstraction from the substrate (R–H) by high-valent iron-oxo species (Fe n=O) generates a substrate radical and a reduced iron hydroxide, [Fe n-1–OH ·R]. This caged radical pair then evolves on a complicated energy landscape through a number of reaction pathways, such as oxygen rebound to form R–OH, rebound to a non-oxygen atom affording R–X, electron transfer of the incipient radicalmore » to yield a carbocation, R +, desaturation to form olefins, and radical cage escape. These various flavors of the rebound process, often in competition with each other, give rise to the wide range of C–H functionalization reactions performed by iron-containing oxygenases. In this review, we first recount the history of radical rebound mechanisms, their general features, and key intermediates involved. We will discuss in detail the factors that affect the behavior of the initial caged radical pair and the lifetimes of the incipient substrate radicals. Several representative examples of enzymatic C–H transformations are selected to illustrate how the behaviors of the radical pair [Fe n-1–OH ·R] determine the eventual reaction outcome. Finally, we discuss the powerful potential of “radical rebound” processes as a general paradigm for developing novel C–H functionalization reactions with synthetic, biomimetic catalysts. We envision that new chemistry will continue to arise by bridging enzymatic “radical rebound” with synthetic organic chemistry.« less

Spin densities from subsystem density-functional theory: Assessment and application to a photosynthetic reaction center complex model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Solovyeva, Alisa; Technical University Braunschweig, Institute for Physical and Theoretical Chemistry, Hans-Sommer-Str. 10, 38106 Braunschweig; Pavanello, Michele

2012-05-21

Subsystem density-functional theory (DFT) is a powerful and efficient alternative to Kohn-Sham DFT for large systems composed of several weakly interacting subunits. Here, we provide a systematic investigation of the spin-density distributions obtained in subsystem DFT calculations for radicals in explicit environments. This includes a small radical in a solvent shell, a {pi}-stacked guanine-thymine radical cation, and a benchmark application to a model for the special pair radical cation, which is a dimer of bacteriochlorophyll pigments, from the photosynthetic reaction center of purple bacteria. We investigate the differences in the spin densities resulting from subsystem DFT and Kohn-Sham DFT calculations.more » In these comparisons, we focus on the problem of overdelocalization of spin densities due to the self-interaction error in DFT. It is demonstrated that subsystem DFT can reduce this problem, while it still allows to describe spin-polarization effects crossing the boundaries of the subsystems. In practical calculations of spin densities for radicals in a given environment, it may thus be a pragmatic alternative to Kohn-Sham DFT calculations. In our calculation on the special pair radical cation, we show that the coordinating histidine residues reduce the spin-density asymmetry between the two halves of this system, while inclusion of a larger binding pocket model increases this asymmetry. The unidirectional energy transfer in photosynthetic reaction centers is related to the asymmetry introduced by the protein environment.« less

The Radical Pair Mechanism and the Avian Chemical Compass: Quantum Coherence and Entanglement

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yiteng; Kais, Sabre; Berman, Gennady Petrovich

2015-02-02

We review the spin radical pair mechanism which is a promising explanation of avian navigation. This mechanism is based on the dependence of product yields on 1) the hyperfine interaction involving electron spins and neighboring nuclear spins and 2) the intensity and orientation of the geomagnetic field. One surprising result is that even at ambient conditions quantum entanglement of electron spins can play an important role in avian magnetoreception. This review describes the general scheme of chemical reactions involving radical pairs generated from singlet and triplet precursors; the spin dynamics of the radical pairs; and the magnetic field dependence ofmore » product yields caused by the radical pair mechanism. The main part of the review includes a description of the chemical compass in birds. We review: the general properties of the avian compass; the basic scheme of the radical pair mechanism; the reaction kinetics in cryptochrome; quantum coherence and entanglement in the avian compass; and the effects of noise. We believe that the quantum avian compass can play an important role in avian navigation and can also provide the foundation for a new generation of sensitive and selective magnetic-sensing nano-devices.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Evans, Emrys W.; Henbest, Kevin B.; Timmel, Christiane R., E-mail: christiane.timmel@chem.ox.ac.uk, E-mail: stuart.mackenzie@chem.ox.ac.uk

Even though the interaction of a <1 mT magnetic field with an electron spin is less than a millionth of the thermal energy at room temperature (k{sub B}T), it still can have a profound effect on the quantum yields of radical pair reactions. We present a study of the effects of sub-millitesla magnetic fields on the photoreaction of flavin mononucleotide with ascorbic acid. Direct control of the reaction pathway is achieved by varying the rate of electron transfer from ascorbic acid to the photo-excited flavin. At pH 7.0, we verify the theoretical prediction that, apart from a sign change, themore » form of the magnetic field effect is independent of the initial spin configuration of the radical pair. The data agree well with model calculations based on a Green’s function approach that allows multinuclear spin systems to be treated including the diffusive motion of the radicals, their spin-selective recombination reactions, and the effects of the inter-radical exchange interaction. The protonation states of the radicals are uniquely determined from the form of the magnetic field-dependence. At pH 3.0, the effects of two chemically distinct radical pair complexes combine to produce a pronounced response to ∼500 μT magnetic fields. These findings are relevant to the magnetic responses of cryptochromes (flavin-containing proteins proposed as magnetoreceptors in birds) and may aid the evaluation of effects of weak magnetic fields on other biologically relevant electron transfer processes.« less

Spin Polarization Transfer from a Photogenerated Radical Ion Pair to a Stable Radical Controlled by Charge Recombination.

PubMed

Horwitz, Noah E; Phelan, Brian T; Nelson, Jordan N; Mauck, Catherine M; Krzyaniak, Matthew D; Wasielewski, Michael R

2017-06-15

Photoexcitation of electron donor-acceptor molecules frequently produces radical ion pairs with well-defined initial spin-polarized states that have attracted significant interest for spintronics. Transfer of this initial spin polarization to a stable radical is predicted to depend on the rates of the radical ion pair recombination reactions, but this prediction has not been tested experimentally. In this study, a stable radical/electron donor/chromophore/electron acceptor molecule, BDPA • -mPD-ANI-NDI, where BDPA • is α,γ-bisdiphenylene-β-phenylallyl, mPD is m-phenylenediamine, ANI is 4-aminonaphthalene-1,8-dicarboximide, and NDI is naphthalene-1,4:5,8-bis(dicarboximide), was synthesized. Photoexcitation of ANI produces the triradical BDPA • -mPD +• -ANI-NDI -• in which the mPD +• -ANI-NDI -• radical ion pair is spin coupled to the BDPA • stable radical. BDPA • -mPD +• -ANI-NDI -• and its counterpart lacking the stable radical are found to exhibit spin-selective charge recombination in which the triplet radical ion pair 3 (mPD +• -ANI-NDI -• ) is in equilibrium with the 3 *NDI charge recombination product. Time-resolved EPR measurements show that this process is associated with an inversion of the sign of the polarization transferred to BDPA • over time. The polarization transfer rates are found to be strongly solvent dependent, as shifts in this equilibrium affect the spin dynamics. These results demonstrate that even small changes in electron transfer dynamics can have a large effect on the spin dynamics of photogenerated multispin systems.

Solid State Photochemical Generation of Triplet Phenoxy-Phenoxy Radical Pairs

DTIC Science & Technology

1990-04-01

of diphenyl oxalate . Tert-butylated bis-aryloxalat s show good radical pair stability, with triplet ESR signals surviving days at room temperature in...between the geminate phenoxyl radicals. The comparable breadth of the spectra for diphenyl carbonate and the oxalates implies a similar interaction strength...ferromagnetic coupling that may be achieved in geminate pairs generated from a diphenyl oxalate vs. a diphenyl carbonate. In addition, we see similar

Lithium formate for EPR dosimetry: radiation-induced radical trapping at low temperatures.

PubMed

Krivokapić, André; Aalbergsjø, Siv G; De Cooman, Hendrik; Hole, Eli Olaug; Nelson, William H; Sagstuen, Einar

2014-05-01

Radiation-induced primary radicals in lithium formate. A material used in EPR dosimetry have been studied using electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR) and ENDOR-Induced EPR (EIE) techniques. In this study, single crystals were X irradiated at 6-8 K and radical formation at these and higher temperatures were investigated. Periodic density functional theory calculations were used to assist in assigning the radical structures. Mainly two radicals are present at 6 K, the well-known CO2(•-) radical and a protonated electron-gain product. Hyperfine coupling tensors for proton and lithium interactions were obtained for these two radicals and show that the latter radical exists in four conformations with various degrees of bending at the radical center. Pairs of CO2(•-) radicals were also observed and the tensor for the electron-electron dipolar coupling was determined for the strongest coupled pair, which exhibited the largest spectral intensity. Upon warming, both the radical pairs and the reduction product decay, the latter apparently by a transient species. Above 200 K the EPR spectrum was mainly due to the CO2(•-) (mono) radicals, which were previously characterized as the dominant species present at room temperature and which account for the dosimetric EPR signal.

Inversion in the magnetic field effect of benzilketyl:SDS radical pair at high fields

NASA Astrophysics Data System (ADS)

Misra, Ajay; Haldar, Mintu; Chowdhury, Mihir

1999-05-01

The effect of a high magnetic field (up to 13.3 T) on radical pairs generated by the hydrogen abstraction of the photoexcited benzil triplet from sodium dodecyl sulphate has been studied. It was found that both the radical pair lifetime and the free radical yield increase with an increase of field from 0 to 4 T. A further increase of field causes a decrease in both. This reversal of the magnetic field effect (MFE) above 4 T has been explained in terms of relaxation mechanism and competition between a number of rate processes. The effect of reducing the micelle size on the MFE inversion has been discussed.

On the use of magnets to disrupt the physiological compass of birds.

PubMed

Wang, K; Mattern, E; Ritz, T

2006-10-04

Behavioral researchers have attached magnets to birds during orientation experiments, assuming that such magnets will disrupt their ability to obtain magnetic information. Here, we investigate the effect of an attached magnet on the ability to derive directional information from a radical-pair based compass mechanism. We outline in some detail the geometrical symmetries that would allow a bird to identify magnetic directions in a radical-pair based compass. We show that the artificial field through an attached magnet will quickly disrupt the birds' ability to distinguish pole-ward from equator-ward headings, but that much stronger fields are necessary to disrupt their ability to detect the magnetic axis. Together with estimates of the functional limits of a radical-pair based compass, our calculations suggest that artificial fields of comparable size to the geomagnetic field are not generally sufficient to render a radical-pair based compass non-functional.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singha, Subhash; Mohanty, Bedangadas; Netrakanti, Pawan Kumar

We compiled the experimentally measured p-bar/p ratio at midrapidity in p+p collisions from {radical}(s)=23 to 7000 GeV and compared it to various mechanisms of baryon production as implemented in the pythia, phojet, and Heavy Ion Jet Interaction Generator (HIJING)/B-B models. For the models studied with default settings, phojet has the best agreement with the measurements, pythia gives a higher value for {radical}(s)<200 GeV, and the ratios from HIJING/B-B are consistently lower for all the {radical}(s) studied. A comparison of the data to different mechanisms of baryon production as implemented in pythia shows that through a suitable tuning of the suppressionmore » of diquark-antidiquark pair production in the color field relative to quark-antiquark production and allowing the diquarks to split according to the popcorn scheme, a fairly reasonable description of the measured p-bar/p ratio for {radical}(s)<200 GeV is given. A comparison of the beam energy dependence of the p-bar/p ratio in p+p and nucleus-nucleus (A + A) collisions at midrapidity shows that the baryon production is significantly more for A + A collisions relative to p+p collisions for {radical}(s)<200 GeV. We also carry out a phenomenological fit to the y{sub beam} dependence of the p-bar/p ratio.« less

Coherent triplet excitation suppresses the heading error of the avian compass

NASA Astrophysics Data System (ADS)

Katsoprinakis, G. E.; Dellis, A. T.; Kominis, I. K.

2010-08-01

Radical-ion pair reactions are currently understood to underlie the biochemical magnetic compass of migratory birds. It was recently shown that radical-ion pair reactions form a rich playground for the application of quantum-information-science concepts and effects. We will show here that the intricate interplay between the quantum Zeno effect and the coherent excitation of radical-ion pairs leads to an exquisite angular sensitivity of the reaction yields. This results in a significant and previously unanticipated suppression of the avian compass heading error, opening the way to quantum engineering precision biological sensors.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aaltonen, T.; Brucken, E.; Devoto, F.

We search for resonant production of tt pairs in 4.8 fb{sup -1} integrated luminosity of pp collision data at {radical}(s)=1.96 TeV in the lepton+jets decay channel, where one top quark decays leptonically and the other hadronically. A matrix-element reconstruction technique is used; for each event a probability density function of the tt candidate invariant mass is sampled. These probability density functions are used to construct a likelihood function, whereby the cross section for resonant tt production is estimated, given a hypothetical resonance mass and width. The data indicate no evidence of resonant production of tt pairs. A benchmark model ofmore » leptophobic Z{sup '}{yields}tt is excluded with m{sub Z}{sup '}<900 GeV/c{sup 2} at 95% confidence level.« less

Theoretical description of spin-selective reactions of radical pairs diffusing in spherical 2D and 3D microreactors

NASA Astrophysics Data System (ADS)

Ivanov, Konstantin L.; Sadovsky, Vladimir M.; Lukzen, Nikita N.

2015-08-01

In this work, we treat spin-selective recombination of a geminate radical pair (RP) in a spherical "microreactor," i.e., of a RP confined in a micelle, vesicle, or liposome. We consider the microreactor model proposed earlier, in which one of the radicals is located at the center of the micelle and the other one undergoes three-dimensional diffusion inside the micelle. In addition, we suggest a two-dimensional model, in which one of the radicals is located at the "pole" of the sphere, while the other one diffuses on the spherical surface. For this model, we have obtained a general analytical expression for the RP recombination yield in terms of the free Green function of two-dimensional diffusion motion. In turn, this Green function is expressed via the Legendre functions and thus takes account of diffusion over a restricted spherical surface and its curvature. The obtained expression allows one to calculate the RP recombination efficiency at an arbitrary magnetic field strength. We performed a comparison of the two models taking the same geometric parameters (i.e., the microreactor radius and the closest approach distance of the radicals), chemical reactivity, magnetic interactions in the RP and diffusion coefficient. Significant difference between the predictions of the two models is found, which is thus originating solely from the dimensionality effect: for different dimensionality of space, the statistics of diffusional contacts of radicals becomes different altering the reaction yield. We have calculated the magnetic field dependence of the RP reaction yield and chemically induced dynamic nuclear polarization of the reaction products at different sizes of the microreactor, exchange interaction, and spin relaxation rates. Interestingly, due to the intricate interplay of diffusional contacts of reactants and spin dynamics, the dependence of the reaction yield on the microreactor radius is non-monotonous. Our results are of importance for (i) interpreting experimental data for magnetic field effects on RP recombination in confined space and (ii) for describing kinetics of chemical reactions, which occur predominantly on the surfaces of biomembranes, i.e., lipid peroxidation reactions.

Theoretical description of spin-selective reactions of radical pairs diffusing in spherical 2D and 3D microreactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivanov, Konstantin L., E-mail: ivanov@tomo.nsc.ru; Lukzen, Nikita N.; Novosibirsk State University, Pirogova St. 2, Novosibirsk 630090

2015-08-28

In this work, we treat spin-selective recombination of a geminate radical pair (RP) in a spherical “microreactor,” i.e., of a RP confined in a micelle, vesicle, or liposome. We consider the microreactor model proposed earlier, in which one of the radicals is located at the center of the micelle and the other one undergoes three-dimensional diffusion inside the micelle. In addition, we suggest a two-dimensional model, in which one of the radicals is located at the “pole” of the sphere, while the other one diffuses on the spherical surface. For this model, we have obtained a general analytical expression formore » the RP recombination yield in terms of the free Green function of two-dimensional diffusion motion. In turn, this Green function is expressed via the Legendre functions and thus takes account of diffusion over a restricted spherical surface and its curvature. The obtained expression allows one to calculate the RP recombination efficiency at an arbitrary magnetic field strength. We performed a comparison of the two models taking the same geometric parameters (i.e., the microreactor radius and the closest approach distance of the radicals), chemical reactivity, magnetic interactions in the RP and diffusion coefficient. Significant difference between the predictions of the two models is found, which is thus originating solely from the dimensionality effect: for different dimensionality of space, the statistics of diffusional contacts of radicals becomes different altering the reaction yield. We have calculated the magnetic field dependence of the RP reaction yield and chemically induced dynamic nuclear polarization of the reaction products at different sizes of the microreactor, exchange interaction, and spin relaxation rates. Interestingly, due to the intricate interplay of diffusional contacts of reactants and spin dynamics, the dependence of the reaction yield on the microreactor radius is non-monotonous. Our results are of importance for (i) interpreting experimental data for magnetic field effects on RP recombination in confined space and (ii) for describing kinetics of chemical reactions, which occur predominantly on the surfaces of biomembranes, i.e., lipid peroxidation reactions.« less

Approaches to Measuring Entanglement in Chemical Magnetometers

PubMed Central

2013-01-01

Chemical magnetometers are radical pair systems such as solutions of pyrene and N,N-dimethylaniline (Py–DMA) that show magnetic field effects in their spin dynamics and their fluorescence. We investigate the existence and decay of quantum entanglement in free geminate Py–DMA radical pairs and discuss how entanglement can be assessed in these systems. We provide an entanglement witness and propose possible observables for experimentally estimating entanglement in radical pair systems with isotropic hyperfine couplings. As an application, we analyze how the field dependence of the entanglement lifetime in Py–DMA could in principle be used for magnetometry and illustrate the propagation of measurement errors in this approach. PMID:24372396

A practical approach to calculate the time evolutions of magnetic field effects on photochemical reactions in nano-structured materials.

PubMed

Yago, Tomoaki; Wakasa, Masanobu

2015-04-21

A practical method to calculate time evolutions of magnetic field effects (MFEs) on photochemical reactions involving radical pairs is developed on the basis of the theory of the chemically induced dynamic spin polarization proposed by Pedersen and Freed. In theory, the stochastic Liouville equation (SLE), including the spin Hamiltonian, diffusion motions of the radical pair, chemical reactions, and spin relaxations, is solved by using the Laplace and the inverse Laplace transformation technique. In our practical approach, time evolutions of the MFEs are successfully calculated by applying the Miller-Guy method instead of the final value theorem to the inverse Laplace transformation process. Especially, the SLE calculations are completed in a short time when the radical pair dynamics can be described by the chemical kinetics consisting of diffusions, reactions and spin relaxations. The SLE analysis with a short calculation time enables one to examine the various parameter sets for fitting the experimental date. Our study demonstrates that simultaneous fitting of the time evolution of the MFE and of the magnetic field dependence of the MFE provides valuable information on the diffusion motions of the radical pairs in nano-structured materials such as micelles where the lifetimes of radical pairs are longer than hundreds of nano-seconds and the magnetic field dependence of the spin relaxations play a major role for the generation of the MFE.

Adenine radicals generated in alternating AT duplexes by direct absorption of low-energy UV radiation.

PubMed

Banyasz, Akos; Ketola, Tiia; Martínez-Fernández, Lara; Improta, Roberto; Markovitsi, Dimitra

2018-04-17

There is increasing evidence that the direct absorption of photons with energies that are lower than the ionization potential of nucleobases may result in oxidative damage to DNA. The present work, which combines nanosecond transient absorption spectroscopy and quantum mechanical calculations, studies this process in alternating adenine-thymine duplexes (AT)n. We show that the one-photon ionization quantum yield of (AT)10 at 266 nm (4.66 eV) is (1.5 ± 0.3) × 10-3. According to our PCM/TD-DFT calculations carried out on model duplexes composed of two base pairs, (AT)1 and (TA)1, simultaneous base pairing and stacking does not induce important changes in the absorption spectra of the adenine radical cation and deprotonated radical. The adenine radicals, thus identified in the time-resolved spectra, disappear with a lifetime of 2.5 ms, giving rise to a reaction product that absorbs at 350 nm. In parallel, the fingerprint of reaction intermediates other than radicals, formed directly from singlet excited states and assigned to AT/TA dimers, is detected at shorter wavelengths. PCM/TD-DFT calculations are carried out to map the pathways leading to such species and to characterize their absorption spectra; we find that, in addition to the path leading to the well-known TA* photoproduct, an AT photo-dimerization path may be operative in duplexes.

Effect of dioxane on the benzil:SDS radical pair system. A study in the presence of high magnetic fields

NASA Astrophysics Data System (ADS)

Misra, Ajay; Dutta, Rina; Chowdhury, Mihir

1995-09-01

The magnetic response of the radical pair generated by the hydrogen abstraction of the photoexcited benzil triplet from sodium dodecyl sulphate is studied. It is found that radical decay curves, with or without magnetic field, are affected on addition of small amphiphiles such as 1,4-dioxane. The results have been interpreted on the basis of the ability of the latter to change the micellar aggregation number and intramicellar viscosity.

Continuous Diffusion Model for Concentration Dependence of Nitroxide EPR Parameters in Normal and Supercooled Water.

PubMed

Merunka, Dalibor; Peric, Miroslav

2017-05-25

Electron paramagnetic resonance (EPR) spectra of radicals in solution depend on their relative motion, which modulates the Heisenberg spin exchange and dipole-dipole interactions between them. To gain information on radical diffusion from EPR spectra demands both reliable spectral fitting to find the concentration coefficients of EPR parameters and valid expressions between the concentration and diffusion coefficients. Here, we measured EPR spectra of the 14 N- and 15 N-labeled perdeuterated TEMPONE radicals in normal and supercooled water at various concentrations. By fitting the EPR spectra to the functions based on the modified Bloch equations, we obtained the concentration coefficients for the spin dephasing, coherence transfer, and hyperfine splitting parameters. Assuming the continuous diffusion model for radical motion, the diffusion coefficients of radicals were calculated from the concentration coefficients using the standard relations and the relations derived from the kinetic equations for the spin evolution of a radical pair. The latter relations give better agreement between the diffusion coefficients calculated from different concentration coefficients. The diffusion coefficients are similar for both radicals, which supports the presented method. They decrease with lowering temperature slower than is predicted by the Stokes-Einstein relation and slower than the rotational diffusion coefficients, which is similar to the diffusion of water molecules in supercooled water.

Chemisorption of hydrogen atoms and hydroxyl groups on stretched graphene: A coupled QM/QM study

NASA Astrophysics Data System (ADS)

Katin, Konstantin P.; Prudkovskiy, Vladimir S.; Maslov, Mikhail M.

2017-09-01

Using the density functional theory coupled with the nonorthogonal tight-binding model, we analyze the chemisorption of hydrogen atoms and hydroxyl groups on the unstrained and stretched graphene sheets. Drawback of finite cluster model of graphene for the chemisorption energy calculation in comparison with the QM/QM approach applied is discussed. It is shown that the chemisorption energy for the hydroxyl group is sufficiently lower than for hydrogen at stretching up to 7.5%. The simultaneous paired chemisorption of hydrogen and hydroxyl groups on the same hexagon has also been examined. Adsorption of two radicals in ortho and para positions is found to be more energetically favorable than those in meta position at any stretching considered. In addition the energy difference between adsorbent pairs in ortho and para positions decreases as the stretching rises. It could be concluded that the graphene stretching leads to the loss of preferred mutual arrangement of two radicals on its surface.

Open quantum system approach to the modeling of spin recombination reactions.

PubMed

Tiersch, M; Steiner, U E; Popescu, S; Briegel, H J

2012-04-26

In theories of spin-dependent radical pair reactions, the time evolution of the radical pair, including the effect of the chemical kinetics, is described by a master equation in the Liouville formalism. For the description of the chemical kinetics, a number of possible reaction operators have been formulated in the literature. In this work, we present a framework that allows for a unified description of the various proposed mechanisms and the forms of reaction operators for the spin-selective recombination processes. On the basis of the concept that master equations can be derived from a microscopic description of the spin system interacting with external degrees of freedom, it is possible to gain insight into the underlying microscopic processes and develop a systematic approach toward determining the specific form of the reaction operator in concrete scenarios.

Verdazyl-ribose: A new radical for solid-state dynamic nuclear polarization at high magnetic field

NASA Astrophysics Data System (ADS)

Thurber, Kent R.; Le, Thanh-Ngoc; Changcoco, Victor; Brook, David J. R.

2018-04-01

Solid-state dynamic nuclear polarization (DNP) using the cross-effect relies on radical pairs whose electron spin resonance (ESR) frequencies differ by the nuclear magnetic resonance (NMR) frequency. We measure the DNP provided by a new water-soluble verdazyl radical, verdazyl-ribose, under both magic-angle spinning (MAS) and static sample conditions at 9.4 T, and compare it to a nitroxide radical, 4-hydroxy-TEMPO. We find that verdazyl-ribose is an effective radical for cross-effect DNP, with the best relative results for a non-spinning sample. Under non-spinning conditions, verdazyl-ribose provides roughly 2× larger 13C cross-polarized (CP) NMR signal than the nitroxide, with similar polarization buildup times, at both 29 K and 76 K. With MAS at 7 kHz and 1.5 W microwave power, the verdazyl-ribose does not provide as much DNP as the nitroxide, with the verdazyl providing less NMR signal and a longer polarization buildup time. When the microwave power is decreased to 30 mW with 5 kHz MAS, the two types of radical are comparable, with the verdazyl-doped sample having a larger NMR signal which compensates for its longer polarization buildup time. We also present electron spin relaxation measurements at Q-band (1.2 T) and ESR lineshapes at 1.2 and 9.4 T. Most notably, the verdazyl radical has a longer T1e than the nitroxide (9.9 ms and 1.3 ms, respectively, at 50 K and 1.2 T). The verdazyl electron spin lineshape is significantly affected by the hyperfine coupling to four 14N nuclei, even at 9.4 T. We also describe 3000-spin calculations to illustrate the DNP potential of possible radical pairs: verdazyl-verdazyl, verdazyl-nitroxide, or nitroxide-nitroxide pairs. These calculations suggest that the verdazyl radical at 9.4 T has a narrower linewidth than optimal for cross-effect DNP using verdazyl-verdazyl pairs. Because of the hyperfine coupling contribution to the electron spin linewidth, this implies that DNP using the verdazyl radical would improve at lower magnetic field. Another conclusion from the calculations is that a verdazyl-nitroxide bi-radical would be expected to be slightly better for cross-effect DNP than the nitroxide-nitroxide bi-radicals commonly used now, assuming the same spin-spin coupling constants.

Benzophenone as a photoprobe of polymer films

NASA Astrophysics Data System (ADS)

Levin, Peter P.; Efremkin, Alexei F.; Khudyakov, Igor V.

2017-09-01

The review article is devoted to kinetics of fast reactions following photoexcitation of benzophenone in polymer films. We observed three processes by ns laser flash photolysis in elastomers: (i) decay of a triple state of benzophenone with hydrogen abstraction from polymer matrix, (ii) formation and decay of geminate radical pairs, (iii) cross-termination of the formed radicals in the polymer bulk. Application of external magnetic field (MF) of B = 0.2 T essentially affects recombination of geminate (G-) and a bimolecular recombination of free radicals, which escaped polymer cage (F-pairs). Theoretical calculation of MF effects on G- and F-pairs is in agreement with corresponding experimental data. Elongation of elastomer leads to an unexpected observation: recombination in the bulk becomes slower. An explanation of this phenomenon based on elastomer free volume Vf approach was suggested.

Approaching magnetic field effects in biology using the radical pair mechanism

NASA Astrophysics Data System (ADS)

Canfield, Jeffrey Michael

1997-11-01

The overall goal of this thesis has been to explain any of the reported magnetic field effects in biology (magnetic orientation of many species and/or health effects, such as cancer, due to man-made electromagnetic fields) using the radical pair mechanism, a quantum mechanical mechanism known for over 20 years that lets singlet-to-triplet yields (which can be related to reaction rates) of radical pair reactions depend on applied magnetic fields. This goal seems reasonable considering the known roles of many biological free radicals in cancer, disease, aging, development, and cellular signaling, the constant reminders in the media to take anti-oxidant vitamins to protect against certain deleterious free radicals, and the success of the radical pair mechanism in explaining magnetic field effects in photosynthetic reaction centers. To approach the above goal, this thesis develops several methods (using perturbation theory and other techniques in the Schrodinger and Liouville formalisms) for calculating singlet-to-triplet yields in combinations of steady and oscillating fields (some of these algorithms are more versatile or efficient while others give more insight, and all serve as cross-checks on each other) and uses these tools to explore and explain a number of interesting phenomena such as yields sensitive to the magnitude and orientation of earth-strength (0.5 G) steady fields as well as the magnitude, orientation, and frequency of very weak (7 mG or less) oscillating fields. In particular, this thesis examines such effects in several coenzyme B12 systems, systems long studied by EPR (Electron Paramagnetic Resonance, the chief method for determining the spin Hamiltonians, spin relaxation rates, and other parameters needed for calculations) in which organometallic cobalt-carbon bonds are often cleaved homolytically to form radical pairs. Among the B12-dependent enzymes are ribonucleotide reductase (which converts RNA to DNA nucleotides), methyl malonyl CoA mutase (which controls the metabolism of certain fatty acids in mammals), and methionine synthase (which in mammals is used to regenerate active methyl groups on S-adenosyl methionine, which is involved in DNA methylation, melatonin and epinephrine synthesis, myelination, and methylation of chemotaxis proteins).* ftn*Originally published in DAI Vol. 58, No. 10. Reprinted here with revised abstract.

Level crossing analysis of chemically induced dynamic nuclear polarization: Towards a common description of liquid-state and solid-state cases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sosnovsky, Denis V.; Ivanov, Konstantin L., E-mail: ivanov@tomo.nsc.ru; Novosibirsk State University, Pirogova 2, 630090, Novosibirsk

Chemically Induced Dynamic Nuclear Polarization (CIDNP) is an efficient method of creating non-equilibrium polarization of nuclear spins by using chemical reactions, which have radical pairs as intermediates. The CIDNP effect originates from (i) electron spin-selective recombination of radical pairs and (ii) the dependence of the inter-system crossing rate in radical pairs on the state of magnetic nuclei. The CIDNP effect can be investigated by using Nuclear Magnetic Resonance (NMR) methods. The gain from CIDNP is then two-fold: it allows one to obtain considerable amplification of NMR signals; in addition, it provides a very useful tool for investigating elusive radicals andmore » radical pairs. While the mechanisms of the CIDNP effect in liquids are well established and understood, detailed analysis of solid-state CIDNP mechanisms still remains challenging; likewise a common theoretical frame for the description of CIDNP in both solids and liquids is missing. Difficulties in understanding the spin dynamics that lead to the CIDNP effect in the solid-state case are caused by the anisotropy of spin interactions, which increase the complexity of spin evolution. In this work, we propose to analyze CIDNP in terms of level crossing phenomena, namely, to attribute features in the CIDNP magnetic field dependence to Level Crossings (LCs) and Level Anti-Crossings (LACs) in a radical pair. This approach allows one to describe liquid-state CIDNP; the same holds for the solid-state case where anisotropic interactions play a significant role in CIDNP formation. In solids, features arise predominantly from LACs, since in most cases anisotropic couplings result in perturbations, which turn LCs into LACs. We have interpreted the CIDNP mechanisms in terms of the LC/LAC concept. This consideration allows one to find analytical expressions for a wide magnetic field range, where several different mechanisms are operative; furthermore, the LAC description gives a way to determine CIDNP sign rules. Thus, LCs/LACs provide a consistent description of CIDNP in both liquids and solids with the prospect of exploiting it for the analysis of short-lived radicals and for optimizing the polarization level.« less

Magnetic Orientation in Birds and Other Animals

NASA Astrophysics Data System (ADS)

Wiltschko, Wolfgang

The use of the geomagnetic field for compass orientation is widespread among animals, with two types of magnetic compass mechanisms described: an shape inclination compass in birds, turtles and salamanders and a shape polarity compass in arthropods, fishes and mammals. Additionally, some vertebrates appear to derive positional information from the total intensity and/or inclination of the geomagnetic field. For magnetoreception by animals, two models are currently discussed, the shape Radical Pair model assuming light-dependent processes by specialized photopigments, and the shape Magnetite hypothesis proposing magnetoreception by crystals of magnetite, Fe304. Behavioral experiments with migratory birds, testing them under monochromatic lights and subjecting them to a brief, strong pulse that could reverse the magnetization of magnetite particles, produced evidence for both mechanisms. However, monochromatic lights affect old, experienced and young birds alike, whereas the pulse affects only experienced birds, leaving young, inexperienced birds unaffected. These observations suggest that a radical pair mechanism provides birds with directional information for their innate magnetic compass and a magnetite-based mechanism possibly mediates information about total intensity for indicating position.

Electron Spin Relaxation Can Enhance the Performance of a Cryptochrome-Based Magnetic Compass Sensor

DTIC Science & Technology

2016-08-19

quantumbiology,migratory birds, animal navigation, radical pairmechanism Supplementarymaterial for this article is available online Abstract The radical ...certain spin relaxationmechanisms can enhance its performance.We focus on the flavin–tryptophan radical pair in cryptochrome, currently the only...candidatemagnetoreceptor molecule. Correlation functions for fluctuations in the distance between the two radicals in Arabidopsis thaliana cryptochrome

Verdazyl-ribose: A new radical for solid-state dynamic nuclear polarization at high magnetic field.

PubMed

Thurber, Kent R; Le, Thanh-Ngoc; Changcoco, Victor; Brook, David J R

2018-04-01

Solid-state dynamic nuclear polarization (DNP) using the cross-effect relies on radical pairs whose electron spin resonance (ESR) frequencies differ by the nuclear magnetic resonance (NMR) frequency. We measure the DNP provided by a new water-soluble verdazyl radical, verdazyl-ribose, under both magic-angle spinning (MAS) and static sample conditions at 9.4 T, and compare it to a nitroxide radical, 4-hydroxy-TEMPO. We find that verdazyl-ribose is an effective radical for cross-effect DNP, with the best relative results for a non-spinning sample. Under non-spinning conditions, verdazyl-ribose provides roughly 2× larger 13 C cross-polarized (CP) NMR signal than the nitroxide, with similar polarization buildup times, at both 29 K and 76 K. With MAS at 7 kHz and 1.5 W microwave power, the verdazyl-ribose does not provide as much DNP as the nitroxide, with the verdazyl providing less NMR signal and a longer polarization buildup time. When the microwave power is decreased to 30 mW with 5 kHz MAS, the two types of radical are comparable, with the verdazyl-doped sample having a larger NMR signal which compensates for its longer polarization buildup time. We also present electron spin relaxation measurements at Q-band (1.2 T) and ESR lineshapes at 1.2 and 9.4 T. Most notably, the verdazyl radical has a longer T 1e than the nitroxide (9.9 ms and 1.3 ms, respectively, at 50 K and 1.2 T). The verdazyl electron spin lineshape is significantly affected by the hyperfine coupling to four 14 N nuclei, even at 9.4 T. We also describe 3000-spin calculations to illustrate the DNP potential of possible radical pairs: verdazyl-verdazyl, verdazyl-nitroxide, or nitroxide-nitroxide pairs. These calculations suggest that the verdazyl radical at 9.4 T has a narrower linewidth than optimal for cross-effect DNP using verdazyl-verdazyl pairs. Because of the hyperfine coupling contribution to the electron spin linewidth, this implies that DNP using the verdazyl radical would improve at lower magnetic field. Another conclusion from the calculations is that a verdazyl-nitroxide bi-radical would be expected to be slightly better for cross-effect DNP than the nitroxide-nitroxide bi-radicals commonly used now, assuming the same spin-spin coupling constants. Published by Elsevier Inc.

Magnetoreception in birds: different physical processes for two types of directional responses

PubMed Central

Wiltschko, Roswitha; Stapput, Katrin; Ritz, Thorsten; Thalau, Peter; Wiltschko, Wolfgang

2007-01-01

Migratory orientation in birds involves an inclination compass based on radical-pair processes. Under certain light regimes, however, “fixed-direction” responses are observed that do not undergo the seasonal change between spring and autumn typical for migratory orientation. To identify the underlying transduction mechanisms, we analyzed a fixed-direction response under a combination of 502 nm turquoise and 590 nm yellow light, with migratory orientation under 565 nm green light serving as the control. High-frequency fields, diagnostic for a radical-pair mechanism, disrupted migratory orientation without affecting fixed-direction responses. Local anaesthesia of the upper beak where magnetite is found in birds, in contrast, disrupted the fixed-direction response without affecting migratory orientation. The two types of responses are thus based on different physical principles, with the compass response based on a radical pair mechanism and the fixed-direction responses probably originating in magnetite-based receptors in the upper beak. Directional input from these receptors seems to affect the behavior only when the regular inclination compass does not work properly. Evolutionary considerations suggest that magnetite-based receptors may represent an ancient mechanism that, in birds, has been replaced by the modern inclination compass based on radical-pair processes now used for directional orientation. PMID:19404459

Muon pair production at 52 GeV le radical s le 57 GeV using the AMY Detector at TRISTAN

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bacala, A.M.

1989-01-01

The reaction e{sup +}e{sup {minus}} {yields} {mu}{sup +}{mu}{sup {minus}} has been observed by the AMY Detector at 52 GeV {le} {radical}s {le} 57 GeV at the TRISTAN storage ring in Tsukuba, Japan. With an integrated luminosity of 18.6 pb{sup {minus}1}, this presents a new test of the standard model of the electroweak interactions in this previously unexplored energy region. The forward-backward charge asymmetry and the cross-section calculated at the various energies show agreement with the standard model predictions. The products of the vector and the axial-vector coupling constants of the electron and muon extracted from these measurements are also consistentmore » with theory. The data were combined at the average energy of {radical}s = 55.2 GeV. The measured asymmetry and cross-section are -34.4 {+-} 7.7% and 29.7 {+-} 2.1 pb respectively. This is in agreement with the standard model prediction of -28.3% for the asymmetry and 29.5 pb for the cross-section. The product of the axial couplings, g{sup e}{sub A}g{sup {mu}}{sub A} = 0.29 {+-} 0.07, and the product of the vector couplings, g{sup e}{sub V}g{sup {mu}}{sub V} = 0.01 {+-} 0.06, agree with the standard model predictions of 0.25 and .002 for these respective constants.« less

Synergies Between Quantum Mechanics and Machine Learning in Reaction Prediction.

PubMed

Sadowski, Peter; Fooshee, David; Subrahmanya, Niranjan; Baldi, Pierre

2016-11-28

Machine learning (ML) and quantum mechanical (QM) methods can be used in two-way synergy to build chemical reaction expert systems. The proposed ML approach identifies electron sources and sinks among reactants and then ranks all source-sink pairs. This addresses a bottleneck of QM calculations by providing a prioritized list of mechanistic reaction steps. QM modeling can then be used to compute the transition states and activation energies of the top-ranked reactions, providing additional or improved examples of ranked source-sink pairs. Retraining the ML model closes the loop, producing more accurate predictions from a larger training set. The approach is demonstrated in detail using a small set of organic radical reactions.

Effects of Preferential Solvation Revealed by Time-Resolved Magnetic Field Effects

PubMed Central

2017-01-01

External magnetic fields can impact recombination yields of photoinduced electron transfer reactions by affecting the spin dynamics in transient, spin-correlated radical pair intermediates. For exciplex-forming donor–acceptor systems, this magnetic field effect (MFE) can be investigated sensitively by studying the delayed recombination fluorescence. Here, we investigate the effect of preferential solvation in microheterogeneous solvent mixtures on the radical pair dynamics of the system 9,10-dimethylanthracene (fluorophore)/N,N-dimethylaniline (quencher) by means of time-resolved magnetic field effect (TR-MFE) measurements, wherein the exciplex emission is recorded in the absence and the presence of an external magnetic field using time-correlated single photon counting (TCSPC). In microheterogeneous environments, the MFE of the exciplex emission occurs on a faster time scale than in iso-dielectric homogeneous solvents. In addition, the local polarity reported by the exciplex is enhanced compared to homogeneous solvent mixtures of the same macroscopic permittivity. Detailed analyses of the TR-MFE reveal that the quenching reaction directly yielding the radical ion pair is favored in microheterogeneous environments. This is in stark contrast to homogeneous media, for which the MFE predominantly involves direct formation of the exciplex, its subsequent dissociation to the magneto-sensitive radical pair, and re-encounters. These observations provide evidence for polar microdomains and enhanced caging, which are shown to have a significant impact on the reaction dynamics in microheterogeneous binary solvents. PMID:28263599

Effects of Preferential Solvation Revealed by Time-Resolved Magnetic Field Effects.

PubMed

Pham, Van Thi Bich; Hoang, Hao Minh; Grampp, Günter; Kattnig, Daniel R

2017-03-30

External magnetic fields can impact recombination yields of photoinduced electron transfer reactions by affecting the spin dynamics in transient, spin-correlated radical pair intermediates. For exciplex-forming donor-acceptor systems, this magnetic field effect (MFE) can be investigated sensitively by studying the delayed recombination fluorescence. Here, we investigate the effect of preferential solvation in microheterogeneous solvent mixtures on the radical pair dynamics of the system 9,10-dimethylanthracene (fluorophore)/N,N-dimethylaniline (quencher) by means of time-resolved magnetic field effect (TR-MFE) measurements, wherein the exciplex emission is recorded in the absence and the presence of an external magnetic field using time-correlated single photon counting (TCSPC). In microheterogeneous environments, the MFE of the exciplex emission occurs on a faster time scale than in iso-dielectric homogeneous solvents. In addition, the local polarity reported by the exciplex is enhanced compared to homogeneous solvent mixtures of the same macroscopic permittivity. Detailed analyses of the TR-MFE reveal that the quenching reaction directly yielding the radical ion pair is favored in microheterogeneous environments. This is in stark contrast to homogeneous media, for which the MFE predominantly involves direct formation of the exciplex, its subsequent dissociation to the magneto-sensitive radical pair, and re-encounters. These observations provide evidence for polar microdomains and enhanced caging, which are shown to have a significant impact on the reaction dynamics in microheterogeneous binary solvents.

Capturing the radical ion-pair intermediate in DNA guanine oxidation

PubMed Central

Jie, Jialong; Liu, Kunhui; Wu, Lidan; Zhao, Hongmei; Song, Di; Su, Hongmei

2017-01-01

Although the radical ion pair has been frequently invoked as a key intermediate in DNA oxidative damage reactions and photoinduced electron transfer processes, the unambiguous detection and characterization of this species remain formidable and unresolved due to its extremely unstable nature and low concentration. We use the strategy that, at cryogenic temperatures, the transient species could be sufficiently stabilized to be detectable spectroscopically. By coupling the two techniques (the cryogenic stabilization and the time-resolved laser flash photolysis spectroscopy) together, we are able to capture the ion-pair transient G+•⋯Cl− in the chlorine radical–initiated DNA guanine (G) oxidation reaction, and provide direct evidence to ascertain the intricate type of addition/charge separation mechanism underlying guanine oxidation. The unique spectral signature of the radical ion-pair G+•⋯Cl− is identified, revealing a markedly intense absorption feature peaking at 570 nm that is distinctive from G+• alone. Moreover, the ion-pair spectrum is found to be highly sensitive to the protonation equilibria within guanine-cytosine base pair (G:C), which splits into two resolved bands at 480 and 610 nm as the acidic proton transfers along the central hydrogen bond from G+• to C. We thus use this exquisite sensitivity to track the intrabase-pair proton transfer dynamics in the double-stranded DNA oligonucleotides, which is of critical importance for the description of the proton-coupled charge transfer mechanisms in DNA. PMID:28630924

New Possibilities for Magnetic Control of Chemical and Biochemical Reactions.

PubMed

Buchachenko, Anatoly; Lawler, Ronald G

2017-04-18

Chemistry is controlled by Coulomb energy; magnetic energy is lower by many orders of magnitude and may be confidently ignored in the energy balance of chemical reactions. The situation becomes less clear, however, when reaction rates are considered. In this case, magnetic perturbations of nearly degenerate energy surface crossings may produce observable, and sometimes even dramatic, effects on reactions rates, product yields, and spectroscopic transitions. A case in point that has been studied for nearly five decades is electron spin-selective chemistry via the intermediacy of radical pairs. Magnetic fields, external (permanent or oscillating) and the internal magnetic fields of magnetic nuclei, have been shown to overcome electron spin selection rules for pairs of reactive paramagnetic intermediates, catalyzing or inhibiting chemical reaction pathways. The accelerating effects of magnetic stimulation may therefore be considered to be magnetic catalysis. This type of catalysis is most commonly observed for reactions of a relatively long-lived radical pair containing two weakly interacting electron spins formed by dissociation of molecules or by electron transfer. The pair may exist in singlet (total electron spin is zero) or triplet (total spin is unity) spin states. In virtually all cases, only the singlet state yields stable reaction products. Magnetic interactions with nuclear spins or applied fields may therefore affect the reactivity of radical pairs by changing the angular momentum of the pairs. Magnetic catalysis, first detected via its effect on spin state populations in nuclear and electron spin resonance, has been shown to function in a great variety of well-characterized reactions of organic free radicals. Considerably less well studied are examples suggesting that the basic mechanism may also explain magnetic effects that stimulate ATP synthesis, eliminating ATP deficiency in cardiac diseases, control cell proliferation, killing cancer cells, and control transcranial magnetic stimulation against cognitive deceases. Magnetic control has also been observed for some processes of importance in materials science and earth and environmental science and may play a role in animal navigation. In this Account, the radical pair mechanism is applied as a consistent explanation for several intriguing new magnetic phenomena. Specific examples include acceleration of solid state reactions of silicon by the magnetic isotope 29 Si, enrichment of 17 O during thermal decomposition of metal carbonates and magnetic effects on crystal plasticity. In each of these cases, the results are consistent with an initial one-electron transfer to generate a radical pair. Similar processes can account for mass-independent fractionation of isotopes of mercury, sulfur, germanium, tin, iron, and uranium in both naturally occurring samples and laboratory experiments. In the area of biochemistry, catalysis by magnetic isotopes has now been reported in several reactions of DNA and high energy phosphate. Possible medical applications of these observations are pointed out.

Hyperfine interaction mechanism of magnetic field effects in sequential fluorophore and exciplex fluorescence.

PubMed

Dodin, Dmitry V; Ivanov, Anatoly I; Burshtein, Anatoly I

2013-03-28

The magnetic field effect on the fluorescence of the photoexcited electron acceptor, (1)A∗, and the exciplex, (1)[D(+δ)A(-δ)] formed at contact of (1)A∗ with an electron donor (1)D, is theoretically explored in the framework of Integral Encounter Theory. It is assumed that the excited fluorophore is equilibrated with the exciplex that reversibly dissociates into the radical-ion pair. The magnetic field sensitive stage is the spin conversion in the resulting geminate radical-ion pair, (1, 3)[D(+)...A(-)] that proceeds due to hyperfine interaction. We confirm our earlier conclusion (obtained with a rate description of spin conversion) that in the model with a single nucleus spin 1/2 the magnitude of the Magnetic Field Effect (MFE) also vanishes in the opposite limits of low and high dielectric permittivity of the solvent. Moreover, it is shown that MFE being positive at small hyperfine interaction A, first increases with A but approaching the maximum starts to decrease and even changes the sign.

Identification of Ion-Pair Structures in Solution by Vibrational Stark Effects.

PubMed

Hack, John; Grills, David C; Miller, John R; Mani, Tomoyasu

2016-02-18

Ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N) infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.

Magnetic field effects in proteins

NASA Astrophysics Data System (ADS)

Jones, Alex R.

2016-06-01

Many animals can sense the geomagnetic field, which appears to aid in behaviours such as migration. The influence of man-made magnetic fields on biology, however, is potentially more sinister, with adverse health effects being claimed from exposure to fields from mobile phones or high voltage power lines. Do these phenomena have a common, biophysical origin, and is it even plausible that such weak fields can profoundly impact noisy biological systems? Radical pair intermediates are widespread in protein reaction mechanisms, and the radical pair mechanism has risen to prominence as perhaps the most plausible means by which even very weak fields might impact biology. In this New Views article, I will discuss the literature over the past 40 years that has investigated the topic of magnetic field effects in proteins. The lack of reproducible results has cast a shadow over the area. However, magnetic field and spin effects have proven to be useful mechanistic tools for radical mechanism in biology. Moreover, if a magnetic effect on a radical pair mechanism in a protein were to influence a biological system, the conditions necessary for it to do so appear increasing unlikely to have come about by chance.

Photoreaction of thioxanthone with indolic and phenolic derivatives of biological relevance: magnetic field effect study.

PubMed

Das, Doyel; Nath, Deb Narayan

2008-11-20

The photoinduced reaction of thioxanthone (TX) with various indolic and phenolic derivatives and amino acids like tryptophan and tyrosine has been monitored in sodium dodecyl sulfate micellar medium. Laser flash photolysis and magnetic field effect (MFE) experiments have been used to study the dynamics of the radical pairs. The quenching rate constant with different quenchers in SDS micellar solution has been measured. For indoles the electron-transfer reaction has been found to be followed by proton transfer from the donor molecule, which gives rise to the TX ketyl radical. On the other hand, the electron-transfer reaction in the case of phenols is preceded with formation of a hydrogen-bonded exciplex. The extent of the MFE and magnitude of the magnetic field corresponding to one-half of the saturation value of MFE ( B 1/2) support the fact that hyperfine mechanism plays the primary role. Quenching of MFE in the presence of gadolinium ions confirms that the radical pair is located near the micellar interface. MFE study has been further extended to protein-like bovine serum albumin in micellar solution. The results indicate loss in mobililty of radical pairs in the protein surfactant complex.

Time-resolved EPR study on the photochemical reactions of benzil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mukai, Masahiro; Yamnauchi, Seigo; Hirota, Noboru

1992-04-16

TREPR and optical studies on the photochemical reactions of benzil in 2-propanol and benzene-TEA conclude that emissive signals are due to the reaction from T{sub n} produced via the S{sub n} pointing right T{sub n} intersystem crossing process. The free-pair radical-pair mechanism can account for the main features of the slow rise component of the chemically induced dynamic electron polarization signal of the ketyl radical in 2-propanol. 27 refs., 10 figs., 2 tabs.

Photochemical primary process of photo-Fries rearrangement reaction of 1-naphthyl acetate as studied by MFE probe.

PubMed

Gohdo, Masao; Takamasu, Tadashi; Wakasa, Masanobu

2011-01-14

Photo-Fries rearrangement reactions of 1-naphthyl acetate (NA) in n-hexane and in cyclohexane were studied by the magnetic field effect probe (MFE probe) under magnetic fields (B) of 0 to 7 T. Transient absorptions of the 1-naphthoxyl radical, T-T absorption of NA, and a short-lifetime intermediate (τ = 24 ns) were observed by a nanosecond laser flash photolysis technique. In n-hexane, the yield of escaped 1-naphthoxyl radicals dropped dramatically upon application of a 3 mT field, but then the yield increased with increasing B for 3 mT < B≤ 7 T. These observed MFEs can be explained by the hyperfine coupling and the Δg mechanisms through the singlet radical pair. The fact that MFEs were observed for the present photo-Fries rearrangement reaction indicates the presence of a singlet radical pair intermediate with a lifetime as long as several tens of nanoseconds.

Polarized light modulates light-dependent magnetic compass orientation in birds

PubMed Central

Muheim, Rachel; Sjöberg, Sissel; Pinzon-Rodriguez, Atticus

2016-01-01

Magnetoreception of the light-dependent magnetic compass in birds is suggested to be mediated by a radical-pair mechanism taking place in the avian retina. Biophysical models on magnetic field effects on radical pairs generally assume that the light activating the magnetoreceptor molecules is nondirectional and unpolarized, and that light absorption is isotropic. However, natural skylight enters the avian retina unidirectionally, through the cornea and the lens, and is often partially polarized. In addition, cryptochromes, the putative magnetoreceptor molecules, absorb light anisotropically, i.e., they preferentially absorb light of a specific direction and polarization, implying that the light-dependent magnetic compass is intrinsically polarization sensitive. To test putative interactions between the avian magnetic compass and polarized light, we developed a spatial orientation assay and trained zebra finches to magnetic and/or overhead polarized light cues in a four-arm “plus” maze. The birds did not use overhead polarized light near the zenith for sky compass orientation. Instead, overhead polarized light modulated light-dependent magnetic compass orientation, i.e., how the birds perceive the magnetic field. Birds were well oriented when tested with the polarized light axis aligned parallel to the magnetic field. When the polarized light axis was aligned perpendicular to the magnetic field, the birds became disoriented. These findings are the first behavioral evidence to our knowledge for a direct interaction between polarized light and the light-dependent magnetic compass in an animal. They reveal a fundamentally new property of the radical pair-based magnetoreceptor with key implications for how birds and other animals perceive the Earth’s magnetic field. PMID:26811473

Polarized light modulates light-dependent magnetic compass orientation in birds.

PubMed

Muheim, Rachel; Sjöberg, Sissel; Pinzon-Rodriguez, Atticus

2016-02-09

Magnetoreception of the light-dependent magnetic compass in birds is suggested to be mediated by a radical-pair mechanism taking place in the avian retina. Biophysical models on magnetic field effects on radical pairs generally assume that the light activating the magnetoreceptor molecules is nondirectional and unpolarized, and that light absorption is isotropic. However, natural skylight enters the avian retina unidirectionally, through the cornea and the lens, and is often partially polarized. In addition, cryptochromes, the putative magnetoreceptor molecules, absorb light anisotropically, i.e., they preferentially absorb light of a specific direction and polarization, implying that the light-dependent magnetic compass is intrinsically polarization sensitive. To test putative interactions between the avian magnetic compass and polarized light, we developed a spatial orientation assay and trained zebra finches to magnetic and/or overhead polarized light cues in a four-arm "plus" maze. The birds did not use overhead polarized light near the zenith for sky compass orientation. Instead, overhead polarized light modulated light-dependent magnetic compass orientation, i.e., how the birds perceive the magnetic field. Birds were well oriented when tested with the polarized light axis aligned parallel to the magnetic field. When the polarized light axis was aligned perpendicular to the magnetic field, the birds became disoriented. These findings are the first behavioral evidence to our knowledge for a direct interaction between polarized light and the light-dependent magnetic compass in an animal. They reveal a fundamentally new property of the radical pair-based magnetoreceptor with key implications for how birds and other animals perceive the Earth's magnetic field.

Probing a chemical compass: novel variants of low-frequency reaction yield detected magnetic resonance.

PubMed

Maeda, Kiminori; Storey, Jonathan G; Liddell, Paul A; Gust, Devens; Hore, P J; Wedge, C J; Timmel, Christiane R

2015-02-07

We present a study of a carotenoid-porphyrin-fullerene triad previously shown to function as a chemical compass: the photogenerated carotenoid-fullerene radical pair recombines at a rate sensitive to the orientation of an applied magnetic field. To characterize the system we develop a time-resolved Low-Frequency Reaction Yield Detected Magnetic Resonance (tr-LF-RYDMR) technique; the effect of varying the relative orientation of applied static and 36 MHz oscillating magnetic fields is shown to be strongly dependent on the strength of the oscillating magnetic field. RYDMR is a diagnostic test for involvement of the radical pair mechanism in the magnetic field sensitivity of reaction rates or yields, and has previously been applied in animal behavioural experiments to verify the involvement of radical-pair-based intermediates in the magnetic compass sense of migratory birds. The spectroscopic selection rules governing RYDMR are well understood at microwave frequencies for which the so-called 'high-field approximation' is valid, but at lower frequencies different models are required. For example, the breakdown of the rotating frame approximation has recently been investigated, but less attention has so far been given to orientation effects. Here we gain physical insights into the interplay of the different magnetic interactions affecting low-frequency RYDMR experiments performed in the challenging regime in which static and oscillating applied magnetic fields as well as internal electron-nuclear hyperfine interactions are of comparable magnitude. Our observations aid the interpretation of existing RYDMR-based animal behavioural studies and will inform future applications of the technique to verify and characterize further the biological receptors involved in avian magnetoreception.

Choice of Bond Dissociation Enthalpies on which to Base the Stabilization Energies of Simple Radicals: DH(R-H)is Preferred because DH(R-Me) is Perturbed by Changes in Chain Branching

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poutsma, Marvin L

2008-01-01

The relative stabilization energies of radicals, SE(R ), along the simple series methyl/ethyl/i-propyl/t-butyl are known to vary in spread and even direction dependent on which dissociation enthalpies, DH(R-X), they are based on. Using a highly electronegative X is recognized as unwise, but it is not clear whether a choice of X = Me or X = R might not be preferred over the almost universal use of R = H. The enthalpies of isomerization of C4 radical pairs that vary only in the substitution pattern at the radical center but not in carbon skeleton illustrate that R = H ismore » indeed the better choice. Comparisons in the context of recent predictive models for alkane and radical stability indicate that, while relative DH(R-H) values highlight the desired difference in substitution pattern at the radical center, relative DH(R-Me) values are perturbed by differences in skeletal branching or protobranching which are well-known to affect thermochemistry. As a result, SE(R ) values derived from relative DH(R-Me) values are consistently too small. The same pattern is illustrated for prim, sec, and tert allylic and benzylic radicals (larger SE(R )) and for the parent vinyl, phenyl, and ethynyl radicals (negative SE(R )).« less

Critical time delay of the pineal melatonin rhythm in humans due to weak electromagnetic exposure.

PubMed

Halgamuge, Malka N

2013-08-01

Electromagnetic fields (EMFs) can increase free radicals, activate the stress response and alter enzyme reactions. Intracellular signalling is mediated by free radicals and enzyme kinetics is affected by radical pair recombination rates. The magnetic field component of an external EMF can delay the "recombination rate" of free radical pairs. Magnetic fields thus increase radical life-times in biological systems. Although measured in nanoseconds, this extra time increases the potential to do more damage. Melatonin regulates the body's sleep-wake cycle or circadian rhythm. The World Health Organization (WHO) has confirmed that prolonged alterations in sleep patterns suppress the body's ability to make melatonin. Considerable cancer rates have been attributed to the reduction of melatonin production as a result of jet lag and night shift work. In this study, changes in circadian rhythm and melatonin concentration are observed due to the external perturbation of chemical reaction rates. We further analyze the pineal melatonin rhythm and investigate the critical time delay or maturation time of radical pair recombination rates, exploring the impact of the mRNA degradation rate on the critical time delay. The results show that significant melatonin interruption and changes to the circadian rhythm occur due to the perturbation of chemical reaction rates, as also reported in previous studies. The results also show the influence of the mRNA degradation rate on the circadian rhythm's critical time delay or maturation time. The results support the hypothesis that exposure to weak EMFs via melatonin disruption can adversely affect human health.

Chemical magnetoreception in birds: The radical pair mechanism

PubMed Central

Rodgers, Christopher T.; Hore, P. J.

2009-01-01

Migratory birds travel vast distances each year, finding their way by various means, including a remarkable ability to perceive the Earth's magnetic field. Although it has been known for 40 years that birds possess a magnetic compass, avian magnetoreception is poorly understood at all levels from the primary biophysical detection events, signal transduction pathways and neurophysiology, to the processing of information in the brain. It has been proposed that the primary detector is a specialized ocular photoreceptor that plays host to magnetically sensitive photochemical reactions having radical pairs as fleeting intermediates. Here, we present a physical chemist's perspective on the “radical pair mechanism” of compass magnetoreception in birds. We outline the essential chemical requirements for detecting the direction of an Earth-strength ≈50 μT magnetic field and comment on the likelihood that these might be satisfied in a biologically plausible receptor. Our survey concludes with a discussion of cryptochrome, the photoactive protein that has been put forward as the magnetoreceptor molecule. PMID:19129499

Damage mechanism of hydroxyl radicals toward adenine—thymine base pair

NASA Astrophysics Data System (ADS)

Tan, Rong-Ri; Wang, Dong-Qi; Zhang, Feng-Shou

2014-02-01

The adenine—thymine base pair was studied in the presence of hydroxyl radicals in order to probe the hydrogen bond effect. The results show that the hydrogen bonds have little effect on the hydroxylation and dehydrogenation happened at the sites, which are not involved in a hydrogen bond, while at the sites involved in hydrogen bond formation in the base pair, the reaction becomes more difficult, both in view of the free energy barrier and the exothermicity. With a 6-311++G(d,p) level of description, both B3LYP and MP2 methods confirm that the C8 site of isolated adenine has the highest possibility to form covalent bond with the hydroxyl radicals, though with different energetics: B3LYP predicts a barrierless pathway, while MP2 finds a transition state with an energy of 106.1 kJ/mol. For the dehydrogenation reactions, B3LYP method predicts that the free energy barrier increases in the order of HN9 < HN61 < HN62 < H2 < H8.

Excimers from stable and persistent supramolecular radical-pairs in red/NIR-emitting organic nanoparticles and polymeric films.

PubMed

Blasi, Davide; Nikolaidou, Domna M; Terenziani, Francesca; Ratera, Imma; Veciana, Jaume

2017-03-29

In this work, the luminescence properties of new materials based on open-shell molecular systems are studied. In particular, we prepared polymeric films and organic nanoparticles (ONPs) doped with triphenylmethyl radical molecules. ONPs exhibit a uniform size distribution, spherical morphology and high colloidal stability. The emission spectrum of low-doped ONP suspensions and low-doped films is very similar to the emission spectrum of TTM in solution, while the luminescence lifetime and the luminescence quantum yield (LQY) are highly increased. Increasing the radical doping leads to a progressive decrease of the LQY and the appearance of a new broad excimeric band at longer wavelengths, both for ONPs and films. Thus, not only the luminescence properties were improved, but also the formation of excimers from stable and persistent supramolecular radical-pairs was observed for the first time. The good stability and luminescence properties with emission in the red-NIR region (650-800 nm), together with the open-shell nature of the emitter, make these free-radical excimer-forming materials promising candidates for optoelectronic and bioimaging applications.

An ESR protocol based on relaxation phenomena of irradiated Japanese pepper

NASA Astrophysics Data System (ADS)

Ukai, Mitsuko; Nakamura, Hideo; Shimoyama, Yuhei

2006-03-01

We found various free radicals in a commercially available pepper in Japan before and after irradiation using electron spin resonance (ESR) spectroscopy. The typical ESR spectrum of the pepper consists of a sextet centered at g = 2.0, a singlet at the same g-value and a singlet at g = 4.0. Upon gamma ray irradiation, a new pair of signals appeared in the pepper. The progressive saturation behavior (PSB) at various microwave power levels indicated quite different relaxation behaviors of those radicals. Namely, the peak intensity of the organic free radical component decreases in a monotonic fashion, whereas the Mn 2+ and Fe 3+ ESR signals substantially keep constant. This reflects the evidence of three independent radicals in the pepper before irradiation. The PSB of the pair peaks as induced by irradiation possessed quite different PSB from that of the free radical located at g = 2.0. We proposed a new protocol for the ESR detection of irradiated foods by the PSB method at different microwave power levels. This would call for a major modification of the CEN protocol in European Union.

Photoinduced Reactions of Benzophenone in Biaxially Oriented Polypropylene.

PubMed

Levin, Peter P; Efremkin, Alexei F; Krivandin, Aleksey V; Lomakin, Sergei M; Shatalova, Olga V; Khudyakov, Igor V

2018-05-03

The photoinduced reactions of benzophenone (B) in biaxially oriented polypropylene (BOPP) were studied with nanosecond laser photolysis (N 2 laser, λ337.1 nm). The first observed transient was a triplet state 3 B*. Decay of 3 B* led to formation of a radical pair (RP) of BH • and R • , where R • is a radical formed by hydrogen abstraction from BOPP (RH) by 3 B*. We studied BOPP after the preheating for a short time in a temperature range 298-423 K, which is essentially lower than its melting point of 453 K. All measurements with not-heated and with preheated (annealed) BOPP were made at 298 K. A radical pair (RP) apparently decays as a contact pair 3 [BH • , R • ] in nonheated BOPP. A critical phenomenon takes place: dissociation of RP with a formation of free radicals in the polymer bulk is observed at preheating temperature T crit ≈ 403 K and at a higher T. The physical process of heating and cooling of BOPP apparently resulted in the restructuring of crystallites, their agglomeration, shrinking of the distribution of crystallites according to their sizes in BOPP. Overall BOPP becomes softer which manifests itself in the radical kinetics. The decay kinetics of 3 B* and RP in the cage fits well the first-order law. Rate constants were obtained. Radicals BH • , which exit into the polymer bulk at temperatures of preheating T ≥ 403 K, decay by cross-termination according to the second-order law. A relatively high rate constant ∼10 8 M -1 ·s -1 for this reaction was obtained due to diffusion of BH • enclosed in the soft amorphous phase of BOPP. Properties of BOPP containing B were studied with ESR, DSC, IR, and WAXD.

Picosecond Control of Photogenerated Radical Pair Lifetimes Using a Stable Third Radical.

PubMed

Horwitz, Noah E; Phelan, Brian T; Nelson, Jordan N; Krzyaniak, Matthew D; Wasielewski, Michael R

2016-05-12

Photoinduced electron transfer reactions in organic donor-acceptor systems leading to long-lived radical ion pairs (RPs) have attracted broad interest for their potential applications in fields as diverse as solar energy conversion and spintronics. We present the photophysics and spin dynamics of an electron donor - electron acceptor - stable radical system consisting of a meta-phenylenediamine (mPD) donor covalently linked to a 4-aminonaphthalene-1,8-dicarboximide (ANI) electron-accepting chromophore as well as an α,γ-bisdiphenylene-β-phenylallyl (BDPA) stable radical. Selective photoexcitation of ANI produces the BDPA-mPD(+•)-ANI(-•) triradical in which the mPD(+•)-ANI(-•) RP spins are strongly exchange coupled. The presence of BDPA is found to greatly increase the RP intersystem crossing rate from the initially photogenerated BDPA-(1)(mPD(+•)-ANI(-•)) to BDPA-(3)(mPD(+•)-ANI(-•)), resulting in accelerated RP recombination via the triplet channel to produce BDPA-mPD-(3*)ANI as compared to a reference molecule lacking the BDPA radical. The RP recombination rates observed are much faster than those previously reported for weakly coupled triradical systems. Time-resolved EPR spectroscopy shows that this process is also associated with strong spin polarization of the stable radical. Overall, these results show that RP intersystem crossing rates can be strongly influenced by stable radicals nearby strongly coupled RP systems, making it possible to use a third spin to control RP lifetimes down to a picosecond time scale.

Estimates of electronic coupling for excess electron transfer in DNA

NASA Astrophysics Data System (ADS)

Voityuk, Alexander A.

2005-07-01

Electronic coupling Vda is one of the key parameters that determine the rate of charge transfer through DNA. While there have been several computational studies of Vda for hole transfer, estimates of electronic couplings for excess electron transfer (ET) in DNA remain unavailable. In the paper, an efficient strategy is established for calculating the ET matrix elements between base pairs in a π stack. Two approaches are considered. First, we employ the diabatic-state (DS) method in which donor and acceptor are represented with radical anions of the canonical base pairs adenine-thymine (AT) and guanine-cytosine (GC). In this approach, similar values of Vda are obtained with the standard 6-31G* and extended 6-31++G** basis sets. Second, the electronic couplings are derived from lowest unoccupied molecular orbitals (LUMOs) of neutral systems by using the generalized Mulliken-Hush or fragment charge methods. Because the radical-anion states of AT and GC are well reproduced by LUMOs of the neutral base pairs calculated without diffuse functions, the estimated values of Vda are in good agreement with the couplings obtained for radical-anion states using the DS method. However, when the calculation of a neutral stack is carried out with diffuse functions, LUMOs of the system exhibit the dipole-bound character and cannot be used for estimating electronic couplings. Our calculations suggest that the ET matrix elements Vda for models containing intrastrand thymine and cytosine bases are essentially larger than the couplings in complexes with interstrand pyrimidine bases. The matrix elements for excess electron transfer are found to be considerably smaller than the corresponding values for hole transfer and to be very responsive to structural changes in a DNA stack.

Biophysics of Magnetic Orientation: Radical Pairs, Biogenic Magnetite, or both?

NASA Astrophysics Data System (ADS)

Kirschvink, Joe

2011-03-01

Two major biophysical mechanisms for magnetoreception in terrestrial animals, one based on biogenic magnetite and another on radical-pair biochemical reactions, have been the subject of experiment and debate for the past 30 years. The magnetite hypothesis has stood the test of time: biogenic magnetite is synthesized biochemically in Bacteria, Protists, and numerous Animal phyla, as well as in some plants. Chains of single-domain crystals have been detected by clean-lab based SQUID magnetometry in animal tissues in all major phyla, followed by high-resolution TEM in selected model organisms, as well as by electrophysiological studies demonstrating the role of the ophthalmic branch of the trigeminal nerve in the magnetoreceptive process. Pulse-remagnetization - configured to uniquely flip the polarity of single-domain ferromagnets - has dramatic effects on the behavior of many birds, honeybees, mole rats, turtles, and bats, to cite a growing list. Magnetite-containing cells in the vicinity of these neurons in fish are now the subject of intense study by our consortium. The existence of a specialized class of magnetite-containing magnetoreceptor cells in animal tissues is no longer controversial. In contrast, less success has been achieved in gaining experimental support across a range of taxa for the radical-pair hypothesis. Although this mechanism was proposed to explain an early observation that birds would not respond to complete inversion of the magnetic vector, many organisms (even some birds) do indeed respond to the field polarity. We also note that few, if any, of these critical experiments have been done using fully double-blind methods. This is joint work with: M. M. Walker (University of Auckland, New Zealand) and M. Winklhofer (LMU Munich, Germany).

Identification of ion-pair structures in solution by vibrational stark effects

DOE PAGES

Hack, John; Mani, Tomoyasu; Grills, David C.; ...

2016-01-25

Here, ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N)more » infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.« less

Identification of ion-pair structures in solution by vibrational stark effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hack, John; Mani, Tomoyasu; Grills, David C.

Here, ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N)more » infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.« less

The Physics of Data: Can your degree in condensed matter theory get you a job at Google?

NASA Astrophysics Data System (ADS)

Byers, Jeff M.

2015-03-01

Migratory birds travel spectacular distances, navigating and orienting by a variety of means, most of which are poorly understood. Among them is a remarkable ability to perceive the intensity and direction of the Earth's magnetic field. Biologically credible mechanisms for the sensing of such weak fields (25-65 microtesla) are scarce and in recent years just two proposals have emerged as frontrunners. One involves biogenic iron-containing nanoparticles; the other relies on the magnetic sensitivity of short-lived photochemical intermediates known as radical pairs. The latter began to attract attention following the proposal 15 years ago that the necessary physics and chemistry could take place in the bird's retina in specialised photoactive proteins called cryptochromes. The coherent dynamics of the electron-nuclear spin systems of pairs of photo-induced radicals is conjectured to form the basis of the sensing mechanism even though the interaction of an electron spin with the geomagnetic field is six orders of magnitude smaller than the thermal energy. The possibility that slowing decohering, entangled electron spins could form the basis of an important sensory mechanism has qualified radical pair magnetoreception for a place under the umbrella of ``Quantum Biology.'' In this talk, I will introduce the radical pair mechanism, comment on the roles of entanglement and quantum coherence, outline some of the experimental evidence for the cryptochrome hypothesis, and summarize what still needs to be done to determine whether birds (and maybe other animals) really do use a chemical compass to find their way around.

Controlling the orientation of spin-correlated radical pairs by covalent linkage to nanoporous anodic aluminum oxide membranes.

PubMed

Chen, Hsiao-Fan; Gardner, Daniel M; Carmieli, Raanan; Wasielewski, Michael R

2013-10-07

Ordered multi-spin assemblies are required for developing solid-state molecule-based spintronics. A linear donor-chromophore-acceptor (D-C-A) molecule was covalently attached inside the 150 nm diam. nanopores of an anodic aluminum oxide (AAO) membrane. Photoexcitation of D-C-A in a 343 mT magnetic field results in sub-nanosecond, two-step electron transfer to yield the spin-correlated radical ion pair (SCRP) (1)(D(+)˙-C-A(-)˙), which then undergoes radical pair intersystem crossing (RP-ISC) to yield (3)(D(+)˙-C-A(-)˙). RP-ISC results in S-T0 mixing to selectively populate the coherent superposition states |S'> and |T'>. Microwave-induced transitions between these states and the unpopulated |T(+1)> and |T(-1)> states result in spin-polarized time-resolved EPR (TREPR) spectra. The dependence of the electron spin polarization (ESP) phase of the TREPR spectra on the orientation of the AAO membrane pores relative to the externally applied magnetic field is used to determine the overall orientation of the SCRPs within the pores at room temperature.

Transient Kinetics and Quantum Yield Studies of Nanocrystalline α-Phenyl-Substituted Ketones: Sorting Out Reactions from Singlet and Triplet Excited States.

PubMed

Park, Jin H; Chung, Tim S; Hipwell, Vince M; Rivera, Edris A; Garcia-Garibay, Miguel A

2018-06-11

Recent work has shown that diarylmethyl radicals generated by pulsed laser excitation in nanocrystalline (NC) suspensions of tetraarylacetones constitute a valuable probe for the detailed mechanistic analysis of the solid-state photodecarbonylation reaction. Using a combination of reaction quantum yields and laser flash photolysis in nanocrystalline suspensions of ketones with different substituents on one of the α-carbons we are able to suggest with confidence that a significant fraction of the initial α-cleavage reaction takes place from the ketone singlet excited state, that the originally formed diarylmethyl-acyl radical pair loses CO in the crystal with time constants in the sub-nanosecond regime, and that the secondary bis(diarylmethyl) triplet radical pair has a lifetime limited by the rate of intersystem crossing of ca. 70 ns.

Ab initio molecular dynamics of the reactivity of vitamin C toward hydroxyl and HO₂/O⁻₂ radicals.

PubMed

Lespade, Laure

2017-11-21

Vitamin C is one of the most abundant exogenous antioxidants in the cell, and it is of the utmost importance to elucidate its mechanism of action against radicals. In this study, the reactivity of vitamin C toward OH and [Formula: see text] radicals in aqueous medium was analyzed by ab initio molecular dynamics using CPMD code. The simulations led to results similar to those of static studies or experiments for the pair of [Formula: see text] radicals but bring new insights for the reactivity with hydroxyl radical: the reaction takes place before the formation of an adduct and consists of two steps: first an electron is transferred to hydroxyl radical and then the ascorbyl radical loses a proton. Graphical Abstract Reactivity of vitamin C toward hydroxyl and [Formula: see text] radicals.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abazov, V.M.; /Dubna, JINR; Abbott, B.

A search is performed for the standard model Higgs boson in 5.2 fb{sup -1} of p{bar p} collisions at {radical}s = 1.96 TeV, collected with the D0 detector at the Fermilab Tevatron Collider. The final state considered is a pair of b jets and large missing transverse energy, as expected from p{bar p} {yields} ZH {yields} {nu}{bar {nu}}b{bar b} production. The search is also sensitive to the WH {yields} {ell}{nu}b{bar b} channel when the charged lepton is not identified. For a Higgs boson mass of 115 GeV, a limit is set at the 95% C.L. on the cross section multipliedmore » by branching fraction for (p{bar p} {yields} (Z/W)H) x (H {yields} b{bar b}) that is a factor of 3.7 larger than the standard model value, consistent with the factor of 4.6 expected.« less

Following radical pair reactions in solution: a step change in sensitivity using cavity ring-down detection.

PubMed

Maeda, Kiminori; Neil, Simon R T; Henbest, Kevin B; Weber, Stefan; Schleicher, Erik; Hore, P J; Mackenzie, Stuart R; Timmel, Christiane R

2011-11-09

The study of radical pair intermediates in biological systems has been hampered by the low sensitivity of the optical techniques usually employed to investigate these highly reactive species. Understanding the physical principles governing the spin-selective and magneto-sensitive yields and kinetics of their reactions is essential in identifying the mechanism governing bird migration, and might have significance in the discussion of potential health hazards of electromagnetic radiation. Here, we demonstrate the powerful capabilities of optical cavity-enhanced techniques, such as cavity ring-down spectroscopy (CRDS) in monitoring radical recombination reactions and associated magnetic field effects (MFEs). These include submicrosecond time-resolution, high sensitivity (baseline noise on the order of 10(-6) absorbance units) and small (μL) sample volumes. Combined, we show that these represent significant advantages over the single-pass flash-photolysis techniques conventionally applied. The studies described here focus on photoinduced radical pair reactions involving the protein lysozyme and one of two possible photosensitizers: anthraquinone-2,6-disulphonate and flavin mononucleotide. CRDS-measured MFEs are observed in pump-probe experiments and discussed in terms of the sensitivity gains and sample-volume minimization afforded by CRDS when compared with flash photolysis methods. Finally, CRDS is applied to an in vitro MFE study of intramolecular electron transfer in the DNA-repair enzyme, Escherichia coli photolyase, a protein closely related to cryptochrome which has been proposed to mediate animal magnetoreception.

Why magnetic and electromagnetic effects in biology are irreproducible and contradictory?

PubMed

Buchachenko, Anatoly

2016-01-01

The main source of magnetic and electromagnetic effects in biological systems is now generally accepted and demonstrated in this paper to be radical pair mechanism which implies pairwise generation of radicals in biochemical reactions. This mechanism was convincingly established for enzymatic adenosine triphosphate (ATP) and desoxynucleic acid (DNA) synthesis by using catalyzing metal ions with magnetic nuclei ((25)Mg, (43)Ca, (67)Zn) and supported by magnetic field effects on these reactions. The mechanism, is shown to function in medicine as a medical remedy or technology (trans-cranial magnetic stimulation, nuclear magnetic control of the ATP synthesis in heart muscle, the killing of cancer cells by suppression of DNA synthesis). However, the majority of magnetic effects in biology remain to be irreproducible, contradictory, and enigmatic. Three sources of such a state are shown in this paper to be: the presence of paramagnetic metal ions as a component of enzymatic site or as an impurity in an uncontrollable amount; the property of the radical pair mechanism to function at a rather high concentration of catalyzing metal ions, when at least two ions enter into the catalytic site; and the kinetic restrictions, which imply compatibility of chemical and spin dynamics in radical pair. It is important to keep in mind these factors to properly understand and predict magnetic effects in magneto-biology and biology itself and deliberately use them in medicine. © 2015 Wiley Periodicals, Inc.

Toward a radically embodied neuroscience of attachment and relationships.

PubMed

Beckes, Lane; IJzerman, Hans; Tops, Mattie

2015-01-01

Attachment theory (Bowlby, 1969/1982) posits the existence of internal working models as a foundational feature of human bonds. Radical embodied approaches instead suggest that cognition requires no computation or representation, favoring a cognition situated in a body in an environmental context with affordances for action (Chemero, 2009; Barrett, 2011; Wilson and Golonka, 2013; Casasanto and Lupyan, 2015). We explore whether embodied approaches to social soothing, interpersonal warmth, separation distress, and support seeking could replace representational constructs such as internal working models with a view of relationship cognition anchored in the resources afforded to the individual by their brain, body, and environment in interaction. We review the neurobiological bases for social attachments and relationships and attempt to delineate how these systems overlap or don't with more basic physiological systems in ways that support or contradict a radical embodied explanation. We suggest that many effects might be the result of the fact that relationship cognition depends on and emerges out of the action of neural systems that regulate several clearly physically grounded systems. For example, the neuropeptide oxytocin appears to be central to attachment and pair-bond behavior (Carter and Keverne, 2002) and is implicated in social thermoregulation more broadly, being necessary for maintaining a warm body temperature (for a review, see IJzerman et al., 2015b). Finally, we discuss the most challenging issues around taking a radically embodied perspective on social relationships. We find the most crucial challenge in individual differences in support seeking and responses to social contact, which have long been thought to be a function of representational structures in the mind (e.g., Baldwin, 1995). Together we entertain the thought to explain such individual differences without mediating representations or computations, but in the end propose a hybrid model of radical embodiment and internal representations.

Toward a radically embodied neuroscience of attachment and relationships

PubMed Central

Beckes, Lane; IJzerman, Hans; Tops, Mattie

2015-01-01

Attachment theory (Bowlby, 1969/1982) posits the existence of internal working models as a foundational feature of human bonds. Radical embodied approaches instead suggest that cognition requires no computation or representation, favoring a cognition situated in a body in an environmental context with affordances for action (Chemero, 2009; Barrett, 2011; Wilson and Golonka, 2013; Casasanto and Lupyan, 2015). We explore whether embodied approaches to social soothing, interpersonal warmth, separation distress, and support seeking could replace representational constructs such as internal working models with a view of relationship cognition anchored in the resources afforded to the individual by their brain, body, and environment in interaction. We review the neurobiological bases for social attachments and relationships and attempt to delineate how these systems overlap or don’t with more basic physiological systems in ways that support or contradict a radical embodied explanation. We suggest that many effects might be the result of the fact that relationship cognition depends on and emerges out of the action of neural systems that regulate several clearly physically grounded systems. For example, the neuropeptide oxytocin appears to be central to attachment and pair-bond behavior (Carter and Keverne, 2002) and is implicated in social thermoregulation more broadly, being necessary for maintaining a warm body temperature (for a review, see IJzerman et al., 2015b). Finally, we discuss the most challenging issues around taking a radically embodied perspective on social relationships. We find the most crucial challenge in individual differences in support seeking and responses to social contact, which have long been thought to be a function of representational structures in the mind (e.g., Baldwin, 1995). Together we entertain the thought to explain such individual differences without mediating representations or computations, but in the end propose a hybrid model of radical embodiment and internal representations. PMID:26052276

Spin-enhanced organic bulk heterojunction photovoltaic solar cells.

PubMed

Zhang, Ye; Basel, Tek P; Gautam, Bhoj R; Yang, Xiaomei; Mascaro, Debra J; Liu, Feng; Vardeny, Z Valy

2012-01-01

Recently, much effort has been devoted to improve the efficiency of organic photovoltaic solar cells based on blends of donors and acceptors molecules in bulk heterojunction architecture. One of the major losses in organic photovoltaic devices has been recombination of polaron pairs at the donor-acceptor domain interfaces. Here, we present a novel method to suppress polaron pair recombination at the donor-acceptor domain interfaces and thus improve the organic photovoltaic solar cell efficiency, by doping the device active layer with spin 1/2 radical galvinoxyl. At an optimal doping level of 3 wt%, the efficiency of a standard poly(3-hexylthiophene)/1-(3-(methoxycarbonyl)propyl)-1-1-phenyl)(6,6)C(61) solar cell improves by 18%. A spin-flip mechanism is proposed and supported by magneto-photocurrent measurements, as well as by density functional theory calculations in which polaron pair recombination rate is suppressed by resonant exchange interaction between the spin 1/2 radicals and charged acceptors, which convert the polaron pair spin state from singlet to triplet.

Randomly distilling W-class states into general configurations of two-party entanglement

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cui, W.; Chitambar, E.; Lo, H. K.

2011-11-15

In this article we obtain results for the task of converting a single N-qubit W-class state (of the form {radical}(x{sub 0})|00...0>+{radical}(x{sub 1})|10...0>+{center_dot}{center_dot}{center_dot}+{radical}(x{sub N})|00...1>) into maximum entanglement shared between two random parties. Previous studies in random distillation have not considered how the particular choice of target pairs affects the transformation, and here we develop a strategy for distilling into general configurations of target pairs. We completely solve the problem of determining the optimal distillation probability for all three-qubit configurations and most four-qubit configurations when x{sub 0}=0. Our proof involves deriving new entanglement monotones defined on the set of four-qubit W-class states.more » As an additional application of our results, we present new upper bounds for converting a generic W-class state into the standard W state |W{sub N}>={radical}((1/N))(|10...0>+{center_dot}{center_dot}{center_dot}+|00...1>).« less

Excitation of photosystem I by 760 nm femtosecond laser pulses: transient absorption spectra and intermediates

NASA Astrophysics Data System (ADS)

Cherepanov, Dmitry A.; Shelaev, Ivan V.; Gostev, Fedor E.; Mamedov, Mahir D.; Petrova, Anastasia A.; Aybush, Arseniy V.; Shuvalov, Vladimir A.; Semenov, Alexey Yu; Nadtochenko, Victor A.

2017-09-01

Excitation of photosystem I (PS I) by a femtosecond 760 nm pump leads to one- and two-photon absorption. The one-photon excitation produces intermediates with transient absorption spectra similar to the spectra of the primary [{{{P}}700}+{{{A}}0}-{{A}}1] and secondary [{{{P}}700}+{{A}}0{{{A}}1}-] ion-radical pairs in the PS I reaction center. The two-photon absorption generates the upper level excited states of chlorophyll (Chl) and carotenoid molecules in the antenna. These excited states are converted into the long-lived intermediates and can be tentatively attributed to the excited and charge-transfer ion-radical states of Chl molecules and to the excited states of carotenoids in the antenna. The transient spectra of intermediates generated by two-photon excitation differ from the transient one-photon spectra of the primary and secondary ion-radical pairs.

Investigation of geminate recombination of radical ion pairs generated by dissociation of exciplexes in moderately polar solvents using the photoconductivity technique

NASA Astrophysics Data System (ADS)

Lukin, Leonid V.

2009-06-01

A new approach to determination of the recombination rate of radical ion pairs in moderately polar solvents is presented. It is based on an investigation of transient photocurrents caused by dissociation of exciplexes generated in photoinduced electron transfer reactions. It has been shown that the recombination rate of geminate ion pairs can be found from the photocurrent rise time. We have applied such an approach to transient photocurrents observed by Hirata et al. [Y. Hirata, Y. Kanda, N. Mataga, J. Phys. Chem. 87 (1983) 1659] for the pyrene/dicyanobenzene system in solvents of moderate polarity. The increase of the obtained recombination rate of photogenerated ions with increasing polarity of solvent testifies that ions recombine mainly by the backward electron transfer from the dicyanobenzene anions to solvent-separated cations of pyrene.

Cryptochrome Mediates Light-Dependent Magnetosensitivity of Drosophila's Circadian Clock

PubMed Central

Yoshii, Taishi; Ahmad, Margaret; Helfrich-Förster, Charlotte

2009-01-01

Since 1960, magnetic fields have been discussed as Zeitgebers for circadian clocks, but the mechanism by which clocks perceive and process magnetic information has remained unknown. Recently, the radical-pair model involving light-activated photoreceptors as magnetic field sensors has gained considerable support, and the blue-light photoreceptor cryptochrome (CRY) has been proposed as a suitable molecule to mediate such magnetosensitivity. Since CRY is expressed in the circadian clock neurons and acts as a critical photoreceptor of Drosophila's clock, we aimed to test the role of CRY in magnetosensitivity of the circadian clock. In response to light, CRY causes slowing of the clock, ultimately leading to arrhythmic behavior. We expected that in the presence of applied magnetic fields, the impact of CRY on clock rhythmicity should be altered. Furthermore, according to the radical-pair hypothesis this response should be dependent on wavelength and on the field strength applied. We tested the effect of applied static magnetic fields on the circadian clock and found that flies exposed to these fields indeed showed enhanced slowing of clock rhythms. This effect was maximal at 300 μT, and reduced at both higher and lower field strengths. Clock response to magnetic fields was present in blue light, but absent under red-light illumination, which does not activate CRY. Furthermore, cryb and cryOUT mutants did not show any response, and flies overexpressing CRY in the clock neurons exhibited an enhanced response to the field. We conclude that Drosophila's circadian clock is sensitive to magnetic fields and that this sensitivity depends on light activation of CRY and on the applied field strength, consistent with the radical pair mechanism. CRY is widespread throughout biological systems and has been suggested as receptor for magnetic compass orientation in migratory birds. The present data establish the circadian clock of Drosophila as a model system for CRY-dependent magnetic sensitivity. Furthermore, given that CRY occurs in multiple tissues of Drosophila, including those potentially implicated in fly orientation, future studies may yield insights that could be applicable to the magnetic compass of migratory birds and even to potential magnetic field effects in humans. PMID:19355790

Light effects on the multicellular magnetotactic prokaryote 'Candidatus Magnetoglobus multicellularis' are cancelled by radiofrequency fields: the involvement of radical pair mechanisms.

PubMed

de Melo, Roger Duarte; Acosta-Avalos, Daniel

2017-02-01

'Candidatus Magnetoglobus multicellularis' is the most studied multicellular magnetotactic prokaryote. It presents a light-dependent photokinesis: green light decreases the translation velocity whereas red light increases it, in comparison to blue and white light. The present article shows that radio-frequency electromagnetic fields cancel the light effect on photokinesis. The frequency to cancel the light effect corresponds to the Zeeman resonance frequency (DC magnetic field of 4 Oe and radio-frequency of 11.5 MHz), indicating the involvement of a radical pair mechanism. An analysis of the orientation angle relative to the magnetic field direction shows that radio-frequency electromagnetic fields disturb the swimming orientation when the microorganisms are illuminated with red light. The analysis also shows that at low magnetic fields (1.6 Oe) the swimming orientation angles are well scattered around the magnetic field direction, showing that magnetotaxis is not efficiently in the swimming orientation to the geomagnetic field. The results do not support cryptochrome as being the responsible chromophore for the radical pair mechanism and perhaps two different chromophores are necessary to explain the radio-frequency effects.

Reversible hydrogen transfer reactions of cysteine thiyl radicals in peptides: the conversion of cysteine into dehydroalanine and alanine, and of alanine into dehydroalanine

PubMed Central

Mozziconacci, Olivier; Kerwin, Bruce A.; Schöneich, Christian

2013-01-01

The photodissociation of disulfide bonds in model peptides containing Ala and Ala-d3 generates a series of photoproducts following the generation of a CysS• thiyl radical pair. These photoproducts include transformations of Cys to dehydroalanine (Dha) and Ala, as well as Ala to Dha. Intramolecular Michael addition of an intact Cys with a photolytically generated Dha results in the formation of cyclic thioethers. The conversion of Cys into Dha likely involves a 1,3-H-shift from the Cys αC-H bond to the thiyl radical, followed by elimination of HS•. The conversion of Dha into Ala most likely involves hydrated electrons, which are generated through the photolysis of Cys, the photoproduct of disulfide photolysis. Prior to stable product formation, CysS• radicals engage in reversible hydrogen transfer reactions with αC-H and βC-H bonds of the surrounding amino acids. Especially for the βC-H bonds of Ala such hydrogen transfer reactions are unexpected based on thermodynamic grounds; however, the replacement of deuterons in Ala-d3 by hydrogens in H2O provides strong experimental evidence for such reactions. PMID:21895001

Fractionation of mercury isotopes by photo-oxidation in aquatic systems

NASA Astrophysics Data System (ADS)

Ghosh, S.; Bergquist, B. A.; Blum, J. D.

2009-12-01

Mercury is a globally distributed pollutant that bioaccumulates in aquatic food webs, even in remote locations. The recent discovery of both large mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) has made the promise of tracing this neurotoxin through the environment by using its isotopes very exciting. So far, the only process demonstrated experimentally to produce large MIF for Hg (similar in magnitude to the MIF observed in natural samples such as fish) is photochemical reduction (Bergquist and Blum, 2007). During photo-reduction, MIF of the odd isotopes was observed with the odd isotopes (199Hg, 201Hg) being preferentially enriched in the aqueous phase. Bergquist and Blum, 2007, suggested that the cause of MIF was the magnetic isotope effect (MIE), which is purely a kinetic phenomenon involving radical pair intermediates. Radical pairs with odd isotopes, which have non-zero nuclear spin and magnetic moments, can undergo spin conversion faster than radical pairs with non-magnetic even isotopes. This allows the odd and even isotopes to be preferentially enriched in different reaction products. MIE is a complex phenomenon that is dependent on several factors including hyperfine coupling, life-time of the radical pair, coupling strength of the radical pair, spin-orbital coupling, diffusion factors, and the solvent cage (space) in which the reaction occurs. Only under rare circumstances will all the factors be suitable for the expression of MIE in natural reactions. The goal of this study was to conduct aqueous photo-oxidation reactions to investigate whether this redox pathway expresses MIF (in the form of MIE) similar to the photo-reduction pathway. In natural systems, net photo-reduction of Hg (II) species results in the release of Hg(0) vapor to the atmosphere. However this net photo-reduction is a combination of both photo-reduction and photo-oxidation. In their experiments, Bergquist and Blum 2007, only investigated the aqueous photo-reduction pathway and suppressed the photo-oxidation reaction. Photochemical oxidation experiments of Hg(0) were performed in quartz reaction chambers using natural sunlight. Solutions of aqueous Hg(0) were prepared by continuously bubbling vapor Hg(0) generated by a gas-liquid separator into the quartz reaction chamber filled with water. Experiments were conducted in the presence of Cl- and other potential oxidants such as semiquinone, hydroxyl radicals and H2O2 to assess if the presence of these different oxidants showed significant differences in the expression of Hg isotopic fractionation during the photo-oxidation process. For experiments run in the presence of Cl- only, ~2% of Hg was oxidized at the end of 7 hours whereas in the presence of both semiquinone radical and Cl- , approximately 20% of Hg was oxidized at the end of 6 hours. In the experiment with hydroxyl radicals present, ~ 7% of Hg was oxidized at the end of 6.5 hours. Another set of experiments were conducted where the net photo-reduction was mimicked, which allowed both photo-oxidation and photo-reduction to occur. Isotopic results and their implications on the redox cycle of mercury obtained from these experiments will be discussed in detail.

Semiclassical description of hyperfine interaction in calculating chemically induced dynamic nuclear polarization in weak magnetic fields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Purtov, P.A.; Salikhov, K.M.

1987-09-01

Semiclassical HFI description is applicable to calculating the integral CIDNP effect in weak fields. The HFI has been calculated for radicals with sufficiently numerous magnetically equivalent nuclei (n greater than or equal to 5) in satisfactory agreement with CIDNP calculations based on quantum-mechanical description of radical-pair spin dynamics.

Dark state population determines magnetic sensitivity in radical pair magnetoreception model.

PubMed

Xu, Bao-Ming; Zou, Jian

2016-03-01

What is the real role of the quantum coherence and entanglement in the radical pair (RP) compass, and what determines the singlet yield have not been fully understood. In this paper, we find that the dark states of the two-electron Zeeman energy operator (TEZE) play an important role in the RP compass. We respectively calculate the singlet yields for two initial states in this dark state basis: the coherent state and the same state just removing the dark state coherence. For the later there is neither dark state coherence nor entanglement in the whole dynamical process. Surprisingly we find that in both cases the singlet yields are the same, and based on this result, we believe that the dark state population determines the singlet yield completely, and the dark state coherence and entanglement have little contribution to it. Finally, we also find that the dark state population as well as the singlet yield anisotropy is fragile to the vertical magnetic noise. However, the orientation is robust and is even enhanced by the parallel magnetic noise because the dark states expand a decoherence-free subspace. The dark state population as well as the orientation is more robust to the hyperfine coupling noise.

Spin-correlated doublet pairs as intermediate states in charge separation processes

NASA Astrophysics Data System (ADS)

Kraffert, Felix; Behrends, Jan

2017-10-01

Spin-correlated charge-carrier pairs play a crucial role as intermediate states in charge separation both in natural photosynthesis as well as in solar cells. Using transient electron paramagnetic resonance (trEPR) spectroscopy in combination with spectral simulations, we study spin-correlated polaron pairs in polymer:fullerene blends as organic solar cells materials. The semi-analytical simulations presented here are based on the well-established theoretical description of spin-correlated radical pairs in biological systems, however, explicitly considering the disordered nature of polymer:fullerene blends. The large degree of disorder leads to the fact that many different relative orientations between both polarons forming the spin-correlated pairs have to be taken into account. This has important implications for the spectra, which differ significantly from those of spin-correlated radical pairs with a fixed relative orientation. We systematically study the influence of exchange and dipolar couplings on the trEPR spectra and compare the simulation results to measured X- and Q-band trEPR spectra. Our results demonstrate that assuming dipolar couplings alone does not allow us to reproduce the experimental spectra. Due to the rather delocalised nature of polarons in conjugated organic semiconductors, a significant isotropic exchange coupling needs to be included to achieve good agreement between experiments and simulations.

Reaction Mechanisms and Structural and Physicochemical Properties of Caffeic Acid Grafted Chitosan Synthesized in Ascorbic Acid and Hydroxyl Peroxide Redox System.

PubMed

Liu, Jun; Pu, Huimin; Chen, Chong; Liu, Yunpeng; Bai, Ruyu; Kan, Juan; Jin, Changhai

2018-01-10

The ascorbic acid (AA) and hydroxyl peroxide (H 2 O 2 ) redox pair induced free radical grafting reaction is a promising approach to conjugate phenolic groups with chitosan (CS). In order to reveal the exact mechanisms of the AA/H 2 O 2 redox pair induced grafting reaction, free radicals generated in the AA/H 2 O 2 redox system were compared with hydroxyl radical ( • OH) produced in the Fe 2+ /H 2 O 2 redox system. Moreover, the structural and physicochemical properties of caffeic acid grafted CS (CA-g-CS) synthesized in these two redox systems were compared. Results showed that only ascorbate radical (Asc •- ) was produced in the AA/H 2 O 2 system. The reaction between Asc •- and CS produced novel carbon-centered radicals, whereas no new free radicals were detected when • OH reacted with CS. Thin layer chromatography, UV-vis, Fourier transform infrared, and nuclear magnetic resonance spectroscopic analyses all confirmed that CA was successfully grafted onto CS through Asc •- . However, CA could be hardly grafted onto CS via • OH. CA-g-CS synthesized through Asc •- exhibited lower thermal stability and crystallinity than the reaction product obtained through • OH. For the first time, our results demonstrated that the synthesis of CA-g-CS in the AA/H 2 O 2 redox system was mediated by Asc •- rather than • OH.

Taming Radical Pairs in Nanocrystalline Ketones: Photochemical Syn-thesis of Compounds with Vicinal Stereogenic All-Carbon Quaternary Centers.

PubMed

Dotson, Jordan J; Perez-Estrada, Salvador; Garcia-Garibay, Miguel A

2018-05-29

Here we describe the use of crystalline ketones to control the fate of the radical pair intermediates generated in the Norrish type I photodecarbonylation reaction to render it a powerful tool in the challenging synthesis of sterically congested carbon-carbon bonds. This methodology makes the synthetically more accessible hexasusbtituted ketones as ideal synthons for the construction of adjacent, all-carbon substituted, stereogenic quaternary stereocenters. We describe here the structural and thermochemical parameters required of the starting ketone in order to react in the solid state. Finally, the scope and scalability of the reaction and its application in the total synthesis of two natural products is described.

Fundamental study of hydrogen-attachment-induced peptide fragmentation occurring in the gas phase and during the matrix-assisted laser desorption/ionization process.

PubMed

Asakawa, Daiki; Takahashi, Hidenori; Iwamoto, Shinichi; Tanaka, Koichi

2018-05-09

Mass spectrometry with hydrogen-radical-mediated fragmentation techniques has been used for the sequencing of proteins/peptides. The two methods, matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) and hydrogen attachment/abstraction dissociation (HAD) are known as hydrogen-radical-mediated fragmentation techniques. MALDI-ISD occurs during laser induced desorption processes, whereas HAD utilizes the association of hydrogen with peptide ions in the gas phase. In this study, the general mechanisms of MALDI-ISD and HAD of peptides were investigated. We demonstrated the fragmentation of four model peptides and investigated the fragment formation pathways using density functional theory (DFT) calculations. The current experimental and computational joint study indicated that MALDI-ISD and HAD produce aminoketyl radical intermediates, which immediately undergo radical-induced cleavage at the N-Cα bond located on the C-terminal side of the radical site, leading to the c'/z˙ fragment pair. In the case of MALDI-ISD, the z˙ fragments undergo a subsequent reaction with the matrix to give z' and matrix adducts of the z fragments. In contrast, the c' and z˙ fragments react with hydrogen atoms during the HAD processes, and various fragment species, such as c˙, c', z˙ and z', were observed in the HAD-MS/MS mass spectra.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharyya, K.; Das, P.K.

In the course of benzophenone triplet quenching by triethylamine (TEA) at high concentrations in alkaline aqueous acetonitrile, two temporally distinct processes are observed for ketyl radical anion formation. The fast component occurs on a nanosecond time scale, has kinetics sensitive to basicity and water content of the medium, and is ascribed to the deprotonation of the diphenylhydroxymethyl radical initially produced as a result of subnanosecond intra-ion-pair proton transfer. The slow process occurs on a microsecond time scale and is characterized by pseudo-first-order rate constants linearly dependent on ketone ground-state concentration; this is assigned to the one-electron reduction of the ketonemore » by the methyl(diethylamino)methyl radical (derived from TEA). Substituent effects on the kinetics of the two processes follow trends expected from those of the acidity of diarylhydroxymethyl radicals and of the behavior of diaryl ketones as oxidants. Neither of the two processes is observed with N,N-dimethylaniline (DMA) and 1,4-diazabicyclo(2.2.2)octane (DABCO) as quenchers. The electron or hydrogen transfer yields in the course of diaryl ketone triplet quenching by the three amines are all close to unity, suggesting that the back electron transfer in the triplet ion pairs is relatively unimportant.« less

Water Molecules Gating a Photoinduced One-Electron Two-Protons Transfer in a Tyrosine/Histidine (Tyr/His) Model of Photosystem II.

PubMed

Chararalambidis, Georgios; Das, Shyamal; Trapali, Adelais; Quaranta, Annamaria; Orio, Maylis; Halime, Zakaria; Fertey, Pierre; Guillot, Régis; Coutsolelos, Athanassios; Leibl, Winfried; Aukauloo, Ally; Sircoglou, Marie

2018-05-22

We investigate a biomimetic model of a Tyr Z /His 190 pair, a hydrogen-bonded phenol/imidazole covalently attached to a porphyrin sensitizer. Laser flash photolysis in the presence of an external electron acceptor reveals the need for water molecules to unlock the light-induced oxidation of the phenol through an intramolecular pathway. Kinetics monitoring encompasses two fast phases with distinct spectral properties. The first phase is related to a one-electron transfer from the phenol to the porphyrin radical cation coupled with a domino two-proton transfer leading to the ejection of a proton from the imidazole-phenol pair. The second phase concerns conveying the released proton to the porphyrin N 4 coordinating cavity. Our study provides an unprecedented example of a light-induced electron-transfer process in a Tyr Z /His 190 model of photosystem II, evidencing the movement of both the phenol and imidazole protons along an isoenergetic pathway. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical compass model of avian magnetoreception.

PubMed

Maeda, Kiminori; Henbest, Kevin B; Cintolesi, Filippo; Kuprov, Ilya; Rodgers, Christopher T; Liddell, Paul A; Gust, Devens; Timmel, Christiane R; Hore, P J

2008-05-15

Approximately 50 species, including birds, mammals, reptiles, amphibians, fish, crustaceans and insects, are known to use the Earth's magnetic field for orientation and navigation. Birds in particular have been intensively studied, but the biophysical mechanisms that underlie the avian magnetic compass are still poorly understood. One proposal, based on magnetically sensitive free radical reactions, is gaining support despite the fact that no chemical reaction in vitro has been shown to respond to magnetic fields as weak as the Earth's ( approximately 50 muT) or to be sensitive to the direction of such a field. Here we use spectroscopic observation of a carotenoid-porphyrin-fullerene model system to demonstrate that the lifetime of a photochemically formed radical pair is changed by application of < or =50 microT magnetic fields, and to measure the anisotropic chemical response that is essential for its operation as a chemical compass sensor. These experiments establish the feasibility of chemical magnetoreception and give insight into the structural and dynamic design features required for optimal detection of the direction of the Earth's magnetic field.

Fourth standard model family neutrino at future linear colliders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ciftci, A.K.; Ciftci, R.; Sultansoy, S.

2005-09-01

It is known that flavor democracy favors the existence of the fourth standard model (SM) family. In order to give nonzero masses for the first three-family fermions flavor democracy has to be slightly broken. A parametrization for democracy breaking, which gives the correct values for fundamental fermion masses and, at the same time, predicts quark and lepton Cabibbo-Kobayashi-Maskawa (CKM) matrices in a good agreement with the experimental data, is proposed. The pair productions of the fourth SM family Dirac ({nu}{sub 4}) and Majorana (N{sub 1}) neutrinos at future linear colliders with {radical}(s)=500 GeV, 1 TeV, and 3 TeV are considered.more » The cross section for the process e{sup +}e{sup -}{yields}{nu}{sub 4}{nu}{sub 4}(N{sub 1}N{sub 1}) and the branching ratios for possible decay modes of the both neutrinos are determined. The decays of the fourth family neutrinos into muon channels ({nu}{sub 4}(N{sub 1}){yields}{mu}{sup {+-}}W{sup {+-}}) provide cleanest signature at e{sup +}e{sup -} colliders. Meanwhile, in our parametrization this channel is dominant. W bosons produced in decays of the fourth family neutrinos will be seen in detector as either di-jets or isolated leptons. As an example, we consider the production of 200 GeV mass fourth family neutrinos at {radical}(s)=500 GeV linear colliders by taking into account di-muon plus four jet events as signatures.« less

Electron paramagnetic resonance of a 10B-containing heterocyclic radical

NASA Astrophysics Data System (ADS)

Eaton, Sandra S.; Ngendahimana, Thacien; Eaton, Gareth R.; Jupp, Andrew R.; Stephan, Douglas W.

2018-05-01

Electron paramagnetic resonance measurements for a 10B-containing heterocyclic phenanthrenedione radical, (C6F5)2B(O2C14H8), were made at X-band in 9:1 toluene:dichloromethane from 10 to 293 K and in toluene from 180 to 293 K. In well-deoxygenated 0.1 mM toluene solution at room temperature hyperfine couplings to 10B, four pairs of protons and five pairs of fluorines contribute to a continuous wave spectrum with many resolved lines. Hyperfine couplings were adjusted to provide the best fit for spectra of the radical enriched in 10B and the analogous radical synthesized with 10,11B in natural abundance, resulting in small refinements of the hyperfine coupling constants previously reported for the natural abundance sample. Electron spin relaxation rates at temperatures between 15 and 293 K were similar for samples containing 10B and natural isotope abundance. Analysis of electron spin echo envelope modulation and hyperfine correlation spectroscopy data at 80 K found Axx = -7.5 ± 0.3, Ayy = -8.5 ± 0.3, and Azz = -10.8 ± 0.3 MHz for 11B, which indicates small spin density on the boron. The spin echo and hyperfine spectroscopy data for the 10B -containing radical are consistent with the factor of 2.99 smaller hyperfine values for 10B than for 11B.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ponomarenko, N. S.; Poluektov, O. G.; Bylina, E. J.

High-field electron paramagnetic resonance (HF EPR) has been employed to investigate the primary electron donor electronic structure of Blastochloris viridis heterodimer mutant reaction centers (RCs). In these mutants the amino acid substitution His(M200)Leu or His(L173)Leu eliminates a ligand to the primary electron donor, resulting in the loss of a magnesium in one of the constituent bacteriochlorophylls (BChl). Thus, the native BChl/BChl homodimer primary donor is converted into a BChl/bacteriopheophytin (BPhe) heterodimer. The heterodimer primary donor radical in chemically oxidized RCs exhibits a broadened EPR line indicating a highly asymmetric distribution of the unpaired electron over both dimer constituents. Observed tripletmore » state EPR signals confirm localization of the excitation on the BChl half of the heterodimer primary donor. Theoretical simulation of the triplet EPR lineshapes clearly shows that, in the case of mutants, triplet states are formed by an intersystem crossing mechanism in contrast to the radical pair mechanism in wild type RCs. Photooxidation of the mutant RCs results in formation of a BPhe anion radical within the heterodimer pair. The accumulation of an intradimer BPhe anion is caused by the substantial loss of interaction between constituents of the heterodimer primary donor along with an increase in the reduction potential of the heterodimer primary donor D/D{sup +} couple. This allows oxidation of the cytochrome even at cryogenic temperatures and reduction of each constituent of the heterodimer primary donor individually. Despite a low yield of primary donor radicals, the enhancement of the semiquinone-iron pair EPR signals in these mutants indicates the presence of kinetically viable electron donors.« less

Millitesla magnetic field effects on the photocycle of an animal cryptochrome

NASA Astrophysics Data System (ADS)

Sheppard, Dean M. W.; Li, Jing; Henbest, Kevin B.; Neil, Simon R. T.; Maeda, Kiminori; Storey, Jonathan; Schleicher, Erik; Biskup, Till; Rodriguez, Ryan; Weber, Stefan; Hore, P. J.; Timmel, Christiane R.; MacKenzie, Stuart R.

2017-02-01

Drosophila have been used as model organisms to explore both the biophysical mechanisms of animal magnetoreception and the possibility that weak, low-frequency anthropogenic electromagnetic fields may have biological consequences. In both cases, the presumed receptor is cryptochrome, a protein thought to be responsible for magnetic compass sensing in migratory birds and a variety of magnetic behavioural responses in insects. Here, we demonstrate that photo-induced electron transfer reactions in Drosophila melanogaster cryptochrome are indeed influenced by magnetic fields of a few millitesla. The form of the protein containing flavin and tryptophan radicals shows kinetics that differ markedly from those of closely related members of the cryptochrome-photolyase family. These differences and the magnetic sensitivity of Drosophila cryptochrome are interpreted in terms of the radical pair mechanism and a photocycle involving the recently discovered fourth tryptophan electron donor.

On the reactivity of methylbenzenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silva, Gabriel da; Bozzelli, Joseph W.

2010-11-15

Alkylated aromatic hydrocarbons, including the methylbenzenes, are a major and growing component of liquid transportation fuels. Reactivity (or lack thereof) for the methylbenzenes in combustion systems, measured by octane rating, ignition delay, and laminar flame speed, varies widely with the number and position of methyl substituents. At present this behaviour is not fully understood. This study demonstrates how the low temperature and ignition reactivity of methylbenzenes is controlled by the presence of isolated methyl groups and adjacent methyl pairs (the ortho effect); this allows for the development of octane number correlations. Introduction of an isolated methyl group, adjacent only tomore » CH ring sites, consistently increases the research octane number (RON) by around 26. This phenomenon is explained by the formation of relatively unreactive benzyl free radicals. When an adjacent pair of methyl substituents is present the RON consistently decreases by between 8 and 26, compared to the case when these methyl groups are isolated from each other (this effect generally diminishes with increasing degree of substitution). Research octane numbers for all aromatics with zero to three methyl substituents are accurately described by the empirical relationship RON = 98 + 24.2n{sub m} - 25.8n{sub p}, where n{sub m} is the total number of methyl groups and n{sub p} is the number of contiguous adjacent methyl pairs. The ortho effect is attributed to the unique oxidation chemistry of o-methylbenzyl, o-methylbenzoxyl, and o-methylphenyl type radicals here we provide a preliminary exploration of this chemistry and highlight areas requiring further research. It is shown that the o-methylbenzyl radical can react with two oxygen molecules to form 1,2-diformylbenzene + 2OH + H, a highly chain-branching process. This chemistry is expected to largely explain the two-stage ignition and negative temperature coefficient (NTC) behavior witnessed for polymethylbenzenes with adjacent methyl pairs. Similar chain branching mechanisms exist in the oxidation of o-methylbenzoxyl radicals that also form during o-xylene ignition. (author)« less

On-line separation and characterization of hyaluronan oligosaccharides derived from radical depolymerization

PubMed Central

Zhao, Xue; Yang, Bo; Li, Lingyun; Zhang, Fuming; Linhardt, Robert J.

2013-01-01

Hydroxyl radicals are widely implicated in the oxidation of carbohydrates in biological and industrial processes and are often responsible for their structural modification resulting in functional damage. In this study, the radical depolymerization of the polysaccharide hyaluronan was studied in a reaction with hydroxyl radicals generated by Fenton Chemistry. A simple method for isolation and identification of the resulting non-sulfated oligosaccharide products of oxidative depolymerization was established. Hyaluronan oligosaccharides were analyzed using ion-pairing reversed phase high performance liquid chromotography coupled with tandem electrospray mass spectrometry. The sequence of saturated hyaluronan oligosaccharides having even- and odd-numbers of saccharide units, afforded through oxidative depolymerization, were identified. This study represents a simple, effective ‘fingerprinting’ protocol for detecting the damage done to hyaluronan by oxidative radicals. This study should help reveal the potential biological outcome of reactive-oxygen radical-mediated depolymerization of hyaluronan. PMID:23768593

Generation and reactivity of ketyl radicals with lignin related structures. On the importance of the ketyl pathway in the photoyellowing of lignin containing pulps and papers.

PubMed

Fabbri, Claudia; Bietti, Massimo; Lanzalunga, Osvaldo

2005-04-01

[reaction: see text] Ketyl radicals with lignin related structures have been generated by means of radiation chemical and photochemical techniques. In the former studies ketyl radicals are produced by reaction of alpha-carbonyl-beta-aryl ether lignin models with the solvated electron produced by pulse radiolysis of an aqueous solution at pH 6.0. The UV-vis spectra of ketyl radicals are characterized by three main absorption bands. The shape and position of these bands slightly change when the spectra are recorded in alkaline solution (pH 11.0) being now assigned to the ketyl radical anions and a pKa = 9.5 is determined for the 1-(3,4,5-trimethoxyphenyl)-2-phenoxyethanol-1-yl radical. Decay rates of ketyl radicals are found to be dose dependent and, at low doses, lie in the range (1.7-2.7) x 10(3) s(-1). In the presence of oxygen a fast decay of the ketyl radicals is observed (k2 = 1.8-2.7 x 10(9) M(-1) s(-1)) that is accompanied by the formation of stable products, i.e., the starting ketones. In the photochemical studies ketyl radicals have been produced by charge-transfer (CT) photoactivation of the electron donor-acceptor salts of methyl viologen (MV2+) with alpha-hydroxy-alpha-phenoxymethyl-aryl acetates. This process leads to the instantaneous formation of the reduced acceptor (methyl viologen radical cation, MV+*), as is clearly shown in a laser flash photolysis experiment by the two absorption bands centered at 390 and 605 nm, and an acyloxyl radical [ArC(CO2*))(OH)CH2(OC6H5)], which undergoes a very fast decarboxylation with formation of the ketyl radicals. Steady-state photoirradiation of the CT ion pairs indicates that 1-aryl-2-phenoxyethanones are formed as primary photoproducts by oxidation of ketyl radicals by MV2+ (under argon) or by molecular oxygen. Small amounts of acetophenones are formed by further photolysis of 1-aryl-2-phenoxyethanones and not by beta-fragmentation of the ketyl radicals. The high reactivity of ketyl radicals with oxygen coupled with the low rates of beta-fragmentation of the same species have an important bearing in the context of the photoyellowing of lignin containing pulps and papers.

Relativistic effects in the double S- and P-wave charmonium production in e{sup +}e{sup -} annihilation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elekina, E. N.; Martynenko, A. P.

2010-03-01

On the basis of perturbative QCD and the relativistic quark model we calculate relativistic and bound state corrections in the pair production of S-wave and P-wave charmonium states. Relativistic factors in the production amplitude connected with the relative motion of heavy quarks and the transformation law of the bound state wave function to the reference frame of the moving S- and P-wave mesons are taken into account. For the gluon and quark propagators entering the production vertex function we use a truncated expansion in the ratio of the relative quark momenta to the center-of-mass energy {radical}(s) up to the secondmore » order. The relativistic treatment of the wave functions makes all such second order terms convergent, thus allowing the reliable calculation of their contributions to the production cross section. Relativistic corrections to the quark bound state wave functions in the rest frame are considered by means of the QCD generalization of the standard Breit potential. It turns out that the examined effects change essentially the nonrelativistic results of the cross section for the reaction e{sup +}+e{sup -{yields}}J/{Psi}({eta}{sub c})+{chi}{sub cJ}(h{sub c}) at the center-of-mass energy {radical}(s)=10.6 GeV.« less

Highly efficient exciplex formation via radical ion pair recombination in X-irradiated alkane solutions for luminophores with short fluorescence lifetimes.

PubMed

Melnikov, Anatoly R; Kalneus, Evgeny V; Korolev, Valeri V; Dranov, Igor G; Kruppa, Alexander I; Stass, Dmitri V

2014-08-01

X-irradiation of alkane solutions of N,N-dimethylaniline with various organic luminophores produces characteristic emission bands ascribed to the corresponding exciplexes. In contrast to optical generation, which requires diffusion-controlled quenching of excited states, an additional channel of exciplex formation via irreversible recombination of radical ion pairs is operative here, which produces exciplexes in solution with high efficiency even for p-terphenyl and diphenylacetylene having fluorescence decay times of 0.95 ns and 8 ps, respectively. The exciplex emission band is sensitive to an external magnetic field and exerts a very large observed magnetic field effect of up to 20%, the maximum possible value under the conditions of the described experiment.

5-Nitrosalicylic Acid as a Novel Matrix for In-Source Decay in Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

PubMed Central

Asakawa, Daiki

2013-01-01

The matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) of peptides and glycans was studied using an oxidizing chemical, 5-nitrosalicylic acid (5-NSA) as the matrix. The use of 5-NSA for the MALDI-ISD of peptides and glycans promoted fragmentation pathways involving “hydrogen-deficient” radical precursors. Hydrogen abstraction from peptides resulted in the production of a “hydrogen-deficient” peptide radical that contained a radical site on the amide nitrogen in the peptide backbone with subsequent radical-induced cleavage at the Cα–C bonds. Cleavage at the Cα–C bond leads to the production of an a•/x fragment pair and the radical a• ions then undergo further hydrogen abstraction to form a ions after Cα–C bond cleavage. Since the Pro residue does not contain a nitrogen-centered radical site, Cα–C bond cleavage does not occur at this site. Alternatively, the specific cleavage of CO−N bonds leads to a b•/y fragment pair at Xxx−Pro which occurs via hydrogen abstraction from the Cα−H in the Pro residue. In contrast, “hydrogen-deficient” glycan radicals were generated by hydrogen abstraction from hydroxyl groups in glycans. Both glycosidic and cross-ring cleavages occurred as the result of the degradation of “hydrogen-deficient” glycan radicals. Cross-ring cleavage ions are potentially useful in linkage analysis, one of the most critical steps in the characterization of glycans. Moreover, isobaric glycans could be distinguished by structure specific ISD ions, and the molar ratio of glycan isomers in a mixture can be estimated from their fragment ions abundance ratios. MALDI-ISD with 5-NSA could be a useful method for the sequencing of peptides including the location of post-translational modifications, identification and semi-quantitative analysis of mixtures of glycan isomers. PMID:24860709

Transient radical pairs studied by time-resolved EPR.

PubMed

Bittl, Robert; Weber, Stefan

2005-02-25

Photogenerated short-lived radical pairs (RP) are common in biological photoprocesses such as photosynthesis and enzymatic DNA repair. They can be favorably probed by time-resolved electron paramagnetic resonance (EPR) methods with adequate time resolution. Two EPR techniques have proven to be particularly useful to extract information on the working states of photoinduced biological processes that is only difficult or sometimes even impossible to obtain by other types of spectroscopy. Firstly, transient EPR yields crucial information on the chemical nature and the geometry of the individual RP halves in a doublet-spin pair generated by a short laser pulse. This time-resolved method is applicable in all magnetic field/microwave frequency regimes that are used for continuous-wave EPR, and is nowadays routinely utilized with a time resolution reaching about 10 ns. Secondly, a pulsed EPR method named out-of-phase electron spin echo envelope modulation (OOP-ESEEM) is increasingly becoming popular. By this pulsed technique, the mutual spin-spin interaction between the RP halves in a doublet-spin pair manifests itself as an echo modulation detected as a function of the microwave-pulse spacing of a two-pulse echo sequence subsequent to a laser pulse. From the dipolar coupling, the distance between the radicals is readily derived. Since the spin-spin interaction parameters are typically not observable by transient EPR, the two techniques complement each other favorably. Both EPR methods have recently been applied to a variety of light-induced RPs in photobiology. This review summarizes the results obtained from such studies in the fields of plant and bacterial photosynthesis and DNA repair mediated by the enzyme DNA photolyase.

Developmental changes in the neural influence of sublexical information on semantic processing.

PubMed

Lee, Shu-Hui; Booth, James R; Chou, Tai-Li

2015-07-01

Functional magnetic resonance imaging (fMRI) was used to examine the developmental changes in a group of normally developing children (aged 8-12) and adolescents (aged 13-16) during semantic processing. We manipulated association strength (i.e. a global reading unit) and semantic radical (i.e. a local reading unit) to explore the interaction of lexical and sublexical semantic information in making semantic judgments. In the semantic judgment task, two types of stimuli were used: visually-similar (i.e. shared a semantic radical) versus visually-dissimilar (i.e. did not share a semantic radical) character pairs. Participants were asked to indicate if two Chinese characters, arranged according to association strength, were related in meaning. The results showed greater developmental increases in activation in left angular gyrus (BA 39) in the visually-similar compared to the visually-dissimilar pairs for the strong association. There were also greater age-related increases in angular gyrus for the strong compared to weak association in the visually-similar pairs. Both of these results suggest that shared semantics at the sublexical level facilitates the integration of overlapping features at the lexical level in older children. In addition, there was a larger developmental increase in left posterior middle temporal gyrus (BA 21) for the weak compared to strong association in the visually-dissimilar pairs, suggesting conflicting sublexical information placed greater demands on access to lexical representations in the older children. All together, these results suggest that older children are more sensitive to sublexical information when processing lexical representations. Copyright © 2015 Elsevier Ltd. All rights reserved.

Is the yeast a relevant model for aging of multicellular organisms? An insight from the total lifespan of Saccharomyces cerevisiae.

PubMed

Zadrag, Renata; Bartosz, Grzegorz; Bilinski, Tomasz

2008-12-01

The applicability of the free radical theory of aging to the yeast S. cerevisiae is a matter of debate. In order to get an insight into this question, we studied the reproductive potential (the number of buds produced), reproductive lifespan (the time during which a yeast cell is able to divide), postreproductive lifespan (duration of life of yeast cells which ceased to divide) and total lifespan (sum of reproductive lifespan and postreproductive lifespan) of three isogenic pairs of yeast strains. Each pair contained a parent strain and a disruptant of gene(s) coding for important antioxidant enzyme(s) (CuZn-superoxide dismutase, all five peroxiredoxins or glutaredoxin 5). Although the reproductive potential was decreased in all antioxidant enzyme-deficient mutants, the differences in the reproductive lifespan between the parent strains and the mutants were less pronounced while postreproductive lifespan and total lifespan were not diminished in the mutants. These results suggest that either the free-radical theory of aging is not applicable to S. cerevisiae or that this yeast is not a proper model organism for the study of aging of higher organisms. In our opinion the latter possibility is more apparent and the increase in cell volume (unavoidable for a cell propagating by budding) rather than accumulation of oxidative damage may be the main reason for the cessation of budding (and perhaps postreproductive death) in S. cerevisiae.

Mechanisms of Geomagnetic Field Influence on Gene Expression Using Influenza as a Model System: Basics of Physical Epidemiology

PubMed Central

Zaporozhan, Valeriy; Ponomarenko, Andriy

2010-01-01

Recent studies demonstrate distinct changes in gene expression in cells exposed to a weak magnetic field (MF). Mechanisms of this phenomenon are not understood yet. We propose that proteins of the Cryptochrome family (CRY) are “epigenetic sensors” of the MF fluctuations, i.e., magnetic field-sensitive part of the epigenetic controlling mechanism. It was shown that CRY represses activity of the major circadian transcriptional complex CLOCK/BMAL1. At the same time, function of CRY, is apparently highly responsive to weak MF because of radical pairs that periodically arise in the functionally active site of CRY and mediate the radical pair mechanism of magnetoreception. It is known that the circadian complex influences function of every organ and tissue, including modulation of both NF-κB- and glucocorticoids- dependent signaling pathways. Thus, MFs and solar cycles-dependent geomagnetic field fluctuations are capable of altering expression of genes related to function of NF-κB, hormones and other biological regulators. Notably, NF-κB, along with its significant role in immune response, also participates in differential regulation of influenza virus RNA synthesis. Presented data suggests that in the case of global application (example—geomagnetic field), MF-mediated regulation may have epidemiological and other consequences. PMID:20617011

Quantum mechanical model for the anticarcinogenic effect of extremely-low-frequency electromagnetic fields on early chemical hepatocarcinogenesis

NASA Astrophysics Data System (ADS)

Godina-Nava, Juan José; Torres-Vega, Gabino; López-Riquelme, Germán Octavio; López-Sandoval, Eduardo; Samana, Arturo Rodolfo; García Velasco, Fermín; Hernández-Aguilar, Claudia; Domínguez-Pacheco, Arturo

2017-02-01

Using the conventional Haberkorn approach, it is evaluated the recombination of the radical pair (RP) singlet spin state to study theoretically the cytoprotective effect of an extremely-low-frequency electromagnetic field (ELF-EMF) on early stages of hepatic cancer chemically induced in rats. The proposal is that ELF-EMF modulates the interconversion rate of singlet and triplet spin states of the RP populations modifying the products from the metabolization of carcinogens. Previously, we found that the daily treatment with ELF-EMF 120 Hz inhibited the number and area of preneoplastic lesions in chemical carcinogenesis. The singlet spin population is evaluated diagonalizing the spin density matrix through the Lanczos method in a radical pair mechanism (RPM). Using four values of the interchange energy, we have studied the variations over the singlet population. The low magnetic field effect as a test of the influence over the enzymatic chemical reaction is evaluated calculating the quantum yield. Through a bootstrap technique the range is found for the singlet decay rate for the process. Applying the quantum measurements concept, we addressed the impact toward hepatic cells. The result contributes to improving our understanding of the chemical carcinogenesis process affected by charged particles that damage the DNA.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abazov, V. M.; Alexeev, G. D.; Kalinin, A. M.

We present the first experimental discrimination between the 2e/3 and 4e/3 top quark electric charge scenarios, using top quark pairs (tt) produced in pp collisions at {radical}(s)=1.96 TeV by the Fermilab Tevatron Collider. We use 370 pb{sup -1} of data collected by the D0 experiment and select events with at least one high transverse momentum electron or muon, high transverse energy imbalance, and four or more jets. We discriminate between b- and b-quark jets by using the charge and momenta of tracks within the jet cones. The data are consistent with the expected electric charge, vertical bar q vertical bar=2e/3.more » We exclude, at the 92% C.L., that the sample is solely due to the production of exotic quark pairs QQ with vertical bar q vertical bar=4e/3. We place an upper limit on the fraction of QQ pairs {rho}<0.80 at the 90% C.L.« less

A bioinspired redox relay that mimics radical interactions of the Tyr-His pairs of photosystem II

NASA Astrophysics Data System (ADS)

Megiatto, Jackson D., Jr.; Méndez-Hernández, Dalvin D.; Tejeda-Ferrari, Marely E.; Teillout, Anne-Lucie; Llansola-Portolés, Manuel J.; Kodis, Gerdenis; Poluektov, Oleg G.; Rajh, Tijana; Mujica, Vladimiro; Groy, Thomas L.; Gust, Devens; Moore, Thomas A.; Moore, Ana L.

2014-05-01

In water-oxidizing photosynthetic organisms, light absorption generates a powerfully oxidizing chlorophyll complex (P680•+) in the photosystem II reaction centre. This is reduced via an electron transfer pathway from the manganese-containing water-oxidizing catalyst, which includes an electron transfer relay comprising a tyrosine (Tyr)-histidine (His) pair that features a hydrogen bond between a phenol group and an imidazole group. By rapidly reducing P680•+, the relay is thought to mitigate recombination reactions, thereby ensuring a high quantum yield of water oxidation. Here, we show that an artificial reaction centre that features a benzimidazole-phenol model of the Tyr-His pair mimics both the short-internal hydrogen bond in photosystem II and, using electron paramagnetic resonance spectroscopy, the thermal relaxation that accompanies proton-coupled electron transfer. Although this artificial system is much less complex than the natural one, theory suggests that it captures the essential features that are important in the function of the relay.

Antioxidant effect of naturally occurring xanthines on the oxidative damage of DNA bases

NASA Astrophysics Data System (ADS)

Vieira, A. J. S. C.; Telo, J. P.; Pereira, H. F.; Patrocínio, P. F.; Dias, R. M. B.

1999-01-01

The repair of the oxidised radicals of adenine and guanosine by several naturally occurring xanthines was studied. Each pair of DNA purine/xanthine was made to react with the sulphate radical and the decrease of the concentration of both compounds was measured by HPLC as a function of irradiation time. The results show that xanthine efficiently prevents the oxidation of the two DNA purines. Theophyline and paraxanthine repair the oxidised radical of adenine but not the one from guanosine. Theobromine and caffeine do not show any protecting effect. An order of the oxidation potentials of all the purines studied is proposed. La réparation des radicaux oxydés de l'adénine et de la guanosine par des xanthines naturelles a été étudiée en soumettant chaque paire base de l'ADN/xanthine à l'oxydation par le radical sulfate et en mesurant par HPLC la disparition des deux composés en fonction du temps d'irradiation. Les résultats montrent que la xanthine joue un rôle protecteur efficace contre l'oxydation des deux purines de l'ADN. La théophyline et la paraxanthine réparent le radical oxydé de l'adénine mais pas celui de la guanosine. La théobromine et la cafeíne n'ont pas d'effet protecteur. Un ordre de potentiels d'oxydation des purines étudiées est proposé.

Search for a neutral Higgs boson decaying to a W boson pair in p antip collisions at s**(1/2) = 1.96-TeV

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abulencia, A.; Acosta, D.; Adelman, Jahred A.

2006-05-01

The authors present the results of a search for standard model Higgs boson production with decay to WW*, identified through the leptonic final states e{sup +}e{sup -} {bar {nu}}{nu}, e{sup {+-}}{mu}{sup {-+}} {bar {nu}}{nu} and {mu}{sup +} {mu}{sup -} {bar {nu}}{nu}. This search uses 360 pb{sup -1} of data collected from p{bar p} collisions at {radical}s = 1.96 TeV by the upgraded Collider Detector at Fermilab (CDF II). They observe no signal excess and set 95% confidence level upper limits on the production cross section times branching ratio for the Higgs boson to WW* or any new scalar particle withmore » similar decay products. These upper limits range from 5.5 to 3.2 pb for Higgs boson masses between 120 and 200 GeV/c{sup 2}.« less

Electron-transfer reactions in cyanine borate ion pairs: photopolymerization initiators sensitive to visible light

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chatterjee, S.; Gottschalk, P.; Davis, P.D.

1988-03-30

Photoinitiation of polymerization is a process of immense practical, economic, and theoretical importance. In typical examples the polymerization of an acrylate or styrene-derived monomer is initiated by irradiation of a sensitizer with ultraviolet light. The excited state of the sensitizer may dissociate directly to form active free radicals as in the case of the benzoin ethers, or it may first undergo a bimolecular electron-transfer reaction whose products initiate polymerization as is the case in the benzophenone-dimethylaniline system. Efforts to extend the range of useful photoinitiators of free-radical polymerization to the visible region of the spectrum have heretofore met with onlymore » modest success. These special initiators typically are sensitive only to blue light or suffer from thermal instability and have low quantum efficiencies. The authors report herein the discovery that triphenylalkylborate salts of cyanine dyes (Chart I) are photoinitiators of free-radical polymerization whose sensitivity throughout the entire visible spectral region is the result of a novel intra-ion-pair electron-transfer reaction.« less

Dynamics of intramolecular electron transfer reaction of FAD studied by magnetic field effects on transient absorption spectra.

PubMed

Murakami, Masaaki; Maeda, Kiminori; Arai, Tatsuo

2005-07-07

The kinetics of intermediates generated from intramolecular electron-transfer reaction by photo irradiation of the flavin adenine dinucleotide (FAD) molecule was studied by a magnetic field effect (MFE) on transient absorption (TA) spectra. Existence time of MFE and MFE action spectra have a strong dependence on the pH of solutions. The MFE action spectra have indicated the existence of interconversion between the radical pair and the cation form of the triplet excited state of flavin part. All rate constants of the triplet and the radical pair were determined by analysis of the MFE action spectra and decay kinetics of TA. The obtained values for the interconversion indicate that the formation of cation radical promotes the back electron-transfer reaction to the triplet excited state. Further, rate constants of spin relaxation and recombination have been studied by the time profiles of MFE at various pH. The drastic change of those two factors has been obtained and can be explained by SOC (spin-orbit coupling) induced back electron-transfer promoted by the formation of a stacking conformation at pH > 2.5.

Intramolecular hydrogen bonding in malonaldehyde and its radical analogues.

PubMed

Lin, Chen; Kumar, Manoj; Finney, Brian A; Francisco, Joseph S

2017-09-28

High level Brueckner doubles with triples correction method-based ab initio calculations have been used to investigate the nature of intramolecular hydrogen bonding and intramolecular hydrogen atom transfer in cis-malonaldehyde (MA) and its radical analogues. The radicals considered here are the ones that correspond to the homolytic cleavage of C-H bonds in cis-MA. The results suggest that cis-MA and its radical analogues, cis-MA RS , and cis-MA RA , both exist in planar geometry. The calculated intramolecular O-H⋯O=C bond in cis-MA is shorter than that in the radical analogues. The intramolecular hydrogen bond in cis-MA is stronger than in its radicals by at least 3.0 kcal/mol. The stability of a cis-malonaldehyde radical correlates with the extent of electron spin delocalization; cis-MA RA , in which the radical spin is more delocalized, is the most stable MA radical, whereas cis-MA RS , in which the radical spin is strongly localized, is the least stable radical. The natural bond orbital analysis indicates that the intramolecular hydrogen bonding (O⋯H⋯O) in cis-malonaldehyde radicals is stabilized by the interaction between the lone pair orbitals of donor oxygen and the σ * orbital of acceptor O-H bond (n → σ * OH ). The calculated barriers indicate that the intramolecular proton transfer in cis-MA involves 2.2 kcal/mol lower barrier than that in cis-MA RS .

Kinetic and ab initio theoretical study of hydrogen atom abstraction from thiols by thiyl radicals: Basis rate expressions for reactions of sulfur-centered radicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alnajjar, M.S.; Garrossian, M.S.; Autrey, S.T.

1992-08-20

Arrhenius rate expressions were determined for the abstraction of hydrogen atom from thiophenol and hexanethiol by the octanethiyl radical at 25-100 {degrees}C in nonane. Octanethiyl radicals were produced by steady-state photolysis of octyl thiobenzoate. Analysis of octyl disulfide and octanethiyl radical. For hexanethiol, log (k{sub abs}/K{sub t}{sup 1/2}) = (2.94 {plus_minus} 0.29) - (3.84 {plus_minus}0.41)/0, and for thiophenol, log (k{sub abs}/k{sub 5}{sup 1/2}) = (2.56 {plus_minus} 0.19) - (2.88 {plus_minus} 0.28)/0;0=2.3RT kcal/mol. Combining these expressions with the Smoluchowski expression for self-termination of octanethiyl in nonane, log (k{sub t}{sup 1/2}) = 5.96 - 1.335/0, which employs experimental diffusion coefficients of octanethiolmore » and a spin selection factor {sigma} = 1, yields, for thiophenol, log (k{sub abs}/M{sup {minus}1}s{sup {minus}1}) = (8.52 {plus_minus} 0.18) = (4.22 {plus_minus} 0.27)/0, and for hexanethiol, log (k{sub abs}/M{sup {minus}1} s{sup {minus}1}) = (8.90 {plus_minus} 0.29) = (5.18 {plus_minus} 0.41)/0 (errors are 2{sigma}). The rate of disappearance of octanethiyl/diphenylketyl radical pairs in SDS micelles, determined by nanosecond optical spectroscopy, was found to be unchanged in a 700-G magnetic field, providing evidence for rapid intersystem crossing of sulfur-centered radical pairs and support for the assignment of {sigma} = 1 above. Ab initio electronic structure calculations on the reaction HS{sup {lg_bullet}} + HSH {r_arrow} HSH + {sup {lg_bullet}}SH, performed at SCF and correlated levels, predict an activation barrier of {Delta}H{sub 298} {sup {double_dagger}}= 4.6 kcal/mol, in close agreement with the experimental barrier for the octanethiyl + hexanethiol reactions. 43 refs., 5 figs., 4 tabs.« less

The behavior of exciplex decay processes and interplay of radiationless transition and preliminary reorganization mechanisms of electron transfer in loose and tight pairs of reactants.

PubMed

Kuzmin, Michael G; Soboleva, Irina V; Dolotova, Elena V

2007-01-18

Exciplex emission spectra and rate constants of their decay via internal conversion and intersystem crossing are studied and discussed in terms of conventional radiationless transition approach. Exciplexes of 9-cyanophenanthrene with 1,2,3-trimethoxybenzene and 1,3,5-trimethoxybenzene were studied in heptane, toluene, butyl acetate, dichloromethane, butyronitrile, and acetonitrile. A better description of spectra and rate constants is obtained using 0-0 transition energy and Gauss broadening of vibrational bands rather than the free energy of electron transfer and reorganization energy. The coincidence of parameters describing exciplex emission spectra and dependence of exciplex decay rate constants on energy gap gives the evidence of radiationless quantum transition mechanism rather than thermally activated medium reorganization mechanism of charge recombination in exciplexes and excited charge transfer complexes (contact radical ion pairs) as well as in solvent separated radical ion pairs. Radiationless quantum transition mechanism is shown to provide an appropriate description also for the main features of exergonic excited-state charge separation reactions if fast mutual transformations of loose and tight pairs of reactants are considered. In particular, very fast electron transfer (ET) in tight pairs of reactants with strong electronic coupling of locally excited and charge transfer states can prevent the observation of an inverted region in bimolecular excited-state charge separation even for highly exergonic reactions.

Search for new particles decaying to ZZ using final states with leptons and jets with the ATLAS detector in root s=7 TeV proton-proton collisions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aad G.; Abbott, B.; Abdallah, J.

2012-06-12

A search is presented for a narrow resonance decaying to a pair of Z bosons using data corresponding to 1.02 fb{sup -1} of integrated luminosity collected by the ATLAS experiment from pp collisions at {radical}s = 7 TeV. Events containing either four charged leptons ({ell}{ell}{ell}{ell}) or two charged leptons and two jets ({ell}{ell}jj) are analyzed and found to be consistent with the Standard Model background expectation. Lower limits on a resonance mass are set using the Randall-Sundrum (RS1) graviton model as a benchmark. Using both {ell}{ell}{ell}{ell} and {ell}{ell}jj events, an RS1 graviton with k/{bar m}{sub pl} = 0.1 and massmore » between 325 and 845 GeV is excluded at 95% confidence level. In addition, the {ell}{ell}{ell}{ell} events are used to set a model-independent fiducial cross section limit of {sigma}{sub fid}(pp {yields} X {yields} ZZ) < 0.92 pb at 95% confidence level for any new sources of ZZ production with m{sub ZZ} greater than 300 GeV.« less

Structure and dynamics in B12 enzyme catalysis revealed by electron paramagnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Warncke, Kurt

2009-03-01

Challenges to the understanding of how protein structure and dynamics contribute to catalysis in enzymes, and the use of time-resolved electron paramagnetic resonance (EPR) spectroscopic techniques to address the challenges, are examined in the context of the coenzyme B12-dependent enzyme, ethanolamine ammonia-lyase (EAL), from Salmonella typhimurium. EAL conducts the homolytic cleavage of the coenzyme cobalt-carbon bond, intraprotein radical migration (5-6 å), and hydrogen atom transfers, which enable the core radical-mediated rearrangement reaction. Thermodynamic and activation parameters are measured in two experimental systems, which were developed to isolate sub-sequences from the multi-step catalytic cycle, as follows: (1) A dimethylsulfoxide (DMSO)/water cryosolvent system is used to prepare the kinetically-arrested enzyme/coenzyme/substrate ternary complex in fluid solution at 230 K.[1] Temperature-step initiated cobalt-carbon bond cleavage and radical pair separation to form the Co(II)-substrate radical pair are monitored by using time-resolved, full-spectrum EPR spectroscopy (234<=T<=250 K).[1] (2) The Co(II)-substrate radical pair is cryotrapped in frozen aqueous solution at T<150 K, and then promoted to react by a temperature step. The reaction of the substrate radical along the native pathway to form the diamagnetic bound products is monitored by using time-resolved, full-spectrum EPR spectroscopy (187<=T<=217 K).[2] High temporal resolution is achieved, because the reactions are dramatically slowed at the low temperatures, relative to the initiation and spectrum acquistion times. The results are combined with high resolution structures of the reactant centers, obtained by pulsed-EPR spectroscopies,[3] and the protein, obtained by structural proteomics[4] and EPR and electron spin echo envelope modulation (ESEEM) in combination with site directed mutagenesis,[5] to approach a molecular level description of protein contributions to catalysis in EAL. [4pt] [1] Wang, M. & Warncke, K. J. Am. Chem. Soc. 2008, 130, 4846. [0pt] [2] Chen, Z. and Warncke, K. Biophys. J. 2008, 95 (December) [0pt] [3] Canfield, J. M. and Warncke, K. J. Phys. Chem. B 2002, 106, 8831. [0pt] [4] Sun, L. and Warncke, K. Proteins 2006, 64, 308. [0pt] [5] Sun, L., Groover, O., Canfield, J. M., and Warncke, K. Biochemistry 2008, 47, 5523.

A unified description of the electrochemical, charge distribution, and spectroscopic properties of the special-pair radical cation in bacterial photosynthesis.

PubMed

Reimers, Jeffrey R; Hush, Noel S

2004-04-07

We apply our four-state 70-vibration vibronic-coupling model for the properties of the photosynthetic special-pair radical cation to: (1) interpret the observed correlations between the midpoint potential and the distribution of spin density between the two bacteriochlorophylls for 30 mutants of Rhodobacter sphaeroides, (2) interpret the observed average intervalence hole-transfer absorption energies as a function of spin density for six mutants, and (3) simulate the recently obtained intervalence electroabsorption Stark spectrum of the wild-type reaction center. While three new parameters describing the location of the sites of mutation with respect to the special pair are required to describe the midpoint-potential data, a priori predictions are made for the transition energies and the Stark spectrum. In general, excellent predictions are made of the observed quantities, with deviations being typically of the order of twice the experimental uncertainties. A unified description of many chemical and spectroscopic properties of the bacterial reaction center is thus provided. Central to the analysis is the assumption that the perturbations made to the reaction center, either via mutations of protein residues or by application of an external electric field, act only to independently modify the oxidation potentials of the two halves of the special pair and hence the redox asymmetry E0. While this appears to be a good approximation, clear evidence is presented that effects of mutation can be more extensive than what is allowed for. A thorough set of analytical equations describing the observed properties is obtained using the Born-Oppenheimer adiabatic approximation. These equations are generally appropriate for intervalence charge-transfer problems and include, for the first time, full treatment of both symmetric and antisymmetric vibrational motions. The limits of validity of the adiabatic approach to the full nonadiabatic problem are obtained.

Charm (and Beauty) Production at the Tevatron

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rademacker, Jonas; /Bristol U.

2007-11-01

The authors present recent results on heavy flavor production at Tevatron Run II for typically {approx} 1 fb{sup -1} of analyzed p{bar p} data at {radical}s = 1.96 TeV. This includes results on single and correlated open charm and bottom cross sections, charm pair production kinematics, J/{psi}, {psi}(2S) and {chi}{sub cJ} cross sections and polarization measurements in J/{psi}, {psi}(2S), {Upsilon}(1S), and {Upsilon}(2S).

Diffusion affected magnetic field effect in exciplex fluorescence

NASA Astrophysics Data System (ADS)

Burshtein, Anatoly I.; Ivanov, Anatoly I.

2014-07-01

The fluorescence of the exciplex, 1[D+δA-δ], formed at contact of photoexcited acceptor 1A* with an electron donor 1D, is known to be very sensitive to an external magnetic field, reducing the spin conversion efficiency in the resulting geminate radical ion pair, 1, 3[D+…A-]. The relative increase of the exciplex fluorescence in the highest magnetic field compared to the lowest one, known as the magnetic field effect, crucially depends on the viscosity of the solvent. This phenomenon first studied experimentally is at first reproduced here theoretically. The magnetic field effect is shown to vanish in both limits of high and low solvent diffusivity reaching a maximum in between. It is also very sensitive to the solvent dielectric constant and to the exciplex and radical-ion pair conversion rates.

Diffusion affected magnetic field effect in exciplex fluorescence.

PubMed

Burshtein, Anatoly I; Ivanov, Anatoly I

2014-07-14

The fluorescence of the exciplex, (1)[D(+δ)A(-δ)], formed at contact of photoexcited acceptor (1)A(*) with an electron donor (1)D, is known to be very sensitive to an external magnetic field, reducing the spin conversion efficiency in the resulting geminate radical ion pair, (1, 3)[D(+)…A(-)]. The relative increase of the exciplex fluorescence in the highest magnetic field compared to the lowest one, known as the magnetic field effect, crucially depends on the viscosity of the solvent. This phenomenon first studied experimentally is at first reproduced here theoretically. The magnetic field effect is shown to vanish in both limits of high and low solvent diffusivity reaching a maximum in between. It is also very sensitive to the solvent dielectric constant and to the exciplex and radical-ion pair conversion rates.

Quantum information processing in the radical-pair mechanism: Haberkorn's theory violates the Ozawa entropy bound

NASA Astrophysics Data System (ADS)

Mouloudakis, K.; Kominis, I. K.

2017-02-01

Radical-ion-pair reactions, central for understanding the avian magnetic compass and spin transport in photosynthetic reaction centers, were recently shown to be a fruitful paradigm of the new synthesis of quantum information science with biological processes. We show here that the master equation so far constituting the theoretical foundation of spin chemistry violates fundamental bounds for the entropy of quantum systems, in particular the Ozawa bound. In contrast, a recently developed theory based on quantum measurements, quantum coherence measures, and quantum retrodiction, thus exemplifying the paradigm of quantum biology, satisfies the Ozawa bound as well as the Lanford-Robinson bound on information extraction. By considering Groenewold's information, the quantum information extracted during the reaction, we reproduce the known and unravel other magnetic-field effects not conveyed by reaction yields.

Influence of anoxia on the induction of mutations by phenylalanine radicals during gamma-irradiation of plasmid DNA in aqueous solution.

PubMed

Kuipers, Gitta K; Slotman, Ben J; Reitsma-Wijker, Carola A; van Andel, Rob J; Poldervaart, Hester A; Lafleur, M Vincent M

2004-12-21

When DNA is irradiated in aqueous solution, most of the damage is inflicted by water-derived radicals. This is called the indirect effect of ionizing radiation. However in whole cells not only the primary formed water radicals play a role, because some cellular compounds form secondary radicals which can also damage DNA. It is known that the amino acid phenylalanine is able to react with water radicals, resulting in the production of secondary phenylalanine radicals which can damage and inactivate DNA. In a previous study the influence of the presence of phenylalanine during gamma-irradiation of DNA in aqueous solution under oxic conditions was studied. Under anoxic irradiation conditions different amounts and types of reactive water-derived radicals are formed compared to oxic conditions and also different phenylalanine radicals are formed. Therefore, this study examines the influence of the presence of phenylalanine under anoxic conditions on the gamma-radiation-induced mutation spectrum. The results indicate that phenylalanine radicals are damaging to DNA, but less effective compared to primary water radicals. On the mutational level, in the presence of phenylalanine radicals under anoxic conditions, the amount of mutations on G:C base pairs was significantly decreased as compared to oxic conditions. Furthermore, the results of this study indicate that nucleotide excision repair is involved in repair of both inactivating and mutagenic damage induced by phenylalanine radicals under anoxic conditions.

Role of viscosity in the magnetic field effect on pyrene-DMA exciplex emission at different permittivities

NASA Astrophysics Data System (ADS)

Jana, Amit Kumar; Roy, Partha; Nath, Deb Narayan

2014-02-01

Effect of viscosity variation on the magnetic field effect in pyrene-N,N-dimethylaniline exciplex luminescence has been studied at different permittivity values. The data is compatible to the model of Krissinel et al. (1999) [10] reported earlier to explain the effect probing the escape yield of radical pairs. It is shown that the data can also be explained on the basis of a simple model. It is interesting to note that the present letter also demonstrates the positive slope of MFE with diffusivity at extremely high viscous condition as predicted by Krissinel et al. (1999) [10] which has not been observed in earlier experiments.

Novel schemes for measurement-based quantum computation.

PubMed

Gross, D; Eisert, J

2007-06-01

We establish a framework which allows one to construct novel schemes for measurement-based quantum computation. The technique develops tools from many-body physics-based on finitely correlated or projected entangled pair states-to go beyond the cluster-state based one-way computer. We identify resource states radically different from the cluster state, in that they exhibit nonvanishing correlations, can be prepared using nonmaximally entangling gates, or have very different local entanglement properties. In the computational models, randomness is compensated in a different manner. It is shown that there exist resource states which are locally arbitrarily close to a pure state. We comment on the possibility of tailoring computational models to specific physical systems.

Theoretical Investigation of Kinetic Processes in Small Radicals of Importance in Combustion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alexander, Millard; Dagdigian, Paul J.

Our group studies inelastic and reactive collisions of small molecules, focusing on radicals important in combustion environments. The goal is the better understanding of kinetic processes that may be difficult to access experimentally. An essential component is the accurate determination and fitting of potential energy surfaces (PESs). After fitting the ab initio points to obtain global PESs, we treat the dynamics using time-independent (close-coupling) methods. Cross sections and rate constants for collisions of are determined with our Hibridon program suite . We have studied energy transfer (rotationally, vibrationally, and/or electronically inelastic) in small hydrocarbon radicals (CH 2 and CH 3)more » and the CN radical. We have made a comparison with experimental measurements of relevant rate constants for collisions of these radicals. Also, we have calculated accurate transport properties using state-of-the-art PESs and to investigate the sensitivity to these parameters in 1-dimensional flame simulations. Of particular interest are collision pairs involving the light H atom.« less

Visible light induction of an electron paramagnetic resonance split signal in Photosystem II in the S(2) state reveals the importance of charges in the oxygen-evolving center during catalysis: a unifying model.

PubMed

Sjöholm, Johannes; Styring, Stenbjörn; Havelius, Kajsa G V; Ho, Felix M

2012-03-13

Cryogenic illumination of Photosystem II (PSII) can lead to the trapping of the metastable radical Y(Z)(•), the radical form of the redox-active tyrosine residue D1-Tyr161 (known as Y(Z)). Magnetic interaction between this radical and the CaMn(4) cluster of PSII gives rise to so-called split electron paramagnetic resonance (EPR) signals with characteristics that are dependent on the S state. We report here the observation and characterization of a split EPR signal that can be directly induced from PSII centers in the S(2) state through visible light illumination at 10 K. We further show that the induction of this split signal takes place via a Mn-centered mechanism, in the same way as when using near-infrared light illumination [Koulougliotis, D., et al. (2003) Biochemistry 42, 3045-3053]. On the basis of interpretations of these results, and in combination with literature data for other split signals induced under a variety of conditions (temperature and light quality), we propose a unified model for the mechanisms of split signal induction across the four S states (S(0), S(1), S(2), and S(3)). At the heart of this model is the stability or instability of the Y(Z)(•)(D1-His190)(+) pair that would be formed during cryogenic oxidation of Y(Z). Furthermore, the model is closely related to the sequence of transfers of protons and electrons from the CaMn(4) cluster during the S cycle and further demonstrates the utility of the split signals in probing the immediate environment of the oxygen-evolving center in PSII.

Synthesis and characterization of a novel hyaluronic acid hydrogel.

PubMed

Zhao, X

2006-01-01

Hyaluronic acid (hyaluronan, HA) has many medical applications as a biomaterial. To enhance its biostability, a novel hydrogel of cross-linked hyaluronic acid was prepared using a double cross-linking process, which involves building cross-linkages between hydroxyl group pairs and carboxyl group pairs. The present study explored a number of cross-linking processes in order to obtain different degrees of cross-linking, which were evaluated by the measurement of water absorption capacity as an index of the gel network density. To gain a better understanding of the stability of the gel, the chemical structure and particularly the rheological behaviour of the cross-linked HA, which included the influences of factors, such as degree of cross-linking, HA concentration and gel particle size, were investigated. The in vitro biostability against hyaluronidase and free radical degradation was tested to show that the cross-linked hydrogel had improved resistance to in vitro hyaluronidase and free radical degradation.

Tropospheric OH and Cl levels deduced from non-methane hydrocarbon measurements in a marine site

NASA Astrophysics Data System (ADS)

Arsene, C.; Bougiatioti, A.; Kanakidou, M.; Bonsang, B.; Mihalopoulos, N.

2007-05-01

In situ continuous hourly measurements of C2-C8 non-methane hydrocarbons (NMHCS) have been performed from March to October 2006 at two coastal locations on the island of Crete, in the Eastern Mediterranean. Well defined diurnal variations were observed for several short lived NMHCS (including ethene, propene, n-butane, n-pentane, n-hexane, 2-methyl-pentane). The daytime concentration of hydroxyl (OH) radicals estimated from these experimental data varied from 1.3×106 to ~4.0×106 radical cm-3, in good agreement with box-model simulations. In addition the relative variability of various hydrocarbon pairs (at least 7) was used to derive the tropospheric levels of Cl atoms. The Cl atom concentration has been estimated to range between 0.6×104 and 4.7×104 atom cm-3, in good agreement with gaseous hydrochloric acid (HCl) observations in the area. Such levels of Cl atoms can be of considerable importance for the oxidation capacity of the troposphere on a regional scale.

Oxygen targeting in preterm infants using the Masimo SET Radical pulse oximeter

PubMed Central

Johnston, Ewen D; Boyle, Breidge; Juszczak, Ed; King, Andy; Brocklehurst, Peter; Stenson, Ben J

2011-01-01

Background A pretrial clinical improvement project for the BOOST-II UK trial of oxygen saturation targeting revealed an artefact affecting saturation profiles obtained from the Masimo Set Radical pulse oximeter. Methods Saturation was recorded every 10 s for up to 2 weeks in 176 oxygen dependent preterm infants in 35 UK and Irish neonatal units between August 2006 and April 2009 using Masimo SET Radical pulse oximeters. Frequency distributions of % time at each saturation were plotted. An artefact affecting the saturation distribution was found to be attributable to the oximeter's internal calibration algorithm. Revised software was installed and saturation distributions obtained were compared with four other current oximeters in paired studies. Results There was a reduction in saturation values of 87–90%. Values above 87% were elevated by up to 2%, giving a relative excess of higher values. The software revision eliminated this, improving the distribution of saturation values. In paired comparisons with four current commercially available oximeters, Masimo oximeters with the revised software returned similar saturation distributions. Conclusions A characteristic of the software algorithm reduces the frequency of saturations of 87–90% and increases the frequency of higher values returned by the Masimo SET Radical pulse oximeter. This effect, which remains within the recommended standards for accuracy, is removed by installing revised software (board firmware V4.8 or higher). Because this observation is likely to influence oxygen targeting, it should be considered in the analysis of the oxygen trial results to maximise their generalisability. PMID:21378398

Oxygen targeting in preterm infants using the Masimo SET Radical pulse oximeter.

PubMed

Johnston, Ewen D; Boyle, Breidge; Juszczak, Ed; King, Andy; Brocklehurst, Peter; Stenson, Ben J

2011-11-01

A pretrial clinical improvement project for the BOOST-II UK trial of oxygen saturation targeting revealed an artefact affecting saturation profiles obtained from the Masimo Set Radical pulse oximeter. Saturation was recorded every 10 s for up to 2 weeks in 176 oxygen dependent preterm infants in 35 UK and Irish neonatal units between August 2006 and April 2009 using Masimo SET Radical pulse oximeters. Frequency distributions of % time at each saturation were plotted. An artefact affecting the saturation distribution was found to be attributable to the oximeter's internal calibration algorithm. Revised software was installed and saturation distributions obtained were compared with four other current oximeters in paired studies. There was a reduction in saturation values of 87-90%. Values above 87% were elevated by up to 2%, giving a relative excess of higher values. The software revision eliminated this, improving the distribution of saturation values. In paired comparisons with four current commercially available oximeters, Masimo oximeters with the revised software returned similar saturation distributions. A characteristic of the software algorithm reduces the frequency of saturations of 87-90% and increases the frequency of higher values returned by the Masimo SET Radical pulse oximeter. This effect, which remains within the recommended standards for accuracy, is removed by installing revised software (board firmware V4.8 or higher). Because this observation is likely to influence oxygen targeting, it should be considered in the analysis of the oxygen trial results to maximise their generalisability.

Oxidation of DNA bases, deoxyribonucleosides and homopolymers by peroxyl radicals.

PubMed Central

Simandan, T; Sun, J; Dix, T A

1998-01-01

DNA base oxidation is considered to be a key event associated with disease initiation and progression in humans. Peroxyl radicals (ROO. ) are important oxidants found in cells whose ability to react with the DNA bases has not been characterized extensively. In this paper, the products resulting from ROO. oxidation of the DNA bases are determined by gas chromatography/MS in comparison with authentic standards. ROO. radicals oxidize adenine and guanine to their 8-hydroxy derivatives, which are considered biomarkers of hydroxyl radical (HO.) oxidations in cells. ROO. radicals also oxidize adenine to its hydroxylamine, a previously unidentified product. ROO. radicals oxidize cytosine and thymine to the monohydroxy and dihydroxy derivatives that are formed by oxidative damage in cells. Identical ROO. oxidation profiles are observed for each base when exposed as deoxyribonucleosides, monohomopolymers and base-paired dihomopolymers. These results have significance for the development, utilization and interpretation of DNA base-derived biomarkers of oxidative damage associated with disease initiation and propagation, and support the idea that the mutagenic potential of N-oxidized bases, when generated in cellular DNA, will require careful evaluation. Adenine hydroxylamine is proposed as a specific molecular probe for the activity of ROO. in cellular systems. PMID:9761719

Vibrational stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments

DOE PAGES

Mani, Tomoyasu; Grills, David C.; Miller, John R.

2015-01-02

A recently-developed instrument for time-resolved infrared detection following pulse radiolysis has been used to measure the ν(C≡N) IR band of the radical anion of a CN-substituted fluorene in tetrahydrofuran. Specific vibrational frequencies can exhibit distinct frequency shifts due to ion-pairing, which can be explained in the framework of the vibrational Stark effect. Measurements of the ratio of free ions and ion-pairs in different electrolyte concentrations allowed us to obtain an association constant and free energy change for ion-pairing. As a result, this new method has the potential to probe the geometry of ion-pairing and allows the reduction potentials of moleculesmore » to be determined in the absence of electrolyte in an environment of low dielectric constant.« less

Non-linear dynamic analysis of geared systems. Final Report Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Singh, Rajendra; Houser, Donald R.; Kahraman, Ahmet

1990-01-01

Under driving conditions, a typical geared system may be subjected to large dynamic loads. Also, the vibration level of the geared system is directly related to the noise radiated from the gear box. The steady state dynamic behavior of the system is examined in order to design reliable and quiet transmissions. The scope is limited to a system containing a spur gear pair with backlash and periodically time varying mesh stiffness, and rolling element bearings with clearance type nonlinearities. The internal static transmission error at the gear mesh, which is of importance from high frequency noise and vibration control view point, is considered in the formulation in sinusoidal or periodic form. A dynamic finite element model of the linear time invariant (LTI) system is developed. Effects of several system parameters, such as torsional and transverse flexibilities of the shafts and prime mover/load inertias, on free and forced vibration characteristics are investigated. Several reduced order LTI models are developed and validated by comparing their eigen solutions with the finite element model results. Using the reduced order formulations, a three degree of freedom dynamic model is developed which includes nonlinearities associated with radical clearances in the radial rolling element bearings, backlash between a spur gear pair and periodically varying gear mesh stiffness. As a limiting case, a single degree of freedom model of the spur gear pair with backlash is considered and mathematical conditions for tooth separation and back collision are defined. Both digital simulation technique and analytical models such as method of harmonic balance and the method of multiple scales were used to develop the steady state frequency response characteristics for various nonlinear and/or time varying cases.

The Inversion Effect for Chinese Characters is Modulated by Radical Organization.

PubMed

Luo, Canhuang; Chen, Wei; Zhang, Ye

2017-06-01

In studies of visual object recognition, strong inversion effects accompany the acquisition of expertise and imply the involvement of configural processing. Chinese literacy results in sensitivity to the orthography of Chinese characters. While there is some evidence that this orthographic sensitivity results in an inversion effect, and thus involves configural processing, that processing might depend on exact orthographic properties. Chinese character recognition is believed to involve a hierarchical process, involving at least two lower levels of representation: strokes and radicals. Radicals are grouped into characters according to certain types of structure, i.e. left-right structure, top-bottom structure, or simple characters with only one radical by itself. These types of radical structures vary in both familiarity, and in hierarchical level (compound versus simple characters). In this study, we investigate whether the hierarchical-level or familiarity of radical-structure has an impact on the magnitude of the inversion effect. Participants were asked to do a matching task on pairs of either upright or inverted characters with all the types of structure. Inversion effects were measured based on both reaction time and response sensitivity. While an inversion effect was observed in all 3 conditions, the magnitude of the inversion effect varied with radical structure, being significantly larger for the most familiar type of structure: characters consisting of 2 radicals organized from left to right. These findings indicate that character recognition involves extraction of configural structure as well as radical processing which play different roles in the processing of compound characters and simple characters.

Interphase cytogenetics of prostatic carcinoma in fine needle aspirate smears of radical prostatectomy specimens: A practical screening tool?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, R.Y.; Troncoso, P.; El-Naggar, A.K.

1994-09-01

Identification of chromosomal aberrations that may be used for diagnostic or prognostic evaluation of prostatic adenocarcinoma has been the subject of great interest. In a previous study, we applied the fluorescence in situ hybridization (FISH) method on paraffin-embedded material to show that trisomy 7 was associated with the progression of human prostate cancer. In this study, we attempted to assess the utility of the FISH technique in detecting aneuploidy in fine needle aspirate (FNA) smears of prostatic tissues and to compare FISH results with that of DNA flow cytometry (FCM). Paired samples of normal and tumor FNA smears were obtainedmore » from 10 radical prostatectomy specimens. Dual-color chromosomes 7 and 9-specific centromeric DNA probes were used for FISH. FISH analysis demonstrated increased frequencies of trisomy 7 cells in all 10 tumors studied when compared with the paired normals. In contrast, 6 of 10 tumors were determined to be diploid by FCM. Our results show that FNA of radical prostatectomy specimens is a practical method for obtaining suitable material for both FISH and FCM analyses of prostate carcinoma. Thus, interphase FISH may be a practical screening tool to determine aneuploidy in FNA smears of prostatic carcinoma.« less

Supramolecular control of the spin-dependent dynamics of long-lived charge-separated states at the micellar interface as studied by magnetic field effect.

PubMed

Miura, Tomoaki

2013-05-30

Spin selectivity in long-lived charge separation at the micellar interface is studied using the magnetic field effect (MFE). An amphiphilic viologen is complexed with a nonionic surfactant to form a supramolecular acceptor cage, of which the size is controlled by the acceptor concentration, as confirmed by dynamic light scattering measurement. Photoinduced electron transfer (ET) from a guest polyaromatic molecule to the viologen moiety is observed spin-dependently with time-resolved fluorescence (trFL) and transient absorption (TA). A negative MFE on the radical yield is successfully observed, which indicates generation of singlet-born long-lived radical pair that is realized by supramolecular control of the donor-acceptor (D-A) distances. The dominance of the singlet-precursor MFE is sensitive to the acceptor concentration, which presumably affects the D-A distance as well as the cage size. However, theoretical analysis of the MFE gives large recombination rates of ca. 10(8) s(-1), which indicate the contribution of spin-allowed recombination of the pseudocontact radical pair generated by still active in-cage diffusion. Dependence of the viologen concentration and alkyl chain length on the recombination and escape dynamics is discussed in terms of precursor spin states and the microenvironments in the cage.

Formation of singlet oxygen by decomposition of protein hydroperoxide in photosystem II.

PubMed

Pathak, Vinay; Prasad, Ankush; Pospíšil, Pavel

2017-01-01

Singlet oxygen (1O2) is formed by triplet-triplet energy transfer from triplet chlorophyll to O2 via Type II photosensitization reaction in photosystem II (PSII). Formation of triplet chlorophyll is associated with the change in spin state of the excited electron and recombination of triplet radical pair in the PSII antenna complex and reaction center, respectively. Here, we have provided evidence for the formation of 1O2 by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. Protein hydroperoxide is formed by protein oxidation initiated by highly oxidizing chlorophyll cation radical and hydroxyl radical formed by Type I photosensitization reaction. Under highly oxidizing conditions, protein hydroperoxide is oxidized to protein peroxyl radical which either cyclizes to dioxetane or recombines with another protein peroxyl radical to tetroxide. These highly unstable intermediates decompose to triplet carbonyls which transfer energy to O2 forming 1O2. Data presented in this study show for the first time that 1O2 is formed by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex.

Formation of singlet oxygen by decomposition of protein hydroperoxide in photosystem II

PubMed Central

Pathak, Vinay; Prasad, Ankush

2017-01-01

Singlet oxygen (1O2) is formed by triplet-triplet energy transfer from triplet chlorophyll to O2 via Type II photosensitization reaction in photosystem II (PSII). Formation of triplet chlorophyll is associated with the change in spin state of the excited electron and recombination of triplet radical pair in the PSII antenna complex and reaction center, respectively. Here, we have provided evidence for the formation of 1O2 by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. Protein hydroperoxide is formed by protein oxidation initiated by highly oxidizing chlorophyll cation radical and hydroxyl radical formed by Type I photosensitization reaction. Under highly oxidizing conditions, protein hydroperoxide is oxidized to protein peroxyl radical which either cyclizes to dioxetane or recombines with another protein peroxyl radical to tetroxide. These highly unstable intermediates decompose to triplet carbonyls which transfer energy to O2 forming 1O2. Data presented in this study show for the first time that 1O2 is formed by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. PMID:28732060

Listing triangles in expected linear time on a class of power law graphs.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nordman, Daniel J.; Wilson, Alyson G.; Phillips, Cynthia Ann

Enumerating triangles (3-cycles) in graphs is a kernel operation for social network analysis. For example, many community detection methods depend upon finding common neighbors of two related entities. We consider Cohen's simple and elegant solution for listing triangles: give each node a 'bucket.' Place each edge into the bucket of its endpoint of lowest degree, breaking ties consistently. Each node then checks each pair of edges in its bucket, testing for the adjacency that would complete that triangle. Cohen presents an informal argument that his algorithm should run well on real graphs. We formalize this argument by providing an analysismore » for the expected running time on a class of random graphs, including power law graphs. We consider a rigorously defined method for generating a random simple graph, the erased configuration model (ECM). In the ECM each node draws a degree independently from a marginal degree distribution, endpoints pair randomly, and we erase self loops and multiedges. If the marginal degree distribution has a finite second moment, it follows immediately that Cohen's algorithm runs in expected linear time. Furthermore, it can still run in expected linear time even when the degree distribution has such a heavy tail that the second moment is not finite. We prove that Cohen's algorithm runs in expected linear time when the marginal degree distribution has finite 4/3 moment and no vertex has degree larger than {radical}n. In fact we give the precise asymptotic value of the expected number of edge pairs per bucket. A finite 4/3 moment is required; if it is unbounded, then so is the number of pairs. The marginal degree distribution of a power law graph has bounded 4/3 moment when its exponent {alpha} is more than 7/3. Thus for this class of power law graphs, with degree at most {radical}n, Cohen's algorithm runs in expected linear time. This is precisely the value of {alpha} for which the clustering coefficient tends to zero asymptotically, and it is in the range that is relevant for the degree distribution of the World-Wide Web.« less

The Quirky Collider Signals of Folded Supersymmetry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burdman, Gustavo; Chacko, Z.; Goh, Hock-Seng

2008-08-01

We investigate the collider signals associated with scalar quirks ('squirks') in folded supersymmetric models. As opposed to regular superpartners in supersymmetric models these particles are uncolored, but are instead charged under a new confining group, leading to radically different collider signals. Due to the new strong dynamics, squirks that are pair produced do not hadronize separately, but rather form a highly excited bound state. The excited 'squirkonium' loses energy to radiation before annihilating back into Standard Model particles. We calculate the branching fractions into various channels for this process, which is prompt on collider time-scales. The most promising annihilation channelmore » for discovery is W+photon which dominates for squirkonium near its ground state. We demonstrate the feasibility of the LHC search, showing that the mass peak is visible above the SM continuum background and estimate the discovery reach.« less

Free-radicals and advanced chemistries involved in cell membrane organization influence oxygen diffusion and pathology treatment.

PubMed

Petersen, Richard C

2017-01-01

A breakthrough has been discovered in pathology chemistry related to increasing molecular structure that can interfere with oxygen diffusion through cell membranes. Free radicals can crosslink unsaturated low-viscosity fatty acid oils by chain-growth polymerization into more viscous liquids and even solids. Free radicals are released by mitochondria in response to intermittent hypoxia that can increase membrane molecular organization to reduce fluidity and oxygen diffusion in a possible continuing vicious cycle toward pathological disease. Alternate computational chemistry demonstrates molecular bond dynamics in free energy for cell membrane physiologic movements. Paired electrons in oxygen and nitrogen atoms require that oxygen bonds rotate and nitrogen bonds invert to seek polar nano-environments and hide from nonpolar nano-environments thus creating fluctuating instability at a nonpolar membrane and polar biologic fluid interface. Subsequent mechanomolecular movements provide free energy to increase diffusion by membrane transport of molecules and oxygen into the cell, cell-membrane signaling/recognition/defense in addition to protein movements for enzyme mixing. In other chemistry calcium bonds to membrane phosphates primarily on the outer plasma cell membrane surface to influence the membrane firing threshold for excitability and better seal out water permeation. Because calcium is an excellent metal conductor and membrane phosphate headgroups form a semiconductor at the biologic fluid interface, excess electrons released by mitochondria may have more broad dissipation potential by safe conduction through calcium atomic-sized circuits on the outer membrane surface. Regarding medical conditions, free radicals are known to produce pathology especially in age-related disease in addition to aging. Because cancer cell membranes develop extreme polymorphism that has been extensively followed in research, accentuated easily-visualized free-radical models are developed. In terms of treatment, use of vitamin nutrient supplements purported to be antioxidants that remove free radicals has not proved worthwhile in clinical trials presumably due to errors with early antioxidant measurements based on inaccurate colorimetry tests. However, newer covalent-bond shrinkage tests now provide accurate measurements for free-radical inhibitor hydroquinone and other molecules toward drug therapy.

Free-radicals and advanced chemistries involved in cell membrane organization influence oxygen diffusion and pathology treatment

PubMed Central

Petersen, Richard C

2017-01-01

A breakthrough has been discovered in pathology chemistry related to increasing molecular structure that can interfere with oxygen diffusion through cell membranes. Free radicals can crosslink unsaturated low-viscosity fatty acid oils by chain-growth polymerization into more viscous liquids and even solids. Free radicals are released by mitochondria in response to intermittent hypoxia that can increase membrane molecular organization to reduce fluidity and oxygen diffusion in a possible continuing vicious cycle toward pathological disease. Alternate computational chemistry demonstrates molecular bond dynamics in free energy for cell membrane physiologic movements. Paired electrons in oxygen and nitrogen atoms require that oxygen bonds rotate and nitrogen bonds invert to seek polar nano-environments and hide from nonpolar nano-environments thus creating fluctuating instability at a nonpolar membrane and polar biologic fluid interface. Subsequent mechanomolecular movements provide free energy to increase diffusion by membrane transport of molecules and oxygen into the cell, cell-membrane signaling/recognition/defense in addition to protein movements for enzyme mixing. In other chemistry calcium bonds to membrane phosphates primarily on the outer plasma cell membrane surface to influence the membrane firing threshold for excitability and better seal out water permeation. Because calcium is an excellent metal conductor and membrane phosphate headgroups form a semiconductor at the biologic fluid interface, excess electrons released by mitochondria may have more broad dissipation potential by safe conduction through calcium atomic-sized circuits on the outer membrane surface. Regarding medical conditions, free radicals are known to produce pathology especially in age-related disease in addition to aging. Because cancer cell membranes develop extreme polymorphism that has been extensively followed in research, accentuated easily-visualized free-radical models are developed. In terms of treatment, use of vitamin nutrient supplements purported to be antioxidants that remove free radicals has not proved worthwhile in clinical trials presumably due to errors with early antioxidant measurements based on inaccurate colorimetry tests. However, newer covalent-bond shrinkage tests now provide accurate measurements for free-radical inhibitor hydroquinone and other molecules toward drug therapy. PMID:29202036

Reliability and Validity of a Smartphone-Paired Pulse Oximeter for Screening of Critical Congenital Heart Defects in Newborns.

PubMed

Huizing, Maurice J; Villamor-Martínez, Eduardo; Chavagne, Ingrid A; Vanagt, Ward Y; Spaanderman, Marc A E; Villamor, Eduardo

2017-01-01

Barriers to widespread implementation of pulse oximetry screening of critical congenital heart defects (CCHD) in newborns include increasing trends of out-of-hospital births and cost of equipment. In recent years, smartphone-compatible pulse oximeters have appeared on the market, but the validity of such devices in the setting of CCHD screening has not been evaluated. To compare the performance in CCHD screening of a smartphone-paired pulse oximeter (Masimo iSpO2-Rx™) and a hospital-grade pulse oximeter (Masimo Radical-7™). Preductal (right hand) and postductal (either foot) saturations were determined in a population of 201 term newborns by 2 independent teams, one using the Radical-7 and the other using the iSpO2-Rx. Bland-Altman analysis was applied to calculate mean bias and 95% limits of agreement between the 2 pulse oximeters. For the preductal oxygen saturation, the mean bias (Radical-7 minus iSpO2-Rx) was -0.08 (SD 1.76) and the lower and upper limits of agreement were -3.52 and 3.36, respectively. For the postductal oxygen saturation, the mean bias was -0.11 (SD 1.68) and the lower and upper limits of agreement were -3.49 and 3.18, respectively. In addition, the iSpO2-Rx provided reliable measurements of saturations below 95% in a group of 12 infants admitted to the neonatal intensive care unit. Our data suggest that CCHD screening with the Masimo iSpO2-Rx is feasible and accurate. The use of reliable smartphone-paired pulse oximeters may contribute to the extension of CCHD screening to home births and low resource settings. © 2017 S. Karger AG, Basel.

Zebra finches have a light-dependent magnetic compass similar to migratory birds.

PubMed

Pinzon-Rodriguez, Atticus; Muheim, Rachel

2017-04-01

Birds have a light-dependent magnetic compass that provides information about the spatial alignment of the geomagnetic field. It is proposed to be located in the avian retina and mediated by a light-induced, radical-pair mechanism involving cryptochromes as sensory receptor molecules. To investigate how the behavioural responses of birds under different light spectra match with cryptochromes as the primary magnetoreceptor, we examined the spectral properties of the magnetic compass in zebra finches. We trained birds to relocate a food reward in a spatial orientation task using magnetic compass cues. The birds were well oriented along the trained magnetic compass axis when trained and tested under low-irradiance 521 nm green light. In the presence of a 1.4 MHz radio-frequency electromagnetic (RF)-field, the birds were disoriented, which supports the involvement of radical-pair reactions in the primary magnetoreception process. Birds trained and tested under 638 nm red light showed a weak tendency to orient ∼45 deg clockwise of the trained magnetic direction. Under low-irradiance 460 nm blue light, they tended to orient along the trained magnetic compass axis, but were disoriented under higher irradiance light. Zebra finches trained and tested under high-irradiance 430 nm indigo light were well oriented along the trained magnetic compass axis, but disoriented in the presence of a RF-field. We conclude that magnetic compass responses of zebra finches are similar to those observed in nocturnally migrating birds and agree with cryptochromes as the primary magnetoreceptor, suggesting that light-dependent, radical-pair-mediated magnetoreception is a common property for all birds, including non-migratory species. © 2017. Published by The Company of Biologists Ltd.

Reaction between peroxynitrite and boronates: EPR spin-trapping, HPLC analyses, and quantum mechanical study of the free radical pathway

PubMed Central

Sikora, Adam; Zielonka, Jacek; Lopez, Marcos; Dybala-Defratyka, Agnieszka; Joseph, Joy; Marcinek, Andrzej; Kalyanaraman, Balaraman

2013-01-01

Recently we showed that peroxynitrite (ONOO−) reacts directly and rapidly with aromatic and aliphatic boronic acids (k ≈ 106 M−1s−1). Product analyses and substrate consumption data indicated that ONOO− reacts stoichiometrically with boronates, yielding the corresponding phenols as the major product (~85–90%), and the remaining products (10–15%) were proposed to originate from free radical intermediates (phenyl and phenoxyl radicals). Here we investigated in detail the minor, free radical pathway of boronate reaction with ONOO−. The electron paramagnetic resonance (EPR) spin-trapping technique was used to characterize the free radical intermediates formed from the reaction between boronates and ONOO−. Using 2-methyl-2-nitrosopropane (MNP) and 5-diethoxyphosphoryl-5-methyl-1-pyrroline-N-oxide (DEPMPO) spin traps, phenyl radicals were trapped and detected. Although phenoxyl radicals were not detected, the positive effects of molecular oxygen, and inhibitory effects of hydrogen atom donors (acetonitrile, and 2-propanol) and general radical scavengers (GSH, NADH, ascorbic acid and tyrosine) on the formation of phenoxyl radical-derived nitrated product, suggest that phenoxyl radical was formed as the secondary species. We propose that the initial step of the reaction involves the addition of ONOO− to the boron atom in boronates. The anionic intermediate undergoes both heterolytic (major pathway) and homolytic (minor pathway) cleavage of the peroxy (O-O) bond to form phenol and nitrite as a major product (via a non-radical mechanism), or a radical pair PhB(OH)2O•−…•NO2 as a minor product. It is conceivable that phenyl radicals are formed by the fragmentation of PhB(OH)2O•− radical anion. According to the DFT quantum mechanical calculations, the energy barrier for the dissociation of PhB(OH)2O•− radical anion to form phenyl radicals is only a few kcal/mol, suggesting rapid and spontaneous fragmentation of PhB(OH)2O•− radical anion in aqueous media. Biological implications of the minor free radical pathway are discussed in the context of ONOO− detection, using the boronate probes. PMID:21434648

Magnetic field effect in fluorescence of excited fluorophore equilibrated with exciplex that reversibly dissociates into radical-ion pair undergoing the spin conversion.

PubMed

Dodin, Dmitry V; Ivanov, Anatoly I; Burshtein, Anatoly I

2012-07-14

The fluorescence of the photoexcited electron acceptor, (1)A∗, and the exciplex, (1)[D(+δ)A(-δ)] formed at contact of (1)A∗ with an electron donor (1)D, is known to be very sensitive to a magnetic field, assisting the spin conversion in the resulting geminate radical ion pair (RIP), (1, 3)[D(+)...A(-)]. The relative increase of the fluorescence in the highest magnetic field compared to the lowest one, known as the magnetic field effect, crucially depends on the dielectric constant of the solvent, ɛ. This phenomenon first studied experimentally is at first reproduced here theoretically by means of the so called integral encounter theory. It was shown to be very sensitive to the position of the exciplex energy level relative to the levels of exciplex precursors and the charged products of its dissociation. The results obtained strongly depend on the dielectric properties of the solvents as well as on the exciplex and RIP formation rates.

Search for first-generation scalar leptoquarks in p anti-p collisions at s**(1/2) = 1.96-TeV

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abazov, V.M.; Abbott, B.; Abolins, M.

2004-12-01

The authors report on a search for pair production of first-generation scalar leptoquarks (LQ) in p{bar p} collisions at {radical}s = 1.96 TeV using an integrated luminosity of 252 pb{sup -1} collected at the Fermilab Tevatron collider by the D0 detector. They observe no evidence for LQ production in the topologies arising from LQ{ovr LQ} {yields} eqeq and LQ{ovr LQ} {yields} eqvq, and derive 95% C.L. lower limits on the LQ mass as a function of {beta}, where {beta} is the branching fraction for LQ {yields} eq. The limits are 241 and 218 GeV/c{sup 2} for {beta} = 1 andmore » 0.5, respectively. These results are combined with those obtained by D0 at {radical}s = 1.8 TeV, which increases these LQ mass limits to 256 and 234 GeV/c{sup 2}.« less

Hydroxyl Radical (OH•) Reaction with Guanine in an Aqueous Environment: A DFT Study

PubMed Central

Kumar, Anil; Pottiboyina, Venkata; Sevilla, Michael D.

2011-01-01

The reaction of hydroxyl radical (OH•) with DNA accounts for about half of radiation-induced DNA damage in living systems. Previous literature reports point out that the reaction of OH• with DNA proceeds mainly through the addition of OH• to the C=C bond of the DNA bases. However, recently it has been reported that the principal reaction of OH• with dGuo (deoxyguanosine) is the direct hydrogen atom abstraction from its exocyclic amine group rather than addition of OH• to the C=C bond. In the present work, these two reaction pathways of OH• attack on guanine (G) in the presence of water molecules (aqueous environment) are investigated using the density functional theory (DFT) B3LYP method with 6-31G* and 6-31++G** basis sets. The calculations show that the initial addition of the OH• at C4=C5 double bond of guanine is barrier free and the adduct radical (G-OH•) has only a small activation barrier of ca. 1 – 6 kcal/mol leading to the formation of a metastable ion-pair intermediate (G•+---OH−). The formation of ion-pair is a result of the highly oxidizing nature of the OH• in aqueous media. The resulting ion-pair (G•+---OH−) deprotonates to form H2O and neutral G radicals favoring G(N1-H)• with an activation barrier of ca. 5 kcal/mol. The overall process from the G(C4)-OH• (adduct) to G(N1-H)• and water is found to be exothermic in nature by more than 13 kcal/mol. (G-OH•), (G•+---OH−), and G(N1-H)• were further characterized by the CAM-B3LYP calculations of their UV-visible spectra and good agreement between theory and experiment is achieved. Our calculations for the direct hydrogen abstraction pathway from N1 and N2 sites of guanine by the OH• show that this is also a competitive route to produce G(N2-H)•, G(N1-H)• and H2O. PMID:22050033

J/psi Polarization in pp collisions at s = 7 TeV

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abelev, B.; Awes, Terry C; Ganoti, P.

The ALICE Collaboration has studied J/{Psi} production in pp collisions at {radical}s = 7 TeV at the LHC through its muon pair decay. The polar and azimuthal angle distributions of the decay muons were measured, and results on the J/{Psi} polarization parameters {lambda}{sub {theta}} and {lambda}{sub {phi}} were obtained. The study was performed in the kinematic region 2.5 < y < 4, 2 < p{sub t} < 8 GeV/c, in the helicity and Collins-Soper reference frames. In both frames, the polarization parameters are compatible with zero, within uncertainties.

Effects of ligand electronegativity on recoupled pair bonds with application to sulfurane precursors.

PubMed

Lindquist, Beth A; Woon, David E; Dunning, Thom H

2014-07-31

Recoupled pair bonds (RPBs) are conditional bonds-they only form for selected central atoms and ligands. A complete theoretical description of RPBs requires an understanding of the properties of the central atom and ligands that enable such bonds to be formed. In this work, we show that ligand electronegativity is positively correlated with recoupled pair bond strength for a variety of ligands interacting with the 3p(2) pair of sulfur. We also describe substituent (X) effects on the SF(a(4)Σ(-)) state by investigating X2SF species. These effects generally mirror those observed for covalently bound analogues, but we found that recoupled pair bonding can lead to breakdowns in the expected relationships among bond length, strength, and force constant for some of these species. Finally, we compare the properties of two molecules of practical interest that are bound by recoupled pair bonds: the dimethyl sulfur fluoride and hydroxide radicals (DMS-F and DMS-OH).

Cisplatin enhances the formation of DNA single- and double-strand breaks by hydrated electrons and hydroxyl radicals.

PubMed

Rezaee, Mohammad; Sanche, Léon; Hunting, Darel J

2013-03-01

The synergistic interaction of cisplatin with ionizing radiation is the clinical rationale for the treatment of several cancers including head and neck, cervical and lung cancer. The underlying molecular mechanism of the synergy has not yet been identified, although both DNA damage and repair processes are likely involved. Here, we investigate the indirect effect of γ rays on strand break formation in a supercoiled plasmid DNA (pGEM-3Zf-) covalently modified by cisplatin. The yields of single- and double-strand breaks were determined by irradiation of DNA and cisplatin/DNA samples with (60)Co γ rays under four different scavenging conditions to examine the involvement of hydrated electrons and hydroxyl radicals in inducing the DNA damage. At 5 mM tris in an N2 atmosphere, the presence of an average of two cisplatins per plasmid increased the yields of single- and double-strand breaks by factors of 1.9 and 2.2, respectively, relative to the irradiated unmodified DNA samples. Given that each plasmid of 3,200 base pairs contained an average of two cisplatins, this represents an increase in radiosensitivity of 3,200-fold on a per base pair basis. When hydrated electrons were scavenged by saturating the samples with N2O, these enhancement factors decreased to 1.5 and 1.2, respectively, for single- and double-strand breaks. When hydroxyl radicals were scavenged using 200 mM tris, the respective enhancement factors were 1.2 and 1.6 for single- and double-strand breaks, respectively. Furthermore, no enhancement in DNA damage by cisplatin was observed after scavenging both hydroxyl radicals and hydrated electrons. These findings show that hydrated electrons can induce both single- and double-strand breaks in the platinated DNA, but not in unmodified DNA. In addition, cisplatin modification is clearly an extremely efficient means of increasing the formation of both single- and double-strand breaks by the hydrated electrons and hydroxyl radicals created by ionizing radiation.

Understanding political radicalization: The two-pyramids model.

PubMed

McCauley, Clark; Moskalenko, Sophia

2017-04-01

This article reviews some of the milestones of thinking about political radicalization, as scholars and security officials struggled after 9/11 to discern the precursors of terrorist violence. Recent criticism of the concept of radicalization has been recognized, leading to a 2-pyramids model that responds to the criticism by separating radicalization of opinion from radicalization of action. Security and research implications of the 2-pyramids model are briefly described, ending with a call for more attention to emotional experience in understanding both radicalization of opinion and radicalization of action. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

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. Copyright © 2015 Elsevier B.V. All rights reserved.

Search for tt-bar-Resonances in the Lepton+Jets Final State

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schliephake, Thorsten

2008-11-23

A search for a narrow-width heavy resonance decaying into top quark pairs (X{yields}tt-bar) in pp-bar collisions at {radical}(s) = 1.96 TeV has been performed using data collected with the DOe detector at the Fermilab Tevatron Collider. This analysis considers tt-bar candidate events in the lepton+jets channel using a neural network tagger to identify b-jets and the tt-bar invariant mass distribution to search for evidence of resonant production. The analyzed dataset corresponds to an integrated luminosity of approximately 2.1 fb{sup -1}. We find no evidence for a narrow resonance X decaying to tt-bar. Therefore, we set upper limits on {sigma}{sub X}{center_dot}B(X{yields}tt-bar)more » for different hypothesized resonance masses using a Bayesian approach. Within a topcolor-assisted technicolor model, the existence of a leptophobic Z' boson with mass M{sub Z'}<760 GeV and width {gamma}{sub Z'} = 0.012M{sub Z'} can be excluded at 95% C.L.« less

Measurement of forward-backward asymmetry A{sub FB} and of the weak mixing angle in processes of dilepton production in proton-proton collisions at {radical} s = 7 TeV in the CMS experiment at the LHC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gorbunov, I. N., E-mail: Ilya.Gorbunov@cern.ch; Shmatov, S. V., E-mail: shmatov@cern.ch

2013-09-15

The results obtained by measuring the forward-backward asymmetry (A{sub FB}) of Drell-Yan lepton pairs in proton-proton collisions at {radical} s = 7 TeV at the LHC are presented. This asymmetry is measured as a function of the dilepton mass and rapidity in the dielectron and dimuon channels. The values of A{sub FB} were found for invariant masses of dileptons in the range of 40 Less-Than-Or-Slanted-Equal-To M{sub ll} Less-Than-Or-Slanted-Equal-To 600 GeV. The results for the effective weak mixing angle that were deduced from data on dimuon production in Drell-Yan processes are also presented. The respective data sample was collected by usingmore » the Compact Muon Solenoid (CMS) detector over the period spanning the years 2010 and 2011. The measured asymmetry and the effective weak mixing are consistent with the respective Standard Model predictions.« less

Tropospheric OH and Cl levels deduced from non-methane hydrocarbon measurements in a marine site

NASA Astrophysics Data System (ADS)

Arsene, C.; Bougiatioti, A.; Kanakidou, M.; Bonsang, B.; Mihalopoulos, N.

2007-09-01

In situ continuous hourly measurements of C2-C8 non-methane hydrocarbons (NMHCS) have been performed from March to October 2006 at two coastal locations (natural and rural) on the island of Crete, in the Eastern Mediterranean. Well defined diel variations were observed for several short lived NMHCS (including ethene, propene, n-butane, n-pentane, n-hexane, 2-methyl-pentane). The daytime concentration of hydroxyl (OH) radicals estimated from these experimental data varied from 1.3×106 to ~4.0×106 radical cm-3, in good agreement with box-model simulations. In addition the relative variability of various hydrocarbon pairs (at least 7) was used to derive the tropospheric levels of Cl atoms. The Cl atom concentration has been estimated to range between 0.6×104 and 4.7×104 atom cm-3, in good agreement with gaseous hydrochloric acid (HCl) observations in the area. Such levels of Cl atoms can be of considerable importance for the oxidation capacity of the troposphere on a regional scale.

Insight into the Chemical Compass Mechanism of Cryptochromes by Computational Investigation

NASA Astrophysics Data System (ADS)

Pachter, Ruth; Hong, Gongyi

2014-03-01

In this work we investigated aspects of the light-dependent inclination compass, largely assumed in avian magnetic perception, e.g. of European robins. It is postulated that radical pairs (RPs) are formed in cryptochrome (Cry) photoreceptors that contain a redox-active flavin adenine dinucleotide (FAD) in proximity to a Trp triad. The hypothesis was previously rationalized theoretically for the Cry from Arabidopsis thaliana (AtCry1), and the pKa of the proximate residue (PR) to the FAD we derived from QM/MM MD simulations is consistent with this assumption. However, attempts to extrapolate the results to other species are complicated. In the Cry from Drosophila melanogaster (DmCry1), which demonstrated a magnetic response, the FAD anionic radical ground state differs from an oxidized form in AtCry1, and the PR to the FAD is Cys rather than Asp in AtCry1. Investigation for DmCry1 model compounds, showing potential feasibility of a RP mechanism, will be described, where the calculated excitation energy is in agreement with experiment. Involvement of a Tyr instead of Trp in the triad was also considered. Because Crys from the garden warbler form RPs, a RP mechanism was examined, based on a 3D structure derived by homology modeling and MD simulations.

Does 8-Nitroguanine Form 8-Oxoguanine? An Insight from Its Reaction with •OH Radical.

PubMed

Bhattacharjee, Kanika; Shukla, P K

2018-02-15

8-Nitroguanine (8-nitroG) formed due to nitration of guanine base of DNA plays an important role in mutagenesis and carcinogenesis. In the present contribution, state-of-the-art quantum chemical calculations using M06-2X density functional and domain-based local pair natural orbital-coupled cluster theory with single, double, and perturbative triple excitations (DLPNO-CCSD(T)) methods have been carried out to investigate the mechanism of reaction of • OH radical with 8-nitroG leading to the formation of 8-oxoguanine (8-oxoG) (one of the most mutagenic and carcinogenic derivatives of guanine) in gas phase and aqueous media. Calculations of barrier energies and rate constants involved in the addition reactions of • OH radical at different sites of 8-nitroguanine show that C8 and C2 sites are the most and least reactive sites, respectively. Relative stability and Boltzmann populations of adducts show that the adduct formed at the C8 site occurs predominantly in equilibrium. Our calculations reveal that 8-nitroG is very reactive toward • OH radical and is converted readily into 8-oxoG when attacked by • OH radicals, in agreement with available experimental observations.

A Model of Rapid Radicalization Behavior Using Agent-Based Modeling and Quorum Sensing

NASA Technical Reports Server (NTRS)

Schwartz, Noah; Drucker, Nick; Campbell, Kenyth

2012-01-01

Understanding the dynamics of radicalization, especially rapid radicalization, has become increasingly important to US policy in the past several years. Traditionally, radicalization is considered a slow process, but recent social and political events demonstrate that the process can occur quickly. Examining this rapid process, in real time, is impossible. However, recreating an event using modeling and simulation (M&S) allows researchers to study some of the complex dynamics associated with rapid radicalization. We propose to adapt the biological mechanism of quorum sensing as a tool to explore, or possibly explain, rapid radicalization. Due to the complex nature of quorum sensing, M&S allows us to examine events that we could not otherwise examine in real time. For this study, we employ Agent Based Modeling (ABM), an M&S paradigm suited to modeling group behavior. The result of this study was the successful creation of rapid radicalization using quorum sensing. The Battle of Mogadishu was the inspiration for this model and provided the testing conditions used to explore quorum sensing and the ideas behind rapid radicalization. The final product has wider applicability however, using quorum sensing as a possible tool for examining other catalytic rapid radicalization events.

Socialization As and through Conversation: Political Discourse in Israeli Families.

ERIC Educational Resources Information Center

Ribak, Rivka

1997-01-01

Survey of Israeli parent-child pairs revealed portraits of moderate parents and radical children, but follow-up of family conversation while watching and discussing television news suggested harmony and unity in Israeli living rooms. Reconceptualization of the theoretical canon of political socialization analyzes the conversation as a moment of…

Chemical nuclear polarization effects in photoreactions of 1,4-diazabicyclo[2.2.2]octane with carbonyl-containing compounds

NASA Astrophysics Data System (ADS)

Porkhun, V. I.; Rakhimov, A. I.

2012-11-01

Elementary acts of the photoreaction of diamine with 2,6-diphenyl- p-benzoquinone are determined from the effects of chemical nuclear polarization effects. Hydrogen atom transfer is shown to occur in two stages with the participation of a radical ion pair.

Direct Observation of Excimer-Mediated Intramolecular Electron Transfer in a Cofacially-Stacked Perylene Bisimide Pair.

PubMed

Sung, Jooyoung; Nowak-Król, Agnieszka; Schlosser, Felix; Fimmel, Benjamin; Kim, Woojae; Kim, Dongho; Würthner, Frank

2016-07-27

We have elucidated excimer-mediated intramolecular electron transfer in cofacially stacked PBIs tethered by two phenylene-butadiynylene loops. The electron transfer between energetically equivalent PBIs is revealed by the simultaneous observation of the PBI radical anion and cation bands in the transient absorption spectra. The fluorescence decay time of the excimer states is in good agreement with the rise time of PBI radical bands in transient absorption spectra suggesting that the electron transfer dynamics proceed via the excimer state. We can conclude that the excimer state effectuates the efficient charge transfer in the cofacially stacked PBI dimer.

An electron spin polarization study of the interaction of photoexcited triplet molecules with mono- and polynitroxyl stable free radicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turro, N.J.; Khudyakov, I.V.; Bossmann, S.H.

1993-02-11

Time-resolved electron spin resonance (TR ESR) has been used to investigate the chemically induced dynamic electron polarization (CIDEP) generated by the interaction of stable free radicals with the triplet states of benzophenone, benzil, and 2-acetylnaphthalene. The stable radicals were mono-, di-, tri-, and tetranitroxyl free radicals possessing the 2,2,6,6-tetramethylpiperidine-N-oxyl moiety. All of the stable radical systems investigated were found to be emissively polarized by interaction with the triplet states, and the phase of polarization was independent of the sign of zero-field splitting (D) of the interacting triple molecule. Possible and likely mechanisms of polarization transfer (creation) resulting from the interactionmore » of photoexcited triplet molecules with nitroxyls in the strong electron exchange are discussed. The emissive CIDEP of nitroxyls observed in the interactions with triplet benzil, which has D > 0, provides strong support for the operation of the radical-triplet pair mechanism. Within the time scale of TR ESR experiments ([approximately]10[sup [minus]7]--10[sup [minus]6] s) no significant variation in the shape of the CIDEP spectra of the nitroxyls was observed, either in viscous media or in micelles. It is concluded that intramolecular spin exchange (or conformational change) of polynitroyls occurs much faster than the time resolution of the experiment. 24 refs., 6 figs., 1 tab.« less

Preparation of chitosan-ferulic acid conjugate: Structure characterization and in the application of pharmaceuticals.

PubMed

Li, Chen; Li, Jian-Bin

2017-12-01

A novel drug delivery system based on chitosan derivatives was prepared by introducting ferulic acid to chitosan adopting a free radical-induced grafting procedure. This paper used an ascorbic acid/hydrogen peroxide redox pair as radical initiator. The chitosan derivative was characterized by Fourier transformed infrared (FTIR), Ultraviolet-visible spectrum (UV), Differential scanning calorimetry (DSC), X-ray diffraction (XRD) and Electron microscopic scanning (SEM). What is more, preparing microcapsules with the chitosan conjugate as wall material, the drug release propertie of chitosan conjugates were compared with that of a blank chitosan, which treated in the same conditions but in the absence of ferulic acid. The study clearly demonstrates that free radical-induced grafting procedure was an effective reaction methods and chitosan-ferulic acid is a potential functionalized carrier material for drug delivery. Copyright © 2017 Elsevier B.V. All rights reserved.

Structural Studies of Perfluoroaryldiselenadiazolyl Radicals: Insights into Dithiadiazolyl Chemistry.

PubMed

Melen, Rebecca L; Less, Robert J; Pask, Christopher M; Rawson, Jeremy M

2016-11-21

The synthesis and structural characterization of a series of perfluoroaryldiselenadiazolyls [DSeDA; p-XC 6 F 4 CNSeSeN (X = F, Cl, Br, CF 3 , NO 2 , and CN for 2a-2f, respectively)] are described. Concentration-dependent solution UV/vis measurements on 2a follow the Beer-Lambert law and the transitions assigned through time-dependent density functional theory (TD-DFT) studies, indicating little propensity for dimerization in solution (10 -3 -10 -4 M). Solution electron paramagnetic resonance (EPR) spectra reveal that these radicals exhibit a broad featureless singlet around g = 2.04 but form well-resolved anisotropic EPR spectra in frozen solution, from which spin densities were determined and found to reflect an increase in the spin density at the chalcogen in relation to the corresponding dithiadiazolyl (DTDA) radicals, p-XC 6 F 4 CNSSN. The solid-state structures of 2a and 2d-2f all adopt spin-paired cis-cofacial dimers in which the dimers are held together via multicenter π*-π* "pancake bonding" interactions. Conversely, 2b and 2c exhibit an orthogonal mode of association, which is unique to DSeDA chemistry but which also affords a singlet ground state evidenced by SQUID magnetometry. The more sterically demanding diselenadiazolyl radical 2f was also prepared and exhibits a trans-antarafacial dimerization mode. DFT studies [UPBE0-D3 ccPVTZ-PP(-F)++] on the model radical HCNSeSeN confirm that each dimer is a stable energy minimum on the potential energy surface, reproducing well the experimental geometric parameters with relative stability in the order cis-cofacial > orthogonal > trans-antarafacial. Computational studies reflect stronger dimerization for DSeDA radicals in relation to their sulfur analogues, consistent with the experimental observation: While 2a and 2d are isomorphous with their corresponding DTDA radicals, 2b, 2c, and 2e-2g are all dimeric, in contrast to their DTDA analogues, which are monomeric in the solid-state. A study on 2f reveals that significant geometric strain accumulates in order to support the propensity for both cis dimerization and intermolecular CN···Se interactions. Conversely, p-NCC 6 F 4 CNSSN likely forfeits dimerization in the analogous packing motif in order to release strain but retains the favorable intermolecular CN···S interactions.

Unusual anal fin in a Devonian jawless vertebrate reveals complex origins of paired appendages

PubMed Central

Sansom, Robert S.; Gabbott, Sarah E.; Purnell, M. A.

2013-01-01

Jawed vertebrates (gnathostomes) have undergone radical anatomical and developmental changes in comparison with their jawless cousins (cyclostomes). Key among these is paired appendages (fins, legs and wings), which first evolved at some point on the gnathostome stem. The anatomy of fossil stem gnathostomes is, therefore, fundamental to our understanding of the nature and timing of the origin of this complex innovation. Here, we show that Euphanerops, a fossil jawless fish from the Devonian, possessed paired anal-fin radials, but no pectoral or pelvic fins. This unique condition occurs at an early stage on the stem-gnathostome lineage. This condition, and comparison with the varied condition of paired fins in other ostracoderms, indicates that there was a large amount of developmental plasticity during this episode—rather than a gradual evolution of this complex feature. Apparently, a number of different clades were exploring morphospace or undergoing multiple losses. PMID:23576777

Embracing the Humanistic Vision: Recurrent Themes in Peter Roberts' Recent Writings

ERIC Educational Resources Information Center

Reveley, James

2018-01-01

Running like a leitmotif through Peter Roberts' recently published philosophico-educational writings there is a humanistic thread, which this article picks out. In order to ascertain the quality of this humanism, Roberts is positioned in relation to a pair of extant humanisms: radical and integral. Points of comparability and contrast are…

Hooking Up: Students' Perception of "Getting Together" on a College Campus.

ERIC Educational Resources Information Center

Durst, Maribeth; Schaeffer, E. Marilyn

1989-01-01

Conducted year-long research project to study student culture on small college campus. Findings from 99 students revealed that students' dating practices differed radically from traditional practice where men take women out to dinner or a movie. Rather, found that pair of students spontaneously agreed to spend evening together. (NB)

Zero Quantum Coherence in a Series of Covalent Spin-Correlated Radical Pairs.

PubMed

Nelson, Jordan N; Krzyaniak, Matthew D; Horwitz, Noah E; Rugg, Brandon K; Phelan, Brian T; Wasielewski, Michael R

2017-03-23

Photoinitiated subnanosecond electron transfer within covalently linked electron donor-acceptor molecules can result in the formation of a spin-correlated radical pair (SCRP) with a well-defined initial singlet spin configuration. Subsequent coherent mixing between the SCRP singlet and triplet m s = 0 spin states, the so-called zero quantum coherence (ZQC), is of potential interest in quantum information processing applications because the ZQC can be probed using pulse electron paramagnetic resonance (pulse-EPR) techniques. Here, pulse-EPR spectroscopy is utilized to examine the ZQC oscillation frequencies and ZQC dephasing in three structurally well-defined D-A systems. While transitions between the singlet and triplet m s = 0 spin states are formally forbidden (Δm s = 0), they can be addressed using specific microwave pulse turning angles to map information from the ZQC onto observable single quantum coherences. In addition, by using structural variations to tune the singlet-triplet energy gap, the ZQC frequencies determined for this series of molecules indicate a stronger dependence on the electronic g-factor than on electron-nuclear hyperfine interactions.

Light-dependent magnetoreception: orientation behaviour of migratory birds under dim red light.

PubMed

Wiltschko, Roswitha; Munro, Ursula; Ford, Hugh; Stapput, Katrin; Wiltschko, Wolfgang

2008-10-01

Magnetic compass orientation in migratory birds has been shown to be based on radical pair processes and to require light from the short wavelength part of the spectrum up to 565 nm Green. Under dim red light of 645 nm wavelength and 1 mW m(-2) intensity, Australian silvereyes and European robins showed a westerly tendency that did not change between spring and autumn, identifying it as a 'fixed direction' response. A thorough analysis revealed that this orientation did not involve the inclination compass, but was a response based on the polarity of the magnetic field. Furthermore, in contrast to the orientation under short-wavelength light, it could be disrupted by local anaesthesia of the upper beak where iron-containing receptors are located, indicating that it is controlled by these receptors. The similarity of the response under dim red light to the response in total darkness suggests that the two responses may be identical. These findings indicate that the observed 'fixed direction' response under dim red light is fundamentally different from the normal compass orientation, which is based on radical pair processes.

CH/sub 3/xxx/sup 13/CO/sub 2/ pairs in irradiated single crystals of CH/sub 3//sup 13/CO/sub 2/Lix2D/sub 2/0. [Gamma rays

DOE Office of Scientific and Technical Information (OSTI.GOV)

Toriyama, K.; Iwasaki, M.

1976-10-01

The CH/sub 3/ radical trapped in irradiated single crystals of CH/sub 3//sup 13/CO/sub 2/Lix2D/sub 2/O has been found to interact with a /sup 13/CO/sub 2/ molecule, which is formed from the C--C bond breakage as a counterpart. The /sup 13/C superhyperfine coupling tensor was determined to be (-4.0, -3.3, -3.5) G. The /sup 13/CO/sub 2/ molecule is located in the direction of the unpaired electron orbital of CH/sub 3/ with the molecular axis perpendicular to it. The spectrum arising from the electron excess center CH/sub 3/ /sup 13/CO/sub 2//sup 2 -/ was also detected together with the CH/sub 3/ radical.more » Our results indicate that the CH/sub 3/xxx/sup 13/CO/sub 2/ pair is essentially a positive hole center formed from one electron loss followed by the C--C bond breakage. (AIP)« less

The influence of ENSO on an oceanic eddy pair in the South China Sea

NASA Astrophysics Data System (ADS)

Chu, Xiaoqing; Dong, Changming; Qi, Yiquan

2017-03-01

An eddy pair off the Vietnam coast is one of the most important features of the summertime South China Sea circulation. Its variability is of interest due to its profound impact on regional climate, ecosystems, biological processes, and fisheries. This study examines the influence of the El Niño-Southern Oscillation (ENSO), a basin-scale climatic mode, on the interannual variability of this regional eddy pair using satellite observational data and historical hydrographic measurements. Over the last three decades, the eddy pair strengthened in 1994 and 2002, and weakened in 2006, 2007, and 2008. It was absent in 1988, 1995, 1998, and 2010, coinciding with strong El Nino-to-La Nina transitions. Composite analyses showed that the strong transition events of ENSO led to radical changes in the summer monsoon, through the forcing of a unique sea surface temperature anomaly structure over the tropical Indo-Pacific basin. With weaker zonal wind, a more northward wind direction, and the disappearance of a pair of positive and negative wind stress curls, the eastward current jet turns northward along the Vietnam coast and the eddy pair disappears.

Reducing capacities and redox potentials of humic substances extracted from sewage sludge.

PubMed

Yang, Zhen; Du, Mengchan; Jiang, Jie

2016-02-01

Humic substances (HS) are redox active organic materials that can be extracted from sewage sludge generated in wastewater treatment processes. Due to the poor understanding of reducing capacity, redox potentials and redox active functional groups of HS in sewage sludge, the potential contribution of sludge HS in transformation of wastewater contaminants is unclear. In the present study, the number of electrons donated or accepted by sewage sludge HS were quantified before and after reduction by iron compounds that possess different redox potentials and defined as the reducing capacity of the sewage sludge. In contrast to previous studies of soil and commercial humic acids (HA), reduced sludge HA showed a lower reducing capacity than that of native HA, which implies formation of semiquinone radicals since the semiquinone radical/hydroquinone pair has a much higher redox potential than the quinone/hydroquinone pair. It is novel that reducing capacities of sludge HA were determined in the redox potential range from -314 to 430 mV. The formation of semiquinone radicals formed during the reduction of quinone moieties in sludge HA is shown by three-dimensional excitation/emission matrix fluorescence spectroscopies information, increasing fluorescence intensities and blue-shifting of the excitation/emission peak of reduced sludge HA. Knowledge of sludge HS redox potentials and corresponding reducing capacities makes it possible to predict the transformation of redox active pollutants and facilitate manipulation and optimization of sludge loading wastewater treatment processes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Optimization of a dual-energy contrast-enhanced technique for a photon-counting digital breast tomosynthesis system: I. A theoretical model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carton, Ann-Katherine; Ullberg, Christer; Lindman, Karin

2010-11-15

Purpose: Dual-energy (DE) iodine contrast-enhanced x-ray imaging of the breast has been shown to identify cancers that would otherwise be mammographically occult. In this article, theoretical modeling was performed to obtain optimally enhanced iodine images for a photon-counting digital breast tomosynthesis (DBT) system using a DE acquisition technique. Methods: In the system examined, the breast is scanned with a multislit prepatient collimator aligned with a multidetector camera. Each detector collects a projection image at a unique angle during the scan. Low-energy (LE) and high-energy (HE) projection images are acquired simultaneously in a single scan by covering alternate collimator slits withmore » Sn and Cu filters, respectively. Sn filters ranging from 0.08 to 0.22 mm thickness and Cu filters from 0.11 to 0.27 mm thickness were investigated. A tube voltage of 49 kV was selected. Tomographic images, hereafter referred to as DBT images, were reconstructed using a shift-and-add algorithm. Iodine-enhanced DBT images were acquired by performing a weighted logarithmic subtraction of the HE and LE DBT images. The DE technique was evaluated for 20-80 mm thick breasts. Weighting factors, w{sub t}, that optimally cancel breast tissue were computed. Signal-difference-to-noise ratios (SDNRs) between iodine-enhanced and nonenhanced breast tissue normalized to the square root of the mean glandular dose (MGD) were computed as a function of the fraction of the MGD allocated to the HE images. Peak SDNR/{radical}(MGD) and optimal dose allocations were identified. SDNR/{radical}(MGD) and dose allocations were computed for several practical feasible system configurations (i.e., determined by the number of collimator slits covered by Sn and Cu). A practical system configuration and Sn-Cu filter pair that accounts for the trade-off between SDNR, tube-output, and MGD were selected. Results: w{sub t} depends on the Sn-Cu filter combination used, as well as on the breast thickness; to optimally cancel 0% with 50% glandular breast tissue, w{sub t} values were found to range from 0.46 to 0.72 for all breast thicknesses and Sn-Cu filter pairs studied. The optimal w{sub t} values needed to cancel all possible breast tissue glandularites vary by less than 1% for 20 mm thick breasts and 18% for 80 mm breasts. The system configuration where one collimator slit covered by Sn is alternated with two collimator slits covered by Cu delivers SDNR/{radical}(MGD) nearest to the peak value. A reasonable compromise is a 0.16 mm Sn-0.23 mm Cu filter pair, resulting in SDNR values between 1.64 and 0.61 and MGD between 0.70 and 0.53 mGy for 20-80 mm thick breasts at the maximum tube current. Conclusions: A DE acquisition technique for a photon-counting DBT imaging system has been developed and optimized.« less

Probing long-range carrier-pair spin–spin interactions in a conjugated polymer by detuning of electrically detected spin beating

PubMed Central

van Schooten, Kipp J.; Baird, Douglas L.; Limes, Mark E.; Lupton, John M.; Boehme, Christoph

2015-01-01

Weakly coupled electron spin pairs that experience weak spin–orbit interaction can control electronic transitions in molecular and solid-state systems. Known to determine radical pair reactions, they have been invoked to explain phenomena ranging from avian magnetoreception to spin-dependent charge-carrier recombination and transport. Spin pairs exhibit persistent spin coherence, allowing minute magnetic fields to perturb spin precession and thus recombination rates and photoreaction yields, giving rise to a range of magneto-optoelectronic effects in devices. Little is known, however, about interparticle magnetic interactions within such pairs. Here we present pulsed electrically detected electron spin resonance experiments on poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) devices, which show how interparticle spin–spin interactions (magnetic-dipolar and spin-exchange) between charge-carrier spin pairs can be probed through the detuning of spin-Rabi oscillations. The deviation from uncoupled precession frequencies quantifies both the exchange (<30 neV) and dipolar (23.5±1.5 neV) interaction energies responsible for the pair's zero-field splitting, implying quantum mechanical entanglement of charge-carrier spins over distances of 2.1±0.1 nm. PMID:25868686

How do honeybees use their magnetic compass? Can they see the North?

PubMed

Válková, T; Vácha, M

2012-08-01

While seeking food sources and routes back to their hive, bees make use of their advanced nervous and sensory capacities, which underlie a diverse behavioral repertoire. One of several honeybee senses that is both exceptional and intriguing is magnetoreception - the ability to perceive the omnipresent magnetic field (MF) of the Earth. The mechanism by which animals sense MFs has remained fascinating as well as elusive because of the intricacies involved, which makes it one of the grand challenges for neural and sensory biology. However, investigations in recent years have brought substantial progress to our understanding of how such magneto-receptor(s) may work. Some terrestrial animals (birds) are reported to be equipped even with a dual perception system: one based on diminutive magnetic particles - in line with the original model which has also always been hypothesized for bees - and the other one, as the more recent model describes, based on a sensitivity of some photochemical reactions to MF (radical-pair or chemical mechanism). The latter model postulates a close link to vision and supposes that the animals can see the position of the geomagnetic North as a visible pattern superimposed on the picture of the environment. In recent years, a growing body of evidence has shown that radical-pair magnetoreception might also be used by insects. It is realistic to expect that such evidence will inspire a re-examination and extension or confirmation of established views on the honeybee magnetic-compass mechanism. However, the problem of bee magnetoreception will not be solved at the moment that a receptor is discovered. On the contrary, the meaning of magnetoreception in insect life and its involvement in the orchestration of other senses is yet to be fully understood. The crucial question to be addressed in the near future is whether the compass abilities of the honeybee could suffer from radio frequency (RF) smog accompanying modern civilization and whether the fitness of this dominant pollinator might be affected by RF fields. The goal of this review is to provide an overview of the path that the behavioral research on honeybee magnetoreception has taken and to discuss it in the context of contemporary data obtained on other insects.

Spatial distribution of CH3 and CH2 radicals in a methane rf discharge

NASA Astrophysics Data System (ADS)

Sugai, H.; Kojima, H.; Ishida, A.; Toyoda, H.

1990-06-01

Spatial distributions of neutral radicals CH3 and CH2 in a capacitively coupled rf glow discharge of methane were measured by threshold ionization mass spectrometry. A strong asymmetry of the density profile was found for the CH2 radical in the high-pressure (˜100 mTorr) discharge. In addition, comprehensive measurements of electron energy distribution, ionic composition, and radical sticking coefficient were made to use as inputs to theoretical modeling of radicals in the methane plasma. The model predictions agree substantially with the measured radical distributions.

Searching the inclusive l{gamma}Ee{sub T}+b-quark signature for radiative top quark decay and non-standard-model processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aaltonen, T.; Maki, T.; Mehtala, P.

We compare the inclusive production of events containing a lepton (l), a photon ({gamma}), significant transverse momentum imbalance (Ee{sub T}), and a jet identified as containing a b-quark, to SM predictions. The search uses data produced in proton-antiproton collisions at {radical}(s)=1.96 TeV corresponding to 1.9 fb{sup -1} of integrated luminosity taken with the CDF detector. We find 28 l{gamma}bEe{sub T} events versus an expectation of 31.0{sub -3.5}{sup +4.1} events. If we further require events to contain at least three jets and large total transverse energy, the largest SM source is radiative top-quark pair production, tt+{gamma}. In the data we observemore » 16 tt{gamma} candidate events versus an expectation from SM sources of 11.2{sub -2.1}{sup +2.3}. Assuming the difference between the observed number and the predicted non-top-quark total of 6.8{sub -2.0}{sup +2.2} is due to SM top-quark production, we estimate the tt{gamma} cross section to be 0.15{+-}0.08 pb.« less

Determination of the Michel Parameters and the tau Neutrino Helicity in tau Decay

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jessop, Colin P.

2003-05-07

Using the CLEO II detector at the e{sup +}e{sup -} storage ring CESR, we have determined the Michel parameters {rho}, {zeta}, and {delta} in {tau}{sup {-+}}{nu}{bar {nu}} decay as well as the {tau} neutrino helicity parameter H{sub {nu}{sub {tau}}} in {tau}{sup {-+}}{pi}{sup 0}{nu} decay. From a data sample of 3.02 x 10{sup 6} {tau} pairs produced at {radical}s = 10.6 GeV, using events of the topology e{sup +}e{sup -} {yields} {tau}{sup +}{tau}{sup -} {yields} (l{sup {+-}}{nu}{bar {nu}})({pi}{sup {-+}}{pi}{sup 0}{nu}) and e{sup +}e{sup -} {yields} {tau}{sup +}{tau}{sup -} {yields} ({pi}{sup {+-}}{pi}{sup 0}{bar {nu}})({pi}{sup {-+}}{pi}{sup 0}{nu}), and the determined sign of h{submore » {nu}{sub {tau}}} [1,2], the combined result of the three samples is: {rho} = 0.747 {+-} 0.010 {+-} 0.006, {zeta} = 1.007 {+-} 0.040 {+-} 0.015, {zeta}{delta} = 0.745 {+-}0.026 {+-}0.009, and h{sub {nu}{sub {tau}}} = -0.995 {+-} 0.010 {+-} 0.003. The results are in agreement with the Standard Model V-A interaction.« less

ESR study of free radicals in mango

NASA Astrophysics Data System (ADS)

Kikuchi, Masahiro; Hussain, Mohammad S.; Morishita, Norio; Ukai, Mitsuko; Kobayashi, Yasuhiko; Shimoyama, Yuhei

2010-01-01

An electron spin resonance (ESR) spectroscopic study of radicals induced in irradiated fresh mangoes was performed. Mangoes in the fresh state were irradiated with γ-rays, lyophilized and then crushed into a powder. The ESR spectrum of the powder showed a strong main peak at g = 2.004 and a pair of peaks centered at the main peak. The main peak was detected from both flesh and skin specimens. This peak height gradually decreased during storage following irradiation. On the other hand, the side peaks showed a well-defined dose-response relationship even at 9 days post-irradiation. The side peaks therefore provide a useful means to define the irradiation of fresh mangoes.

Radiofrequency attenuator and method

DOEpatents

Warner, Benjamin P [Los Alamos, NM; McCleskey, T Mark [Los Alamos, NM; Burrell, Anthony K [Los Alamos, NM; Agrawal, Anoop [Tucson, AZ; Hall, Simon B [Palmerston North, NZ

2009-01-20

Radiofrequency attenuator and method. The attenuator includes a pair of transparent windows. A chamber between the windows is filled with molten salt. Preferred molten salts include quarternary ammonium cations and fluorine-containing anions such as tetrafluoroborate (BF.sub.4.sup.-), hexafluorophosphate (PF.sub.6.sup.-), hexafluoroarsenate (AsF.sub.6.sup.-), trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Radicals or radical cations may be added to or electrochemically generated in the molten salt to enhance the RF attenuation.

Radiofrequency attenuator and method

DOEpatents

Warner, Benjamin P [Los Alamos, NM; McCleskey, T Mark [Los Alamos, NM; Burrell, Anthony K [Los Alamos, NM; Agrawal, Anoop [Tucson, AZ; Hall, Simon B [Palmerston North, NZ

2009-11-10

Radiofrequency attenuator and method. The attenuator includes a pair of transparent windows. A chamber between the windows is filled with molten salt. Preferred molten salts include quarternary ammonium cations and fluorine-containing anions such as tetrafluoroborate (BF.sub.4.sup.-), hexafluorophosphate (PF.sub.6.sup.-), hexafluoroarsenate (AsF.sub.6.sup.-), trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3 C.sup.-). Radicals or radical cations may be added to or electrochemically generated in the molten salt to enhance the RF attenuation.

Une nouvelle théorie de la cinétique des réactions radical-radical

NASA Astrophysics Data System (ADS)

Green, N. J. B.; Rickerby, A. G.

1999-01-01

Radical recombination reactions are of central importance in radiation chemistry. In general such reactions are slower than diffusion-controlled because of the radical spins. The rate constant is corrected by a multiplicative spin statistical factor, which represents the probability that the radicals encounter one another in a reactive state. However, this method does not account for the possibility that the reactivity of a pair may recover following an unreactive encounter, for example by spin relaxation or by a coherent evolution of the spin function. In this paper we show how the spin statistical factor can be corrected for the recovery of reactivity. The new theory covers a large range of mechanisms for the recovery of reactivity, and gives simple analytical results. Both steady-state and transient solutions are presented and the former are tested against experiment for the reaction between the hydrated electron and oxygen, and for the magnetic field effect on the rate constant of an elementary reaction. Les réactions de recombinaison entre deux radicaux libres ont une grande importance en chimie sous rayonnement. En général, du fait du spin des radicaux, de telles réactions sont moins rapides que celles qui sont contrôlées par la diffusion. Les constantes de vitesse sont corrigées par un facteur multiplicatif, le facteur statistique de spin, qui représente la probabilité pour que les radicaux se rencontrent, l'un avec l'autre, dans un état réactif. Cependant, cette méthode ne tient pas compte de la possibilité pour que la même paire se rencontre plusieurs fois en raison de rencontres non-réactives. Ensuite la réactivité de cette paire peut se rétablir par exemple par relaxation de spins, ou par évolution cohérente d'une superposition des états de spin. Dans cet article on démontre comment on peut corriger le facteur statistique de spin pour le rétablissement de la réactivité. La nouvelle théorie couvre un large domaine de mécanismes de rétablissement de la réactivité ; elle donne des résultats analytiques simples pour le facteur statistique modifié. On présente des solutions dans l'état stationnaire et des solutions transitoires; les premières sont testées pour la réaction entre l'électron hydraté et l'oxygène et également pour l'effet d'un champ magnétique sur la constante de vitesse d'une réaction élémentaire.

Magnetic properties of single crystal alpha-benzoin oxime: An EPR study

NASA Astrophysics Data System (ADS)

Sayin, Ulku; Dereli, Ömer; Türkkan, Ercan; Ozmen, Ayhan

2012-02-01

The electron paramagnetic resonance (EPR) spectra of gamma irradiated single crystals of alpha-benzoinoxime (ABO) have been examined between 120 and 440 K. Considering the dependence on temperature and the orientation of the spectra of single crystals in the magnetic field, we identified two different radicals formed in irradiated ABO single crystals. To theoretically determine the types of radicals, the most stable structure of ABO was obtained by molecular mechanic and B3LYP/6-31G(d,p) calculations. Four possible radicals were modeled and EPR parameters were calculated for the modeled radicals using the B3LYP method and the TZVP basis set. Calculated values of two modeled radicals were in strong agreement with experimental EPR parameters determined from the spectra. Additional simulated spectra of the modeled radicals, where calculated hyperfine coupling constants were used as starting points for simulations, were well matched with experimental spectra.

The quest for significance model of radicalization: implications for the management of terrorist detainees.

PubMed

Dugas, Michelle; Kruglanski, Arie W

2014-01-01

Radicalization and its culmination in terrorism represent a grave threat to the security and stability of the world. A related challenge is effective management of extremists who are detained in prison facilities. The major aim of this article is to review the significance quest model of radicalization and its implications for management of terrorist detainees. First, we review the significance quest model, which elaborates on the roles of motivation, ideology, and social processes in radicalization. Secondly, we explore the implications of the model in relation to the risks of prison radicalization. Finally, we analyze the model's implications for deradicalization strategies and review preliminary evidence for the effectiveness of a rehabilitation program targeting components of the significance quest. Based on this evidence, we argue that the psychology of radicalization provides compelling reason for the inclusion of deradicalization efforts as an essential component of the management of terrorist detainees. Copyright © 2014 John Wiley & Sons, Ltd.

Magnetic field-dependent molecular and chemical processes in biochemistry, genetics and medicine

NASA Astrophysics Data System (ADS)

Buchachenko, A. L.

2014-01-01

The molecular concept (paradigm) in magnetobiology seems to be most substantiated and significant for explaining the biomedical effects of electromagnetic fields, for the new medical technology of transcranial magnetic stimulation of cognitive activity, for the nuclear magnetic control of biochemical processes and for the search of new magnetic effects in biology and medicine. The key structural element of the concept is a radical ion pair as the receiver of magnetic fields and the source of magnetic effects. The existence of such pairs was recently detected in the two life-supporting processes of paramount importance — in enzymatic ATP and DNA syntheses. The bibliography includes 80 references.

Ontology aided modeling of organic reaction mechanisms with flexible and fragment based XML markup procedures.

PubMed

Sankar, Punnaivanam; Aghila, Gnanasekaran

2007-01-01

The mechanism models for primary organic reactions encoding the structural fragments undergoing substitution, addition, elimination, and rearrangements are developed. In the proposed models, each and every structural component of mechanistic pathways is represented with flexible and fragment based markup technique in XML syntax. A significant feature of the system is the encoding of the electron movements along with the other components like charges, partial charges, half bonded species, lone pair electrons, free radicals, reaction arrows, etc. needed for a complete representation of reaction mechanism. The rendering of reaction schemes described with the proposed methodology is achieved with a concise XML extension language interoperating with the structure markup. The reaction scheme is visualized as 2D graphics in a browser by converting them into SVG documents enabling the desired layouts normally perceived by the chemists conventionally. An automatic representation of the complex patterns of the reaction mechanism is achieved by reusing the knowledge in chemical ontologies and developing artificial intelligence components in terms of axioms.

Probing long-range carrier-pair spin–spin interactions in a conjugated polymer by detuning of electrically detected spin beating

DOE PAGES

van Schooten, Kipp J.; Baird, Douglas L.; Limes, Mark E.; ...

2015-04-14

Here, weakly coupled electron spin pairs that experience weak spin–orbit interaction can control electronic transitions in molecular and solid-state systems. Known to determine radical pair reactions, they have been invoked to explain phenomena ranging from avian magnetoreception to spin-dependent charge-carrier recombination and transport. Spin pairs exhibit persistent spin coherence, allowing minute magnetic fields to perturb spin precession and thus recombination rates and photoreaction yields, giving rise to a range of magneto-optoelectronic effects in devices. Little is known, however, about interparticle magnetic interactions within such pairs. Here we present pulsed electrically detected electron spin resonance experiments on poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) devices,more » which show how interparticle spin–spin interactions (magnetic-dipolar and spin-exchange) between charge-carrier spin pairs can be probed through the detuning of spin-Rabi oscillations. The deviation from uncoupled precession frequencies quantifies both the exchange (<30 neV) and dipolar (23.5±1.5 neV) interaction energies responsible for the pair’s zero-field splitting, implying quantum mechanical entanglement of charge-carrier spins over distances of 2.1±0.1 nm.« less

Magnetoconductivity and magnetoluminescence studies in bipolar and almost hole-only sandwich devices made from films of a π-conjugated molecule

PubMed Central

Duc Nguyen, Tho; Sheng, Yugang; Rybicki, James E; Wohlgenannt, Markus

2008-01-01

We present magnetoconductivity and magnetoluminescence measurements in sandwich devices made from films of a π-conjugated molecule and demonstrate effects of more than 30 and 50% magnitude, respectively, in fields of 100 mT at room-temperature. It has previously been recognized that the effect is caused by hyperfine coupling, and that it is phenomenologically similar to other magnetic field effects that act on electron–hole pairs, which are well-known in spin-chemistry. However, we show that the very large magnitude of the effect contradicts present knowledge of the electron–hole pair recombination processes in electroluminescent π-conjugated molecules, and that the effect persists even in almost hole-only devices. Therefore, this effect is likely caused by the interaction of radical pairs of equal charge. PMID:27877957

Single jet and prompt-photon inclusive production with multi-Regge kinematics: From Tevatron to LHC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kniehl, B. A.; Saleev, V. A.; Shipilova, A. V.

2011-10-01

We study single jet and prompt-photon inclusive hadroproduction with multi-Regge kinematics invoking the hypothesis of parton Reggeization in t-channel exchanges at high energy. In this approach, the leading contributions are due to the fusion of two Reggeized gluons into a Yang-Mills gluon and the annihilation of a Reggeized quark-antiquark pair into a photon, respectively. Adopting the Kimber-Martin-Ryskin and Bluemlein prescriptions to derive unintegrated gluon and quark distribution functions of the proton from their collinear counterparts, for which we use the Martin-Roberts-Stirling-Thorne set, we evaluate cross section distributions in transverse momentum (p{sub T}) and rapidity. Without adjusting any free parameters, wemore » find good agreement with measurements by the CDF and D0 Collaborations at the Tevatron and by the ATLAS Collaboration at the LHC in the region 2p{sub T}/{radical}(S) < or approx. 0.1, where {radical}(S) is the hadronic c.m. energy.« less

Functionalization of chitosan by a free radical reaction: Characterization, antioxidant and antibacterial potential.

PubMed

Moreno-Vásquez, María Jesús; Valenzuela-Buitimea, Emma Lucía; Plascencia-Jatomea, Maribel; Encinas-Encinas, José Carmelo; Rodríguez-Félix, Francisco; Sánchez-Valdes, Saúl; Rosas-Burgos, Ema Carina; Ocaño-Higuera, Víctor Manuel; Graciano-Verdugo, Abril Zoraida

2017-01-02

Chitosan was functionalized with epigallocatechin gallate (EGCG) by a free radical-induced grafting procedure, which was carried out by a redox pair (ascorbic acid/hydrogen peroxide) as the radical initiator. The successful preparation of EGCG grafted-chitosan was verified by spectroscopic (UV, FTIR and XPS) and thermal (DSC and TGA) analyses. The degree of grafting of phenolic compounds onto the chitosan was determined by the Folin-Ciocalteu procedure. Additionally, the biological activities (antioxidant and antibacterial) of pure EGCG, blank chitosan and EGCG grafted-chitosan were evaluated. The spectroscopic and thermal results indicate chitosan functionalization with EGCG; the EGCG content was 25.8mg/g of EGCG grafted-chitosan. The antibacterial activity of the EGCG grafted-chitosan was increased compared to pure EGCG or blank chitosan against S. aureus and Pseudomonas sp. (p<0.05). Additionally, EGCG grafted-chitosan showed higher antioxidant activity than blank chitosan. These results indicate that EGCG grafted-chitosan might be useful in active food packaging. Copyright © 2016 Elsevier Ltd. All rights reserved.

Truncated Cross Effect Dynamic Nuclear Polarization: An Overhauser Effect Doppelgänger.

PubMed

Equbal, Asif; Li, Yuanxin; Leavesley, Alisa; Huang, Shengdian; Rajca, Suchada; Rajca, Andrzej; Han, Songi

2018-05-03

The discovery of a truncated cross-effect (CE) in dynamic nuclear polarization (DNP) NMR that has the features of an Overhauser-effect DNP (OE-DNP) is reported here. The apparent OE-DNP, where minimal μw power achieved optimum enhancement, was observed when doping Trityl-OX063 with a pyrroline nitroxide radical that possesses electron-withdrawing tetracarboxylate substituents (tetracarboxylate-ester-pyrroline or TCP) in vitrified water/glycerol at 6.9 T and at 3.3 to 85 K, in apparent contradiction to expectations. While the observations are fully consistent with OE-DNP, we discover that a truncated cross-effect ( tCE) is the underlying mechanism, owing to TCP's shortened T 1e . We take this observation as a guideline and demonstrate that a crossover from CE to tCE can be replicated by simulating the CE of a narrow-line (Trityl-OX063) and a broad-line (TCP) radical pair, with a significantly shortened T 1e of the broad-line radical.

miCLIP-MaPseq, a Substrate Identification Approach for Radical SAM RNA Methylating Enzymes.

PubMed

Stojković, Vanja; Chu, Tongyue; Therizols, Gabriel; Weinberg, David E; Fujimori, Danica Galonić

2018-06-13

Although present across bacteria, the large family of radical SAM RNA methylating enzymes is largely uncharacterized. Escherichia coli RlmN, the founding member of the family, methylates an adenosine in 23S rRNA and several tRNAs to yield 2-methyladenosine (m 2 A). However, varied RNA substrate specificity among RlmN enzymes, combined with the ability of certain family members to generate 8-methyladenosine (m 8 A), makes functional predictions across this family challenging. Here, we present a method for unbiased substrate identification that exploits highly efficient, mechanism-based cross-linking between the enzyme and its RNA substrates. Additionally, by determining that the thermostable group II intron reverse transcriptase introduces mismatches at the site of the cross-link, we have identified the precise positions of RNA modification using mismatch profiling. These results illustrate the capability of our method to define enzyme-substrate pairs and determine modification sites of the largely uncharacterized radical SAM RNA methylating enzyme family.

Estimation of Free Radical Ionization Energies by the Kinetic Method and the Relationship between the Kinetic Method and the Hammett Equation.

PubMed

Chen, G; Wong, P; Cooks, R G

1997-09-01

Substituted 1,2-diphenylethanes undergo competitive dissociations upon electron ionization (EI) to generate substituted benzyl cation and benzyl radical pairs. Application of the kinetic method to the previous reported EI mass spectra of these covalently bound precursor ions (data are taken from McLafferty et al. J. Am. Chem. Soc. 1970, 92, 6867)) is used to estimate the ionization energies of substituted benzyl free radicals. A correlation is observed between the Hammett σ constant of the substituents and the kinetic method parameter, ln(k(x)/k(H)), where k(x) is the rate of fragmentation to give the substituted product ion and k(H) is the rate to give the benzyl ion itself. Systems involving weakly bound cluster ions, including proton-bound dimers of meta- and para-substituted pyridines and meta- and para-substituted anilines, and electron-bound dimers of meta- and para-substituted nitrobenzenes, also show good correlations between the kinetic method parameter and the Hammett σ constant.

A mechanistic model for mercury capture with in situ-generated titania particles: role of water vapor.

PubMed

Rodríguez, Sylian; Almquist, Catherine; Lee, Tai Gyu; Furuuchi, Masami; Hedrick, Elizabeth; Biswas, Pratim

2004-02-01

A mechanistic model to predict the capture of gas-phase mercury (Hg) species using in situ-generated titania nanosize particles activated by UV irradiation is developed. The model is an extension of a recently reported model for photochemical reactions by Almquist and Biswas that accounts for the rates of electron-hole pair generation, the adsorption of the compound to be oxidized, and the adsorption of water vapor. The role of water vapor in the removal efficiency of Hg was investigated to evaluate the rates of Hg oxidation at different water vapor concentrations. As the water vapor concentration is increased, more hydroxy radical species are generated on the surface of the titania particle, increasing the number of active sites for the photooxidation and capture of Hg. At very high water vapor concentrations, competitive adsorption is expected to be important and reduce the number of sites available for photooxidation of Hg. The predictions of the developed phenomenological model agreed well with the measured Hg oxidation rates in this study and with the data on oxidation of organic compounds reported in the literature.

Dimeric Structure of the Blue Light Sensor Protein Photozipper in the Active State.

PubMed

Ozeki, Kohei; Tsukuno, Hiroyuki; Nagashima, Hiroki; Hisatomi, Osamu; Mino, Hiroyuki

2018-02-06

The light oxygen voltage-sensing (LOV) domain plays a crucial role in blue light (BL) sensing in plants and microorganisms. LOV domains are usually associated with the effector domains and regulate the activities of effector domains in a BL-dependent manner. Photozipper (PZ) is monomeric in the dark state. BL induces reversible dimerization of PZ and subsequently increases its affinity for the target DNA sequence. In this study, we report the analyses of PZ by pulsed electron-electron double resonance (PELDOR). The neutral flavin radical was formed by BL illumination in the presence of dithiothreitol in the LOV-C254S (without the bZIP domain) and PZ-C254S mutants, where the cysteine residue responsible for adduct formation was replaced with serine. The magnetic dipole interactions of 3 MHz between the neutral radicals were detected in both LOV-C254S and PZ-C254S, indicating that these mutants are dimeric in the radical state. The PELDOR simulation showed that the distance between the radical pair is close to that estimated from the dimeric crystal structure in the "light state" [Heintz, U., and Schlichting, I. (2016) eLife 5, e11860], suggesting that in the radical state, LOV domains in PZ-C254S form a dimer similar to that of LOV-C254S, which lacks the bZIP domain.

Alkoxyl- and carbon-centered radicals as primary agents for degrading non-phenolic lignin-substructure model compounds.

PubMed

Ohashi, Yasunori; Uno, Yukiko; Amirta, Rudianto; Watanabe, Takahito; Honda, Yoichi; Watanabe, Takashi

2011-04-07

Lignin degradation by white-rot fungi proceeds via free radical reaction catalyzed by oxidative enzymes and metabolites. Basidiomycetes called selective white-rot fungi degrade both phenolic and non-phenolic lignin substructures without penetration of extracellular enzymes into the cell wall. Extracellular lipid peroxidation has been proposed as a possible ligninolytic mechanism, and radical species degrading the recalcitrant non-phenolic lignin substructures have been discussed. Reactions between the non-phenolic lignin model compounds and radicals produced from azo compounds in air have previously been analysed, and peroxyl radical (PR) is postulated to be responsible for lignin degradation (Kapich et al., FEBS Lett., 1999, 461, 115-119). However, because the thermolysis of azo compounds in air generates both a carbon-centred radical (CR) and a peroxyl radical (PR), we re-examined the reactivity of the three radicals alkoxyl radical (AR), CR and PR towards non-phenolic monomeric and dimeric lignin model compounds. The dimeric lignin model compound is degraded by CR produced by reaction of 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH), which under N(2) atmosphere cleaves the α-β bond in 1-(4-ethoxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)-1,3-propanediol to yield 4-ethoxy-3-methoxybenzaldehyde. However, it is not degraded by the PR produced by reaction of Ce(4+)/tert-BuOOH. In addition, it is degraded by AR produced by reaction of Ti(3+)/tert-BuOOH. PR and AR are generated in the presence and absence of veratryl alcohol, respectively. Rapid-flow ESR analysis of the radical species demonstrates that AR but not PR reacts with the lignin model compound. Thus, AR and CR are primary agents for the degradation of non-phenolic lignin substructures.

Radical constructivism: Between realism and solipsism

NASA Astrophysics Data System (ADS)

Martínez-Delgado, Alberto

2002-11-01

This paper criticizes radical constructivism of the Glasersfeld type, pointing out some contradictions between the declared radical principles and their theoretical and practical development. These contradictions manifest themselves in a frequent oscillation between solipsism and realism, despite constructivist claims to be an anti-realist theory. The paper also points out the contradiction between the relativism of the radical constructivist principles and the constructivist exclusion of other epistemological or educational paradigms. It also disputes the originality and importance of the radical constructivist paradigm, suggesting the idea of an isomorphism between radical constructivist theory and contemplative realism. In addition, some pedagogical and scientific methodological aspects of the radical constructivist model are examined. Although radical constructivism claims to be a rational theory and advocates deductive thinking, it is argued that there is no logical deductive connection between the radical principles of constructivism and the radical constructivist ideas about scientific research and learning. The paper suggests the possibility of an ideological substratum in the construction and hegemonic success of subjective constructivism and, finally, briefly advances an alternative realist model to epistemological and educational radical constructivism.

Annihilation of p-bar + p {yields} e{sup +} + e{sup -} + {pi}{sup 0} and p-bar + p {yields} {gamma} + {pi}{sup 0} through an {omega}-Meson intermediate state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuraev, E. A., E-mail: kuraev@theor.jinr.ru; Bystritskiy, Yu. M., E-mail: bystr@theor.jinr.ru; Bytev, V. V., E-mail: bvv@jinr.ru

2012-07-15

The s-channel annihilation of a proton and an antiproton into a neutral pion and a real or virtual photon followed by lepton pair emission is studied. Such a mechanism is expected to play a role at moderate values of the total energy {radical}s, when the pion is emitted in the angular region around 90 Degree-Sign in the center-of-mass system. A fair comparison with the existing data is obtained taking scattering and annihilation channels into account. The cross section is calculated and numerical results are given in the kinematical range accessible in the PANDA experiment at FAIR.

Understanding in situ ozone production in the summertime through radical observations and modelling studies during the Clean air for London project (ClearfLo)

NASA Astrophysics Data System (ADS)

Whalley, Lisa K.; Stone, Daniel; Dunmore, Rachel; Hamilton, Jacqueline; Hopkins, James R.; Lee, James D.; Lewis, Alastair C.; Williams, Paul; Kleffmann, Jörg; Laufs, Sebastian; Woodward-Massey, Robert; Heard, Dwayne E.

2018-02-01

Measurements of OH, HO2, RO2i (alkene and aromatic-related RO2) and total RO2 radicals taken during the ClearfLo campaign in central London in the summer of 2012 are presented. A photostationary steady-state calculation of OH which considered measured OH reactivity as the OH sink term and the measured OH sources (of which HO2+ NO reaction and HONO photolysis dominated) compared well with the observed levels of OH. Comparison with calculations from a detailed box model utilising the Master Chemical Mechanism v3.2, however, highlighted a substantial discrepancy between radical observations under lower NOx conditions ([NO] < 1 ppbv), typically experienced during the afternoon hours, and indicated that the model was missing a significant peroxy radical sink; the model overpredicted HO2 by up to a factor of 10 at these times. Known radical termination steps, such as HO2 uptake on aerosols, were not sufficient to reconcile the model-measurement discrepancies alone, suggesting other missing termination processes. This missing sink was most evident when the air reaching the site had previously passed over central London to the east and when elevated temperatures were experienced and, hence, contained higher concentrations of VOCs. Uncertainties in the degradation mechanism at low NOx of complex biogenic and diesel related VOC species, which were particularly elevated and dominated OH reactivity under these easterly flows, may account for some of the model-measurement disagreement. Under higher [NO] (> 3 ppbv) the box model increasingly underpredicted total [RO2]. The modelled and observed HO2 were in agreement, however, under elevated NO concentrations ranging from 7 to 15 ppbv. The model uncertainty under low NO conditions leads to more ozone production predicted using modelled peroxy radical concentrations ( ˜ 3 ppbv h-1) versus ozone production from peroxy radicals measured ( ˜ 1 ppbv h-1). Conversely, ozone production derived from the predicted peroxy radicals is up to an order of magnitude lower than from the observed peroxy radicals as [NO] increases beyond 7 ppbv due to the model underprediction of RO2 under these conditions.

Comparison of exciplex generation under optical and X-ray excitation

NASA Astrophysics Data System (ADS)

Kipriyanov, A. A.; Melnikov, A. R.; Stass, D. V.; Doktorov, A. B.

2017-09-01

Exciplex generation under optical and X-ray excitation in identical conditions is experimentally compared using a specially chosen model donor-acceptor system, anthracene (electron acceptor) and N,N-dimethylaniline (electron donor) in non-polar solution, and the results are analyzed and interpreted based on analytically calculated luminescence quantum yields. Calculations are performed on the basis of kinetic equations for multistage schemes of bulk exciplex production reaction under optical excitation and combination of bulk and geminate reactions of radical ion pairs under X-ray excitation. These results explain the earlier experimentally found difference in the ratio of the quantum yields of exciplexes and excited electron acceptors (exciplex generation efficiency) and the corresponding change in the exciplex generation efficiency under X-irradiation as compared to the reaction under optical excitation.

Comparison of exciplex generation under optical and X-ray excitation.

PubMed

Kipriyanov, A A; Melnikov, A R; Stass, D V; Doktorov, A B

2017-09-07

Exciplex generation under optical and X-ray excitation in identical conditions is experimentally compared using a specially chosen model donor-acceptor system, anthracene (electron acceptor) and N,N-dimethylaniline (electron donor) in non-polar solution, and the results are analyzed and interpreted based on analytically calculated luminescence quantum yields. Calculations are performed on the basis of kinetic equations for multistage schemes of bulk exciplex production reaction under optical excitation and combination of bulk and geminate reactions of radical ion pairs under X-ray excitation. These results explain the earlier experimentally found difference in the ratio of the quantum yields of exciplexes and excited electron acceptors (exciplex generation efficiency) and the corresponding change in the exciplex generation efficiency under X-irradiation as compared to the reaction under optical excitation.

Reactivity of vinyl ethers and vinyl ribosides in UV-initiated free radical copolymerization with acceptor monomers.

PubMed

Pichavant, Loic; Guillermain, Céline; Coqueret, Xavier

2010-09-13

The reactivity of various vinyl ethers and vinyloxy derivatives of ribose in the presence of diethyl fumarate or diethyl maleate was investigated for evaluating the potential of donor-acceptor-type copolymerization applied to unsaturated monomers derived from renewable feedstock. The photochemically induced polymerization of model monomer blends in the bulk state was monitored by infrared spectroscopy. The method allowed us to examine the influence of monomer pair structure on the kinetic profiles. The simultaneous consumption of both monomers was observed, supporting an alternating copolymerization mechanism. A lower reactivity of the blends containing maleates compared with fumarates was confirmed. The obtained kinetic data revealed a general correlation between the initial polymerization rate and the Hansen parameter δ(H) associated with the H-bonding aptitude of the donor monomer.

Reaction of hydroxyl radicals with azacytosines: a pulse radiolysis and theoretical study.

PubMed

Pramod, G; Prasanthkumar, K P; Mohan, Hari; Manoj, V M; Manoj, P; Suresh, C H; Aravindakumar, C T

2006-10-12

Pulse radiolysis and density functional theory (DFT) calculations at B3LYP/6-31+G(d,p) level have been carried out to probe the reaction of the water-derived hydroxyl radicals (*OH) with 5-azacytosine (5Ac) and 5-azacytidine (5Acyd) at near neutral and basic pH. A low percentage of nitrogen-centered oxidizing radicals, and a high percentage of non-oxidizing carbon-centered radicals were identified based on the reaction of transient intermediates with 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate), ABTS2-. Theoretical calculations suggests that the N3 atom in 5Ac is the most reactive center as it is the main contributor of HOMO, whereas C5 atom is the prime donor for the HOMO of cytosine (Cyt) where the major addition site is C5. The order of stability of the adduct species were found to be C6-OH_5Ac*>C4-OH_5Ac*>N3-OH_5Ac*>N5-OH_5Ac* both in the gaseous and solution phase (using the PCM model) respectively due to the additions of *OH at C6, C4, N3, and N5 atoms. These additions occur in direct manner, without the intervention of any precursor complex formation. The possibility of a 1,2-hydrogen shift from the C6 to N5 in the nitrogen-centered C6-OH_5Ac* radical is considered in order to account for the experimental observation of the high yield of non-oxidizing radicals, and found that such a conversion requires activation energy of about 32 kcal/mol, and hence this possibility is ruled out. The hydrogen abstraction reactions were assumed to occur from precursor complexes (hydrogen bonded complexes represented as S1, S2, S3, and S4) resulted from the electrostatic interactions of the lone pairs on the N3, N5, and O8 atoms with the incoming *OH radical. It was found that the conversion of these precursor complexes to their respective transition states has ample barrier heights, and it persists even when the effect of solvent is considered. It was also found that the formation of precursor complexes itself is highly endergonic in solution phase. Hence, the abstraction reactions will not occur in the present case. Finally, the time dependent density functional theory (TDDFT) calculations predicted an absorption maximum of 292 nm for the N3-OH_5Ac* adduct, which is close to the experimentally observed spectral maxima at 290 nm. Hence, it is assumed that the addition to the most reactive center N3, which results the N3-OH_5Ac* radical, occurs via a kinetically driven process.

Effect of ultraviolet irradiation on free radical scavenging activity of immunosuppressants used in lung transplantation and comparative electron paramagnetic resonance study of kinetics of their interactions with model free radicals.

PubMed

Stanjek-Cichoracka, A; Żegleń, S; Ramos, P; Pilawa, B; Wojarski, J

2018-06-01

The immunosuppressive drugs used in solid organ transplantation or autoimmunological processes were studied by electron paramagnetic resonance (EPR) spectroscopy to estimate their free radical scavenging activity. The interactions of immunosuppressants with free radicals were examined by an X-band (9.3 GHz) EPR spectroscopy and a model of DPPH free radicals. The EPR spectra of DPPH and DPPH interacting with individual drugs were compared. Kinetic studies were performed, and the effect of ultraviolet (UV) irradiation on the free radical scavenging activity of the tested drugs was determined. The free radical scavenging activity of non-irradiated drugs decreased in the order: rapamycin > mycophenolate mofetil > ciclosporin > tacrolimus. UV irradiation increased the free radical scavenging activity of all the tested immunosuppressive drugs, and the effect was highest for tacrolimus. For the non-irradiated samples, the speed of free radical interactions decreased in the order: ciclosporin > tacrolimus > mycophenolate mofetil > rapamycin. UV irradiation only slightly affected the speed of interactions of the immunosuppressive drugs with the model DPPH free radicals. Electron paramagnetic resonance spectroscopy is useful for obtaining information on interactions of immunosuppressive drugs with free radicals. We hypothesized that the long-term immunosuppressive effects of these drugs after transplantation or during autoimmune disorders may be mediated by anti-inflammatory action in addition to the known receptor/cell cycle inhibition. © 2018 John Wiley & Sons Ltd.

Habitat of in vivo transformation influences the levels of free radical scavengers in Clinostomum complanatum: implications for free radical scavenger based vaccines against trematode infections.

PubMed

Zafar, Atif; Rizvi, Asim; Ahmad, Irshad; Ahmad, Masood

2014-01-01

Since free radical scavengers of parasite origin like glutathione-S-transferase and superoxide dismutase are being explored as prospective vaccine targets, availability of these molecules within the parasite infecting different hosts as well as different sites of infection is of considerable importance. Using Clinostomum complanatum, as a model helminth parasite, we analysed the effects of habitat of in vivo transformation on free radical scavengers of this trematode parasite. Using three different animal models for in vivo transformation and markedly different sites of infection, progenetic metacercaria of C. complanatum were transformed to adult ovigerous worms. Whole worm homogenates were used to estimate the levels of lipid peroxidation, a marker of oxidative stress and free radical scavengers. Site of in vivo transformation was found to drastically affect the levels of free radical scavengers in this model trematode parasite. It was observed that oxygen availability at the site of infection probably influences levels of free radical scavengers in trematode parasites. This is the first report showing that habitat of in vivo transformation affects levels of free radical scavengers in trematode parasites. Since free radical scavengers are prospective vaccine targets and parasite infection at ectopic sites is common, we propose that infections at different sites, may respond differently to free radical scavenger based vaccines.

Modeling and measurement of hydrogen radical densities of in situ plasma-based Sn cleaning source

NASA Astrophysics Data System (ADS)

Elg, Daniel T.; Panici, Gianluca A.; Peck, Jason A.; Srivastava, Shailendra N.; Ruzic, David N.

2017-04-01

Extreme ultraviolet (EUV) lithography sources expel Sn debris. This debris deposits on the collector optic used to focus the EUV light, lowering its reflectivity and EUV throughput to the wafer. Consequently, the collector must be cleaned, causing source downtime. To solve this, a hydrogen plasma source was developed to clean the collector in situ by using the collector as an antenna to create a hydrogen plasma and create H radicals, which etch Sn as SnH4. This technique has been shown to remove Sn from a 300-mm-diameter stainless steel dummy collector. The H radical density is of key importance in Sn etching. The effects of power, pressure, and flow on radical density are explored. A catalytic probe has been used to measure radical density, and a zero-dimensional model is used to provide the fundamental science behind radical creation and predict radical densities. Model predictions and experimental measurements are in good agreement. The trends observed in radical density, contrasted with measured Sn removal rates, show that radical density is not the limiting factor in this etching system; other factors, such as SnH4 redeposition and energetic ion bombardment, must be more fully understood in order to predict removal rates.

Development of a PERCA Instrument for Ambient Peroxy Radical Measurements

NASA Astrophysics Data System (ADS)

Dusanter, S.; Duncianu, M.; Lahib, A.; Tomas, A.; Stevens, P. S.

2017-12-01

Peroxy radicals (HO2 and RO2) are key species in atmospheric chemistry, which together with the hydroxyl radical (OH), lead to the oxidation of volatile organic compounds and the formation of secondary pollutants such as ozone and secondary organic aerosols. Monitoring these short-lived species during intensive field campaigns and comparing the measured concentrations to model outputs allows assessing the reliability of chemical mechanisms implemented in atmospheric models. However, ambient measurements of peroxy radicals are still considered challenging and only a few techniques have been used for field measurements. The PEroxy Radical Chemical Amplifier (PERCA) approach, whose principle is based on amplification and a conversion of ambient peroxy radicals into nitrogen dioxide (NO2), has recently seen renewed interests due to the availability of sensitive NO2 monitors. We will present (i) the construction of a PERCA instrument, (ii) experiments conducted to quantify the radical chain length for HO2 and several RO2 radicals, including those produced during the OH-oxidation of isoprene, and (iii) a comparison of the conventional CO/NO and recently proposed ethane/NO amplification chemistries. In this context, box modelling of the PERCA chemistry will be discussed.

Predicting the effect of angular momentum on the dissociation dynamics of highly rotationally excited radical intermediates.

PubMed

Brynteson, Matthew D; Butler, Laurie J

2015-02-07

We present a model which accurately predicts the net speed distributions of products resulting from the unimolecular decomposition of rotationally excited radicals. The radicals are produced photolytically from a halogenated precursor under collision-free conditions so they are not in a thermal distribution of rotational states. The accuracy relies on the radical dissociating with negligible energetic barrier beyond the endoergicity. We test the model predictions using previous velocity map imaging and crossed laser-molecular beam scattering experiments that photolytically generated rotationally excited CD2CD2OH and C3H6OH radicals from brominated precursors; some of those radicals then undergo further dissociation to CD2CD2 + OH and C3H6 + OH, respectively. We model the rotational trajectories of these radicals, with high vibrational and rotational energy, first near their equilibrium geometry, and then by projecting each point during the rotation to the transition state (continuing the rotational dynamics at that geometry). This allows us to accurately predict the recoil velocity imparted in the subsequent dissociation of the radical by calculating the tangential velocities of the CD2CD2/C3H6 and OH fragments at the transition state. The model also gives a prediction for the distribution of angles between the dissociation fragments' velocity vectors and the initial radical's velocity vector. These results are used to generate fits to the previously measured time-of-flight distributions of the dissociation fragments; the fits are excellent. The results demonstrate the importance of considering the precession of the angular velocity vector for a rotating radical. We also show that if the initial angular momentum of the rotating radical lies nearly parallel to a principal axis, the very narrow range of tangential velocities predicted by this model must be convoluted with a J = 0 recoil velocity distribution to achieve a good result. The model relies on measuring the kinetic energy release when the halogenated precursor is photodissociated via a repulsive excited state but does not include any adjustable parameters. Even when different conformers of the photolytic precursor are populated, weighting the prediction by a thermal conformer population gives an accurate prediction for the relative velocity vectors of the fragments from the highly rotationally excited radical intermediates.

Resonant tunneling of fluctuation Cooper pairs

DOE PAGES

Galda, Alexey; Mel'nikov, A. S.; Vinokur, V. M.

2015-02-09

Superconducting fluctuations have proved to be an irreplaceable source of information about microscopic and macroscopic material parameters that could be inferred from the experiment. According to common wisdom, the effect of thermodynamic fluctuations in the vicinity of the superconducting transition temperature, T c, is to round off all of the sharp corners and discontinuities, which otherwise would have been expected to occur at T c. Here we report the current spikes due to radiation-induced resonant tunneling of fluctuation Cooper pairs between two superconductors which grow even sharper and more pronounced upon approach to T c. This striking effect offers anmore » unprecedented tool for direct measurements of fluctuation Cooper pair lifetime, which is key to our understanding of the fluctuation regime, most notably to nature of the pseudogap state in high-temperature superconductors. Lastly, our finding marks a radical departure from the conventional view of superconducting fluctuations as a blurring and rounding phenomenon.« less

Resonant tunneling of fluctuation Cooper pairs

PubMed Central

Galda, Alexey; Mel'nikov, A. S.; Vinokur, V. M.

2015-01-01

Superconducting fluctuations have proved to be an irreplaceable source of information about microscopic and macroscopic material parameters that could be inferred from the experiment. According to common wisdom, the effect of thermodynamic fluctuations in the vicinity of the superconducting transition temperature, Tc, is to round off all of the sharp corners and discontinuities, which otherwise would have been expected to occur at Tc. Here we report the current spikes due to radiation-induced resonant tunneling of fluctuation Cooper pairs between two superconductors which grow even sharper and more pronounced upon approach to Tc. This striking effect offers an unprecedented tool for direct measurements of fluctuation Cooper pair lifetime, which is key to our understanding of the fluctuation regime, most notably to nature of the pseudogap state in high-temperature superconductors. Our finding marks a radical departure from the conventional view of superconducting fluctuations as a blurring and rounding phenomenon. PMID:25661237

Resonant tunneling of fluctuation Cooper pairs.

PubMed

Galda, Alexey; Mel'nikov, A S; Vinokur, V M

2015-02-09

Superconducting fluctuations have proved to be an irreplaceable source of information about microscopic and macroscopic material parameters that could be inferred from the experiment. According to common wisdom, the effect of thermodynamic fluctuations in the vicinity of the superconducting transition temperature, Tc, is to round off all of the sharp corners and discontinuities, which otherwise would have been expected to occur at Tc. Here we report the current spikes due to radiation-induced resonant tunneling of fluctuation Cooper pairs between two superconductors which grow even sharper and more pronounced upon approach to Tc. This striking effect offers an unprecedented tool for direct measurements of fluctuation Cooper pair lifetime, which is key to our understanding of the fluctuation regime, most notably to nature of the pseudogap state in high-temperature superconductors. Our finding marks a radical departure from the conventional view of superconducting fluctuations as a blurring and rounding phenomenon.

Antioxidant Effects of Herbal Tea Leaves from Yacon (Smallanthus sonchifolius) on Multiple Free Radical and Reducing Power Assays, Especially on Different Superoxide Anion Radical Generation Systems.

PubMed

Sugahara, Shintaro; Ueda, Yuto; Fukuhara, Kumiko; Kamamuta, Yuki; Matsuda, Yasushi; Murata, Tatsuro; Kuroda, Yasuhiro; Kabata, Kiyotaka; Ono, Masateru; Igoshi, Keiji; Yasuda, Shin

2015-11-01

Yacon (Smallanthus sonchifolius), a native Andean plant, has been cultivated as a crop and locally used as a traditional folk medicine for the people suffering from diabetes and digestive/renal disorders. However, the medicinal properties of this plant and its processed foods have not been completely established. This study investigates the potent antioxidative effects of herbal tea leaves from yacon in different free radical models and a ferric reducing model. A hot-water extract exhibited the highest yield of total polyphenol and scavenging effect on 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical among four extracts prepared with hot water, methanol, ethanol, and ethylacetate. In addition, a higher reducing power of the hot-water extract was similarly demonstrated among these extracts. Varying concentrations of the hot-water extract resulted in different scavenging activities in four synthetic free radical models: DPPH radical (EC50 28.1 μg/mL), 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) cation radical (EC50 23.7 μg/mL), galvinoxyl radical (EC50 3.06 μg/mL), and chlorpromazine cation radical (EC50 475 μg/mL). The yacon tea-leaf extract further demonstrated superoxide anion (O2(-)) radical scavenging effects in the phenazine methosulfate-NADH-nitroblue tetrazolium (EC50 64.5 μg/mL) and xanthine oxidase assay systems (EC50 20.7 μg/mL). Subsequently, incubating human neutrophilic cells in the presence of the tea-leaf extract could suppress the cellular O2(-) radical generation (IC50 65.7 μg/mL) in a phorbol 12-myristate 13-acetate-activated cell model. These results support yacon tea leaves may be a good source of natural antioxidants for preventing O2(-) radical-mediated disorders. Yacon has been considered to be a potent alternative food source for patients who require a dietary cure in regional area, while the leaf part has been provided and consumed as an herbal tea in local markets. We demonstrated here potent antioxidative effects of the tea leaves from yacon in different free radical assays, reducing power assay, and cellular superoxide anion radical generation assay. Results support yacon tea leaves may be a good source of natural antioxidants for preventing O2(-) radical-mediated disorders. © 2015 Institute of Food Technologists®

In Vivo and In Situ Detection of Macromolecular Free Radicals Using Immuno-Spin Trapping and Molecular Magnetic Resonance Imaging.

PubMed

Towner, Rheal A; Smith, Nataliya

2018-05-20

In vivo free radical imaging in preclinical models of disease has become a reality. Free radicals have traditionally been characterized by electron spin resonance (ESR) or electron paramagnetic resonance (EPR) spectroscopy coupled with spin trapping. The disadvantage of the ESR/EPR approach is that spin adducts are short-lived due to biological reductive and/or oxidative processes. Immuno-spin trapping (IST) involves the use of an antibody that recognizes macromolecular 5,5-dimethyl-pyrroline-N-oxide (DMPO) spin adducts (anti-DMPO antibody), regardless of the oxidative/reductive state of trapped radical adducts. Recent Advances: The IST approach has been extended to an in vivo application that combines IST with molecular magnetic resonance imaging (mMRI). This combined IST-mMRI approach involves the use of a spin-trapping agent, DMPO, to trap free radicals in disease models, and administration of an mMRI probe, an anti-DMPO probe, which combines an antibody against DMPO-radical adducts and an MRI contrast agent, resulting in targeted free radical adduct detection. The combined IST-mMRI approach has been used in several rodent disease models, including diabetes, amyotrophic lateral sclerosis (ALS), gliomas, and septic encephalopathy. The advantage of this approach is that heterogeneous levels of trapped free radicals can be detected directly in vivo and in situ to pin point where free radicals are formed in different tissues. The approach can also be used to assess therapeutic agents that are either free radical scavengers or generate free radicals. Smaller probe constructs and radical identification approaches are being considered. The focus of this review is on the different applications that have been studied, advantages and limitations, and future directions. Antioxid. Redox Signal. 28, 1404-1415.

Initiator system in holographic photopolymer materials

NASA Astrophysics Data System (ADS)

Ortuño, M.; Fernández, E.; Fuentes, R.; Gallego, S.; Márquez, A.

2010-05-01

The photopolymers with a hydrophilic matrix as poly(vinyl alcohol), PVA, are versatile holographic recording materials in hologram recording experiments. They use water as solvent and they can be made in layers with several thickness. One of the photopolymers more used is composed of acrylamide as polymerizable monomer, PVA and water as binder. The pair: triethanolamine, TEA, and the dye yellowish eosin, YE, is widely used as initiator system due to its high sensitivity and efficiency. TEA is the radical initiator more used with dyes derived from fluorescein as YE because they can generate a radical by redox reaction under dye excitation by light. The dye is bleached in this process because is decomposed in the photoinitiation reaction. The ethylenediaminetetraacetic acid EDTA has a molecular structure very similar to TEA and therefore could replace it in this kind of photopolymers. The 4,4' azo-bis-(4-cyanopentanoic acid), ACPA, is a radical initiator that is soluble in water and usually used in polymerizations in solution with thermal initiation. In this work, we use EDTA and ACPA in order to check their properties as radical initiator in the photochemical reaction that takes place inside the photopolymer while a hologram is being recorded. We will compare the results obtained with those derived from TEA and will evaluate the possibilities for these substances.

What Hinders Electron Transfer Dissociation (ETD) of DNA Cations?

NASA Astrophysics Data System (ADS)

Hari, Yvonne; Leumann, Christian J.; Schürch, Stefan

2017-12-01

Radical activation methods, such as electron transfer dissociation (ETD), produce structural information complementary to collision-induced dissociation. Herein, electron transfer dissociation of 3-fold protonated DNA hexamers was studied to gain insight into the fragmentation mechanism. The fragmentation patterns of a large set of DNA hexamers confirm cytosine as the primary target of electron transfer. The reported data reveal backbone cleavage by internal electron transfer from the nucleobase to the phosphate linker leading either to a•/ w or d/ z• ion pairs. This reaction pathway contrasts with previous findings on the dissociation processes after electron capture by DNA cations, suggesting multiple, parallel dissociation channels. However, all these channels merely result in partial fragmentation of the precursor ion because the charge-reduced DNA radical cations are quite stable. Two hypotheses are put forward to explain the low dissociation yield of DNA radical cations: it is either attributed to non-covalent interactions between complementary fragments or to the stabilization of the unpaired electron in stacked nucleobases. MS3 experiments suggest that the charge-reduced species is the intact oligonucleotide. Moreover, introducing abasic sites significantly increases the dissociation yield of DNA cations. Consequently, the stabilization of the unpaired electron by π-π-stacking provides an appropriate rationale for the high intensity of DNA radical cations after electron transfer. [Figure not available: see fulltext.

Leadership Styles for the Five Stages of Radical Change

DTIC Science & Technology

1998-04-01

radical change. This article continues prior work on radical change with theory and research on leadership style. The result is a model of radical...every stage of that process. Leadership style and organiza- tional change theory and re- search have ex- isted for de- cades, but have rarely con... Leadership Styles for the Five Stages of Radical Change 129 TUTORIAL LEADERSHIP STYLES FOR THE FIVE STAGES OF RADICAL CHANGE Dr. Kathleen K. Reardon

Understanding in-situ ozone production in the summertime through radical observations and modelling studies during the Clean air for London project

NASA Astrophysics Data System (ADS)

Whalley, Lisa; Stone, Daniel; Sharp, Thomas; Garraway, Shani; Bannan, Thomas; Percival, Carl; Hopkins, James; Holmes, Rachel; Hamilton, Jacqui; Lee, James; Laufs, Sebastian; Kleffmann, Jörg; Heard, Dwayne

2014-05-01

With greater than 50 % of the global population residing in urban conurbations, poor urban air quality has a demonstrable effect on human health. OH and HO2 radicals, (collectively termed HOx) together with RO2 radicals, mediate virtually all of the oxidative chemistry in the atmosphere, being responsible for the transformation of primary emissions into secondary pollutants such as NO2, O3 and particulates. Here we present measurements of OH, HO2, partially speciated RO2 (distinguishing smaller alkane related RO2 from larger alkane/alkene/aromatic related RO2), ClNO2 and OH reactivity measurements taken during the ClearfLo campaign in central London in the summer of 2012. Comparison with calculations from a detailed box model utilising the Master Chemical Mechanism v3.2 tested our ability to reproduce radical levels, and enabled detailed radical budgets to be determined, highlighting for example the important role of the photolysis of nitrous acid (HONO) and carbonyl species as radical sources. Speciation of RO2 enabled the break-down of ozone production from different classes of VOCs to be calculated directly and compared with model calculations. Summertime observations of radicals have helped to identify that increases in photolytic sources of radicals on warm, sunny days can significantly increase local ozone concentrations leading to exceedances of EU air quality recommendations of 60 ppbV. The photolytic breakdown of ClNO2 to Cl atoms can more than double radical concentrations in the early morning; although the integrated increase in radical concentrations over a 24 hr period in model runs when ClNO2 photolysis is included is more modest. On average we calculate just under a 1 ppb increase in ozone due to the presence of ClNO2 in London air. OH reactivity was found to be greatest during morning and evening rush hours. Good agreement between the modelled OH reactivity and observations could be achieved when reactivity associated with model generated photo-oxidation products was considered in addition to the measured primary OH reactants. Carbonyl species such as formaldehyde, acetaldehyde and acetone have been identified as the VOC class dominating organic OH reactivity. As such, together with the direct radical source contribution by photolysis, these species dominate local ozone production in London. Modelling studies comparing the observed carbonyl concentrations with model predictions suggest that over 50% of the total concentration may be directly emitted and, hence, London's in-situ chemistry may be considered to contribute significantly to the ozone levels observed.

Free radical reactions of isoxazole and pyrazole derivatives of hispolon: kinetics correlated with molecular descriptors.

PubMed

Shaikh, Shaukat Ali M; Barik, Atanu; Singh, Beena G; Modukuri, Ramani V; Balaji, Neduri V; Subbaraju, Gottumukkala V; Naik, Devidas B; Priyadarsini, K Indira

2016-12-01

Hispolon (HS), a natural polyphenol found in medicinal mushrooms, and its isoxazole (HI) and pyrazole (HP) derivatives have been examined for free radical reactions and in vitro antioxidant activity. Reaction of these compounds with one-electron oxidant, azide radicals ([Formula: see text]) and trichloromethyl peroxyl radicals ([Formula: see text]), model peroxyl radicals, studied by nanosecond pulse radiolysis technique, indicated formation of phenoxyl radicals absorbing at 420 nm with half life of few hundred microseconds (μs). The formation of phenoxyl radicals confirmed that the phenolic OH is the active centre for free radical reactions. Rate constant for the reaction of these radicals with these compounds were in the order k HI ≅ k HP  >   k HS . Further the compounds were examined for their ability to inhibit lipid peroxidation in model membranes and also for the scavenging of 2,2'-diphenyl-1-picrylhydrazyl (DPPH) radical and superoxide ([Formula: see text]) radicals. The results suggested that HP and HI are less efficient than HS towards these radical reactions. Quantum chemical calculations were performed on these compounds to understand the mechanism of reaction with different radicals. Lower values of adiabatic ionization potential (AIP) and elevated highest occupied molecular orbital (HOMO) for HI and HP compared with HS controlled their activity towards [Formula: see text] and [Formula: see text] radicals, whereas the contribution of overall anion concentration was responsible for higher activity of HS for DPPH, [Formula: see text], and lipid peroxyl radical. The results confirm the role of different structural moieties on the antioxidant activity of hispolon derivatives.

High-resolution laser spectroscopy and magnetic effect of the B{sup ~2}E′ ← X{sup ~2}A{sub 2}′ transition of {sup 14}NO{sub 3} radical

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tada, Kohei; Kashihara, Wataru; Baba, Masaaki

2014-11-14

Rotationally resolved high-resolution fluorescence excitation spectra of {sup 14}NO{sub 3} radical have been observed for the 662 nm band, which is assigned as the 0–0 band of the B{sup ~2}E′ ←X{sup ~2}A{sub 2}′ transition, by crossing a single-mode laser beam perpendicularly to a collimated molecular beam. More than 3000 rotational lines were detected in 15 070–15 145 cm{sup −1} region, but it is difficult to find the rotational line series. Remarkable rotational line pairs, whose interval is about 0.0246 cm{sup −1}, were found in the observed spectrum. This interval is the same amount with the spin-rotation splitting of the X{sup ~2}A{sub 2}′more » (υ = 0, k = 0, N = 1) level. From this interval and the observed Zeeman splitting up to 360 G, seven line pairs were assigned as the transitions to the {sup 2}E′{sub 3/2} (J′ = 1.5) levels and 15 line pairs were assigned as the transitions to the {sup 2}E′{sub 1/2} (J′ = 0.5) levels. From the rotational analysis, we recognized that the {sup 2}E′ state splits into {sup 2}E′{sub 3/2} and {sup 2}E′{sub 1/2} by the spin-orbit interaction and the effective spin-orbit interaction constant was roughly estimated as –21 cm{sup −1}. From the number of the rotational line pairs, we concluded that the complicated rotational structure of this 662 nm band of {sup 14}NO{sub 3} mainly owes to the vibronic interaction between the B{sup ~2}E′ state and the dark A{sup ~2}E″ state through the a{sub 2}″ symmetry vibrational mode.« less

Comparative antioxidant activity of tocotrienols and other natural lipid-soluble antioxidants in a homogeneous system, and in rat and human lipoproteins.

PubMed

Suarna, C; Hood, R L; Dean, R T; Stocker, R

1993-02-24

The antioxidant activity of tocotrienols toward peroxyl radicals was compared with that of other natural lipid-soluble antioxidants in three different systems by measuring the temporal disappearance of antioxidants and the formation of lipid hydroperoxides. In homogeneous solution, the initial rates of consumption of the various antioxidants, assessed by competition experiments between pairs of antioxidants for radicals, decreased in the order: ubiquinol-10 approximately ubiquinol-9 > alpha-tocopherol approximately alpha-tocotrienol > beta-carotene approximately lycopene > gamma-tocopherol approximately gamma-tocotrienol. Following in vitro incubation of human plasma with alpha-tocotrienol, this form of vitamin E was present in all classes of lipoproteins isolated from the supplemented plasma. Dietary supplementation of rats and humans with a tocotrienol-rich preparation resulted in a dose-dependent appearance of alpha- and gamma-tocotrienols in plasma and all circulating lipoproteins, respectively. Exposure of such enriched rat plasma to aqueous peroxyl radicals resulted in simultaneous consumption of the alpha- and then gamma-isomers of vitamin E. The sequence of radical-induced consumption of antioxidants in freshly isolated, in vitro and in vivo tocotrienol-enriched low density lipoprotein (LDL) was again ubiquinol-10 > alpha-tocotrienol approximately alpha-tocopherol > carotenoids > gamma-tocopherol approximately gamma-tocotrienol. Under conditions where radicals were generated at constant rates, the rate of lipid hydroperoxide formation in LDL was not constant. It proceeded in at least three stages separated by the phase of ubiquinol-10 consumption and, subsequently, that of alpha-tocopherol/alpha-tocotrienol. Our results show that dietary tocotrienols become incorporated into circulating human lipoproteins where they react with peroxyl radicals as efficiently as the corresponding tocopherol isomers.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Inbar, S.; Linschitz, H.; Cohen, S.G.

Nanosecond flash photolysis, steady irradiation, and deuterium substitution studies have been carried out on solutions of benzophenone with added reductants. Quantum yields (phi/sub ketyl/) for reduction in benzene of benzophenone triplet to ketyl radical, based on phi = 2 for benzhydrol (I), were approx. 1 for cyclohexane (II), tert-butylamine (III), 2-aminobutane (IV), cyclohexylamine (V), di-n-propylamine (VI), and triethylamine (VII), approx. 0.7 for 1,4-diazabicyclo(2.2.2)octane (VIII), and approx. 0 for tert-butyl alcohol (IX). Thus, quenching, without radical formation by H abstraction from N and/or ..cap alpha..-C, does not occur with common aliphatic amines but does with Dabco (VIII). The latter quenching ismore » markedly increased by small additions of acetonitrile; the flash spectrum from this compound indicates formation of a triplet amine CT complex or radical ion pair. Triplet-reductant interaction rate constants, k/sur ir/, are high for the amines (approx. 10/sup 8/-10/sup 9/ M/sup -1/ s/sup -1/) but also show significant deuterium kinetic isotope effects: 1.9 with III-N-d/sub 2/; 1.4 with IV-N-d/sub 2/; 1.2-1.3 with IV-..cap alpha..-C-d. It is proposed that k/sub ir/ measures H atom abstraction, favored in the transition state by an initial charge-transfer interaction. Overall steady irradiation quantum yields of reduction by amines, phi/sub Red/, are much lower than phi/sub ketyl/. This is attributed to disproportionationreactions of ketyl and alkylaminyl radicals for primary and secondary amines, and, possibly, aminoalkyl radicals for tertiary amines. In the case of tert-butylamine, the rate constant for disproportionation is obtained from the decay kinetics of ketyl radical and leads to phi/sub Red/ in agreement with that directly measured.« less

Tuning the Ground State Symmetry of Acetylenyl Radicals

PubMed Central

2015-01-01

The lowest excited state of the acetylenyl radical, HCC, is a 2Π state, only 0.46 eV above the ground state, 2Σ+. The promotion of an electron from a π bond pair to a singly occupied σ hybrid orbital is all that is involved, and so we set out to tune those orbital energies, and with them the relative energetics of 2Π and 2Σ+ states. A strategy of varying ligand electronegativity, employed in a previous study on substituted carbynes, RC, was useful, but proved more difficult to apply for substituted acetylenyl radicals, RCC. However, π-donor/acceptor substitution is effective in modifying the state energies. We are able to design molecules with 2Π ground states (NaOCC, H2NCC (2A″), HCSi, FCSi, etc.) and vary the 2Σ+–2Π energy gap over a 4 eV range. We find an inconsistency between bond order and bond dissociation energy measures of the bond strength in the Si-containing molecules; we provide an explanation through an analysis of the relevant potential energy curves. PMID:27162981

Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds.

PubMed

García Einschlag, Fernando S; Carlos, Luciano; Capparelli, Alberto L

2003-10-01

The rate constants for hydroxyl radical reaction toward a set of nitroaromatic substrates kS, have been measured at 25 degrees C using competition experiments in the UV/H2O2 process. For a given pair of substrates S1 and S2, the relative reactivity beta (defined as kS1/kS2) was calculated from the slope of the corresponding double logarithmic plot, i.e., of ln[S1] vs. ln[S2]. This method is more accurate and remained linear for larger conversions in comparison with the plots of ln[S1] and ln[S2] against time. The rate constants measured ranged from 0.33 to 8.6 x 10(9) M(-1)s(-1). A quantitative structure-reactivity relationship was found using the Hammett equation. Assuming sigma values to be additive, a value of -0.60 was obtained for the reaction constant rho. This value agrees with the high reactivity and the electrophilic nature of HO* radical.

Bioeffects of Static Magnetic Fields: Oxidative Stress, Genotoxic Effects, and Cancer Studies

PubMed Central

Ghodbane, Soumaya; Lahbib, Aida; Sakly, Mohsen; Abdelmelek, Hafedh

2013-01-01

The interaction of static magnetic fields (SMFs) with living organisms is a rapidly growing field of investigation. The magnetic fields (MFs) effect observed with radical pair recombination is one of the well-known mechanisms by which MFs interact with biological systems. Exposure to SMF can increase the activity, concentration, and life time of paramagnetic free radicals, which might cause oxidative stress, genetic mutation, and/or apoptosis. Current evidence suggests that cell proliferation can be influenced by a treatment with both SMFs and anticancer drugs. It has been recently found that SMFs can enhance the anticancer effect of chemotherapeutic drugs; this may provide a new strategy for cancer therapy. This review focuses on our own data and other data from the literature of SMFs bioeffects. Three main areas of investigation have been covered: free radical generation and oxidative stress, apoptosis and genotoxicity, and cancer. After an introduction on SMF classification and medical applications, the basic phenomena to understand the bioeffects are described. The scientific literature is summarized, integrated, and critically analyzed with the help of authoritative reviews by recognized experts; international safety guidelines are also cited. PMID:24027759

Effect of ascorbic acid on prevention of hypercholesterolemia induced atherosclerosis.

PubMed

Das, S; Ray, R; Snehlata; Das, N; Srivastava, L M

2006-04-01

The notion that oxidation of lipids and propagation of free radicals may contribute to the pathogenesis of atherosclerosis is supported by a large body of evidence. To circumvent the damage caused by oxygen free radicals, antioxidants are needed which provide the much needed neutralization of free radical by allowing the pairing of electrons. In this study we have investigated the effect of ascorbic acid, a water soluble antioxidant on the development of hypercholesterolemia induced atherosclerosis in rabbits. Rabbits were made hypercholesterolemic and atherosclerotic by feeding 100 mg cholesterol/day. Different doses of ascorbic acid were administered to these rabbits. Low dose of ascorbic acid (0.5 mg/100 g body weight/day) did not have any significant effect on the percent of total area covered by atherosclerotic plaque. However, ascorbic acid when fed at a higher dose (15 mg/100 g body weight/day) was highly effective in reducing the atherogenecity. With this dose the percent of total surface area covered by atherosclerotic plaque was significantly less (p < 0.001). This suggests that use of ascorbic acid may have great promise in the prevention of hypercholesterolemia induced atherosclerosis.

Ionization dynamics of the water trimer: A direct ab initio MD study

NASA Astrophysics Data System (ADS)

Tachikawa, Hiroto; Takada, Tomoya

2013-03-01

Ionization dynamics of the cyclic water trimer (H2O)3 have been investigated by means of direct ab initio molecular dynamics (AIMD) method. Two reaction channels, complex formation and OH dissociation, were found following the ionization of (H2O)3. In both channels, first, a proton was rapidly transferred from H2O+ to H2O (time scale is ˜15 fs after the ionization). In complex channel, an ion-radical contact pair (H3O+-OH) solvated by the third water molecule was formed as a long-lived H3O+(OH)H2O complex. In OH dissociation channel, the second proton transfer further takes place from H3O+(OH) to H2O (time scale is 50-100 fs) and the OH radical is separated from the H3O+. At the same time, the OH dissociation takes place when the excess energy is efficiently transferred into the kinetic energy of OH radical. The OH dissociation channel is significantly minor, and almost all product channels were the complex formation. The reaction mechanism was discussed on the basis of theoretical results.

The segment polarity network is a robust developmental module

NASA Astrophysics Data System (ADS)

von Dassow, George; Meir, Eli; Munro, Edwin M.; Odell, Garrett M.

2000-07-01

All insects possess homologous segments, but segment specification differs radically among insect orders. In Drosophila, maternal morphogens control the patterned activation of gap genes, which encode transcriptional regulators that shape the patterned expression of pair-rule genes. This patterning cascade takes place before cellularization. Pair-rule gene products subsequently `imprint' segment polarity genes with reiterated patterns, thus defining the primordial segments. This mechanism must be greatly modified in insect groups in which many segments emerge only after cellularization. In beetles and parasitic wasps, for instance, pair-rule homologues are expressed in patterns consistent with roles during segmentation, but these patterns emerge within cellular fields. In contrast, although in locusts pair-rule homologues may not control segmentation, some segment polarity genes and their interactions are conserved. Perhaps segmentation is modular, with each module autonomously expressing a characteristic intrinsic behaviour in response to transient stimuli. If so, evolution could rearrange inputs to modules without changing their intrinsic behaviours. Here we suggest, using computer simulations, that the Drosophila segment polarity genes constitute such a module, and that this module is resistant to variations in the kinetic constants that govern its behaviour.

Spin Biochemistry Modulates Reactive Oxygen Species (ROS) Production by Radio Frequency Magnetic Fields

PubMed Central

Usselman, Robert J.; Hill, Iain; Singel, David J.; Martino, Carlos F.

2014-01-01

The effects of weak magnetic fields on the biological production of reactive oxygen species (ROS) from intracellular superoxide (O2 •−) and extracellular hydrogen peroxide (H2O2) were investigated in vitro with rat pulmonary arterial smooth muscle cells (rPASMC). A decrease in O2 •− and an increase in H2O2 concentrations were observed in the presence of a 7 MHz radio frequency (RF) at 10 μTRMS and static 45 μT magnetic fields. We propose that O2 •− and H2O2 production in some metabolic processes occur through singlet-triplet modulation of semiquinone flavin (FADH•) enzymes and O2 •− spin-correlated radical pairs. Spin-radical pair products are modulated by the 7 MHz RF magnetic fields that presumably decouple flavin hyperfine interactions during spin coherence. RF flavin hyperfine decoupling results in an increase of H2O2 singlet state products, which creates cellular oxidative stress and acts as a secondary messenger that affects cellular proliferation. This study demonstrates the interplay between O2 •− and H2O2 production when influenced by RF magnetic fields and underscores the subtle effects of low-frequency magnetic fields on oxidative metabolism, ROS signaling, and cellular growth. PMID:24681944

Kinetic magnetic-field effect involving the small biologically relevant inorganic radicals NO and O2(·-).

PubMed

Karogodina, Tatiana Y; Dranov, Igor G; Sergeeva, Svetlana V; Stass, Dmitry V; Steiner, Ulrich E

2011-06-20

Oxidation of dihydrorhodamine 123 (DHR) to rhodamine 123 (RH) by oxoperoxonitrite (ONOO(-)), formed through recombination of NO and O(2)(·-) radicals resulting from thermal decomposition of 3-morpholinosydnonimine (SIN-1) in buffered aerated aqueous solution at pH 7.6, represents a kinetic model system of the reactivity of NO and O(2)(·-) in biochemical systems. A magnetic-field effect (MFE) on the yield of RH detected in this system is explored in the full range of fields between 0 and 18 T. It is found to increase in a nearly linear fashion up to a value of 5.5±1.6 % at 18 T and 23 °C (3.1±0.7 % at 40 °C). A theoretical framework to analyze the MFE in terms of the magnetic-field-enhanced recombination rate constant k(rec) of NO and O(2)(·-) due to magnetic mixing of T(0) and S spin states of the radical pair by the Δg mechanism is developed, including estimation of magnetic properties (g tensor and spin relaxation times) of NO and O(2)(·-) in aqueous solution, and calculation of the MFE on k(rec) using the theoretical formalism of Gorelik at al. The factor with which the MFE on k(rec) is translated to the MFE on the yield of ONOO(-) and RH is derived for various kinetic scenarios representing possible sink channels for NO and O(2)(·-). With reasonable assumptions for the values of some unknown kinetic parameters, the theoretical predictions account well for the observed MFE. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nature and kinetic analysis of carbon-carbon bond fragmentation reactions of cation radicals derived from SET-oxidation of lignin model compounds.

PubMed

Cho, Dae Won; Parthasarathi, Ramakrishnan; Pimentel, Adam S; Maestas, Gabriel D; Park, Hea Jung; Yoon, Ung Chan; Dunaway-Mariano, Debra; Gnanakaran, S; Langan, Paul; Mariano, Patrick S

2010-10-01

Features of the oxidative cleavage reactions of diastereomers of dimeric lignin model compounds, which are models of the major types of structural units found in the lignin backbone, were examined. Cation radicals of these substances were generated by using SET-sensitized photochemical and Ce(IV) and lignin peroxidase promoted oxidative processes, and the nature and kinetics of their C-C bond cleavage reactions were determined. The results show that significant differences exist between the rates of cation radical C1-C2 bond cleavage reactions of 1,2-diaryl-(β-1) and 1-aryl-2-aryloxy-(β-O-4) propan-1,3-diol structural units found in lignins. Specifically, under all conditions C1-C2 bond cleavage reactions of cation radicals of the β-1 models take place more rapidly than those of the β-O-4 counterparts. The results of DFT calculations on cation radicals of the model compounds show that the C1-C2 bond dissociation energies of the β-1 lignin model compounds are significantly lower than those of the β-O-4 models, providing clear evidence for the source of the rate differences.

Observation and Modelling of the OH, HO2 and RO2 Radicals at a Regional Site of Beijing in Winter 2016.

NASA Astrophysics Data System (ADS)

Tan, Z.; Lu, K.; Ma, X.; Bohn, B.; Hofzumahaus, A.; Broch, S.; Fuchs, H.; Holland, F.; Liu, Y.; Li, X.; Novelli, A.; Rohrer, F.; Wang, H.; Wu, Y.; Shao, M.; Zeng, L.; Kiendler-Scharr, A.; Wahner, A.; Zhang, Y.

2017-12-01

A comprehensive field campaign was carried out in winter 2016 in the campus of UCAS (University of Chinese Academy of Science), located in a small town 60 km northeast of urban Beijing. Concentrations of OH, HO2 and RO2 radicals as well as the total OH reactivity were measured by a laser induced fluorescence instrument. Maximum hourly averaged OH, HO2 and RO2 radical concentrations were (3±2)×106cm-3, (8±6)×107 cm-3 and (7±5)×107 cm-3, respectively. These radical concentrations were smaller than those observed during summer because of the reduced solar radiation. A chemical modulation device to separate atmospheric OH radicals from any interfering species was applied for few days showing negligible interference for both clean and polluted air masses.HONO and HCHO photolysis were found to be the most important primary sources of ROx radicals. CO and NOx were the important OH reactants which contributed more than half of the total OH reactivity. The relative high OH concentrations in polluted episode enabled a fast oxidation of fresh emitted pollutants and the formation of secondary air products. The observed radical concentrations were compared with the results from a chemical box model. The model is capable of reproducing radical concentrations for moderate NOx conditions but larger discrepancies are observed for both low and high NOx regimes for the peroxy radical concentrations. The underestimation of RO2 radical concentrations for high NOx conditions is discussed in the context of recent campaigns.

Recent data for the p p at tevatron and odderon description

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fazal-e-Aleem; Ali, M.; Rashid, H.

1991-06-01

The experimental data for pp and {bar p}p at {radical}s = 53 GeV shows the difference between the differential cross sections in the dip region. This prompted the need for a crossing-odd amplitude even at this energy. Further support to this idea was provided by the order of magnitude rise of the measured pp differential cross section in the dip region as we go from ISR to CERN collider energies. In order to overcome the difficulty to explain these phenomena, Gauron et al used the idea of an odderon in addition to the pomeron and explained the then available datamore » for pp and {bar p}p. Dynamical origin to the idea of an odderon was later provided by Islam. He has pointed out that, if the nucleon consists of a core of valence quarks surrounded by a cloud of quark-antiquark pairs, then in elastic scattering an odderon amplitude occurs when the cores interact by exchanging a J = 1, C = {minus}1, u{bar u} + d{bar d} state and the cloud undergoes maximal diffraction scattering. The model has recently been modified by these authors so as to fit the very recent data of {bar p}p at 546 GeV and make predictions at 1.8 TeV. The same idea was also used by Barnbard et al to explain the pp and {bar p}p data , Jankovszky et al have also fitted the data for p ({bar p}) p by employing the odderon in conjunction with the dipole pomeron. In this paper the authors will compare the results of these models with the most recent measurements at tevatron and also compare them with those of other models.« less

Biophysics of magnetic orientation: strengthening the interface between theory and experimental design

PubMed Central

Kirschvink, Joseph L.; Winklhofer, Michael; Walker, Michael M.

2010-01-01

The first demonstrations of magnetic effects on the behaviour of migratory birds and homing pigeons in laboratory and field experiments, respectively, provided evidence for the longstanding hypothesis that animals such as birds that migrate and home over long distances would benefit from possession of a magnetic sense. Subsequent identification of at least two plausible biophysical mechanisms for magnetoreception in animals, one based on biogenic magnetite and another on radical-pair biochemical reactions, led to major efforts over recent decades to test predictions of the two models, as well as efforts to understand the ultrastructure and function of the possible magnetoreceptor cells. Unfortunately, progress in understanding the magnetic sense has been challenged by: (i) the availability of a relatively small number of techniques for analysing behavioural responses to magnetic fields by animals; (ii) difficulty in achieving reproducible results using the techniques; and (iii) difficulty in development and implementation of new techniques that might bring greater experimental power. As a consequence, laboratory and field techniques used to study the magnetic sense today remain substantially unchanged, despite the huge developments in technology and instrumentation since the techniques were developed in the 1950s. New methods developed for behavioural study of the magnetic sense over the last 30 years include the use of laboratory conditioning techniques and tracking devices based on transmission of radio signals to and from satellites. Here we consider methodological developments in the study of the magnetic sense and present suggestions for increasing the reproducibility and ease of interpretation of experimental studies. We recommend that future experiments invest more effort in automating control of experiments and data capture, control of stimulation and full blinding of experiments in the rare cases where automation is impossible. We also propose new experiments to confirm whether or not animals can detect magnetic fields using the radical-pair effect together with an alternate hypothesis that may explain the dependence on light of responses by animals to magnetic field stimuli. PMID:20071390

Polysulfide chemistry in sodium-sulfur batteries and related systems--a computational study by G3X(MP2) and PCM calculations.

PubMed

Steudel, Ralf; Steudel, Yana

2013-02-25

The sodium-sulfur (NAS) battery is a candidate for energy storage and load leveling in power systems, by using the reversible reduction of elemental sulfur by sodium metal to give a liquid mixture of polysulfides (Na(2)S(n)) at approximately 320°C. We investigated a large number of reactions possibly occurring in such sodium polysulfide melts by using density functional calculations at the G3X(MP2)/B3LYP/6-31+G(2df,p) level of theory including polarizable continuum model (PCM) corrections for two polarizable phases, to obtain geometric and, for the first time, thermodynamic data for the liquid sodium-sulfur system. Novel reaction sequences for the electrochemical reduction of elemental sulfur are proposed on the basis of their Gibbs reaction energies. We suggest that the primary reduction product of S(8) is the radical anion S(8)(˙-), which decomposes at the operating temperature of NAS batteries exergonically to the radicals S(2)(˙-) and S(3)(˙-) together with the neutral species S(6) and S(5), respectively. In addition, S(8)(˙-) is predicted to disproportionate exergonically to S(8) and S(8)(2-) followed by the dissociation of the latter into two S(4)(˙-) radical ions. By recombination reactions of these radicals various polysulfide dianions can in principle be formed. However, polysulfide dianions larger than S(4)(2-) are thermally unstable at 320°C and smaller dianions as well as radical monoanions dominate in Na(2)S(n) (n=2-5) melts instead. The reverse reactions are predicted to take place when the NAS battery is charged. We show that ion pairs of the types NaS(2)˙, NaS(n)(-), and Na(2)S(n) can be expected at least for n=2 and 3 in NAS batteries, but are unlikely in aqueous sodium polysulfide except at high concentrations. The structures of such radicals and anions with up to nine sulfur atoms are reported, because they are predicted to play a key role in the electrochemical reduction process. A large number of isomerization, disproportionation, and sulfurization reactions of polysulfide mono- and dianions have been investigated in the gas phase and in a polarizable continuum, and numerous reaction enthalpies as well as Gibbs energies are reported. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The formation of DNA sugar radicals from photoexcitation of guanine cation radicals.

PubMed

Shukla, Lata I; Pazdro, Robert; Huang, James; DeVreugd, Christopher; Becker, David; Sevilla, Michael D

2004-05-01

In this investigation of radical formation and reaction in gamma- irradiated DNA and model compounds, we report the conversion of the guanine cation radical (one-electron oxidized guanine, G(.+)) to the C1' sugar radical and another sugar radical at the C3' or C4' position (designated C3'(.)/C4'(.)) by visible and UV photolysis. Electron spin resonance (ESR) spectroscopic investigations were performed on salmon testes DNA as well as 5'-dGMP, 3'-dGMP, 2'-deoxyguanosine and other nucleosides/nucleotides as model systems. DNA samples (25- 150 mg/ml D(2)O) were prepared with Tl(3+) or Fe(CN)(3-)(6) as electron scavengers. Upon gamma irradiation of such samples at 77 K, the electron-gain path in the DNA is strongly suppressed and predominantly G(.+) is found; after UV or visible photolysis, the fraction of the C1' sugar radical increases with a concomitant reduction in the fraction of G(.+). In model systems, 3'- dGMP(+.) and 5'-dGMP(+.) were produced by attack of Cl(.-)(2) on the parent nucleotide in 7 M LiCl glass. Subsequent visible photolysis of the 3'-dGMP(+.) (77 K) results predominantly in formation of C1'(.) whereas photolysis of 5'-dGMP(+.) results predominantly in formation of C3'(.)/C4'(.). We propose that sugar radical formation is a result of delocalization of the hole in the electronically excited base cation radical into the sugar ring, followed by deprotonation at specific sites on the sugar.

Observation and modelling of the OH, HO_{2} and RO_{2} radicals at a suburban site of Beijing (Huairou) in winter 2016

NASA Astrophysics Data System (ADS)

Tan, Zhaofeng; Lu, Keding; Ma, Xuefei; Birger, Bohn; Broch, Sebastian; Fuchs, Hendrik; Hofzumahaus, Andreas; Holland, Frank; Li, Xin; Liu, Yuhan; Novelli, Anna; Rohrer, Franz; Shao, Min; Wang, Haichao; Wu, Yusheng; Zeng, Limin; Kiendler-Scharr, Astrid; Wahner, Andreas; Zhang, Yuanhang

2017-04-01

A comprehensive field campaign was carried out in winter 2016 in Huairou, a small town located 60 km northeast of Beijing downtown. Concentrations of OH, HO2and RO2 radicals were measured by a laser induced fluorescence instrument. Radical concentrations were smaller than during summer because of reduced solar radiation. Maximum hourly averaged OH, HO2 and RO2 radical concentrations were (3±2)×106cm-3, (8±6)×107 cm-3 and (7±5)×107 cm-3, respectively. Chemical modulation measurements were applied on a few days showing no significant OH interference for different chemical conditions. HONO and HCHO photolysis were found to be the most important primary source of ROx radicals. OH reactivity, the inverse of the OH radical lifetime, was also measured by a laser-photolysis and laser induced fluorescence instrument. In general, CO and NOx were the dominated OH reactants which contributed more than half of the total OH reactivity. The relative high OH concentrations in polluted episode enabled a fast oxidation of fresh emitted pollutants and the formation of secondary products. The observed radical concentrations were compared with the results from a chemical box model. The model is capable of reproducing radical concentrations in the moderate NOx conditions but has difficulty in both the low and high NOx regimes. The underestimation of RO2 radical concentrations in the high NOx conditions indicate a missing RO2 source.

Pharmacophore Modelling and Synthesis of Quinoline-3-Carbohydrazide as Antioxidants

PubMed Central

El Bakkali, Mustapha; Ismaili, Lhassane; Tomassoli, Isabelle; Nicod, Laurence; Pudlo, Marc; Refouvelet, Bernard

2011-01-01

From well-known antioxidants agents, we developed a first pharmacophore model containing four common chemical features: one aromatic ring and three hydrogen bond acceptors. This model served as a template in virtual screening of Maybridge and NCI databases that resulted in selection of sixteen compounds. The selected compounds showed a good antioxidant activity measured by three chemical tests: DPPH radical, OH° radical, and superoxide radical scavenging. New synthetic compounds with a good correlation with the model were prepared, and some of them presented a good antioxidant activity. PMID:25954520

Mechanism of Action of Sulforaphane as a Superoxide Radical Anion and Hydrogen Peroxide Scavenger by Double Hydrogen Transfer: A Model for Iron Superoxide Dismutase.

PubMed

Prasad, Ajit Kumar; Mishra, P C

2015-06-25

The mechanism of action of sulforaphane as a scavenger of superoxide radical anion (O2(•-)) and hydrogen peroxide (H2O2) was investigated using density functional theory (DFT) in both gas phase and aqueous media. Iron superoxide dismutase (Fe-SOD) involved in scavenging superoxide radical anion from biological media was modeled by a complex consisting of the ferric ion (Fe(3+)) attached to three histidine rings. Reactions related to scavenging of superoxide radical anion by sulforaphane were studied using DFT in the presence and absence of Fe-SOD represented by this model in both gas phase and aqueous media. The scavenging action of sulforaphane toward both superoxide radical anion and hydrogen peroxide was found to involve the unusual mechanism of double hydrogen transfer. It was found that sulforaphane alone, without Fe-SOD, cannot scavenge superoxide radical anion in gas phase or aqueous media efficiently as the corresponding reaction barriers are very high. However, in the presence of Fe-SOD represented by the above-mentioned model, the scavenging reactions become barrierless, and so sulforaphane scavenges superoxide radical anion by converting it to hydrogen peroxide efficiently. Further, sulforaphane was found to scavenge hydrogen peroxide also very efficiently by converting it into water. Thus, the mechanism of action of sulforaphane as an excellent antioxidant has been unravelled.

Intermolecular electron-transfer mechanisms via quantitative structures and ion-pair equilibria for self-exchange of anionic (dinitrobenzenide) donors.

PubMed

Rosokha, Sergiy V; Lü, Jian-Ming; Newton, Marshall D; Kochi, Jay K

2005-05-25

Definitive X-ray structures of "separated" versus "contact" ion pairs, together with their spectral (UV-NIR, ESR) characterizations, provide the quantitative basis for evaluating the complex equilibria and intrinsic (self-exchange) electron-transfer rates for the potassium salts of p-dinitrobenzene radical anion (DNB(-)). Three principal types of ion pairs, K(L)(+)DNB(-), are designated as Classes S, M, and C via the specific ligation of K(+) with different macrocyclic polyether ligands (L). For Class S, the self-exchange rate constant for the separated ion pair (SIP) is essentially the same as that of the "free" anion, and we conclude that dinitrobenzenide reactivity is unaffected when the interionic distance in the separated ion pair is r(SIP) > or =6 Angstroms. For Class M, the dynamic equilibrium between the contact ion pair (with r(CIP) = 2.7 Angstroms) and its separated ion pair is quantitatively evaluated, and the rather minor fraction of SIP is nonetheless the principal contributor to the overall electron-transfer kinetics. For Class C, the SIP rate is limited by the slow rate of CIP right arrow over left arrow SIP interconversion, and the self-exchange proceeds via the contact ion pair by default. Theoretically, the electron-transfer rate constant for the separated ion pair is well-accommodated by the Marcus/Sutin two-state formulation when the precursor in Scheme 2 is identified as the "separated" inner-sphere complex (IS(SIP)) of cofacial DNB(-)/DNB dyads. By contrast, the significantly slower rate of self-exchange via the contact ion pair requires an associative mechanism (Scheme 3) in which the electron-transfer rate is strongly governed by cationic mobility of K(L)(+) within the "contact" precursor complex (IS(CIP)) according to the kinetics in Scheme 4.

Toward the Development of a Fundamentally Based Chemical Model for Cyclopentanone: High-Pressure-Limit Rate Constants for H Atom Abstraction and Fuel Radical Decomposition

DOE PAGES

Zhou, Chong-Wen; Simmie, John M.; Pitz, William J.; ...

2016-08-25

Theoretical aspects of the development of a chemical kinetic model for the pyrolysis and combustion of a cyclic ketone, cyclopentanone, are considered. We present calculated thermodynamic and kinetic data for the first time for the principal species including 2- and 3-oxo-cyclopentyl radicals, which are in reasonable agreement with the literature. Furthermore, these radicals can be formed via H atom abstraction reactions by H and Ö atoms and OH, HO 2, and CH 3 radicals, the rate constants of which have been calculated. Abstraction from the β-hydrogen atom is the dominant process when OH is involved, but the reverse holds truemore » for HO 2 radicals. We also determined the subsequent β-scission of the radicals formed, and it is shown that recent tunable VUV photoionization mass spectrometry experiments can be interpreted in this light. The bulk of the calculations used the composite model chemistry G4, which was benchmarked in the simplest case with a coupled cluster treatment, CCSD(T), in the complete basis set limit.« less

Oxygen radicals shaping evolution: why fatty acid catabolism leads to peroxisomes while neurons do without it: FADH₂/NADH flux ratios determining mitochondrial radical formation were crucial for the eukaryotic invention of peroxisomes and catabolic tissue differentiation.

PubMed

Speijer, Dave

2011-02-01

Oxygen radical formation in mitochondria is a highly important, but incompletely understood, attribute of eukaryotic cells. I propose a kinetic model in which the ratio between electrons entering the respiratory chain via FADH₂ or NADH is a major determinant in radical formation. During the breakdown of glucose, this ratio is low; during fatty acid breakdown, this ratio is much higher. The longer the fatty acid, the higher the ratio and the higher the level of radical formation. This means that very long chain fatty acids should be broken down without generation of FADH₂ for mitochondria. This is accomplished in peroxisomes, thus explaining their role and evolution. The model explains many recent observations regarding radical formation by the respiratory chain. It also sheds light on the reasons for the lack of neuronal fatty acid (beta-) oxidation and for beneficial aspects of unsaturated fatty acids. Last but not least, it has very important implications for all models describing eukaryotic origins.

Reaction between peroxynitrite and triphenylphosphonium-substituted arylboronic acid isomers–Identification of diagnostic marker products and biological implications

PubMed Central

Sikora, Adam; Zielonka, Jacek; Adamus, Jan; Debski, Dawid; Dybala-Defratyka, Agnieszka; Michalowski, Bartosz; Joseph, Joy; Hartley, Richard C.; Murphy, Michael P.; Kalyanaraman, Balaraman

2013-01-01

Aromatic boronic acids react rapidly with peroxynitrite (ONOO−) to yield phenols as major products. This reaction was used to monitor ONOO− formation in cellular systems. Previously, we proposed that the reaction between ONOO− and arylboronates (PhB(OH)2) yields a phenolic product (major pathway) and a radical pair PhB(OH)2O•−…•NO2 (minor pathway). [Sikora A. et al., Chem Res Toxicol 24, 687-97, 2011]. In this study, we investigated the influence of a bulky triphenylphosphonium (TPP) group on the reaction between ONOO− and mitochondria-targeted arylboronate isomers (o-, m-, and p-MitoPhB(OH)2). Results from the electron paramagnetic resonance (EPR) spin-trapping experiments unequivocally showed the presence of a phenyl radical intermediate from meta and para isomers, and not from the ortho isomer. The yield of o-MitoPhNO2 formed from the reaction between o-MitoPhB(OH)2 and ONOO− was not diminished by phenyl radical scavengers, suggesting a rapid fragmentation of the o-MitoPhB(OH)2O•− radical anion with subsequent reaction of the resulting phenyl radical with •NO2 in the solvent cage. The DFT quantum mechanical calculations showed that the energy barrier for the dissociation of o-MitoPhB(OH)2O•− radical anion is significantly lower than that of m-MitoPhB(OH)2O•− and p-MitoPhB(OH)2O•− radical anions. The nitrated product, o-MitoPhNO2, is not formed by nitrogen dioxide radical generated by myeloperoxidase in the presence of nitrite anion and hydrogen peroxide, indicating that this specific nitrated product may be used as a diagnostic marker product for ONOO−. Incubation of o-MitoPhB(OH)2 with RAW 264.7 macrophages activated to produce ONOO− yielded the corresponding phenol o-MitoPhOH as well as the diagnostic nitrated product, o-MitoPhNO2. We conclude that the ortho isomer probe reported here is most suitable for specific detection of ONOO− in biological systems. PMID:23611338

Polymeric Ionic Networks with High Charge Density: Solid-like Electrolytes in Lithium Metal Batteries

DOE PAGES

Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; ...

2015-11-02

Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10 -3 S cm -1 at 22 °C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes.

Organic spintronic devices and methods for making the same

DOEpatents

Vardeny, Zee Valentine; Ndobe, Alex

2014-09-23

An organic spintronic photovoltaic device (100) having an organic electron active layer (102) functionally associated with a pair of electrodes (104, 106). The organic electron active layer (102) can include a spin active molecular radical distributed in the active layer (102) which increases spin-lattice relaxation rates within the active layer (102). The increased spin lattice relaxation rate can also influence the efficiency of OLED and charge mobility in FET devices.

Quark matter or new particles?

NASA Technical Reports Server (NTRS)

Michel, F. Curtis

1988-01-01

It has been argued that compression of nuclear matter to somewhat higher densities may lead to the formation of stable quark matter. A plausible alternative, which leads to radically new astrophysical scenarios, is that the stability of quark matter simply represents the stability of new particles compounded of quarks. A specific example is the SU(3)-symmetric version of the alpha particle, composed of spin-zero pairs of each of the baryon octet (an 'octet' particle).

Dynamics and Stabilization of Materials Possessing High Energy Content

DTIC Science & Technology

1991-10-31

Barton, Nucl. Acids Res., J2, 2595 (1991). 24. "Diffusion and Percolation of Radical Pairs in Zeolite Media. A Product Analysis Study," J. Am. Chem...Photobiol. A: Chem., i, 35 (1991). 33. "Effect of External Pressure on Photoinduced Electron-Transfer Reactions in the Marcus Inverted Region," W.-S. Chung...duPont (Towanda, PA), Unilever USA Research (Edgewater, NJ), IBM Almaden Research Labs (San Jose, CA), Hoeschst Chemical Company (Frankfurt, Germany

The scavenging of free radical and oxygen species activities and hydration capacity of collagen hydrolysates from walleye pollock ( Theragra chalcogramma) skin

NASA Astrophysics Data System (ADS)

Zhuang, Yongliang; Li, Bafang; Zhao, Xue

2009-06-01

Fish skin collagen hydrolysates (FSCH) were prepared from walleye pollock ( Theragra chalcogramma) using a mixture of enzymes, namely trypsin and flavourzyme. The degree of hydrolysis of the skin collagen was 27.3%. FSCH was mainly composed of low-molecular-weight peptides and the relative proportion of <1000Da fraction was 70.6%. Free radical and oxygen species scavenging activities of FSCH were investigated in four model systems, including diphenylpicrylhy-drazyl radical (DPPH), superoxide anion radical, hydroxyl radical and hydrogen peroxide model, and compared with that of a native antioxidant, reduced glutathione (GSH). FSCH was also evaluated by water-absorbing and water-holding capacity. The results showed that FSCH was able to scavenge free radical and oxygen species significantly and to enhance water-absorbing and water-holding capacity remarkably. Therefore, FSCH may have potential applications in the medicine and food industries.

Measurements of hydroxyl and hydroperoxy radicals during CalNex-LA: Model comparisons and radical budgets

NASA Astrophysics Data System (ADS)

Griffith, S. M.; Hansen, R. F.; Dusanter, S.; Michoud, V.; Gilman, J. B.; Kuster, W. C.; Veres, P. R.; Graus, M.; de Gouw, J. A.; Roberts, J.; Young, C.; Washenfelder, R.; Brown, S. S.; Thalman, R.; Waxman, E.; Volkamer, R.; Tsai, C.; Stutz, J.; Flynn, J. H.; Grossberg, N.; Lefer, B.; Alvarez, S. L.; Rappenglueck, B.; Mielke, L. H.; Osthoff, H. D.; Stevens, P. S.

2016-04-01

Measurements of hydroxyl (OH) and hydroperoxy (HO2*) radical concentrations were made at the Pasadena ground site during the CalNex-LA 2010 campaign using the laser-induced fluorescence-fluorescence assay by gas expansion technique. The measured concentrations of OH and HO2* exhibited a distinct weekend effect, with higher radical concentrations observed on the weekends corresponding to lower levels of nitrogen oxides (NOx). The radical measurements were compared to results from a zero-dimensional model using the Regional Atmospheric Chemical Mechanism-2 constrained by NOx and other measured trace gases. The chemical model overpredicted measured OH concentrations during the weekends by a factor of approximately 1.4 ± 0.3 (1σ), but the agreement was better during the weekdays (ratio of 1.0 ± 0.2). Model predicted HO2* concentrations underpredicted by a factor of 1.3 ± 0.2 on the weekends, while measured weekday concentrations were underpredicted by a factor of 3.0 ± 0.5. However, increasing the modeled OH reactivity to match the measured total OH reactivity improved the overall agreement for both OH and HO2* on all days. A radical budget analysis suggests that photolysis of carbonyls and formaldehyde together accounted for approximately 40% of radical initiation with photolysis of nitrous acid accounting for 30% at the measurement height and ozone photolysis contributing less than 20%. An analysis of the ozone production sensitivity reveals that during the week, ozone production was limited by volatile organic compounds throughout the day during the campaign but NOx limited during the afternoon on the weekends.

Ab Initio Kinetics of Hydrogen Abstraction from Methyl Acetate by Hydrogen, Methyl, Oxygen, Hydroxyl, and Hydroperoxy Radicals.

PubMed

Tan, Ting; Yang, Xueliang; Krauter, Caroline M; Ju, Yiguang; Carter, Emily A

2015-06-18

The kinetics of hydrogen abstraction by five radicals (H, O((3)P), OH, CH3, and HO2) from methyl acetate (MA) is investigated theoretically in order to gain further understanding of certain aspects of the combustion chemistry of biodiesels, such as the effect of the ester moiety. We employ ab initio quantum chemistry methods, coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) and multireference averaged coupled pair functional theory (MRACPF2), to predict chemically accurate reaction energetics. Overall, MRACPF2 predicts slightly higher barrier heights than CCSD(T) for MA + H/CH3/O/OH, but slightly lower barrier heights for hydrogen abstraction by HO2. Based on the obtained reaction energies, we also report high-pressure-limit rate constants using transition state theory (TST) in conjunction with the separable-hindered-rotor approximation, the variable reaction coordinate TST, and the multi-structure all-structure approach. The fitted modified Arrhenius expressions are provided over a temperature range of 250 to 2000 K. The predictions are in good agreement with available experimental results. Abstractions from both of the methyl groups in MA are expected to contribute to consumption of the fuel as they exhibit similar rate coefficients. The reactions involving the OH radical are predicted to have the highest rates among the five abstracting radicals, while those initiated by HO2 are expected to be the lowest.

Effects of electrolytes on redox potentials through ion pairing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bird, Matthew J.; Iyoda, Tomokazu; Bonura, Nicholas

Here, reduction potentials have been determined for two molecules, benzophenone (BzPh) and perylene (Per), effectively in the complete absence of electrolyte as well as in the presence of three different supporting electrolytes in the moderately polar solvent THF. A description of how this can be so, and qualifications, are described in the discussion section. The primary tool in this work, pulse radiolysis, measures electron transfer (ET) equilibria in solution to obtain differences in redox potentials. Voltammetry measures redox potentials by establishing ET equilibria at electrodes, but electrolytes are needed for current flow. Results here show that without electrolyte the redoxmore » potentials were 100–451 mV more negative than those with 100 mM electrolyte. These changes depended both on the molecule and the electrolyte. In THF the dominant contributor to stabilization of radical anions by electrolyte was ion pairing. An equation was derived to give changes in redox potentials when electrolyte is added in terms of ion pair dissociation constants and activity coefficients. Definite values were determined for energetics, ΔG d°, of ion pairing. Values of ΔG d° for pairs with TBA + give some doubt that it is a “weakly-coordinating cation.” Computations with DFT methods were moderately successful at describing the ion paring energies.« less

Effects of electrolytes on redox potentials through ion pairing

DOE PAGES

Bird, Matthew J.; Iyoda, Tomokazu; Bonura, Nicholas; ...

2017-09-21

Here, reduction potentials have been determined for two molecules, benzophenone (BzPh) and perylene (Per), effectively in the complete absence of electrolyte as well as in the presence of three different supporting electrolytes in the moderately polar solvent THF. A description of how this can be so, and qualifications, are described in the discussion section. The primary tool in this work, pulse radiolysis, measures electron transfer (ET) equilibria in solution to obtain differences in redox potentials. Voltammetry measures redox potentials by establishing ET equilibria at electrodes, but electrolytes are needed for current flow. Results here show that without electrolyte the redoxmore » potentials were 100–451 mV more negative than those with 100 mM electrolyte. These changes depended both on the molecule and the electrolyte. In THF the dominant contributor to stabilization of radical anions by electrolyte was ion pairing. An equation was derived to give changes in redox potentials when electrolyte is added in terms of ion pair dissociation constants and activity coefficients. Definite values were determined for energetics, ΔG d°, of ion pairing. Values of ΔG d° for pairs with TBA + give some doubt that it is a “weakly-coordinating cation.” Computations with DFT methods were moderately successful at describing the ion paring energies.« less

Model studies in cytochrome P-450-mediated toxicity of halogenated compounds: radical processes involving iron porphyrins.

PubMed Central

Brault, D

1985-01-01

Haloalkane toxicity originates from attack on biological targets by reactive intermediates derived from haloalkane metabolism by a hemoprotein, cytochrome P-450. Carbon-centered radicals and their peroxyl derivatives are most likely involved. The reactions of iron porphyrin--a model for cytochrome P-450--with various carbon-centered and peroxyl radicals generated by pulse radiolysis are examined. Competition between iron porphyrin and unsaturated fatty acids for attack by peroxyl radicals is pointed out. These kinetic data are used to derive a model for toxicity of haloalkanes with particular attention to carbon tetrachloride and halothane. The importance of local oxygen concentration and structural arrangement of fatty acids around cytochrome P-450 is emphasized. PMID:3007100

Theoretical calculations of Electron Paramagnetic Resonance parameters of liquid phase Orotic acid radical

NASA Astrophysics Data System (ADS)

Sarikaya, Ebru Karakaş; Dereli, Ömer

2017-02-01

To obtain liquid phase molecular structure, conformational analysis of Orotic acid was performed and six conformers were determined. For these conformations, eight possible radicals were modelled by using Density Functional Theory computations with respect to molecular structure. Electron Paramagnetic Resonance parameters of these model radicals were calculated and then they were compared with the experimental ones. Geometry optimizations of the molecule and modeled radicals were performed using Becke's three-parameter hybrid-exchange functional combined with the Lee-Yang-Parr correlation functional of Density Functional Theory and 6-311++G(d,p) basis sets in p-dioxane solution. Because Orotic acid can be mutagenic in mammalian somatic cells and it is also mutagenic for bacteria and yeast, it has been studied.

Modelled and Measured Abundances of Free Radicals in the Marine Boundary Layer During NEAQS 2004 and TEXAQS 2006

NASA Astrophysics Data System (ADS)

Sommariva, R.; Brown, S. S.; Roberts, J. M.; Monks, P. S.; Parker, A. E.; Osthoff, H. D.; Ravishankara, A. R.; Trainer, M.

2006-12-01

Chemistry of free radicals in the marine boundary layer was investigated during two cruises of the NOAA Research Vessel Ronald H. Brown as parts of the NEAQS-ITCT 2004 and TexAQS-GoMACCS 2006 campaigns. The nitrate radical (NO{_3}) and dinitrogen pentoxide (N{_2}O{_5}) were measured during the NEAQS campaign by Cavity Ring-Down Spectroscopy (CaRDS). NO{_3} abundances measured under the conditions encountered during the cruise were investigated using a zero-dimensional model based upon the Master Chemical Mechanism (MCMv3.1, http://mcm.leeds.ac.uk). The model was constrained to measurements of chemical and physical parameters taken during the campaign. The high level of chemical detail in the MCM allowed us to calculate abundances of the alkyl peroxy radicals that were to be expected and to study the interactions during the night between these alkyl peroxy radicals (RO{_2}) and NO{_3}. In particular, the importance of the reaction between RO{_2} and NO{_3} as a sink for NO{_3} under different conditions was assessed. CaRDS NO{_3} measurements during TexAQS campaign were made in conjunction with measurements of total peroxy radicals (HO{_2}+RO{_2}) by a chemical amplification technique (PERCA), allowing for experimental verification of the relationships between these radicals at night. The preliminary measurements taken during TeXAQS 2006 will be presented and they will be used to investigate the night-time chemistry of the peroxy radicals, and especially the interactions between NO{_3} and peroxy radical in a polluted nighttime environment.

The Influences of Airmass Histories on Radical Species During POLARIS

NASA Technical Reports Server (NTRS)

Pierson, James M.; Kawa, S. R.

1998-01-01

The POLARIS mission focused on understanding the processes associated with the decrease of polar stratospheric ozone from spring to fall at high latitudes. This decrease is linked primarily to in situ photochemical destruction by reactive nitrogen species, NO and NO2, which also control other catalytic loss cycles. Steady state models have been used to test photochemistry and radical behavior but are not always adequate in simulating radical species observations. In some cases, air mass history can be important and trajectory models give an improved simulation of the radical species. Trajectory chemistry models, however, still consistently underestimate NO and NO2 abundances compared to measurements along the ER-2 flight track. The Goddard chemistry on trajectory model has been used to test updated rate constants for NO2 + OH, NO2 + O and OH + HNO3, key reactions that affect NO and NO2 abundances. We present comparisons between the modified Goddard chemistry on trajectory model, the JPL steady state model and observations from selected flights.

QSPR prediction of the hydroxyl radical rate constant of water contaminants.

PubMed

Borhani, Tohid Nejad Ghaffar; Saniedanesh, Mohammadhossein; Bagheri, Mehdi; Lim, Jeng Shiun

2016-07-01

In advanced oxidation processes (AOPs), the aqueous hydroxyl radical (HO) acts as a strong oxidant to react with organic contaminants. The hydroxyl radical rate constant (kHO) is important for evaluating and modelling of the AOPs. In this study, quantitative structure-property relationship (QSPR) method is applied to model the hydroxyl radical rate constant for a diverse dataset of 457 water contaminants from 27 various chemical classes. The constricted binary particle swarm optimization and multiple-linear regression (BPSO-MLR) are used to obtain the best model with eight theoretical descriptors. An optimized feed forward neural network (FFNN) is developed to investigate the complex performance of the selected molecular parameters with kHO. Although the FFNN prediction results are more accurate than those obtained using BPSO-MLR, the application of the latter is much more convenient. Various internal and external validation techniques indicate that the obtained models could predict the logarithmic hydroxyl radical rate constants of a large number of water contaminants with less than 4% absolute relative error. Finally, the above-mentioned proposed models are compared to those reported earlier and the structural factors contributing to the AOP degradation efficiency are discussed. Copyright © 2016 Elsevier Ltd. All rights reserved.

Standard Gibbs free energies of reactions of ozone with free radicals in aqueous solution: quantum-chemical calculations.

PubMed

Naumov, Sergej; von Sonntag, Clemens

2011-11-01

Free radicals are common intermediates in the chemistry of ozone in aqueous solution. Their reactions with ozone have been probed by calculating the standard Gibbs free energies of such reactions using density functional theory (Jaguar 7.6 program). O(2) reacts fast and irreversibly only with simple carbon-centered radicals. In contrast, ozone also reacts irreversibly with conjugated carbon-centered radicals such as bisallylic (hydroxycylohexadienyl) radicals, with conjugated carbon/oxygen-centered radicals such as phenoxyl radicals, and even with nitrogen- oxygen-, sulfur-, and halogen-centered radicals. In these reactions, further ozone-reactive radicals are generated. Chain reactions may destroy ozone without giving rise to products other than O(2). This may be of importance when ozonation is used in pollution control, and reactions of free radicals with ozone have to be taken into account in modeling such processes.

Volume and porosity thermal regulation in lipid mesophases by coupling mobile ligands to soft membranes

NASA Astrophysics Data System (ADS)

Parolini, Lucia; Mognetti, Bortolo M.; Kotar, Jurij; Eiser, Erika; Cicuta, Pietro; di Michele, Lorenzo

2015-01-01

Short DNA linkers are increasingly being exploited for driving-specific self-assembly of Brownian objects. DNA-functionalized colloids can assemble into ordered or amorphous materials with tailored morphology. Recently, the same approach has been applied to compliant units, including emulsion droplets and lipid vesicles. The liquid structure of these substrates introduces new degrees of freedom: the tethers can diffuse and rearrange, radically changing the physics of the interactions. Unlike droplets, vesicles are extremely deformable and DNA-mediated adhesion causes significant shape adjustments. We investigate experimentally the thermal response of pairs and networks of DNA-tethered liposomes and observe two intriguing and possibly useful collective properties: negative thermal expansion and tuneable porosity of the liposome networks. A model providing a thorough understanding of this unexpected phenomenon is developed, explaining the emergent properties out of the interplay between the temperature-dependent deformability of the vesicles and the DNA-mediated adhesive forces.

Volume and porosity thermal regulation in lipid mesophases by coupling mobile ligands to soft membranes

PubMed Central

Parolini, Lucia; Mognetti, Bortolo M.; Kotar, Jurij; Eiser, Erika; Cicuta, Pietro; Di Michele, Lorenzo

2015-01-01

Short DNA linkers are increasingly being exploited for driving-specific self-assembly of Brownian objects. DNA-functionalized colloids can assemble into ordered or amorphous materials with tailored morphology. Recently, the same approach has been applied to compliant units, including emulsion droplets and lipid vesicles. The liquid structure of these substrates introduces new degrees of freedom: the tethers can diffuse and rearrange, radically changing the physics of the interactions. Unlike droplets, vesicles are extremely deformable and DNA-mediated adhesion causes significant shape adjustments. We investigate experimentally the thermal response of pairs and networks of DNA-tethered liposomes and observe two intriguing and possibly useful collective properties: negative thermal expansion and tuneable porosity of the liposome networks. A model providing a thorough understanding of this unexpected phenomenon is developed, explaining the emergent properties out of the interplay between the temperature-dependent deformability of the vesicles and the DNA-mediated adhesive forces. PMID:25565580

Protonated o-semiquinone radical as a mimetic of the humic acids native radicals: A DFT approach to the molecular structure and EPR properties

NASA Astrophysics Data System (ADS)

Witwicki, Maciej; Jezierska, Julia

2012-06-01

Organic radicals are known to be an indispensable component of the humic acids (HA) structure. In HA two forms of radicals, stable (native) and short-lived (transient), are identified. Importantly, these radical forms can be easily differentiated by electron paramagnetic resonance (EPR) spectroscopy. This article provides a DFT-based insight into the electronic and molecular structure of the native radicals. The molecular models including an increase of the radical aromaticity and the hydrogen bonding between the radical and other functional groups of HA are taken under investigation. In consequence the interesting pieces of information on the structure of the native radical centers in HA are revealed and discussed, especially in terms of differences between the electronic structure of the native and transient forms.

Extendable pipe crawler

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hapstack, M.

1990-05-01

A pipe crawler having a front leg assembly and a back leg assembly connected together by two air cylinders, each leg assembly having four extendable legs and a pair of actuators for sliding the extendable legs radically outward to increase the range of the legs when the pipe crawler enters a section of pipe having a larger diameter. The crawler crawls by inchworm''-like motion, the front leg assembly and back leg assembly alternately engaging and disengaging the wall of the pipe to hold the pipe crawler as the air cylinders alternately advance the front leg assembly and bring up themore » rear leg assembly. The pair of actuators of each leg assembly are parallel, adjacent and opposing acting so that each slides two adjacent extendable legs radially outward. 5 figs.« less

Evaluation of antioxidant activity and electronic structure of aspirin and paracetamol

NASA Astrophysics Data System (ADS)

Motozaki, W.; Nagatani, Y.; Kimura, Y.; Endo, K.; Takemura, T.; Kurmaev, E. Z.; Moewes, A.

2011-01-01

We present a study of electronic structure, chemical bonding, and antioxidant activity of phenolic antioxidants (aspirin and paracetamol). X-ray photoelectron and emission spectra of the antioxidants have been simulated by deMon density functional theory (DFT) calculations of the molecules. The chemical bonding of aspirin is characterized by the formation of oxygen 'lone-pair' π-orbitals which can neutralize free radicals and thus be related to antioxidant properties of the drug. In the case of paracetamol the additional nitrogen 'lone pair' is formed which can explain toxicity of the drug. We propose an evaluation method of antioxidant activity based on the relationship between experimental half-wave oxidation potential ( Ep/2 ) and calculated ionization potentials ( IP) by the DFT calculations, and can conclude that paracetamol has the higher antioxidant activity than aspirin.

Solid-state EPR strategies for the structural characterization of paramagnetic NO adducts of frustrated Lewis pairs (FLPs)

NASA Astrophysics Data System (ADS)

de Oliveira, Marcos; Wiegand, Thomas; Elmer, Lisa-Maria; Sajid, Muhammad; Kehr, Gerald; Erker, Gerhard; Magon, Claudio José; Eckert, Hellmut

2015-03-01

Anisotropic interactions present in three new nitroxide radicals prepared by N,N addition of NO to various borane-phosphane frustrated Lewis pairs (FLPs) have been characterized by continuous-wave (cw) and pulsed X-band EPR spectroscopies in solid FLP-hydroxylamine matrices at 100 K. Anisotropic g-tensor values and 11B, 14N, and 31P hyperfine coupling tensor components have been extracted from continuous-wave lineshape analyses, electron spin echo envelope modulation (ESEEM), and hyperfine sublevel correlation spectroscopy (HYSCORE) experiments with the help of computer simulation techniques. Suitable fitting constraints are developed on the basis of density functional theory (DFT) calculations. These calculations reveal that different from the situation in standard nitroxide radicals (TEMPO), the g-tensors are non-coincident with any of the nuclear hyperfine interaction tensors. The determination of these interaction parameters turns out to be successful, as the cw- and pulse EPR experiments are highly complementary in informational content. While the continuous-wave lineshape is largely influenced by the anisotropic hyperfine coupling to 14N and 31P, the ESEEM and HYSCORE spectra contain important information about the 11B hyperfine coupling and nuclear electric quadrupolar interaction. The set of cw- and pulsed EPR experiments, with fitting constraints developed by DFT calculations, defines an efficient strategy for the structural analysis of paramagnetic FLP adducts.

Solid-state EPR strategies for the structural characterization of paramagnetic NO adducts of frustrated Lewis pairs (FLPs)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oliveira, Marcos de; Magon, Claudio José; Wiegand, Thomas

2015-03-28

Anisotropic interactions present in three new nitroxide radicals prepared by N,N addition of NO to various borane-phosphane frustrated Lewis pairs (FLPs) have been characterized by continuous-wave (cw) and pulsed X-band EPR spectroscopies in solid FLP-hydroxylamine matrices at 100 K. Anisotropic g-tensor values and {sup 11}B, {sup 14}N, and {sup 31}P hyperfine coupling tensor components have been extracted from continuous-wave lineshape analyses, electron spin echo envelope modulation (ESEEM), and hyperfine sublevel correlation spectroscopy (HYSCORE) experiments with the help of computer simulation techniques. Suitable fitting constraints are developed on the basis of density functional theory (DFT) calculations. These calculations reveal that differentmore » from the situation in standard nitroxide radicals (TEMPO), the g-tensors are non-coincident with any of the nuclear hyperfine interaction tensors. The determination of these interaction parameters turns out to be successful, as the cw- and pulse EPR experiments are highly complementary in informational content. While the continuous-wave lineshape is largely influenced by the anisotropic hyperfine coupling to {sup 14}N and {sup 31}P, the ESEEM and HYSCORE spectra contain important information about the {sup 11}B hyperfine coupling and nuclear electric quadrupolar interaction. The set of cw- and pulsed EPR experiments, with fitting constraints developed by DFT calculations, defines an efficient strategy for the structural analysis of paramagnetic FLP adducts.« less

Molecular mechanisms in the pyrolysis of unsaturated chlorinated hydrocarbons: formation of benzene rings. 1. Quantum chemical studies.

PubMed

McIntosh, Grant J; Russell, Douglas K

2013-05-23

Analogues of important aromatic growth mechanisms in hydrocarbon pyrolysis and combustion systems are extended to chlorinated systems. We consider the addition of C2Cl2 to both C4Cl3 and C4Cl5 radicals at the M06-2X/6-311+G(3df,3p)//B3LYP/6-31G(d) level of theory, and we demonstrate that these reaction systems have much in common with those of nonchlorinated species. In particular, we find that these radicals appear to lead preferentially to fulvenes, and not to the observed aromatic products, as is found in nonchlorinated systems. We have therefore also considered nonradical C4/C2 channels by way of Diels-Alder cyclization of C4Cl4/C2Cl2 and C4H2Cl2/C2HCl pairs to describe aromatic formation. While the latter pair readily leads to the formation of partially chlorinated benzenes, the fully chlorinated congeners are sterically prohibited from ring closing directly; this leads to a series of novel rearrangement processes which predict the formation of hexachloro-1,5-diene-3-yne, in addition to hexachlorobenzene, in good agreement with experiment. This suggests, for the first time, that facile nonradical routes to aromatic formation are operative in partially and fully chlorinated pyrolysis and combustion systems.

Visual Field Differences in Visual Word Recognition Can Emerge Purely from Perceptual Learning: Evidence from Modeling Chinese Character Pronunciation

ERIC Educational Resources Information Center

Hsiao, Janet Hui-wen

2011-01-01

In Chinese orthography, a dominant character structure exists in which a semantic radical appears on the left and a phonetic radical on the right (SP characters); a minority opposite arrangement also exists (PS characters). As the number of phonetic radical types is much greater than semantic radical types, in SP characters the information is…

High Resolution Spectroscopy and Dynamics: from Jet Cooled Radicals to Gas-Liquid Interfaces

NASA Astrophysics Data System (ADS)

Sharp-Williams, E.; Roberts, M. A.; Roscioli, J. R.; Gisler, A. W.; Ziemkiewicz, M.; Nesbitt, D. J.; Dong, F.; Perkins, B. G., Jr.

2010-06-01

This talk will attempt to reflect recent work in our group involving two quite different but complementary applications of high resolution molecular spectroscopy for detailed study of intramolecular as well as intermolecular dynamics in small molecules. The first is based on direct infrared absorption spectroscopy in a 100 KHz slit supersonic discharge, which provides a remarkably versatile and yet highly sensitive probe for study of important chemical transients such as open shell combustion species and molecular ions under jet cooled (10-20K), sub-Doppler conditions. For this talk will focus on gas phase spectroscopic results for a series of unsaturated hydrocarbon radical species (ethynyl, vinyl, and phenyl) reputed to be critical intermediates in soot formation. Secondly, we will discuss recent applications of high resolution IR and velocity map imaging spectroscopy toward quantum state resolved collision dynamics of jet cooled molecules from gas-room temperature ionic liquid (RTIL) and gas-self assembled monolayer (SAM) interfaces. Time permitting, we will also present new results on hyperthermal scattering of jet cooled NO radical from liquid Ga, which offer a novel window into non-adiabatic energy transfer and electron-hole pair dynamics at the gas-molten metal interface.

SOMO–HOMO Level Inversion in Biologically Important Radicals

PubMed Central

2017-01-01

Conventionally, the singly occupied molecular orbital (SOMO) of a radical species is considered to be the highest occupied molecular orbital (HOMO), but this is not the case always. In this study, we considered a number of radicals from smallest diatomic anion radicals such as superoxide anion radical to one-electron oxidized DNA related base radicals that show the SOMO is energetically lower than one or more doubly occupied molecular orbitals (MOs) (SOMO–HOMO level inversion). The electronic configurations are calculated employing the B3LYP/6-31++G** method, with the inclusion of aqueous phase via the integral equation formalism of the polarized continuum model solvation model. From the extensive study of the electronic configurations of radicals produced by one-electron oxidation or reduction of natural-DNA bases, bromine-, sulfur-, selenium-, and aza-substituted DNA bases, as well as 20 diatomic molecules, we highlight the following important findings: (i) SOMO–HOMO level inversion is a common phenomenon in radical species. (ii) The more localized spin density in σ-orbital on a single atom (carbon, nitrogen, oxygen, sulfur, or selenium), the greater the gap between HOMO and SOMO. (iii) In species with SOMO–HOMO level inversion, one-electron oxidation takes place from HOMO not from the SOMO, which produces a molecule in its triplet ground state. Oxidation of aqueous superoxide anion producing triplet molecular oxygen is one example of many. (iv) These results are for conventional radicals and in contrast with those reported for distonic radical anions in which SOMO–HOMO gaps are smaller for more localized radicals and the orbital inversions vanish in water. Our findings yield new insights into the properties of free radical systems. PMID:29240424

Cometary atmospheres: Modeling the spatial distribution of observed neutral radicals

NASA Technical Reports Server (NTRS)

Combi, M. R.

1985-01-01

Progress on modeling the spatial distributions of cometary radicals is described. The Monte Carlo particle-trajectory model was generalized to include the full time dependencies of initial comet expansion velocities, nucleus vaporization rates, photochemical lifetimes and photon emission rates which enter the problem through the comet's changing heliocentric distance and velocity. The effect of multiple collisions in the transition zone from collisional coupling to true free flow were also included. Currently available observations of the spatial distributions of the neutral radicals, as well as the latest available photochemical data were re-evaluated. Preliminary exploratory model results testing the effects of various processes on observable spatial distributions are also discussed.

Pulse radiolysis in model studies toward radiation processing

NASA Astrophysics Data System (ADS)

Von Sonntag, C.; Bothe, E.; Ulanski, P.; Deeble, D. J.

1995-02-01

Using the pulse radiolysis technique, the OH-radical-induced reactions of poly(vinyl alcohol) PVAL, poly(acrylic acid) PAA, poly(methacrylic acid) PMA, and hyaluronic acid have been investigated in dilute aqueous solution. The reactions of the free-radical intermediates were followed by UV-spectroscopy and low-angle laser light-scattering; the scission of the charged polymers was also monitored by conductometry. For more detailed product studies, model systems such as 2,4-dihydroxypentane (for PVAL) and 2,4-dimethyl glutaric acid (for PAA) was also investigated. With PVA, OH-radicals react predominantly by abstraction of an H-atom in α-position to the hydroxyl group (70%). The observed bimolecular decay rate constant of the PVAL-radicals decreases with time. This has been interpreted as being due to an initially fast decay of proximate radicals and a decrease of the probability of such encounters with time. Intramolecular crosslinking (loop formation) predominates at high doses per pulse. In the presence of O 2, peroxyl radicals are formed which in the case of the α-hydroxyperoxyl radicals can eliminate HO 2-radicals in competition with bimolecular decay processes which lead to a fragmentation of the polymer. In PAA, radicals both in α-position (characterized by an absorption near 300 nm) and in β-position to the carboxylate groups are formed in an approximately 1:2 ratio. The lifetime of the radicals increases with increasing electrolytic dissociation of the polymer. The β-radicals undergo a slow (intra- as well as intermolecular) H-abstraction yielding α-radicals, in competition to crosslinking and scission reactions. In PMA only β-radicals are formed. Their fragmentation has been followed by conductometry. In hyaluronic acid, considerable fragmeentation is observed even in the absence of oxygen which, in fact, has some protective effect against this process. Thus free-radical attack on this important biopolymer makes it especially vulnerable with respect to a reduction of its viscosity, and in rheumatic diseases this effect may be the reason for their painfulnes.

Free radical scavenging activity and neuroprotective potentials of D138, one Cu(II)/Zn(II) Schiff-base complex derived from N,N'-bis(2-hydroxynaphthylmethylidene)-1,3-propanediamine.

PubMed

Wang, Che; Cai, Zheng-Xu; You, Zhong-Lu; Guo, Hui-Shu; Shang, De-Jing; Wang, Xiao-Ling; Zhang, Liang; Ma, Li-Jie; Tan, Jun; Le, Wei-Dong; Li, Song

2014-09-01

There is increasing evidence that free radicals play an important role in neuronal damages induced by diabetes mellitus or cerebral ischemia insults. Antioxidants with free radical scavenging activities have been shown to be beneficial and neuroprotective for these pathological conditions. Here, we report free radical scavenging activity and neuroprotective potential of D138, one copper(II)/zinc(II) Schiff-base complex derived from N,N'-2(2-hydroxynaphthylmethylidene)-1,3-propanediamine. The data from three in vitro assays, 2,2-diphenyl-1-picrylhydrazyl assay, nitro blue tetrazolium assay and hydroxyl radical scavenging assay, indicated that D138 presented a potent free radical scavenging activity. The neuroprotective and antioxidative effects of D138 were further evaluated in vivo using bilateral common carotid artery occlusion (BCCAO) mouse model and streptozotocin (STZ) diabetic mouse model. Our results indicated that treatment of D138 significantly ameliorated the hippocampal neuronal damage and the oxidative stress levels in these animal models. Moreover, D138 also reversed the behavioral deficiencies induced by BCCAO or STZ, as assessed by Y-maze test and fear conditioning test. In conclusion, all these findings support that D138 exerts free radical scavenging and neuroprotective activities and has the potentials to be a potent therapeutic candidate for brain oxidative damage induced by cerebral ischemia or diabetes mellitus.

OH, HO2, and HO2* Radical Chemistry During PROPHET-AMOS 2016: Measurements and Model Comparison

NASA Astrophysics Data System (ADS)

Bottorff, B.; Lew, M.; Rickly, P.; Stevens, P. S.

2017-12-01

The hydroxyl (OH) and peroxy radicals, both the hydroperoxy radical (HO2) and organic peroxy radicals (RO2), play an important role in atmospheric chemistry. In addition to controlling lifetimes of many trace gases important to issues of global climate change, reactions of these radicals can also lead to the production of ozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicals in remote forest environments have shown serious discrepancies with modeled concentrations. These results bring into question our understanding of the atmospheric chemistry of isoprene and other biogenic VOCs under low NOX conditions. In the summer of 2016, OH, HO2 and HO2* (HO2 + αRO2) radicals were measured using the Indiana University Laser-Induced Fluorescence Fluorescence Assay by Gas Expansion (LIF-FAGE) technique as part of the Program for Research on Oxidants: PHtochemistry, Emissions, and Transport- Atmospheric Measurements of Oxidants in Summer (PROPHET-AMOS). This campaign took place in a forested area in northern Michigan characterized by high mixing ratios of isoprene and low mixing ratios of NOX. Ambient measurements from this campaign will be compared to previous measurements at this site and to modeled predictions using both the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism. Potential interferences associated with the OH measurements will also be examined.

Distance measurements in Au nanoparticles functionalized with nitroxide radicals and Gd(3+)-DTPA chelate complexes.

PubMed

Yulikov, Maxim; Lueders, Petra; Warsi, Muhammad Farooq; Chechik, Victor; Jeschke, Gunnar

2012-08-14

Nanosized gold particles were functionalised with two types of paramagnetic surface tags, one having a nitroxide radical and the other one carrying a DTPA complex loaded with Gd(3+). Selective measurements of nitroxide-nitroxide, Gd(3+)-nitroxide and Gd(3+)-Gd(3+) distances were performed on this system and information on the distance distribution in the three types of spin pairs was obtained. A numerical analysis of the dipolar frequency distributions is presented for Gd(3+) centres with moderate magnitudes of zero-field splitting, in the range of detection frequencies and resonance fields where the high-field approximation is only roughly valid. The dipolar frequency analysis confirms the applicability of DEER for distance measurements in such complexes and gives an estimate for the magnitudes of possible systematic errors due to the non-ideality of the measurement of the dipole-dipole interaction.

Magnetic field affects enzymatic ATP synthesis.

PubMed

Buchachenko, Anatoly L; Kuznetsov, Dmitry A

2008-10-01

The rate of ATP synthesis by creatine kinase extracted from V. xanthia venom was shown to depend on the magnetic field. The yield of ATP produced by enzymes with 24Mg2+ and 26Mg2+ ions in catalytic sites increases by 7-8% at 55 mT and then decreases at 80 mT. For enzyme with 25Mg2+ ion in a catalytic site, the ATP yield increases by 50% and 70% in the fields 55 and 80 mT, respectively. In the Earth field the rate of ATP synthesis by enzyme, in which Mg2+ ion has magnetic nucleus 25Mg, is 2.5 times higher than that by enzymes, in which Mg2+ ion has nonmagnetic, spinless nuclei 24Mg or 26Mg. Both magnetic field effect and magnetic isotope effect demonstrate that the ATP synthesis is an ion-radical process, affected by Zeeman interaction and hyperfine coupling in the intermediate ion-radical pair.

Polyarene mediators for mediated redox flow battery

DOEpatents

Delnick, Frank M.; Ingersoll, David; Liang, Chengdu

2018-01-02

The fundamental charge storage mechanisms in a number of currently studied high energy redox couples are based on intercalation, conversion, or displacement reactions. With exception to certain metal-air chemistries, most often the active redox materials are stored physically in the electrochemical cell stack thereby lowering the practical gravimetric and volumetric energy density as a tradeoff to achieve reasonable power density. In a general embodiment, a mediated redox flow battery includes a series of secondary organic molecules that form highly reduced anionic radicals as reaction mediator pairs for the reduction and oxidation of primary high capacity redox species ex situ from the electrochemical cell stack. Arenes are reduced to stable anionic radicals that in turn reduce a primary anode to the charged state. The primary anode is then discharged using a second lower potential (more positive) arene. Compatible separators and solvents are also disclosed herein.

Reactions of singly-reduced ethylene carbonate in lithium battery electrolytes: a molecular dynamics simulation study using the ReaxFF.

PubMed

Bedrov, Dmitry; Smith, Grant D; van Duin, Adri C T

2012-03-22

We have conducted quantum chemistry calculations and gas- and solution-phase reactive molecular dynamics simulation studies of reactions involving the ethylene carbonate (EC) radical anion EC(-) using the reactive force field ReaxFF. Our studies reveal that the substantial barrier for transition from the closed (cyclic) form, denoted c-EC(-), of the radical anion to the linear (open) form, denoted o-EC(-), results in a relatively long lifetime of the c-EC(-) allowing this compound to react with other singly reduced alkyl carbonates. Using ReaxFF, we systematically investigate the fate of both c-EC(-) and o-EC(-) in the gas phase and EC solution. In the gas phase and EC solutions with a relatively low concentration of Li(+)/x-EC(-) (where x = o or c), radical termination reactions between radical pairs to form either dilithium butylene dicarbonate (CH(2)CH(2)OCO(2)Li)(2) (by reacting two Li(+)/o-EC(-)) or ester-carbonate compound (by reacting Li(+)/o-EC(-) with Li(+)/c-EC(-)) are observed. At higher concentrations of Li(+)/x-EC(-) in solution, we observe the formation of diradicals which subsequently lead to formation of longer alkyl carbonates oligomers through reaction with other radicals or, in some cases, formation of (CH(2)OCO(2)Li)(2) through elimination of C(2)H(4). We conclude that the local ionic concentration is important in determining the fate of x-EC(-) and that the reaction of c-EC(-) with o-EC(-) may compete with the formation of various alkyl carbonates from o-EC(-)/o-EC(-) reactions. © 2012 American Chemical Society

Quenching mechanisms and diffusional pathways in micellar systems unravelled by time-resolved magnetic-field effects.

PubMed

Goez, Martin; Henbest, Kevin B; Windham, Emma G; Maeda, Kiminori; Timmel, Christiane R

2009-06-08

Magnetic-field effects (MFEs) are used to investigate the photoreaction of xanthone (A) and DABCO (D) in anionic (SDS) or cationic (DTAC) micelles at high pH (DABCO = 1,4-diazabicyclo[2.2.2]octane, SDS = sodium dodecyl sulfate, DTAC = dodecyl trimethyl ammonium chloride). From MFE experiments with nanosecond time resolution, the radical anion A(.)(-) can be observed without any interference from the much more strongly absorbing triplet (3)A*, the different quenching processes can be separated and their rates can be measured. Triplet (3)A* is quenched dynamically both by the SDS micelle (k(1) = 5.0x10(5) s(-1)) and by DABCO approaching from the aqueous phase (k(2) = 2.0x10(9) M(-1) s(-1)). Static quenching by solubilised DABCO (association constant with the SDS micelles, 1.5 M(-1)) also participates at high DABCO concentrations, but is chemically nonproductive and does not lead to MFE generation. The MFEs stemming from the radical ion pairs A(.)(-) D(.)(+) are about 40 times larger in the anionic micelles than in the cationic ones despite a higher yield of free radicals in the latter case. This can be rationalised by different diffusional dynamics: Because of the location of their precursors, A(.)(-) and D(.)(+) are formed at opposite sides of the micelle boundary. Subsequently, the negatively charged Stern layer of the SDS micelle traps the radical cation, which then undergoes surface diffusion, so both the recombination probability and the spin mixing are high; in contrast, the positive surface charge of the DTAC micelle forces the radical cation into the bulk of the solution, thus efficiently blocking a recombination.

Electron attachment to the guanine-cytosine nucleic acid base pair and the effects of monohydration and proton transfer.

PubMed

Gupta, Ashutosh; Jaeger, Heather M; Compaan, Katherine R; Schaefer, Henry F

2012-05-17

The guanine-cytosine (GC) radical anion and its interaction with a single water molecule is studied using ab initio and density functional methods. Z-averaged second-order perturbation theory (ZAPT2) was applied to GC radical anion for the first time. Predicted spin densities show that the radical character is localized on cytosine. The Watson-Crick monohydrated GC anion is compared to neutral GC·H2O, as well as to the proton-transferred analogue on the basis of structural and energetic properties. In all three systems, local minima are identified that correspond to water positioned in the major and minor grooves of macromolecular DNA. On the anionic surface, two novel structures have water positioned above or below the GC plane. On the neutral and anionic surfaces, the global minimum can be described as water interacting with the minor groove. These structures are predicted to have hydration energies of 9.7 and 11.8 kcal mol(-1), respectively. Upon interbase proton-transfer (PT), the anionic global minimum has water positioned in the major groove, and the hydration energy increases to 13.4 kcal mol(-1). PT GC·H2O(•-) has distonic character; the radical character resides on cytosine, while the negative charge is localized on guanine. The effects of proton transfer are further investigated through the computed adiabatic electron affinities (AEA) of GC and monohydrated GC, and the vertical detachment energies (VDE) of the corresponding anions. Monohydration increases the AEAs and VDEs by only 0.1 eV, while proton-transfer increases the VDEs substantially (0.8 eV). The molecular charge distribution of monohydrated guanine-cytosine radical anion depends heavily on interbase proton transfer.

Catalytic Hydroxylation of Benzene to Phenol by Dioxygen with an NADH Analogue.

PubMed

Hirose, Kensaku; Ohkubo, Kei; Fukuzumi, Shunichi

2016-08-26

Hydroxylation of benzene by molecular oxygen (O2 ) occurs efficiently with 10-methyl-9,10-dihydroacridine (AcrH2 ) as an NADH analogue in the presence of a catalytic amount of Fe(ClO4 )3 or Fe(ClO4 )2 with excess trifluoroacetic acid in a solvent mixture of benzene and acetonitrile (1:1 v/v) to produce phenol, 10-methylacridinium ion and hydrogen peroxide (H2 O2 ) at 298 K. The catalytic oxidation of benzene by O2 with AcrH2 in the presence of a catalytic amount of Fe(ClO4 )3 is started by the formation of H2 O2 from AcrH2 , O2 , and H(+) . Hydroperoxyl radical (HO2 (.) ) is produced from H2 O2 with the redox pair of Fe(3+) /Fe(2+) by a Fenton type reaction. The rate-determining step in the initiation is the proton-coupled electron transfer from Fe(2+) to H2 O2 to produce HO(.) and H2 O. HO(.) abstracts hydrogen rapidly from H2 O2 to produce HO2 (.) and H2 O. The Fe(3+) produced was reduced back to Fe(2+) by H2 O2 . HO2 (.) reacts with benzene to produce the radical adduct, which abstracts hydrogen from AcrH2 to give the corresponding hydroperoxide, accompanied by generation of acridinyl radical (AcrH(.) ) to constitute the radical chain reaction. Hydroperoxyl radical (HO2 (.) ), which was detected by using the spin trap method with EPR analysis, acts as a chain carrier for the two radical chain pathways: one is the benzene hydroxylation with O2 and the second is oxidation of an NADH analogue with O2 to produce H2 O2 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactive oxygen species and associated reactivity of peroxymonosulfate activated by soluble iron species

NASA Astrophysics Data System (ADS)

Watts, Richard J.; Yu, Miao; Teel, Amy L.

2017-10-01

The activation of peroxymonosulfate by iron (II), iron (III), and iron (III)-EDTA for in situ chemical oxidation (ISCO) was compared using nitrobenzene as a hydroxyl radical probe, anisole as a hydroxyl radical + sulfate radical probe, and hexachloroethane as a reductant + nucleophile probe. In addition, activated peroxymonosulfate was investigated for the treatment of the model groundwater contaminants perchloroethylene (PCE) and trichloroethylene (TCE). The relative activities of hydroxyl radical and sulfate radical in the degradation of the probe compounds and PCE and TCE were isolated using the radical scavengers tert-butanol and isopropanol. Iron (II), iron (III), and iron (III)-EDTA effectively activated peroxymonosulfate to generate hydroxyl radical and sulfate radical, but only a minimal flux of reductants or nucleophiles. Iron (III)-EDTA was a more effective activator than iron (II) and iron (III), and also provided a non-hydroxyl radical, non-sulfate radical degradation pathway. The contribution of sulfate radical relative to hydroxyl radical followed the order of anisole > > TCE > PCE > > nitrobenzene; i.e., sulfate radical was less dominant in the oxidation of more oxidized target compounds. Sulfate radical is often assumed to be the primary oxidant in activated peroxymonosulfate and persulfate systems, but the results of this research demonstrate that the reactivity of sulfate radical with the target compound must be considered before drawing such a conclusion.

Developments in laser-induced fluorescence spectroscopy for quantitative in situ measurements of free radicals in the troposphere

NASA Astrophysics Data System (ADS)

Heard, Dwayne

2015-04-01

Photo-oxidation in the troposphere is highly complex, being initiated by short lived free radical species, in the daytime dominated by the hydroxyl radical, OH. Chemical oxidation cycles, which also involve peroxy radicals (HO2 and RO2), remove natural or anthropogenic emissions (for example methane) and generate a range of secondary products, for example ozone, nitrogen dioxide, acidic and multifunctional organic species, and secondary organic aerosol, which impact on human health and climate. Owing to their short lifetime in the atmosphere, the abundance of radicals is determined solely by their rate of chemical production and loss, and not by transport. Field measurements of the concentrations of radicals and comparison with calculations using a numerical model therefore constitutes one of the very best ways to test whether the chemistry in each of these locations is understood and accurately represented in the model. Validation of the chemistry is important, as the predictions of climate and air quality models containing this chemistry are used to drive the formulation of policy and legislation. However, in situ measurements of radical species, owing to their very low abundance (often sub part per trillion) and short lifetimes (< 1 second for OH), remain extremely challenging. Laser-induced fluorescence spectroscopy (LIF) has enjoyed considerable success worldwide for the quantitative detection of radicals in a range of environments. The radicals are either excited directly by the laser (e.g. OH, IO) or are first chemically converted to OH prior to detection (e.g. HO2, RO2). Recent developments in the LIF technique for radical detection, which uses a supersonic expansion with detection at low pressure and multi kHz pulse repetition rate tunable laser systems, will be discussed, together with calibration methods to make signals absolute, and identification of potential interferences. LIF instruments have been operated on ground, ship and aircraft platforms at a number of locations worldwide, and examples from recent fieldwork involving the Leeds instruments will be presented.

Inhibition of platelet aggregation and in vitro free radical scavenging activity of dried fruiting bodies of Pleurotus eous.

PubMed

Suseem, S R; Saral, Mary

2015-07-01

To evaluate the ethyl acetate, methanol and aqueous extracts of dried fruiting bodies of Pleurotus eous for its anti-platelet activity on human volunteer's blood. And also to analyze the free radical scavenging property of the extracts of P.eous by using various in vitro models. Anti-platelet activity of dried fruiting bodies of P.eous was evaluated by in vitro model using blood platelets. Inhibition of platelet aggregation was monitored after pre-incubation of platelets with the crude extracts of mushroom P.eous. Antioxidant activities of extracts of P.eous were evaluated by different in vitro experiments, namely, 1, 1-diphenyl-2-picryl hydrazyl (DPPH), superoxide, hydroxyl radical and lipid peroxide radical models. Crude extracts of mushroom P.eous inhibited platelet aggregation dose-dependently which was induced by adenosine diphosphate (ADP). At a maximum concentration of 10 mg/mL, methanol extract effected 64.02% inhibition of lipid per-oxidation and 50.12% scavenging effect on superoxide anion radical. Aqueous extract of P.eous have shown 69.43% chelating ability on ferrous ions, 24.27% scavenging effect on hydroxyl radical and 49.57% scavenging effect on DPPH radical at 10 mg/mL. Increasing concentrations of the extract were found to cause progressively decreasing of the intensity of absorbance. Anti-platelet effects could be related in part to the polyphenolic compounds present in the extracts. Antioxidant activity results indicated the free radical scavenging property of the extracts of P.eous which might be due to the high content of phenolic compounds and flavonoids.

A pulse radiolysis study of the dynamics of ascorbic acid free radicals within a liposomal environment.

PubMed

Kobayashi, Kazuo; Seike, Yumiko; Saeki, Akinori; Kozawa, Takahiro; Takeuchi, Fusako; Tsubaki, Motonari

2014-10-06

The dynamics of free-radical species in a model cellular system are examined by measuring the formation and decay of ascorbate radicals within a liposome with pulse radiolysis techniques. Upon pulse radiolysis of an N2O-saturated aqueous solution containing ascorbate-loaded liposome vesicles, ascorbate radicals are formed by the reaction of OH(·) radicals with ascorbate in unilamellar vesicles exclusively, irrespective of the presence of vesicle lipids. The radicals are found to decay rapidly compared with the decay kinetics in an aqueous solution. The distinct radical reaction kinetics in the vesicles and in bulk solution are characterized, and the kinetic data are analyzed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Distribution of Hydrogen, Nitrogen, and Chlorine Radicals in the Lower Stratosphere: Implications for Changes in O3 due to Emission of NO(y) from Supersonic Aircraft

NASA Technical Reports Server (NTRS)

Salawitch, R. J.; Wofsy, S. C.; Wennberg, P. O.; Cohen, R. C.; Anderson, J. G.; Fahey, D. W.; Gao, R. S.; Keim, E. R.; Woodbridge, E. L.; Stimpfle, R. M.;

The distribution of hydrogen, nitrogen, and chlorine radicals in the lower stratosphere: Implications for changes in O3 due to emission of NO(y) from supersonic aircraft

NASA Technical Reports Server (NTRS)

Salawitch, R. J.; Wofsy, S. C.; We-Nnberg, P. O.; Cohen, R. C.; Anderson, J. G.; Fahey, D. W.; Gao, R. S.; Keim, E. R.; Woodbridge, E. L.; Stimpfle, R. M.

1994-01-01

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained in the lower statosphere during SPADE are compared to results from a photochemical model that assimilates measurements of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N2O5 agree well with measured concentrations of NO and ClO, but concentrations of HO2 and OH are underestimated by 10 to 25%, concentrations of NO2 are overestimated by 10 to 30%, and concentrations of HCl are overestimated by a factor of 2. Discrepancies for (OH) and (HO2) are reduced if we allow for higher yields of O((1)D) from O2 photolysis and for heterogeneous production of HNO2. The data suggest more efficent catalytic removal of O3 by hydrogen and halogen radicals relative to nitrogen oxide radicals than predicted by models using recommendend rates and cross sections. Increased in (O3) in the lower stratosphere may be larger in response to inputs of NO(y) from supersonic aircraft than estimated by current assessment models.

Tropospheric OH and HO2 radicals: field measurements and model comparisons.

PubMed

Stone, Daniel; Whalley, Lisa K; Heard, Dwayne E

2012-10-07

The hydroxyl radical, OH, initiates the removal of the majority of trace gases in the atmosphere, and together with the closely coupled species, the hydroperoxy radical, HO(2), is intimately involved in the oxidation chemistry of the atmosphere. This critical review discusses field measurements of local concentrations of OH and HO(2) radicals in the troposphere, and in particular the comparisons that have been made with numerical model calculations containing a detailed chemical mechanism. The level of agreement between field measurements of OH and HO(2) concentrations and model calculations for a given location provides an indication of the degree of understanding of the underlying oxidation chemistry. We review the measurement-model comparisons for a range of different environments sampled from the ground and from aircraft, including the marine boundary layer, continental low-NO(x) regions influenced by biogenic emissions, the polluted urban boundary layer, and polar regions. Although good agreement is found for some environments, there are significant discrepancies which remain unexplained, a notable example being unpolluted, forested regions. OH and HO(2) radicals are difficult species to measure in the troposphere, and we also review changes in detection methodology, quality assurance procedures such as instrument intercomparisons, and potential interferences.

Systematic research on Ag2X (X = O, S, Se, Te) as visible and near-infrared light driven photocatalysts and effects of their electronic structures

NASA Astrophysics Data System (ADS)

Jiang, Wei; Wu, Zhaomei; Zhu, Yingming; Tian, Wen; Liang, Bin

2018-01-01

Four silver chalcogen compounds, Ag2O, Ag2S, Ag2Se and Ag2Te, can be utilized as visible-light-driven photocatalysts. In this research, the electronic structures of these compounds were analyzed by simulation and experiments to systematically reveal the relationship between photocatalytic performance and energetic structure. All four chalcogenides exhibited interesting photocatalytic activities under ultraviolet, visible and near-infrared light. However, their photocatalytic performances and stability significantly depended on the band gap width, and the valence band and conduct band position, which was determined by their composition. Increasing the X atomic number from O to Te resulted in the upward movement of the valence band top and the conduct band bottom, which resulted in narrower band gaps, a wider absorption spectrum, a weaker photo-oxidization capacity, a higher recombination probability of hole and electron pairs, lower quantum efficiency, and worse stability. Among them, Ag2O has the highest photocatalytic performance and stability due to its widest band gap and lowest position of VB and CB. The combined action of photogenerated holes and different radicals, depending on the different electronic structures, including anion ozone radical, hydroxide radical, and superoxide radical, was observed and understood. The results of experimental observations and simulations of the four silver chalcogen compounds suggested that a proper electronic structure is necessary to obtain a balance between photocatalytic performance and absorbable light region in the development of new photocatalysts.

The Oxime Portmanteau Motif: Released Heteroradicals Undergo Incisive EPR Interrogation and Deliver Diverse Heterocycles

PubMed Central

2014-01-01

Conspectus Selective syntheses are now available for compounds of many classes, based on C-centered radicals, exploiting a diverse range of mechanisms. The prospect for chemistry based around N- and O-centered radicals is probably more favorable because of the importance of heterocycles as biologically active materials. Heteroradical chemistry is still comparatively underdeveloped due to the need for safe and easy ways of generating them. Oxime esters appeared promising candidates to meet this need because literature reports and our EPR spectroscopic examinations showed they readily dissociated on photolysis with production of a pair of N- and O-centered radicals. It soon became apparent that a whole suite of benign oxime-containing molecules could be pressed into service. The bimodality of the oxime motif meant that by suitable choice of functionality the reactions could be directed to yield selectively products from either the N-centered radicals or from the O-centered radicals. We found that on one hand photolyses of acetophenone oxime esters of carboxylic acids yielded alicyclics. On the other hand, aromatic and heteroaromatic acyl oximes (as well as dioxime oxalates) afforded good yields of phenanthridines and related heterocycles. Easily prepared oxime oxalate amides released carbamoyl radicals, and pleasingly, β-lactams were thereby obtained. Oxime carbonates and oxime carbamates, available via our novel 1,1'-carbonyldiimidazole (CDI)-based preparations, were accessible alternatives for iminyl radicals and hence for phenanthridine preparations. In their second modes, these compounds proved their value as precursors for exotic alkoxycarbonyloxyl and carbamoyloxyl radicals. Microwave-assistance was shown to be a particularly convenient procedure with O-phenyl oxime ethers. The iminyl radicals generated from such precursors with alkene, alkyne, and aromatic acceptor substituents furnished pyrrole, quinoline, phenanthridine, benzonaphthiridine, indolopyridine, and other systems. Microwave irradiations with 2-(aminoaryl)alkanone O-phenyl oximes enabled either dihydroquinazolines or quinazolines to be obtained in very good yields. The fine quality of the EPR spectra, acquired during photolyses of all the O-carbonyl oxime types, marked this as an important complement to existing ways of obtaining such spectra in solution. Quantifications enabled SARs to be obtained for key reaction types of N- and O-centered radicals, thus putting mechanistic chemistry in this area on a much firmer footing. Surprises included the inverse gem-dimethyl effect in 5-exo-cyclizations of iminyls and the interplay of spiro- with ortho-cyclization onto aromatics. Insights into unusual 4-exo-cyclizations of carbamoyl radicals showed the process to be more viable than pent-4-enyl 4-exo-ring closure. Another surprise was the magnitude of the difference in CO2 loss rate from alkoxycarbonyloxyl radicals as compared with acyloxyl radicals. Their rapid 5-exo-cyclization was charted, as was their preferred spiro-cyclization onto aromatics. The first evidence that N-monosubstituted carbamoyloxyls had finite lifetimes was also forthcoming. It is evident that oxime derivatives have excellent credentials as reagents for radical generation and that there is ample room to extend their applications to additional radical types and for further heterocycle syntheses. There is also clear scope for the development of preparative procedures based around the alkoxyl and aminyl radicals that emerge downstream from oxime carbonate and oxime carbamate dissociations. PMID:24654991

Molecular weight growth in Titan's atmosphere: Branching pathways for the reaction of 1-propynyl radical (H 3CC≡C˙) with small alkenes and alkynes

DOE PAGES

Kirk, Benjamin B.; Savee, John D.; Trevitt, Adam J.; ...

2015-07-16

The reaction of small hydrocarbon radicals (i.e. ˙CN, ˙C 2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C 2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC≡C˙), a likely product frommore » the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d 4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (–H = 27%, –CH 3 = 73%) and (–H = 14%, –CH 3 = 86%), respectively. Altogether, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.« less

Molecular weight growth in Titan's atmosphere: branching pathways for the reaction of 1-propynyl radical (H3CC≡C˙) with small alkenes and alkynes.

PubMed

Kirk, Benjamin B; Savee, John D; Trevitt, Adam J; Osborn, David L; Wilson, Kevin R

2015-08-28

The reaction of small hydrocarbon radicals (i.e.˙CN, ˙C2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC[triple bond, length as m-dash]C˙), a likely product from the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (-H = 27%, -CH3 = 73%) and (-H = 14%, -CH3 = 86%), respectively. Together, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.

Molecular weight growth in Titan's atmosphere: Branching pathways for the reaction of 1-propynyl radical (H 3CC≡C˙) with small alkenes and alkynes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kirk, Benjamin B.; Savee, John D.; Trevitt, Adam J.

The reaction of small hydrocarbon radicals (i.e. ˙CN, ˙C 2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C 2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC≡C˙), a likely product frommore » the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d 4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (–H = 27%, –CH 3 = 73%) and (–H = 14%, –CH 3 = 86%), respectively. Altogether, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.« less

Object-adapted trapping and shape-tracking to probe a bacterial protein chain motor

NASA Astrophysics Data System (ADS)

Roth, Julian; Koch, Matthias; Rohrbach, Alexander

2015-03-01

The helical bacterium Spiroplasma is a motile plant and anthropod pathogen which swims by propagating pairs of kinks along its cell body. As a well suited model system for bacterial locomotion, understanding the cell's molecular motor is of vital interest also regarding the combat of bacterial diseases. The extensive deformations related to these kinks are caused by a contractile cytoskeletal protein ribbon representing a linear motor in contrast to common rotary motors as, e.g., flagella. We present new insights into the working of this motor through experiments with object-adapted optical traps and shape-tracking techniques. We use the given laser irradiation from the optical trap to hinder bacterial energy (ATP) production through the production of O2 radicals. The results are compared with experiments performed under the influence of an O2-Scavenger and ATP inhibitors, respectively. Our results show clear dependences of the kinking properties on the ATP concentration inside the bacterium. The experiments are supported by a theoretical model which we developed to describe the switching of the ribbon's protein subunits.

H + O3 Fourier-transform infrared emission and laser absorption studies of OH(X2Pi) radical - An experimental dipole moment function and state-to-state Einstein A coefficients

NASA Technical Reports Server (NTRS)

Nelson, David D., Jr.; Schiffman, Aram; Nesbitt, David J.; Orlando, John J.; Burkholder, James B.

1990-01-01

FTIR emission/absorption spectroscopy is used to measure the relative intensities of 88 pairs of rovibrational transitions of OH(X2Pi) distributed over 16 vibrational bands. The experimental technique used to obtain the Einstein A ratios is discussed. The dipole moment function which follows from the intensity ratios along with Einstein A coefficients calculated from mu(r) is presented.

The Impact of Modernization on the Military Capabilities of the People’s Republic of China.

DTIC Science & Technology

1982-04-19

pair of allies on the Standing Committee were Ye Jianying and Li Xiannian, who represented both the veteran cadres who had survived the Cultural...in October with the arrest of the four leading radical figures ("Gang of Four") in a coup lead by the Defense Minister, Marshall Ye Jianying who...Dengkui, and Wu De, from the Politburo. A new Standing Committee was constituted on which Hua Guofeng now sat in lonely isolation; Marshal Ye Jianying and

Exploring Electrical and Magnetic Resonances from Coherently Correlated Long-Lived Radical Pairs towards Development of Negative Refractive-Index Materials

DTIC Science & Technology

2015-04-29

during reporting period: Changes in research objectives (if any): Change in AFOSR Program Manager, if any: Extensions granted or milestones slipped , if...SUBTITLE TOWARDS COMBINED ACTIVE CONTROL OF FILM COOLING AND TURBINE BLADE AERODYNAMICS 5a. CONTRACT NUMBER FA9550-08-1-0440 5b. GRANT NUMBER N/A 5c...release. Project Title: Towards Combined Active Control of Film Cooling and Turbine Blade Aerodynamics. Award Number: FA9550-08-1-0440 Dates Covered

Exploring Electrical and Magnetic Resonances from Coherently Correlated Long-Lived Radical Pairs towards Development of Negative Refractive-Index Materials

DTIC Science & Technology

2015-01-03

Dissociation in Perovskite Solar Cells Yu-Che Hsiao, Ting Wu, Mingxing Li, and Bin Hu Advanced Materials, DOI: 10.1002/adma.201405946, 2015 2...Electrode Interface and Donor/Acceptor Interface via Charge Dissociation in Organic Solar Cells at Device-Operating Condition Ting Wu, Yu-Che Hsiao...exchange energy at donor:acceptor interfaces in organic solar cells Mingxing Li, Hongfeng Wang, Lei He, Huidong Zang, Hengxing Xu, and Bin Hu Appl

Radicalization in the National Economic Climate: Discovery Workshop at DRDC Toronto 7-8 December 2009

DTIC Science & Technology

2010-04-01

self-blame, and guilt or shame. The model provides an account of how economic Radicalization in the National Economic Climate Discovery Workshop at...RADICALIZATION IN THE NATIONAL ECONOMIC CLIMATE DISCOVERY WORKSHOP AT DRDC TORONTO 7-8 DECEMBER 2009 Gauthier, M.; Lamoureux, T. CAE...1 0 . Radicalization in the National Economic Climate Discovery Workshop at DRDC Toronto 7-8 December 2009 April 2010 – ii – © Her Majesty

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

PubMed Central

Szaleniec, Maciej; Heider, Johann

2016-01-01

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

HOx Radical Chemistry in an Indiana Forest Environment: Measurement and Model Comparison

NASA Astrophysics Data System (ADS)

Lew, M.; Bottorff, B.; Sigler, P. S. R.; Stevens, P. S.; Sklaveniti, S.; Leonardis, T.; Locoge, N.; Dusanter, S.; Kundu, S.; Deming, B.; Wood, E. C. D.; Gentner, D. R.

2015-12-01

Reactions of the hydroxyl (OH) and peroxy radicals (HO2 and RO2) play a central role in the chemistry of the atmosphere. In addition to controlling the lifetimes of many trace gases important to issues of global climate change, OH radical reactions initiate the oxidation of volatile organic compounds (VOCs) which can lead to the production of ozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicals in forest environments characterized by high mixing ratios of isoprene and low mixing ratios of NOx have shown serious discrepancies with modeled concentrations. These results bring into question our understanding of the atmospheric chemistry of isoprene and other biogenic VOCs under low NOx conditions. In the summer of 2015, HOx radicals were measured using Laser-Induced Fluorescence Fluorescence Assay by Gas Expansion (LIF-FAGE) technique as part of the Indiana Radical, Reactivity and Ozone Production Intercomparison (IRRONIC). This campaign took place in a forested area at the Indiana Research and Teaching Preserve (IURTP) near the Bloomington campus characterized by high mixing ratios of isoprene and low mixing ratios of NOx. Supporting measurements of photolysis rates, volatile organic compounds, nitrogen oxides, and other species were used to constrain a zero-dimensional box model based on the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism (MCM).

Fostering radical conceptual change through dual-situated learning model

NASA Astrophysics Data System (ADS)

She, Hsiao-Ching

2004-02-01

This article examines how the Dual-Situated Learning Model (DSLM) facilitates a radical change of concepts that involve the understanding of matter, process, and hierarchical attributes. The DSLM requires knowledge of students' prior beliefs of science concepts and the nature of these concepts. In addition, DSLM also serves two functions: it creates dissonance with students' prior knowledge by challenging their epistemological and ontological beliefs about science concepts, and it provides essential mental sets for students to reconstruct a more scientific view of the concepts. In this study, the concept heat transfer: heat conduction and convection, which requires an understanding of matter, process, and hierarchical attributes, was chosen to examine how DSLM can facilitate radical conceptual change among students. Results show that DSLM has great potential to foster a radical conceptual change process in learning heat transfer. Radical conceptual change can definitely be achieved and does not necessarily involve a slow or gradual process.

Charge transfer and charge localization in extended radical cations: Investigation of model molecules for peptides

NASA Astrophysics Data System (ADS)

Weinkauf, Rainer; Lehrer, Florian

1998-12-01

Molecules consisting of a flexible tail and an aromatic chromophore are used as model systems to understand the situation of a single chromophore in a small peptide. Their S0-S1 resonant multiphoton ionization (REMPI) spectra show, that in neutral molecules the tail-chromophore interaction is weak and electronic excitation is localized at the chromophore. For molecules, where the ionization energy of the tail is considerable higher than that of the chromophore, by high resolution REMPI photoelectron spectroscopy we find the charge to be localized on the aromatic chromophore. This scheme also in suitable peptides allows local ionization at the aromatic chromophore. An estimate for various charge positions in peptide chains, however, shows, that for most of the amino acids electron hole positions in the nitrogen and oxygen "lone pair" orbitals of the peptide bond are nearly degenerate. REMPI photoelectron spectra of phenylethylamine, which as a model system contains such two degenerate charge positions, show small energetic shift of the ionization energy but strong geometry changes upon electron removal. This result is interpreted as direct ionization into a mixed charge delocalized state. Consequences for the charge transfer mechanism in peptides are discussed.

Direct observation of the oxidation of DNA bases by phosphate radicals formed under radiation: a model of the backbone-to-base hole transfer.

PubMed

Ma, Jun; Marignier, Jean-Louis; Pernot, Pascal; Houée-Levin, Chantal; Kumar, Anil; Sevilla, Michael D; Adhikary, Amitava; Mostafavi, Mehran

2018-05-30

In irradiated DNA, by the base-to-base and backbone-to-base hole transfer processes, the hole (i.e., the unpaired spin) localizes on the most electropositive base, guanine. Phosphate radicals formed via ionization events in the DNA-backbone must play an important role in the backbone-to-base hole transfer process. However, earlier studies on irradiated hydrated DNA, on irradiated DNA-models in frozen aqueous solution and in neat dimethyl phosphate showed the formation of carbon-centered radicals and not phosphate radicals. Therefore, to model the backbone-to-base hole transfer process, we report picosecond pulse radiolysis studies of the reactions between H2PO4˙ with the DNA bases - G, A, T, and C in 6 M H3PO4 at 22 °C. The time-resolved observations show that in 6 M H3PO4, H2PO4˙ causes the one-electron oxidation of adenine, guanine and thymine, by forming the cation radicals via a single electron transfer (SET) process; however, the rate constant of the reaction of H2PO4˙ with cytosine is too low (<107 L mol-1 s-1) to be measured. The rates of these reactions are influenced by the protonation states and the reorganization energies of the base radicals and of the phosphate radical in 6 M H3PO4.

In vivo detection of free radicals using molecular MRI and immuno-spin trapping in a mouse model for amyotrophic lateral sclerosis.

PubMed

Towner, Rheal A; Smith, Nataliya; Saunders, Debra; Lupu, Florea; Silasi-Mansat, Robert; West, Melinda; Ramirez, Dario C; Gomez-Mejiba, Sandra E; Bonini, Marcelo G; Mason, Ronald P; Ehrenshaft, Marilyn; Hensley, Kenneth

2013-10-01

Free radicals associated with oxidative stress play a major role in amyotrophic lateral sclerosis (ALS). By combining immuno-spin trapping and molecular magnetic resonance imaging, in vivo trapped radical adducts were detected in the spinal cords of SOD1(G93A)-transgenic (Tg) mice, a model for ALS. For this study, the nitrone spin trap DMPO (5,5-dimethyl-1-pyrroline N-oxide) was administered (ip) over 5 days before administration (iv) of an anti-DMPO probe (anti-DMPO antibody covalently bound to an albumin-gadolinium-diethylenetriamine pentaacetic acid-biotin MRI contrast agent) to trap free radicals. MRI was used to detect the presence of the anti-DMPO radical adducts by a significant sustained increase in MR signal intensities (p < 0.05) or anti-DMPO probe concentrations measured from T₁ relaxations (p < 0.01). The biotin moiety of the anti-DMPO probe was targeted with fluorescence-labeled streptavidin to locate the probe in excised tissues. Negative controls included either Tg ALS mice initially administered saline rather than DMPO followed by the anti-DMPO probe or non-Tg mice initially administered DMPO and then the anti-DMPO probe. The anti-DMPO probe was found to bind to neurons via colocalization fluorescence microscopy. DMPO adducts were also confirmed in diseased/nondiseased tissues from animals administered DMPO. Apparent diffusion coefficients from diffusion-weighted images of spinal cords from Tg mice were significantly elevated (p < 0.001) compared to wild-type controls. This is the first report regarding the detection of in vivo trapped radical adducts in an ALS model. This novel, noninvasive, in vivo diagnostic method can be applied to investigate the involvement of free radical mechanisms in ALS rodent models. Copyright © 2013 Elsevier Inc. All rights reserved.

IRON AND FREE RADICAL OXIDATIONS IN CELL MEMBRANES

PubMed Central

Schafer, Freya Q.; Yue Qian, Steven; Buettner, Garry R.

2013-01-01

Brain tissue being rich in polyunsaturated fatty acids, is very susceptible to lipid peroxidation. Iron is well known to be an important initiator of free radical oxidations. We propose that the principal route to iron-mediated lipid peroxidations is via iron-oxygen complexes rather than the reaction of iron with hydrogen peroxide, the Fenton reaction. To test this hypothesis, we enriched leukemia cells (K-562 and L1210 cells) with docosahexaenoic acid (DHA) as a model for brain tissue, increasing the amount of DHA from approximately 3 mole % to 32 mole %. These cells were then subjected to ferrous iron and dioxygen to initiate lipid peroxidation in the presence or absence of hydrogen peroxide. Lipid-derived radicals were detected using EPR spin trapping with α-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN). As expected, lipid-derived radical formation increases with increasing cellular lipid unsaturation. Experiments with Desferal demonstrate that iron is required for the formation of lipid radicals from these cells. Addition of iron to DHA-enriched L1210 cells resulted in significant amounts of radical formation; radical formation increased with increasing amount of iron. However, the exposure of cells to hydrogen peroxide before the addition of ferrous iron did not increase cellular radical formation, but actually decreased spin adduct formation. These data suggest that iron-oxygen complexes are the primary route to the initiation of biological free radical oxidations. This model proposes a mechanism to explain how catalytic iron in brain tissue can be so destructive. PMID:10872752

Microhydration and the Enhanced Acidity of Free Radicals.

PubMed

Walton, John C

2018-02-14

Recent theoretical research employing a continuum solvent model predicted that radical centers would enhance the acidity (RED-shift) of certain proton-donor molecules. Microhydration studies employing a DFT method are reported here with the aim of establishing the effect of the solvent micro-structure on the acidity of radicals with and without RED-shifts. Microhydration cluster structures were obtained for carboxyl, carboxy-ethynyl, carboxy-methyl, and hydroperoxyl radicals. The numbers of water molecules needed to induce spontaneous ionization were determined. The hydration clusters formed primarily round the CO₂ units of the carboxylate-containing radicals. Only 4 or 5 water molecules were needed to induce ionization of carboxyl and carboxy-ethynyl radicals, thus corroborating their large RED-shifts.

Reactive oxygen species and associated reactivity of peroxymonosulfate activated by soluble iron species.

PubMed

Watts, Richard J; Yu, Miao; Teel, Amy L

2017-10-01

The activation of peroxymonosulfate by iron (II), iron (III), and iron (III)-EDTA for in situ chemical oxidation (ISCO) was compared using nitrobenzene as a hydroxyl radical probe, anisole as a hydroxyl radical+sulfate radical probe, and hexachloroethane as a reductant+nucleophile probe. In addition, activated peroxymonosulfate was investigated for the treatment of the model groundwater contaminants perchloroethylene (PCE) and trichloroethylene (TCE). The relative activities of hydroxyl radical and sulfate radical in the degradation of the probe compounds and PCE and TCE were isolated using the radical scavengers tert-butanol and isopropanol. Iron (II), iron (III), and iron (III)-EDTA effectively activated peroxymonosulfate to generate hydroxyl radical and sulfate radical, but only a minimal flux of reductants or nucleophiles. Iron (III)-EDTA was a more effective activator than iron (II) and iron (III), and also provided a non-hydroxyl radical, non-sulfate radical degradation pathway. The contribution of sulfate radical relative to hydroxyl radical followed the order of anisole>TCE>PCE >nitrobenzene; i.e., sulfate radical was less dominant in the oxidation of more oxidized target compounds. Sulfate radical is often assumed to be the primary oxidant in activated peroxymonosulfate and persulfate systems, but the results of this research demonstrate that the reactivity of sulfate radical with the target compound must be considered before drawing such a conclusion. Published by Elsevier B.V.

Does public reporting influence antibiotic and injection prescribing to all patients? A cluster-randomized matched-pair trial in china.

PubMed

Liu, Chenxi; Zhang, Xinping; Wang, Xuan; Zhang, Xiaopeng; Wan, Jie; Zhong, Fangying

2016-06-01

The inappropriate use and overuse of antibiotics and injections are serious threats to global population, and the public reporting of health care performance (PRHCP) has been an important instrument for improving the quality of care. However, existing evidence shows a mixed effect of PRHCP. This study is to explore the potential effectiveness of PRHCP that contributes to the convincing evidence of health policy and reform.This study was undertaken in Qian Jiang City, applying a matched-pair cluster-randomized trial. Twenty primary care institutions were treated as clusters and were matched into 10 pairs. Clusters in each pair were randomly assigned into a control or an intervention group. Physicians' prescribing information was publicly reported to patients and physicians monthly in the intervention group from October 2013. A total of 748,632 outpatient prescriptions were included for difference-in-difference (DID) regression model and subgroups (SGs) analysis.Overall, PRHCP intervention led to a slight reduction in the use of combined antibiotics (odds ratio [OR] = 0.870, P < 0.001) and slowed the average expenditure increase of patients (coefficient = -0.051, P < 0.001). SG analysis showed the effect of PRHCP varied among patients with different characteristics. PRHCP decreased the probability of prescriptions requiring antibiotics, combined antibiotics, and injections of patients aged 18 to 64 years old (OR < 1), and all results were statistically significant. By contrast, the results of elderly and minor patients with health insurance showed that PRHCP increased their probability of prescriptions requiring antibiotics and injections. PRHCP slowed the increase of average expenditure of most SGs.PRHCP intervention can influence the prescribing pattern of physicians. Patient factors such as age and health insurance influence the effect of PRHCP intervention, which imply that PRHCP should be designed for different patients. Patient education, aiming at radically changing attitudes toward antibiotics and injections, should be taken to promote the effectiveness of public reporting in China.

Missing Peroxy Radical Sources within a Summertime Ponderosa Pine Forest

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolfe, G. M.; Cantrell, Chris; Kim, S.

2014-05-13

Organic peroxy (RO2) and hydroperoxy (HO2) radicals are key intermediates in the photochemical processes that generate ozone, secondary organic aerosol and reactive nitrogen reservoirs throughout the troposphere. In regions with ample biogenic hydrocarbons, the richness and complexity of peroxy radical chemistry presents a significant challenge to current-generation models, especially given the scarcity of measurements in such environments. We present peroxy radical observations acquired within a Ponderosa pine forest during the summer 2010 Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen – Rocky Mountain Organic Carbon Study (BEACHON-ROCS). Total peroxy radical mixing ratios reach as high as 180 pptvmore » and are among the highest yet recorded. Using the comprehensive measurement suite to constrain a near-explicit 0-D box model, we investigate the sources, sinks and distribution of peroxy radicals below the forest canopy. The base chemical mechanism underestimates total peroxy radicals by as much as a factor of 3. Peroxy radical sinks are unlikely to be overestimated, suggesting missing sources. A close comparison of model results with observations reveals at least two distinct source signatures. The first missing source, characterized by a sharp midday maximum and a strong dependence on solar radiation, is consistent with photolytic production of HO2. The diel profile of the second missing source peaks in the afternoon and suggests a process that generates RO2 independently of sun-driven photochemistry, such as ozonolysis of reactive hydrocarbons. The maximum magnitudes of these missing sources (~120 and 50 pptv min-1, respectively) are consistent with previous observations alluding to unexpectedly intense oxidation within the forest, and we conclude that a similar mechanism may underlie many such anomalous findings.« less

Missing Peroxy Radical Sources Within a Rural Forest Canopy

NASA Technical Reports Server (NTRS)

Wolfe, G. M.; Cantrell, C.; Kim, S.; Mauldin, R. L., III; Karl, T.; Harley, P.; Turnipseed, A.; Zheng, W.; Flocke, F.; Apel, E. C.;

Oxygen free radicals and acute pancreatitis: fact or fiction?

PubMed

Creagh, T A; Leahy, A L; Bouchier-Hayes, D J; Tormey, W; Leader, M; Broe, P J

1993-12-01

The effect of oxygen free radical suppression was studied in the taurocholate model of acute pancreatitis in the rat using systemic allopurinol, superoxide dismutase (S.O.D.) and catalase. None of the treatments were beneficial which suggests that oxygen free radical suppression is unlikely to be clinically beneficial in acute pancreatitis.

Reactivity of CF(n) (n = 1-3) Radicals with a Silica Surface

NASA Technical Reports Server (NTRS)

Ricca, Alessandra

1999-01-01

The trends in reactivity of CF(n) radicals with SiO2 and the site selectivity of the attack are studied using two different cluster models. The reaction barriers for the most energetically favorable reaction are computed. It is shown that CF(n) radicals are fairly unreactive towards SiO2.

Prediction of Radical Scavenging Activities of Anthocyanins Applying Adaptive Neuro-Fuzzy Inference System (ANFIS) with Quantum Chemical Descriptors

PubMed Central

Jhin, Changho; Hwang, Keum Taek

2014-01-01

Radical scavenging activity of anthocyanins is well known, but only a few studies have been conducted by quantum chemical approach. The adaptive neuro-fuzzy inference system (ANFIS) is an effective technique for solving problems with uncertainty. The purpose of this study was to construct and evaluate quantitative structure-activity relationship (QSAR) models for predicting radical scavenging activities of anthocyanins with good prediction efficiency. ANFIS-applied QSAR models were developed by using quantum chemical descriptors of anthocyanins calculated by semi-empirical PM6 and PM7 methods. Electron affinity (A) and electronegativity (χ) of flavylium cation, and ionization potential (I) of quinoidal base were significantly correlated with radical scavenging activities of anthocyanins. These descriptors were used as independent variables for QSAR models. ANFIS models with two triangular-shaped input fuzzy functions for each independent variable were constructed and optimized by 100 learning epochs. The constructed models using descriptors calculated by both PM6 and PM7 had good prediction efficiency with Q-square of 0.82 and 0.86, respectively. PMID:25153627

Reaction of long-lived radicals and vitamin C in γ-irradiated mammalian cells and their model system at 295 K. Tunneling reaction in biological system

NASA Astrophysics Data System (ADS)

Matsumoto, Takuro; Miyazaki, Tetsuo; Kosugi, Yoshio; Kumada, Takayuki; Koyama, Sinji; Kodama, Seiji; Watanabe, Masami

1997-05-01

When golden hamster embryo (GHE) cells or concentrated albumin solution (0.1 kg dm -3) that is a model system of cells is irradiated with γ-rays at 295 K, organic radicals produced can be observed by ESR. The organic radicals survive at both 295 and 310 K for such a long time as 20 h. The long-lived radicals in GHE cells and the albumin solution react with vitamin C by the rate constants of 0.007 dm 3 mol -1 s -1 and 0.014 dm 3 mol -1 s -1, respectively. The long-lived radicals in human cells cause gene mutation, which is suppressed by addition of vitamin C. The isotope effect on the rate constant ( k) for the reaction of the long-lived radicals and vitamin C has been studied in the albumin solution by use of protonated vitamin C and deuterated vitamin C. The isotope effect ( kH/ kD) was more than 20 ≈ 50 and was interpreted in terms of tunneling reaction.

Computational analysis of vertical axis wind turbine arrays

NASA Astrophysics Data System (ADS)

Bremseth, J.; Duraisamy, K.

2016-10-01

Canonical problems involving single, pairs, and arrays of vertical axis wind turbines (VAWTs) are investigated numerically with the objective of understanding the underlying flow structures and their implications on energy production. Experimental studies by Dabiri (J Renew Sustain Energy 3, 2011) suggest that VAWTs demand less stringent spacing requirements than their horizontal axis counterparts and additional benefits may be obtained by optimizing the placement and rotational direction of VAWTs. The flowfield of pairs of co-/counter-rotating VAWTs shows some similarities with pairs of cylinders in terms of wake structure and vortex shedding. When multiple VAWTs are placed in a column, the extent of the wake is seen to spread further downstream, irrespective of the direction of rotation of individual turbines. However, the aerodynamic interference between turbines gives rise to regions of excess momentum between the turbines which lead to significant power augmentations. Studies of VAWTs arranged in multiple columns show that the downstream columns can actually be more efficient than the leading column, a proposition that could lead to radical improvements in wind farm productivity.

Molecular mechanism of plasma sterilization in solution with the reduced pH method: importance of permeation of HOO radicals into the cell membrane

NASA Astrophysics Data System (ADS)

Takai, Eisuke; Ikawa, Satoshi; Kitano, Katsuhisa; Kuwabara, Junpei; Shiraki, Kentaro

2013-07-01

Sterilization of certain infected areas of the human body surface is necessary for dental and surgical therapies. Because the blood is filled with body fluid, sterilization in solution is essential. In vitro solution sterilization has been successively carried out using a combination of low-temperature atmospheric-pressure plasma and the reduced pH method, where the solution is sufficiently acidic. Here, we show the molecular mechanism of such plasma sterilization in solution based on microbiology. Three kinds of bacteria were inactivated by plasma treatment under various pH conditions. The theoretical and experimental models revealed that the sterilization was characterized by the concentration of hydroperoxy radicals (HOO·), which were dependent on the pH value. Bacterial inactivation rates were proportional to the HOO· concentrations calculated by the theoretical model. To evaluate the penetration of radicals into the cell membrane, a bacterial model using dye-included micelles was used. Decolouration rates of the model were also in proportion with the calculated HOO· concentrations. These results indicate that the key species for plasma sterilization were hydroperoxy radicals. More importantly, the high permeation of hydroperoxy radicals into the cell membrane plays a key role for efficient bactericidal inactivation using the reduced pH method.

Proton-Coupled Electron Transfer and a Tyrosine-Histidine Pair in a Photosystem II-Inspired β-Hairpin Maquette: Kinetics on the Picosecond Time Scale.

PubMed

Pagba, Cynthia V; McCaslin, Tyler G; Chi, San-Hui; Perry, Joseph W; Barry, Bridgette A

2016-02-25

Photosystem II (PSII) and ribonucleotide reductase employ oxidation and reduction of the tyrosine aromatic ring in radical transport pathways. Tyrosine-based reactions involve either proton-coupled electron transfer (PCET) or electron transfer (ET) alone, depending on the pH and the pKa of tyrosine's phenolic oxygen. In PSII, a subset of the PCET reactions are mediated by a tyrosine-histidine redox-driven proton relay, YD-His189. Peptide A is a PSII-inspired β-hairpin, which contains a single tyrosine (Y5) and histidine (H14). Previous electrochemical characterization indicated that Peptide A conducts a net PCET reaction between Y5 and H14, which have a cross-strand π-π interaction. The kinetic impact of H14 has not yet been explored. Here, we address this question through time-resolved absorption spectroscopy and 280-nm photolysis, which generates a neutral tyrosyl radical. The formation and decay of the neutral tyrosyl radical at 410 nm were monitored in Peptide A and its variant, Peptide C, in which H14 is replaced by cyclohexylalanine (Cha14). Significantly, both electron transfer (ET, pL 11, L = lyonium) and PCET (pL 9) were accelerated in Peptide A and C, compared to model tyrosinate or tyrosine at the same pL. Increased electronic coupling, mediated by the peptide backbone, can account for this rate acceleration. Deuterium exchange gave no significant solvent isotope effect in the peptides. At pL 9, but not at pL 11, the reaction rate decreased when H14 was mutated to Cha14. This decrease in rate is attributed to an increase in reorganization energy in the Cha14 mutant. The Y5-H14 mechanism in Peptide A is reminiscent of proton- and electron-transfer events involving YD-H189 in PSII. These results document a mechanism by which proton donors and acceptors can regulate the rate of PCET reactions.

Study on the free radical scavenging activity of sea cucumber (Paracaudina chinens var.) gelatin hydrolysate

NASA Astrophysics Data System (ADS)

Zeng, Mingyong; Xiao, Feng; Zhao, Yuanhui; Liu, Zunying; Li, Bafang; Dong, Shiyuan

2007-07-01

Gelatin from the sea cucumber (Paracaudina chinens var.) was hydrolyzed by bromelain and the hydrolysate was found to have a high free radical scavenging activity. The hydrolysate was fractionated through an ultrafiltration membrane with 5 kDa molecular weight cutoff (MWCO). The portion (less than 5 kDa) was further separated by Sephadex G-25. The active peak was collected and assayed for free radical scavenging activity. The scavenging rates for superoxide anion radicals (O2·-) and hydroxyl radicals (·OH) of the fraction with the highest activity were 29.02% and 75.41%, respectively. A rabbit liver mitochondrial free radical damage model was adopted to study the free radical scavenging activity of the fraction. The results showed that the sea cucumber gelatin hydrolysate can prevent the damage of rabbit liver and mitochondria.

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

Interaction of magnetite-based receptors in the beak with the visual system underlying 'fixed direction' responses in birds

PubMed Central

2010-01-01

Background European robins, Erithacus rubecula, show two types of directional responses to the magnetic field: (1) compass orientation that is based on radical pair processes and lateralized in favor of the right eye and (2) so-called 'fixed direction' responses that originate in the magnetite-based receptors in the upper beak. Both responses are light-dependent. Lateralization of the 'fixed direction' responses would suggest an interaction between the two magnetoreception systems. Results Robins were tested with either the right or the left eye covered or with both eyes uncovered for their orientation under different light conditions. With 502 nm turquoise light, the birds showed normal compass orientation, whereas they displayed an easterly 'fixed direction' response under a combination of 502 nm turquoise with 590 nm yellow light. Monocularly right-eyed birds with their left eye covered were oriented just as they were binocularly as controls: under turquoise in their northerly migratory direction, under turquoise-and-yellow towards east. The response of monocularly left-eyed birds differed: under turquoise light, they were disoriented, reflecting a lateralization of the magnetic compass system in favor of the right eye, whereas they continued to head eastward under turquoise-and-yellow light. Conclusion 'Fixed direction' responses are not lateralized. Hence the interactions between the magnetite-receptors in the beak and the visual system do not seem to involve the magnetoreception system based on radical pair processes, but rather other, non-lateralized components of the visual system. PMID:20707905

Epigenomic profiling of DNA methylation in paired prostate cancer versus adjacent benign tissue

PubMed Central

Geybels, Milan S.; Zhao, Shanshan; Wong, Chao-Jen; Bibikova, Marina; Klotzle, Brandy; Wu, Michael; Ostrander, Elaine A.; Fan, Jian-Bing; Feng, Ziding; Stanford, Janet L.

2016-01-01

Background Aberrant DNA methylation may promote prostate carcinogenesis. We investigated epigenome-wide DNA methylation profiles in prostate cancer (PCa) compared to adjacent benign tissue to identify differentially methylated CpG sites. Methods The study included paired PCa and adjacent benign tissue samples from 20 radical prostatectomy patients. Epigenetic profiling was done using the Infinium HumanMethylation450 BeadChip. Linear models that accounted for the paired study design and False Discovery Rate Q-values were used to evaluate differential CpG methylation. mRNA expression levels of the genes with the most differentially methylated CpG sites were analyzed. Results In total, 2,040 differentially methylated CpG sites were identified in PCa versus adjacent benign tissue (Q-value <0.001), the majority of which were hypermethylated (n = 1,946; 95%). DNA methylation profiles accurately distinguished between PCa and benign tissue samples. Twenty-seven top-ranked hypermethylated CpGs had a mean methylation difference of at least 40% between tissue types, which included 25 CpGs in 17 genes. Furthermore, for ten genes over 50% of promoter region CpGs were hypermethylated in PCa versus benign tissue. The top-ranked differentially methylated genes included three genes that were associated with both promoter hypermethylation and reduced gene expression: SCGB3A1, HIF3A, and AOX1. Analysis of The Cancer Genome Atlas (TCGA) data provided confirmatory evidence for our findings. Conclusions This study of PCa versus adjacent benign tissue showed many differentially methylated CpGs and regions in and outside gene promoter regions, which may potentially be used for the development of future epigenetic-based diagnostic tests or as therapeutic targets. PMID:26383847

Epigenomic profiling of DNA methylation in paired prostate cancer versus adjacent benign tissue.

PubMed

Geybels, Milan S; Zhao, Shanshan; Wong, Chao-Jen; Bibikova, Marina; Klotzle, Brandy; Wu, Michael; Ostrander, Elaine A; Fan, Jian-Bing; Feng, Ziding; Stanford, Janet L

2015-12-01

Aberrant DNA methylation may promote prostate carcinogenesis. We investigated epigenome-wide DNA methylation profiles in prostate cancer (PCa) compared to adjacent benign tissue to identify differentially methylated CpG sites. The study included paired PCa and adjacent benign tissue samples from 20 radical prostatectomy patients. Epigenetic profiling was done using the Infinium HumanMethylation450 BeadChip. Linear models that accounted for the paired study design and False Discovery Rate Q-values were used to evaluate differential CpG methylation. mRNA expression levels of the genes with the most differentially methylated CpG sites were analyzed. In total, 2,040 differentially methylated CpG sites were identified in PCa versus adjacent benign tissue (Q-value < 0.001), the majority of which were hypermethylated (n = 1,946; 95%). DNA methylation profiles accurately distinguished between PCa and benign tissue samples. Twenty-seven top-ranked hypermethylated CpGs had a mean methylation difference of at least 40% between tissue types, which included 25 CpGs in 17 genes. Furthermore, for 10 genes over 50% of promoter region CpGs were hypermethylated in PCa versus benign tissue. The top-ranked differentially methylated genes included three genes that were associated with both promoter hypermethylation and reduced gene expression: SCGB3A1, HIF3A, and AOX1. Analysis of The Cancer Genome Atlas (TCGA) data provided confirmatory evidence for our findings. This study of PCa versus adjacent benign tissue showed many differentially methylated CpGs and regions in and outside gene promoter regions, which may potentially be used for the development of future epigenetic-based diagnostic tests or as therapeutic targets. © 2015 Wiley Periodicals, Inc.

Hydroxyl radical generation in electro-Fenton process with a gas-diffusion electrode: Linkages with electro-chemical generation of hydrogen peroxide and iron redox cycle.

PubMed

Yatagai, Tomonori; Ohkawa, Yoshiko; Kubo, Daichi; Kawase, Yoshinori

2017-01-02

The hydroxyl radical generation in an electro-Fenton process with a gas-diffusion electrode which is strongly linked with electro-chemical generation of hydrogen peroxide and iron redox cycle was studied. The OH radical generation subsequent to electro-chemical generations of H 2 O 2 was examined under the constant potential in the range of Fe 2+ dosage from 0 to 1.0 mM. The amount of generated OH radical initially increased and gradually decreased after the maximum was reached. The initial rate of OH radical generation increased for the Fe 2+ dosage <0.25 mM and at higher Fe 2+ dosages remained constant. At higher Fe 2+ dosages the precipitation of Fe might inhibit the enhancement of OH radical generation. The experiments for decolorization and total organic carbon (TOC) removal of azo-dye Orange II by the electro-Fenton process were conducted and the quick decolorization and slow TOC removal of Orange II were found. To quantify the linkages of OH radical generation with dynamic behaviors of electro-chemically generated H 2 O 2 and iron redox cycle and to investigate effects of OH radical generation on the decolorization and TOC removal of Orange II, novel reaction kinetic models were developed. The proposed models could satisfactory clarify the linkages of OH radical generation with electro-chemically generated H 2 O 2 and iron redox cycle and simulate the decolorization and TOC removal of Orange II by the electro-Fenton process.

Comparing association of preoperative transrectal ultrasound prostate weight with prostate weight obtained after radical prostatectomy after adjustment for other prognostic factors in a subset of the Northwestern University Prostate SPORE database

NASA Astrophysics Data System (ADS)

Helenowski, Irene; Jovanovic, Borko; Gurley, Michael; Leikin, Robin; Catalona, William; Roston, Arden; Kuzel, Timothy

Transrectal ultrasound (TRUS) is a non-invasive approach to measure prostate size as a surrogate (density =1.0) for prostate weight with implications in prostate cancer prognosis. But the question is how reliable is this preoperative measurement compared to other measures of prostate weight. This work presents the correlations between preoperative TRUS prostate weight and prostate weight obtained after radical prostatectomy in 434 patients with mean TRUS weight 36g (range: 10g-120g) and the mean prostate weight obtained after radical prostatectomy 51g (range: 16g-180g) from the Northwestern University Prostate SPORE database. 311 patients with weight obtained by digital rectal exam (DRE) were also compared to the TRUS prostate weights with mean and range of DRE weights 33g (10g - 78g). Correlations were adjusted by age, BMI, an indicator variable for a pathological stage of III or greater, and for Gleason score greater than 7. Correlations were also computed for separately for European American and Other Race populations. Differences in means were evaluated via the paired t-test. Results indicate TRUS measures obtained via ultrasound as promising but improvement in the technology still appears needed.

Characteristics of Surface Sterilization using ECR Plasma

NASA Astrophysics Data System (ADS)

Yonesu, Akira; Hara, Kazufumi; Nishikawa, Tatsuya; Hayashi, Nobuya

2015-09-01

Plasma sterilization techniques have superior characteristics such as a short treatment times, non-toxicity and low thermal damages on the sterilized materials. In plasma sterilization, microorganisms can be sterilized by active radicals, energetic charged particles, and vacuum UV radiation. The influence of each factor depends on the plasma operating parameters. Microwave discharges under the electron cyclotron resonance (ECR) condition produce higher electron temperature and density plasma as compared with other plasma generation techniques. In the present study, characteristics of surface sterilization using ECR plasma have been investigated.The experiment was performed in the vacuum chamber which contains a magnet holder. A pair of rectangular Sm-Co permanent magnets is aligned parallel to each other within the magnet holder. The region of the magnetic field for ECR exists near the magnet holder surface. When the microwave is introduced into the vacuum chamber, a ECR plasma is produced around surface of the magnet holder. High energy electrons and oxygen radicals were observed at ECR zone by electric probe method and optical spectroscopic method. Biological indicators (B.I.) having spore of 106 was sterilized in 2min for oxygen discharge. The temperature of the B.I. installation position was about 55°. The sterilization was achieved by the effect of oxygen radicals and high energy electrons.

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.

Kr-86 Ion-Beam Irradiation of Hydrated DNA: Free Radical and Unaltered Base Yields

PubMed Central

Becker, David; Adhikary, Amitava; Tetteh, Smedley T.; Bull, Arthur W.; Sevilla, Michael D.

2012-01-01

This work reports an ESR and product analysis investigation of Kr-86 ion-beam irradiation of hydrated DNA at 77 K. The irradiation results in the formation and trapping of both base radicals and sugar phosphate radicals (DNA backbone radicals). The absolute yields (G, μmol/J) of the base radicals are smaller than the yields found in similarly prepared γ-irradiated DNA samples, and the relative yields of backbone radicals relative to base radicals are much higher than that found in γ-irradiated samples. From these results, we have elaborated our radiation chemical model of the track structure for ion-beam irradiated DNA as it applies to krypton ion-beams. The base radicals, which are trapped as ion radicals or reversibly protonated or deprotonated ion radicals, are formed almost entirely in the track penumbra, a region in which radiation chemical effects are similar to those found in γ-irradiated samples. By comparing the yields of base radicals in ion-beam samples to the yields of the same radicals in γ-irradiated samples, the partition of energy between the low-LET region (penumbra) and the core is experimentally determined. The neutral sugar and other backbone radicals, which are not as susceptible to recombination as are ion radicals, are formed largely in the track core. The backbone radicals show a linear dose response up to very high doses. Unaltered base release yields in Kr-86 irradiated hydrated DNA are equal to sugar radical yields within experimental error limits, consistent with radiation-chemical processes in which all base release originates with sugar radicals. Two phosphorus-centered radicals from fragmentation of the DNA backbone are found in low yields. PMID:23106211

Kr-86 ion-beam irradiation of hydrated DNA: free radical and unaltered base yields.

PubMed

Becker, David; Adhikary, Amitava; Tetteh, Smedley T; Bull, Arthur W; Sevilla, Michael D

2012-12-01

This work reports an ESR and product analysis investigation of Kr-86 ion-beam irradiation of hydrated DNA at 77 K. The irradiation results in the formation and trapping of both base radicals and sugar phosphate radicals (DNA backbone radicals). The absolute yields (G, μmol/J) of the base radicals are smaller than the yields found in similarly prepared γ-irradiated DNA samples, and the relative yields of backbone radicals relative to base radicals are much higher than that found in γ-irradiated samples. From these results, we have elaborated our radiation chemical model of the track structure for ion-beam irradiated DNA as it applies to krypton ion-beams. The base radicals, which are trapped as ion radicals or reversibly protonated or deprotonated ion radicals, are formed almost entirely in the track penumbra, a region in which radiation chemical effects are similar to those found in γ-irradiated samples. By comparing the yields of base radicals in ion-beam samples to the yields of the same radicals in γ-irradiated samples, the partition of energy between the low-LET region (penumbra) and the core is experimentally determined. The neutral sugar and other backbone radicals, which are not as susceptible to recombination as are ion radicals, are formed largely in the track core. The backbone radicals show a linear dose response up to very high doses. Unaltered base release yields in Kr-86 irradiated hydrated DNA are equal to sugar radical yields within experimental error limits, consistent with radiation-chemical processes in which all base release originates with sugar radicals. Two phosphorus-centered radicals from fragmentation of the DNA backbone are found in low yields.

Health-related Quality of Life After Radical Cystectomy: A Cross-sectional Study With Matched-pair Analysis on Ileal Conduit vs Ileal Orthotopic Neobladder Diversion.

PubMed

Cerruto, Maria Angela; D'Elia, Carolina; Siracusano, Salvatore; Saleh, Omar; Gacci, Mauro; Cacciamani, Giovanni; De Marco, Vincenzo; Porcaro, Antonio Benito; Balzarro, Matteo; Niero, Mauro; Lonardi, Cristina; Iafrate, Massimo; Bassi, Pierfrancesco; Imbimbo, Ciro; Racioppi, Marco; Talamini, Renato; Ciciliato, Stefano; Serni, Sergio; Carini, Marco; Verze, Paolo; Artibani, Walter

2017-10-01

To examine the different and health-related quality of life (HR-QoL) outcomes between ileal conduit (IC) and ileal orthotopic neobladder (IONB) in patients who underwent radical cystectomy (RC), by using validated self-reported cancer-specific instruments. This retrospective, cross-sectional, multicenter cohort study included 148 and 171 patients with either IC or IONB. HR-QoL was evaluated with Quality of Life Core Questionnaire and bladder module (BLM)-30 European Organisation for Research and Treatment of Cancer questionnaires. Baseline HR-QoL scores were dichotomized at the median to give "good" or "poor" score profiles. A matched-pair analysis compared HR-QoL aspects between 79 IC patients and 79 IONB patients. At univariate analysis IONB resulted favorable for physical functioning, emotional functioning, cognitive functioning (CF), fatigue, dyspnea, appetite loss, constipation (CO), and abdominal bloating flatulence (AB). At multivariate analyses, IONB showed better scores for emotional functioning (85 vs 79, P = .023), CF (93 vs 85, P <.001), CO (16 vs 31, P <.001), and AB (12 vs 25, P <.001). A significant worsening of sexual and urinary function was observed for IONB patients in the long-term. At matched-pair analysis, global health status was similar (65 vs 62, P = .385). Significantly better scores were observed in the IONB group for the following items: CF (P = .007), fatigue (P = .003), pain (P = .019), dyspnea (P = .016), CO (P = .001), and AB (P = .00). IONB and IC after RC were similar in terms of global health status. IONB provides better results in some aspects of HR-QoL related to bowel function, but a worsening of urinary and sexual functions. Further randomized controlled trials are needed to confirm these data. Copyright © 2017 Elsevier Inc. All rights reserved.

Influence of Hydration on Proton Transfer in the Guanine-Cytosine Radical Cation (G•+-C) Base Pair: A Density Functional Theory Study

PubMed Central

Kumar, Anil; Sevilla, Michael D.

2009-01-01

On one-electron oxidation all molecules including DNA bases become more acidic in nature. For the GC base pair experiments suggest that a facile proton transfer takes place in the G•+-C base pair from N1 of G•+ to N3 of cytosine. This intra-base pair proton transfer reaction has been extensively considered using theoretical methods for the gas phase and it is predicted that the proton transfer is slightly unfavorable in disagreement with experiment. In the present study, we consider the effect of the first hydration layer on the proton transfer reaction in G•+-C by the use of density functional theory (DFT), B3LYP/6-31+G** calculations of the G•+-C base pair in the presence of 6 and 11 water molecules. Under the influence of hydration of 11 waters, a facile proton transfer from N1 of G•+ to N3 of C is predicted. The zero point energy (ZPE) corrected forward and backward energy barriers, for the proton transfer from N1 of G•+ to N3 of C, was found to be 1.4 and 2.6 kcal/mol, respectively. The proton transferred G•-(H+)C + 11H2O was found to be 1.2 kcal/mol more stable than G•+-C + 11H2O in agreement with experiment. The present calculation demonstrates that the inclusion of the first hydration shell around G•+-C base pair has an important effect on the internal proton transfer energetics. PMID:19485319

Quantitative structure-activity relationships for reactivities of sulfate and hydroxyl radicals with aromatic contaminants through single-electron transfer pathway.

PubMed

Luo, Shuang; Wei, Zongsu; Spinney, Richard; Villamena, Frederick A; Dionysiou, Dionysios D; Chen, Dong; Tang, Chong-Jian; Chai, Liyuan; Xiao, Ruiyang

2018-02-15

Sulfate radical anion (SO 4 •- ) and hydroxyl radical (OH) based advanced oxidation technologies has been extensively used for removal of aromatic contaminants (ACs) in waters. In this study, we investigated the Gibbs free energy (ΔG SET ∘ ) of the single electron transfer (SET) reactions for 76 ACs with SO 4 •- and OH, respectively. The result reveals that SO 4 •- possesses greater propensity to react with ACs through the SET channel than OH. We hypothesized that the electron distribution within the molecule plays an essential role in determining the ΔG SET ∘ and subsequent SET reactions. To test the hypothesis, a quantitative structure-activity relationship (QSAR) model was developed for predicting ΔG SET ∘ using the highest occupied molecular orbital energies (E HOMO ), a measure of electron distribution and donating ability. The standardized QSAR models are reported to be ΔG ° SET =-0.97×E HOMO - 181 and ΔG ° SET =-0.97×E HOMO - 164 for SO 4 •- and OH, respectively. The models were internally and externally validated to ensure robustness and predictability, and the application domain and limitations were discussed. The single-descriptor based models account for 95% of the variability for SO 4 •- and OH. These results provide the mechanistic insight into the SET reaction pathway of radical and non-radical bimolecular reactions, and have important applications for radical based oxidation technologies to remove target ACs in different waters. Copyright © 2017 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Chong-Wen; Simmie, John M.; Pitz, William J.

Theoretical aspects of the development of a chemical kinetic model for the pyrolysis and combustion of a cyclic ketone, cyclopentanone, are considered. We present calculated thermodynamic and kinetic data for the first time for the principal species including 2- and 3-oxo-cyclopentyl radicals, which are in reasonable agreement with the literature. Furthermore, these radicals can be formed via H atom abstraction reactions by H and Ö atoms and OH, HO 2, and CH 3 radicals, the rate constants of which have been calculated. Abstraction from the β-hydrogen atom is the dominant process when OH is involved, but the reverse holds truemore » for HO 2 radicals. We also determined the subsequent β-scission of the radicals formed, and it is shown that recent tunable VUV photoionization mass spectrometry experiments can be interpreted in this light. The bulk of the calculations used the composite model chemistry G4, which was benchmarked in the simplest case with a coupled cluster treatment, CCSD(T), in the complete basis set limit.« less

A Monte Carlo Sensitivity Analysis of CF2 and CF Radical Densities in a c-C4F8 Plasma

NASA Technical Reports Server (NTRS)

Bose, Deepak; Rauf, Shahid; Hash, D. B.; Govindan, T. R.; Meyyappan, M.

2004-01-01

A Monte Carlo sensitivity analysis is used to build a plasma chemistry model for octacyclofluorobutane (c-C4F8) which is commonly used in dielectric etch. Experimental data are used both quantitatively and quantitatively to analyze the gas phase and gas surface reactions for neutral radical chemistry. The sensitivity data of the resulting model identifies a few critical gas phase and surface aided reactions that account for most of the uncertainty in the CF2 and CF radical densities. Electron impact dissociation of small radicals (CF2 and CF) and their surface recombination reactions are found to be the rate-limiting steps in the neutral radical chemistry. The relative rates for these electron impact dissociation and surface recombination reactions are also suggested. The resulting mechanism is able to explain the measurements of CF2 and CF densities available in the literature and also their hollow spatial density profiles.

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

The benzylperoxyl radical as a source of hydroxyl and phenyl radicals.

PubMed

Sander, Wolfram; Roy, Saonli; Bravo-Rodriguez, Kenny; Grote, Dirk; Sanchez-Garcia, Elsa

2014-09-26

The benzyl radical (1) is a key intermediate in the combustion and tropospheric oxidation of toluene. Because of its relevance, the reaction of 1 with molecular oxygen was investigated by matrix-isolation IR and EPR spectroscopy as well as computational methods. The primary reaction product of 1 and O2 is the benzylperoxyl radical (2), which exists in several conformers that can easily interconvert even at cryogenic temperatures. Photolysis of radical 2 at 365 nm results in a formal [1,3]-H migration and subsequent cleavage of the O-O bond to produce a hydrogen-bonded complex between the hydroxyl radical and benzaldehyde (4). Prolonged photolysis produces the benzoyl radical (5) and water, which finally yield the phenyl radical (7), CO, and H2O. Thus, via a sequence of exothermic reactions 1 is transformed into radicals of even higher reactivity, such as OH and 7. Our results have implications for the development of models for the highly complicated process of combustion of aromatic compounds. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron spin resonance study of thermal instability reactions in jet fuels

NASA Technical Reports Server (NTRS)

Zeldes, H.; Livingston, R.

1984-01-01

Free radicals were studied by electron spin resonance (ESR) using model compounds that are representative of constituents of jet fuels. Radical formation was initiated with peroxides and hydroperoxides by using UV photolysis at and near room temperature and thermal initiation at higher temperatures. Both oxygen free and air saturated systems were studied. N-Dodecane was frequently used as a solvent, and a mixture of n-dodecyl radicals was made with a peroxide initiator in n-dodecane (free of oxygen) thermally at 212 C and photolytically at room temperature. Hydrogen abstraction from the 3,4,5 and 6-positions gives radicals that are sufficiently alike that their spectra are essentially superimposed. The radical formed by abstract of hydrogen from the 2-position gives a different spectrum. ESR parameters for these radicals were measured. The radical formed by abstraction of a primary hydrogen was not observed. Similar radicals are formed from n-decane. A variety of exploratory experiments were carried out with systems that give free radical spectra to which was added small amounts of 2,5-dimethylpyrrole.

Fostering Radical Conceptual Change through Dual-Situated Learning Model

ERIC Educational Resources Information Center

She, Hsiao-Ching

2004-01-01

This article examines how the Dual-Situated Learning Model (DSLM) facilitates a radical change of concepts that involve the understanding of matter, process, and hierarchical attributes. The DSLM requires knowledge of students' prior beliefs of science concepts and the nature of these concepts. In addition, DSLM also serves two functions: it…

Room-temperature and temperature-dependent QSRR modelling for predicting the nitrate radical reaction rate constants of organic chemicals using ensemble learning methods.

PubMed

Gupta, S; Basant, N; Mohan, D; Singh, K P

2016-07-01

Experimental determinations of the rate constants of the reaction of NO3 with a large number of organic chemicals are tedious, and time and resource intensive; and the development of computational methods has widely been advocated. In this study, we have developed room-temperature (298 K) and temperature-dependent quantitative structure-reactivity relationship (QSRR) models based on the ensemble learning approaches (decision tree forest (DTF) and decision treeboost (DTB)) for predicting the rate constant of the reaction of NO3 radicals with diverse organic chemicals, under OECD guidelines. Predictive powers of the developed models were established in terms of statistical coefficients. In the test phase, the QSRR models yielded a correlation (r(2)) of >0.94 between experimental and predicted rate constants. The applicability domains of the constructed models were determined. An attempt has been made to provide the mechanistic interpretation of the selected features for QSRR development. The proposed QSRR models outperformed the previous reports, and the temperature-dependent models offered a much wider applicability domain. This is the first report presenting a temperature-dependent QSRR model for predicting the nitrate radical reaction rate constant at different temperatures. The proposed models can be useful tools in predicting the reactivities of chemicals towards NO3 radicals in the atmosphere, hence, their persistence and exposure risk assessment.

Pro-Oxidant Biological Effects of Inorganic Component of Petroleum: Vanadium and Oxidative Stress

DTIC Science & Technology

1996-08-01

independent existence. Pro-Oxidant Chemicals and Free Radicals Involved in Oxidative Stress Pro-Oxidant Chemicals Chemical and Metabolic Generation... metabolic reactions may generate primary free radicals (Fig. 1). Then, in an avalanche-type process, secondary free radicals and reactive oxygen species...vanadium absorption, distribution, metabolism , and disposition, and no pharmacokinetic model is available describing comparative kinetics and toxicity

Investigations on the photoreactions of phenothiazine and phenoxazine in presence of 9-cyanoanthracene by using steady state and time resolved spectroscopic techniques.

PubMed

Bardhan, Munmun; Mandal, Paulami; Tzeng, Wen-Bih; Ganguly, Tapan

2010-09-01

By using electrochemical, steady state and time resolved (fluorescence lifetime and transient absorption) spectroscopic techniques, detailed investigations were made to reveal the mechanisms of charge separation or forward electron transfer reactions within the electron donor phenothiazine (PTZH) or phenoxazine (PXZH) and well known electron acceptor 9-cyanoanthracene (CNA). The transient absorption spectra suggest that the charge separated species formed in the excited singlet state resulted from intermolecular photoinduced electron transfer reactions within the donor PTZH (or PXZH) and CNA acceptor relaxes to the corresponding triplet state. Though alternative mechanisms of via formations of contact neutral radical by H-transfer reaction have been proposed but the observed results obtained from the time resolved measurements indicate that the regeneration of ground state reactants is primarily responsible due to direct recombination of triplet contact ion-pair (CIP) or solvent-separated ion-pair (SSIP).

Tetrapod trackways from the early Middle Devonian period of Poland.

PubMed

Niedźwiedzki, Grzegorz; Szrek, Piotr; Narkiewicz, Katarzyna; Narkiewicz, Marek; Ahlberg, Per E

2010-01-07

The fossil record of the earliest tetrapods (vertebrates with limbs rather than paired fins) consists of body fossils and trackways. The earliest body fossils of tetrapods date to the Late Devonian period (late Frasnian stage) and are preceded by transitional elpistostegids such as Panderichthys and Tiktaalik that still have paired fins. Claims of tetrapod trackways predating these body fossils have remained controversial with regard to both age and the identity of the track makers. Here we present well-preserved and securely dated tetrapod tracks from Polish marine tidal flat sediments of early Middle Devonian (Eifelian stage) age that are approximately 18 million years older than the earliest tetrapod body fossils and 10 million years earlier than the oldest elpistostegids. They force a radical reassessment of the timing, ecology and environmental setting of the fish-tetrapod transition, as well as the completeness of the body fossil record.

Ultrafast electron transfer processes studied by pump-repump-probe spectroscopy.

PubMed

Fischer, Martin K; Gliserin, Alexander; Laubereau, Alfred; Iglev, Hristo

2011-03-01

The photodetachment of Br(-), I(-) and OH(-) in aqueous solution is studied by 2- and 3-pulse femtosecond spectroscopy. The UV excitation leads to fast electron separation followed by formation of a donor-electron pairs. An additional repump pulse is used for secondary excitation of the intermediates. The 3-pulse technique allows distinguishing the pair-intermediate from the fully separated electron. Using this method we observe a novel geminate recombination channel of .OH with adjacent hydrated electrons. The process leads to an ultrafast quenching (0.7 ps) of almost half the initial number of radicals. The phenomenon is not observed in Br(-) and I(-). Our results demonstrate the potential of the 3-pulse spectroscopy to elucidate the mechanism of ultrafast ET reactions. Photodetachment of aqueous anions studied by two- and three pulse spectroscopy. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Negative differential conductance in doped-silicon nanoscale devices with superconducting electrodes

NASA Astrophysics Data System (ADS)

Shapovalov, A.; Shaternik, V.; Suvorov, O.; Zhitlukhina, E.; Belogolovskii, M.

2018-02-01

We present a proof-of-concept nanoelectronics device with a negative differential conductance, an attractive from the applied viewpoint functionality. The device, characterized by the decreasing current with increasing voltage in a certain voltage region above a threshold bias of about several hundred millivolts, consists of two superconducting electrodes with an amorphous 10-nm-thick silicon interlayer doped by tungsten nano-inclusions. We show that small changes in the W content radically modify the shape of the trilayer current-voltage dependence and identify sudden conductance switching at a threshold voltage as an effect of Andreev fluctuators. The latter entities are two-level systems at the superconductor-doped silicon interface where a Cooper pair tunnels from a superconductor and occupies a pair of localized electronic states. We argue that in contrast to previously proposed devices, our samples permit very large-scale integration and are practically feasible.

Kinetic Model for the Radical Degradation of Tri-Halonitromethane Disinfection Byproducts in Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stephen P. Mezyk; Bruce J. Mincher; William J. Cooper

The halonitromethanes (HNMs) are byproducts of the ozonation and chlorine/chloramine treatment of drinking waters. Although typically occurring at low concentrations HNMs have high cytotoxicity and mutagenicity, and may therefore represent a significant human health hazard. In this study, we have investigated the radical based mineralization of fully-halogenated HNMs in water using the congeners bromodichloronitromethane and chlorodibromonitromethane. We have combined absolute reaction rate constants for their reactions with the hydroxyl radical and the hydrated electron as measured by electron pulse radiolysis and analytical measurements of stable product concentrations obtained by 60Co steady-state radiolysis with a kinetic computer model that includes watermore » radiolysis reactions and halide/nitrogen oxide radical chemistry to fully elucidate the reaction pathways of these HNMs. These results are compared to our previous similar study of the fully chlorinated HNM chloropicrin. The full optimized computer model, suitable for predicting the behavior of this class of compounds in irradiated drinking water is provided.« less

Protective effects of astaxanthin from Paracoccus carotinifaciens on murine gastric ulcer models.

PubMed

Murata, Kenta; Oyagi, Atsushi; Takahira, Dai; Tsuruma, Kazuhiro; Shimazawa, Masamitsu; Ishibashi, Takashi; Hara, Hideaki

2012-08-01

The purpose of this study was to investigate the effect of astaxanthin extracted from Paracoccus carotinifaciens on gastric mucosal damage in murine gastric ulcer models. Mice were pretreated with astaxanthin for 1 h before ulcer induction. Gastric ulcers were induced in mice by oral administration of hydrochloride (HCl)/ethanol or acidified aspirin. The effect of astaxanthin on lipid peroxidation in murine stomach homogenates was also evaluated by measuring the level of thiobarbituric acid reactive substance (TBARS). The free radical scavenging activities of astaxanthin were also measured by electron spin resonance (ESR) measurements. Astaxanthin significantly decreased the extent of HCl/ethanol- and acidified aspirin-induced gastric ulcers. Astaxanthin also decreased the level of TBARS. The ESR measurement showed that astaxanthin had radical scavenging activities against the 1,1-diphenyl-2-picrylhydrazyl radical and the superoxide anion radical. These results suggest that astaxanthin has antioxidant properties and exerts a protective effect against ulcer formation in murine models. Copyright © 2011 John Wiley & Sons, Ltd.

Homoleptic 2,2'-bipyridine metalates(-I) of iron and cobalt, one cocrystallized with an anthracene radical anion and the other with neutral anthracene.

PubMed

Brennessel, William W; Ellis, John E

2014-08-01

Homoleptic 2,2'-bipyridine (bipy) metalates of iron and cobalt have been synthesized directly from the corresponding homoleptic anthracene metalates. In the iron structure, bis[([2.2.2]cryptand)potassium(I)] tris(2,2'-bipyridine)ferrate(-I) anthracene(-I), [K(C18H36N2O6)]2[Fe(C10H8N2)3](C14H10), the asymmetric unit contains one potassium complex cation in a general position, the Fe center and one and a half bipy ligands of the ferrate complex on a crystallographic twofold axis that includes the Fe atom, and one half of an anthracene radical anion whose other half is generated by a crystallographic inversion center. The cations and anions are well separated and the geometry about the Fe center is essentially octahedral. In the cobalt structure, ([2.2.2]cryptand)potassium(I) bis(2,2'-bipyridine)cobaltate(-I) anthracene hemisolvate tetrahydrofuran (THF) disolvate, [K(C18H36N2O6)][Co(C10H8N2)2]·0.5C14H10·2C4H8O, the asymmetric unit contains the cation, anion, and both cocrystallized THF solvent molecules in general positions, and one half of a cocrystallized anthracene molecule whose other half is generated by a crystallographic inversion center. The cation and anion are well separated and the ligand planes in the cobaltate anion are periplanar. Each anthracene molecule is midway between and is oriented perpendicular to a pair of symmetry-related bipy ligands such that aromatic donor-acceptor interactions may play a role in the packing arrangement. The lengths of the bonds that connect the bipy rings support the assertion that the ligands are bipy radical anions in the iron structure. However, in the case of cobalt, these lengths are between the known ranges for a bipy radical anion and a bipy dianion, and therefore no conclusion can be made from the crystallography alone. One cocrystallized THF solvent molecule in the cobalt structure was modeled as disordered over three positions with appropriate geometric and thermal restraints, which resulted in a refined component mass ratio of 0.412 (4):0.387 (3):0.201 (3).

Recurrence risk model for esophageal cancer after radical surgery.

PubMed

Lu, Jincheng; Tao, Hua; Song, Dan; Chen, Cheng

2013-10-01

The aim of the present study was to construct a risk assessment model which was tested by disease-free survival (DFS) of esophageal cancer after radical surgery. A total of 164 consecutive esophageal cancer patients who had undergone radical surgery between January 2005 and December 2006 were retrospectively analyzed. The cutpoint of value at risk (VaR) was inferred by stem-and-leaf plot, as well as by independent-samples t-test for recurrence-free time, further confirmed by crosstab chi-square test, univariate analysis and Cox regression analysis for DFS. The cutpoint of VaR was 0.3 on the basis of our model. The rate of recurrence was 30.3% (30/99) and 52.3% (34/65) in VaR <0.3 and VaR ≥0.3 (chi-square test, (χ) (2) =7.984, P=0.005), respectively. The 1-, 3-, and 5-year DFS of esophageal cancer after radical surgery was 70.4%, 48.7%, and 45.3%, respectively in VaR ≥0.3, whereas 91.5%, 75.8%, and 67.3%, respectively in VaR <0.3 (Log-rank test, (χ) (2) =9.59, P=0.0020), and further confirmed by Cox regression analysis [hazard ratio =2.10, 95% confidence interval (CI): 1.2649-3.4751; P=0.0041]. The model could be applied for integrated assessment of recurrence risk after radical surgery for esophageal cancer.

Recurrence risk model for esophageal cancer after radical surgery

PubMed Central

Tao, Hua; Song, Dan; Chen, Cheng

2013-01-01

Objective The aim of the present study was to construct a risk assessment model which was tested by disease-free survival (DFS) of esophageal cancer after radical surgery. Methods A total of 164 consecutive esophageal cancer patients who had undergone radical surgery between January 2005 and December 2006 were retrospectively analyzed. The cutpoint of value at risk (VaR) was inferred by stem-and-leaf plot, as well as by independent-samples t-test for recurrence-free time, further confirmed by crosstab chi-square test, univariate analysis and Cox regression analysis for DFS. Results The cutpoint of VaR was 0.3 on the basis of our model. The rate of recurrence was 30.3% (30/99) and 52.3% (34/65) in VaR <0.3 and VaR ≥0.3 (chi-square test, χ2 =7.984, P=0.005), respectively. The 1-, 3-, and 5-year DFS of esophageal cancer after radical surgery was 70.4%, 48.7%, and 45.3%, respectively in VaR ≥0.3, whereas 91.5%, 75.8%, and 67.3%, respectively in VaR <0.3 (Log-rank test, χ2 =9.59, P=0.0020), and further confirmed by Cox regression analysis [hazard ratio =2.10, 95% confidence interval (CI): 1.2649-3.4751; P=0.0041]. Conclusions The model could be applied for integrated assessment of recurrence risk after radical surgery for esophageal cancer. PMID:24255579

Biomedical conflicts of interest: a defence of the sequestration thesis-learning from the cases of Nancy Olivieri and David Healy.

PubMed

Schafer, A

2004-02-01

No discussion of academic freedom, research integrity, and patient safety could begin with a more disquieting pair of case studies than those of Nancy Olivieri and David Healy. The cumulative impact of the Olivieri and Healy affairs has caused serious self examination within the biomedical research community. The first part of the essay analyses these recent academic scandals. The two case studies are then placed in their historical context-that context being the transformation of the norms of science through increasingly close ties between research universities and the corporate world. After a literature survey of the ways in which corporate sponsorship has biased the results of clinical drug trials, two different strategies to mitigate this problem are identified and assessed: a regulatory approach, which focuses on managing risks associated with industry funding of university research, and a more radical approach, the sequestration thesis, which counsels the outright elimination of corporate sponsorship. The reformist approach is criticised and the radical approach defended.

Observation of correlated excitations in bimolecular collisions

NASA Astrophysics Data System (ADS)

Gao, Zhi; Karman, Tijs; Vogels, Sjoerd N.; Besemer, Matthieu; van der Avoird, Ad; Groenenboom, Gerrit C.; van de Meerakker, Sebastiaan Y. T.

2018-02-01

Although collisions between atoms and molecules are largely understood, collisions between two molecules have proven much harder to study. In both experiment and theory, our ability to determine quantum-state-resolved bimolecular cross-sections lags behind their atom-molecule counterparts by decades. For many bimolecular systems, even rules of thumb—much less intuitive understanding—of scattering cross sections are lacking. Here, we report the measurement of state-to-state differential cross sections on the collision of state-selected and velocity-controlled nitric oxide (NO) radicals and oxygen (O2) molecules. Using velocity map imaging of the scattered NO radicals, the full product-pair correlations of rotational excitation that occurs in both collision partners from individual encounters are revealed. The correlated cross sections show surprisingly good agreement with quantum scattering calculations using ab initio NO-O2 potential energy surfaces. The observations show that the well-known energy-gap law that governs atom-molecule collisions does not generally apply to bimolecular excitation processes, and reveal a propensity rule for the vector correlation of product angular momenta.

Stressing biological samples with pulsed magnetic fields: physical aspects and experimental results

NASA Astrophysics Data System (ADS)

Delle Side, D.; Specchia, V.; D'Attis, S.; Giuffreda, E.; Quarta, G.; Calcagnile, L.; Bozzetti, M. P.; Nassisi, V.

2016-05-01

Magnetic field effects are diffused among living organisms. They are mainly studied with static or extremely low frequency fields, while scarce information is available for pulsed fields. This work is devoted to the study of the interaction between Drosophila melanogaster, both adults and larvae, and pulsed magnetic fields. We exposed the organisms to a peak field of 0.4 T, lasting for about 2 μ s, within an ad hoc designed copper coil. Adult individuals didn't present any deregulation of repetitive sequences in the germ line of Drosophila. Instead, we noticed a marked magnetic field effect in larvae. Polytene chromosomes coming from treated individuals showed the presence of heat shock puffs; the same organisms revealed also an upregulation of the genes encoding for the Hsp70 protein. These observations suggest that the larvae underwent an oxidative stress caused by the modulation of free radicals' yield induced by the magnetic field through a radical pair mechanism.

Electrophilic and free radical nitration of benzene and toluene with various nitrating agents*

PubMed Central

Olah, George A.; Lin, Henry C.; Olah, Judith A.; Narang, Subhash C.

1978-01-01

Electrophilic nitration of toluene and benzene was studied under various conditions with several nitrating systems. It was found that high orthopara regioselectivity is prevalent in all reactions and is independent of the reactivity of the nitrating agent. The methyl group of toluene is predominantly ortho-para directing under all reaction conditions. Steric factors are considered to be important but not the sole reason for the variation in the ortho/para ratio. The results reinforce our earlier views that, in electrophilic aromatic nitrations with reactive nitrating agents, substrate and positional selectivities are determined in two separate steps. The first step involves a π-aromatic-NO2+ ion complex or encounter pair, whereas the subsequent step is of arenium ion nature (separate for the ortho, meta, and para positions). The former determines substrate selectivity, whereas the latter determines regioselectivity. Thermal free radical nitration of benzene and toluene with tetranitromethane in sharp contrast gave nearly statistical product distributions. PMID:16592503

Search for gluinos and squarks using like-sign dileptons in {ovr p}p collisions at {radical}{ovr s}= 1.8 TeV.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Affolder, T.; Akimoto, H.; Akopian, A.

2001-12-17

We present results of the first search for like-sign dilepton ( e{sup {+-}}e{sup {+-}}, e{sup {+-}}{mu}{sup {+-}}, {mu}{sup {+-}}{mu}{sup {+-}}) events associated with multijets and large missing energy using 10{sup 6} pb{sup -1} of data in p{bar p} collisions at sqrt[s] = 1.8 TeV collected during 1992-1995 by the CDF experiment. Finding no events that pass our selection, we examine pair production of gluinos ( g'') and squarks ( q'') in a constrained framework of the minimal supersymmetric standard model. At tan{eta} = 2 and {mu} = -800 GeV/c{sup 2}, we set 95% confidence level limits of M{sub g}>221 GeV/c2more » for M{sub g}{approx}M{sub q}, and M{sub g}>168 GeV/c2 for {sub q}>>{sub g}, both with small variation as a function of {mu}.« less

The anionic (9-methyladenine)-(1-methylthymine) base pair solvated by formic acid. A computational and photoelectron spectroscopy study.

PubMed

Storoniak, Piotr; Mazurkiewicz, Kamil; Haranczyk, Maciej; Gutowski, Maciej; Rak, Janusz; Eustis, Soren N; Ko, Yeon Jae; Wang, Haopeng; Bowen, Kit H

2010-09-02

The photoelectron spectrum for (1-methylthymine)-(9-methyladenine)...(formic acid) (1MT-9MA...FA) anions with the maximum at ca. 1.87 eV was recorded with 2.54 eV photons and interpreted through the quantum-chemical modeling carried out at the B3LYP/6-31+G(d,p) level. The relative free energies of the anions and their calculated vertical detachment energies suggest that only seven anionic structures contribute to the observed PES signal. We demonstrate that electron binding to the (1MT-9MA...FA) complex can trigger intermolecular proton transfer from formic acid, leading to the strong stabilization of the resulting radical anion. The SOMO distribution indicates that an excess electron may localize not only on the pyrimidine but also on the purine moiety. The biological context of DNA-environment interactions concerning the formation of single-strand breaks induced by excess electrons has been briefly discussed.

Monomer volume fraction profiles in pH responsive planar polyelectrolyte brushes

DOE PAGES

Mahalik, Jyoti P.; Yang, Yubo; Deodhar, Chaitra V.; ...

2016-03-06

Spatial dependencies of monomer volume fraction profiles of pH responsive polyelectrolyte brushes were investigated using field theories and neutron reflectivity experiments. In particular, planar polyelectrolyte brushes in good solvent were studied and direct comparisons between predictions of the theories and experimental measurements are presented. The comparisons between the theories and the experimental data reveal that solvent entropy and ion-pairs resulting from adsorption of counterions from the added salt play key roles in affecting the monomer distribution and must be taken into account in modeling polyelectrolyte brushes. Furthermore, the utility of this physics-based approach based on these theories for the predictionmore » and interpretation of neutron reflectivity profiles in the context of pH responsive planar polyelectrolyte brushes such as polybasic poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and polyacidic poly(methacrylic acid) (PMAA) brushes is demonstrated. The approach provides a quantitative way of estimating molecular weights of the polymers polymerized using surface-initiated atom transfer radical polymerization.« less

Topical beta-carotene protects against infra-red-light-induced free radicals.

PubMed

Darvin, Maxim E; Fluhr, Joachim W; Meinke, Martina C; Zastrow, Leonhard; Sterry, Wolfram; Lademann, Juergen

2011-02-01

The influence of stress factors on human skin induces the production of free radicals. Free radicals react immediately with antioxidants contained in the skin, giving rise to their depletion and with the surrounding molecules, resulting in their damage, disorganization and even destruction. High amounts of free radicals are produced in the upper skin layers, i.e. mainly in the epidermis, subsequent to sun irradiation. Irradiation of the skin in the infra-red (IR) range of the spectra, applied at physiological doses, can produce free radicals. The magnitude of destruction of antioxidants, such as carotenoids, can serve as a marker of the extent of the stress factor, characterized by the quantity of produced free radicals. In this study, measurements on the degradation of cutaneous carotenoids following IR skin irradiation of 12 healthy volunteers (skin type II), with two IR sources (standard infrared radiator = SIR and water filter infrared = wIRA) were taken using resonance Raman spectroscopy. Topical application of the antioxidant beta-carotene (2 mg/cm(2) ) provided protection for the human skin when exposed to IR radiation. The magnitude of the degradation of dermal carotenoids after IR irradiation was significantly higher for SIR than for wIRA irradiation, for both non-treated and cream-treated skin areas. The amount of destroyed carotenoids after IR irradiation was higher in the case of pretreatment with beta-carotene than for the untreated skin, indicating that the superficial part of antioxidants is most important for protecting against external stressors. The direct comparison of beta-carotene content was significantly higher for the cream-treated compared to untreated areas for all pairs: baseline, wIRA, after wIRA, baseline SIR and after SIR. Additionally, topically applied carotenoids as a single antioxidant component are less stable than the carotenoids in the skin incorporated by nutrition and accumulated in a mixture with different antioxidant substances. Resonance Raman spectroscopy can be used for the non-invasive measurements of carotenoids, which can be rated as marker substances of redox processes. © 2011 John Wiley & Sons A/S.

Effect of metal ions on the reactions of the cumyloxyl radical with hydrogen atom donors. Fine control on hydrogen abstraction reactivity determined by Lewis acid-base interactions.

PubMed

Salamone, Michela; Mangiacapra, Livia; DiLabio, Gino A; Bietti, Massimo

2013-01-09

A time-resolved kinetic study on the effect of metal ions (M(n+)) on hydrogen abstraction reactions from C-H donor substrates by the cumyloxyl radical (CumO(•)) was carried out in acetonitrile. Metal salt addition was observed to increase the CumO(•) β-scission rate constant in the order Li(+) > Mg(2+) > Na(+). These effects were explained in terms of the stabilization of the β-scission transition state determined by Lewis acid-base interactions between M(n+) and the radical. When hydrogen abstraction from 1,4-cyclohexadiene was studied in the presence of LiClO(4) and Mg(ClO(4))(2), a slight increase in rate constant (k(H)) was observed indicating that interaction between M(n+) and CumO(•) can also influence, although to a limited extent, the hydrogen abstraction reactivity of alkoxyl radicals. With Lewis basic C-H donors such as THF and tertiary amines, a decrease in k(H) with increasing Lewis acidity of M(n+) was observed (k(H)(MeCN) > k(H)(Li(+)) > k(H)(Mg(2+))). This behavior was explained in terms of the stronger Lewis acid-base interaction of M(n+) with the substrate as compared to the radical. This interaction reduces the degree of overlap between the α-C-H σ* orbital and a heteroatom lone-pair, increasing the C-H BDE and destabilizing the carbon centered radical formed after abstraction. With tertiary amines, a >2-order of magnitude decrease in k(H) was measured after Mg(ClO(4))(2) addition up to a 1.5:1 amine/Mg(ClO(4))(2) ratio. At higher amine concentrations, very similar k(H) values were measured with and without Mg(ClO(4))(2). These results clearly show that with strong Lewis basic substrates variations in the nature and concentration of M(n+) can dramatically influence k(H), allowing for a fine control of the substrate hydrogen atom donor ability, thus providing a convenient method for C-H deactivation. The implications and generality of these findings are discussed.

EPR parameters of L-α-alanine radicals in aqueous solution: a first-principles study

NASA Astrophysics Data System (ADS)

Janbazi, Mehdi; T. Azar, Yavar; Ziaie, Farhood

2018-07-01

EPR (electron paramagnetic resonance) response for a wide range of possible alanine radicals has been analysed employing quantum chemical methods. The strong correlation between geometry and EPR parameter structure of these radicals has been shown in this research work. Significant solvent effect on EPR parameters has been shown employing both explicit and implicit solvent models. In a relatively good agreement with the experiment, stable conformation of these radicals in acidic and basic conditions was determined, and a new conformation was suggested based on possible proton transfer in the intermediate pH range. The employed methodology along with experimental results may be used for the characterisation of different radiation-induced amino acid radicals.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samskog, P.; Kispert, L.D.; Lund, A.

Three different radicals were identified by EPR in x-ray irradiated single crystals of trehalose at 3 K. The species are the trapped electron, a hydroxy alkyl radical, and an alkoxy radical. The electron is trapped in an intermolecular site formed by two hydroxyl groups, one on the carbohydrate and the other on a water molecule as evidenced by the anisotropic proton hyperfine couplings. A geometric model for the trapping site is presented. The trapped electron decays by cleavage of an OH bond and the liberated hydrogen atom abstracts another hydrogen atom from an adjacent carbon atom forming a hydroxy alkylmore » radical. The site of the alkoxy radical has been identified. The primary reaction mechanism is discussed.« less

Intramolecular addition of cysteine thiyl radical to phenylalanine and tyrosine in model peptides, Phe (CysS•) and Tyr(CysS•): a computational study

PubMed Central

Naumov, Sergej; Schöneich, Christian

2009-01-01

Density Functional Theory (DFT) and ab initio calculations were carried out to evaluate the potential for intramolecular addition of cysteine (Cys) thiyl radicals (CysS•) to aromatic amino acids (Phe and Tyr) in water. These calculations yielded stable cyclic conformations, in which π-complexes were more stable than cyclohexadienyl radicals in water. In these π-complexes, the C2-S distances were significantly shorter compared to the C1-S and C3-S distances. Comparable results on the relative stabilities were obtained for model calculations for the addition of HS•/CH3S• to toluene and para-hydroxytoluene. The adduct of thiyl radicals with Phe was more stable than that with Tyr, and the stabilization energies depended on the C-terminal substituents. PMID:19309133

Analysis of electrophoresis performance

NASA Technical Reports Server (NTRS)

Roberts, G. O.

1984-01-01

The SAMPLE computer code models electrophoresis separation in a wide range of conditions. Results are included for steady three dimensional continuous flow electrophoresis (CFE), time dependent gel and acetate film experiments in one or two dimensions and isoelectric focusing in one dimension. The code evolves N two dimensional radical concentration distributions in time, or distance down a CFE chamber. For each time or distance increment, there are six stages, successively obtaining the pH distribution, the corresponding degrees of ionization for each radical, the conductivity, the electric field and current distribution, and the flux components in each direction for each separate radical. The final stage is to update the radical concentrations. The model formulation for ion motion in an electric field ignores activity effects, and is valid only for low concentrations; for larger concentrations the conductivity is, therefore, also invalid.

The Process of Adapting a German Pedagogy for Modern Mathematics Teaching in Japan

ERIC Educational Resources Information Center

Yamamoto, Shinya

2006-01-01

Modern geometry teaching in schools in Japan was modeled on the pedagogies of western countries. However, the core ideas of these pedagogies were often radically changed in the process of adaptation, resulting in teaching differing fundamentally from the original models. This paper discusses the radical changes the pedagogy of a German mathematics…

Investigation of OH Radical Regeneration from Isoprene Oxidation Across Different NOx Regimes in the Atmosphere Simulation Chamber SAPHIR

NASA Astrophysics Data System (ADS)

Novelli, A.; Bohn, B.; Dorn, H. P.; Häseler, R.; Hofzumahaus, A.; Kaminski, M.; Yu, Z.; Li, X.; Tillmann, R.; Wegener, R.; Fuchs, H.; Kiendler-Scharr, A.; Wahner, A.

2017-12-01

The hydroxyl radical (OH) is the dominant daytime oxidant in the troposphere. It starts the degradation of volatile organic compounds (VOC) originating from both anthropogenic and biogenic emissions. Hence, it is a crucial trace species in model simulations as it has a large impact on many reactive trace gases. Many field campaigns performed in isoprene dominated environment in low NOx conditions have shown large discrepancies between the measured and the modelled OH radical concentrations. These results have contributed to the discovery of new regeneration paths for OH radicals from isoprene-OH second generation products with maximum efficiency at low NO. The current chemical models (e.g. MCM 3.3.1) include this novel chemistry allowing for an investigation of the validity of the OH regeneration at different chemical conditions. Over 11 experiments focusing on the OH oxidation of isoprene were performed at the SAPHIR chamber in the Forschungszentrum Jülich. Measurements of VOCs, NOx, O3, HONO were performed together with the measurement of OH radicals (by both LIF-FAGE and DOAS) and OH reactivity. Within the simulation chamber, the NO mixing ratio was varied between 0.05 to 2 ppbv allowing the investigation of both the "new" regeneration path for OH radicals and the well-known NO+HO2 mechanism. A comparison with the MCM 3.3.1 that includes the upgraded LIM1 mechanism showed very good agreement (within 10%) for the OH data at all concentrations of NOx investigated. Comparison with different models, without LIM1 and with updated rates for the OH regeneration, will be presented together with a detailed analysis of the impact of this study on results from previous field campaigns.

Development of an in Silico Model of DPPH• Free Radical Scavenging Capacity: Prediction of Antioxidant Activity of Coumarin Type Compounds.

PubMed

Goya Jorge, Elizabeth; Rayar, Anita Maria; Barigye, Stephen J; Jorge Rodríguez, María Elisa; Sylla-Iyarreta Veitía, Maité

2016-06-07

A quantitative structure-activity relationship (QSAR) study of the 2,2-diphenyl-l-picrylhydrazyl (DPPH•) radical scavenging ability of 1373 chemical compounds, using DRAGON molecular descriptors (MD) and the neural network technique, a technique based on the multilayer multilayer perceptron (MLP), was developed. The built model demonstrated a satisfactory performance for the training ( R 2 = 0.713 ) and test set ( Q ext 2 = 0.654 ) , respectively. To gain greater insight on the relevance of the MD contained in the MLP model, sensitivity and principal component analyses were performed. Moreover, structural and mechanistic interpretation was carried out to comprehend the relationship of the variables in the model with the modeled property. The constructed MLP model was employed to predict the radical scavenging ability for a group of coumarin-type compounds. Finally, in order to validate the model's predictions, an in vitro assay for one of the compounds (4-hydroxycoumarin) was performed, showing a satisfactory proximity between the experimental and predicted pIC50 values.

[Photometric micro-titration model of DPPH radicals scavenging activity and its application].

PubMed

Gao, Yun-tao; Wei, Wei; Ye, Li-qing; Li, Xiao-fen; Liu, Ping; Zhang, Hong-jiao; Yang, Lu; Yu, Jiao-jiao; Cha, Jia-wei

2015-02-01

In the present paper, the stoichiometric ratio (R) for the interreaction of DPPH radicals with the antoxidant was employed as a evaluation index for DPPH radicals scavenging activity of antioxidants. This evaluation index was related only with the stoichiometric relationship between DPPH radicals and the antioxidant, not the relationship with the initial DPPH amount and the volume of sample, which could offer a solution for the problem of poor comparability of EC50 under different conditions. A novel photometric micro-titration method was proposed for the determination of the stoichiometric ratio (R) for the interreaction of DPPH radicals with the antoxidant. The titration equation was established based on the absorbance difference (deltaA) of DPPH radicals in the titration process and the added amount of antoxidant. The stoichiometric ratio (R) for the reaction of DPPH radicals with the addition amount of antoxidant was determined by the titration equation obtained, while, the DPPH median elimination concentration (EC50) of antoxidant can be calculated by the stoichiometric ratio (R). The above photometric micro-titration model was verified using rutin as DPPH radicals scavenger. As experiment results, the stoichiometric ratio (R) of DPPH radicals to rutin was determined to be in the range of 1.817-1.846. The calculated value of EC50 was 1.196 x 10(-3), 2.392 x 10(-3), 4.819 x 10(-3) and 7.292 x 10(-3) mg x mL(-1) for 1.12 x 10(-7), 2.24 x 10(-7), 4.48 x 10(-7) and 6.72 x 10(-7) mol of the additon amount of DPPH radicals, respectively. The proposed method has better precision and reliability with smaller amount of sample than conventional method. While, the obtained stoichiometric ratio value (R) of rutin was employed to calculate the rutin median elimination concentration for DPPH EC50) according to the conditions as reported in the literatures, and the calculated results were consistent with that reported in the literatures.

Fluid modeling of radical species generation mechanism in dense methane-air mixture streamer discharge

NASA Astrophysics Data System (ADS)

Qian, Muyang; Li, Gui; Kang, Jinsong; Liu, Sanqiu; Ren, Chunsheng; Zhang, Jialiang; Wang, Dezhen

2018-01-01

Atmospheric dielectric barrier discharge (DBD) was found to be promising in the context of plasma chemistry, plasma medicine, and plasma-assisted combustion. In this paper, we present a detailed fluid modeling study of abundant radical species produced by a positive streamer in atmospheric dense methane-air DBD. A two-dimensional axisymmetric fluid model is constructed, in which 82 plasma chemical reactions and 30 different species are considered. Spatial and temporal density distributions of dominant radicals and ions are presented. We lay our emphasis on the effect of varying relative permittivity (ɛr = 2, 4.5, and 9) on the streamer dynamics in the plasma column, such as electric field behavior, production, and destruction pathways of dominant radical species. We find that higher relative permittivity promotes propagation of electric field and formation of conduction channel in the plasma column. The streamer discharge is sustained by the direct electron-impact ionization of methane molecule. Furthermore, the electron-impact dissociation of methane (e + CH4 = >e + H+CH3) is found to be the dominant reaction pathway to produce CH3 and H radicals. Similarly, the electron-impact dissociations of oxygen (e + O2 = >e + O+O(1D), e + O2 = >e + O+O) are the major routes for O production.

Hydroxyl and Hydroperoxy Chemistry at the CalNex-LA 2010 Site: Measurements and Modeling

NASA Astrophysics Data System (ADS)

Griffith, S. M.; Hansen, R. F.; Dusanter, S.; Stevens, P. S.; Gilman, J. B.; Kuster, W. C.; Veres, P. R.; Graus, M.; Warneke, C.; De Gouw, J. A.; Young, C. J.; Washenfelder, R. A.; Brown, S. S.; Flynn, J. H.; Alvarez, S. L.; Grossberg, N.; Lefer, B. L.; Rappenglueck, B.; Mielke, L. H.; Osthoff, H. D.

2011-12-01

Hydroxyl (OH) and hydroperoxy (HO2) radicals are key species in the atmosphere driving the oxidation of organic trace gases leading to the production of ozone and secondary organic aerosols. Previous measurements of these radicals in urban environments have shown similarities and differences across sites due to differing levels of nitrogen oxides (NOx) and volatile organic compounds (VOCs), and the control strategies for dealing with these chemical species. Understanding the free radical chemistry is essential for effectively regulating NOx and VOC emissions and controlling ozone and other secondary pollutants. Measurements of OH and HO2 radicals were made using a laser-induced fluorescence technique as part of the CalNex LA campaign during May-June, 2010. Median HOx (OH + HO2) concentrations, as well as HO2-to-OH ratios, were similar to previous measurements in other urban areas. An extensive suite of supporting measurements including photolysis rates, NOx, and other inorganic species, biogenic, aromatic, and other anthropogenic VOCs are used to constrain a zero-dimensional box model based on the Regional Atmospheric Chemistry Mechanism. Model comparisons provide details about the ability of commonly used chemical mechanisms to reproduce HOx production and loss rates, the radical cycling, and instantaneous O3 production rates in the Los Angeles area.

The influence of genistein on free radicals in normal dermal fibroblasts and keloid fibroblasts examined by EPR spectroscopy.

PubMed

Jurzak, Magdalena; Ramos, Paweł; Pilawa, Barbara

2017-01-01

Normal and keloid fibroblasts were examined using X-band (9.3 GHz) electron paramagnetic resonance spectroscopy. The effect of genistein on the concentration of free radicals in both normal dermal and keloid fibroblasts after ultraviolet irradiation was investigated. The highest concentration of free radicals was seen in keloid fibroblasts, with normal fibroblasts containing a lower concentration. The concentration of free radicals in both normal and keloid fibroblasts was altered in a concentration-dependent manner by the presence of genistein. The change in intra-cellular free radical concentration after the ultraviolet irradiation of both normal and keloid fibroblasts is also discussed. The antioxidant properties of genistein, using its 1,1-Diphenyl-2-picrylhydrazyl (DPPH) free radical-scavenging activity as a model, were tested, and the effect of ultraviolet irradiation on its interaction with free radicals was examined. The electron paramagnetic resonance spectra of DPPH showed quenching by genistein. The interaction of genistein with DPPH free radicals in the absence of ultraviolet irradiation was shown to be slow, but this interaction was much faster under ultraviolet irradiation. Ultraviolet irradiation enhanced the free radical-scavenging activity of genistein.

Radiolysis of poly(acrylic acid) in aqueous solution

NASA Astrophysics Data System (ADS)

Ulanski, Piotr; Bothe, Eberhard; Hildenbrand, Knut; Rosiak, Janusz M.; von Sonntag, Clemens

1995-02-01

Poly(acrylic acid), PAA, reacts with OH-radicals yielding -CHCH(CO 2H)- (β-radicals) and -CH 2C(CO 2H)- (α-radicals) in a ratio of approximately 2:1. This estimate is based on pulse radiolysis data where the absorption spectrum of the PAA-radicals was compared with the spectra of α-radicals from model systems. The β-radicals convert slowly into α-radicals ( k = 0.7 s -1 at pH 10). This process has also been observed by ESR. At PAA-concentrations of 10 -2 mol dm -3 chain scission dominates over other competing reactions except at low pH. The rate of chain scission was followed by pulse conductometry and in the pH range 7-9 k = 4 × 10 -2s -1 was observed. Oxygen reacts with PAA-radicals with k = 3.1 × 10 8 dm 3 mol -1 s -1 at pH 3.5 and k = 1.0 × 10 8 dm 3 mol -1 s -1 at pH 10. The corresponding peroxyl radicals undergo slow intramolecular H-transfer yielding a UV-absorbing product whose properties are that of 1,3-diketones.

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

Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Saewung; Kim, So-Young; Lee, Meehye

Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Gangzhou, and Beijing are surrounded by densely forested areas and recent research has consistently demonstrated the importance of biogenic volatile organic compounds from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical concentrations, undermine our ability to assess regional photochemical air pollution problems. We present an observational dataset of CO, NOX, SO2, ozone, HONO, andmore » VOCs (anthropogenic and biogenic) from Taehwa Research Forest (TRF) near the Seoul Metropolitan Area (SMA) in early June 2012. The data show that TRF is influenced both by aged pollution and fresh BVOC emissions. With the dataset, we diagnose HOx (OH, HO2, and RO2) distributions calculated with the University of Washington Chemical Box Model (UWCM v 2.1). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that 1) different model simulation scenarios cause systematic differences in HOX distributions especially OH levels (up to 2.5 times) and 2) radical destruction (HO2+HO2 or HO2+RO2) could be more efficient than radical recycling (HO2+NO) especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone-VOC-NOX sensitivity and oxidation product formation rates. Overall, the VOC limited regime in ozone photochemistry is predicted but the degree of sensitivity can significantly vary depending on the model scenarios. The model results also suggest that RO2 levels are positively correlated with OVOCs production that is not routinely constrained by observations. These unconstrained OVOCs can cause higher than expected OH loss rates (missing OH reactivity) and secondary organic aerosol formation. The series of modeling experiments constrained by observations strongly urge observational constraint of the radical pool to enable precise understanding of regional photochemical pollution problems in the East Asian megacity region.« less

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.

Gamma and Ion-Beam Irradiation of DNA: Free Radical Mechanisms, Electron Effects, and Radiation Chemical Track Structure

PubMed Central

Sevilla, Michael D.; Becker, David; Kumar, Anil; Adhikary, Amitava

2016-01-01

The focus of our laboratory’s investigation is to study the direct-type DNA damage mechanisms resulting from γ-ray and ion-beam radiation-induced free radical processes in DNA which lead to molecular damage important to cellular survival. This work compares the results of low LET (γ−) and high LET (ion-beam) radiation to develop a chemical track structure model for ion-beam radiation damage to DNA. Recent studies on protonation states of cytosine cation radicals in the N1-substituted cytosine derivatives in their ground state and 5-methylcytosine cation radicals in ground as well as in excited state are described. Our results exhibit a radical signature of excitations in 5-methylcytosine cation radical. Moreover, our recent theoretical studies elucidate the role of electron-induced reactions (low energy electrons (LEE), presolvated electrons (epre−), and aqueous (or, solvated) electrons (eaq−)). Finally DFT calculations of the ionization potentials of various sugar radicals show the relative reactivity of these species. PMID:27695205

Gamma and ion-beam irradiation of DNA: Free radical mechanisms, electron effects, and radiation chemical track structure

NASA Astrophysics Data System (ADS)

Sevilla, Michael D.; Becker, David; Kumar, Anil; Adhikary, Amitava

2016-11-01

The focus of our laboratory's investigation is to study the direct-type DNA damage mechanisms resulting from γ-ray and ion-beam radiation-induced free radical processes in DNA which lead to molecular damage important to cellular survival. This work compares the results of low LET (γ-) and high LET (ion-beam) radiation to develop a chemical track structure model for ion-beam radiation damage to DNA. Recent studies on protonation states of cytosine cation radicals in the N1-substituted cytosine derivatives in their ground state and 5-methylcytosine cation radicals in ground as well as in excited state are described. Our results exhibit a radical signature of excitations in 5-methylcytosine cation radical. Moreover, our recent theoretical studies elucidate the role of electron-induced reactions (low energy electrons (LEE), presolvated electrons (epre-), and aqueous (or, solvated) electrons (eaq-)). Finally DFT calculations of the ionization potentials of various sugar radicals show the relative reactivity of these species.

Damage of polyesters by the atmospheric free radical oxidant NO3 •: a product study involving model systems

PubMed Central

Goeschen, Catrin

2013-01-01

Summary Manufactured polymer materials are used in increasingly demanding applications, but their lifetime is strongly influenced by environmental conditions. In particular, weathering and ageing leads to dramatic changes in the properties of the polymers, which results in decreased service life and limited usage. Despite the heavy reliance of our society on polymers, the mechanism of their degradation upon exposure to environmental oxidants is barely understood. In this work, model systems of important structural motifs in commercial high-performing polyesters were used to study the reaction with the night-time free radical oxidant NO3 • in the absence and presence of other radical and non-radical oxidants. Identification of the products revealed ‘hot spots’ in polyesters that are particularly vulnerable to attack by NO3 • and insight into the mechanism of oxidative damage by this environmentally important radical. It is suggested that both intermediates as well as products of these reactions are potentially capable of promoting further degradation processes in polyesters under environmental conditions. PMID:24204400

Weakly Bound Free Radicals in Combustion: "Prompt" Dissociation of Formyl Radicals and Its Effect on Laminar Flame Speeds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Labbe, Nicole J.; Sivaramakrishnan, Raghu; Goldsmith, C. Franklin

2016-01-07

Weakly bound free radicals have low-dissociation thresholds such that at high temperatures, timescales for dissociation and collisional relaxation become comparable, leading to significant dissociation during the vibrational-rotational relaxation process. Here we characterize this “prompt” dissociation of formyl (HCO), an important combustion radical, using direct dynamics calculations for OH + CH2O and H + CH2O (key HCO-forming reactions). For all other HCO-forming reactions, presumption of a thermal incipient HCO distribution was used to derive prompt dissociation fractions. Inclusion of these theoretically derived HCO prompt dissociation fractions into combustion kinetics models provides an additional source for H-atoms that feeds chain branching reactions.more » Simulations using these updated combustion models are therefore shown to enhance flame propagation in 1,3,5-trioxane and acetylene. The present results suggest that HCO prompt dissociation should be included when simulating flames of hydrocarbons and oxygenated molecules and that prompt dissociations of other weakly bound radicals may also impact combustion simulations« less

Evaluation of pulsed streamer corona experiments to determine the O* radical yield

NASA Astrophysics Data System (ADS)

van Heesch, E. J. M.; Winands, G. J. J.; Pemen, A. J. M.

2008-12-01

The production of O* radicals in air by a pulsed streamer plasma is studied by integration of a large set of precise experimental data and the chemical kinetics of ozone production. The measured data comprise ozone production, plasma energy, streamer volume, streamer length, streamer velocity, humidity and gas-flow rate. Instead of entering input parameters into a kinetic model to calculate the end products the opposite strategy is followed. Since the amount of end-products (ozone) is known from the measurements the model had to be applied in the reverse direction to determine the input parameters, i.e. the O* radical concentration.

Kinetics, Thermodynamics and Modelling of Amido Black Dye Photodegradation in Water Using Co/TiO2 Nanoparticles.

PubMed

Ali, Imran; M L Alharbi, Omar; A Alothman, Zeid; Badjah, Ahmad Yacine

2018-05-16

Titanium oxide nanoparticles were doped with copper and characterized by XRD, FT-IR, TEM and SEM. The surface morphology was spherical with 15-26 nm as particle size. The doped titanium oxide (Co/TiO 2 ) nanomaterial was used for photodegradation of amido black dye in water. The maximum photodegradation of amido black obtained was 90%. The values of free energy, and enthalpy were negative, indicating spontaneous photodegradation of amido black dye. The photodegradation of amido black dye obeyed first order kinetic model. The photodegradation mechanism of amido black involved adsorption of the dye on the surface of cobalt doped titanium oxide and its degradation under UV radiation. The electron (e - ) and hole (h + ) pairs are generated by Co/TiO 2 , which consequently generated superoxide oxygen anion and hydroxyl free radical. These species degraded amido black dye. The reported method is fast, effective and economic, which may be utilized to remove amido black in water. The doped TiO 2 catalyst was quite stable and can be used up to 5 cycles. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Rotational and fine structure of open-shell molecules in nearly degenerate electronic states

NASA Astrophysics Data System (ADS)

Liu, Jinjun

2018-03-01

An effective Hamiltonian without symmetry restriction has been developed to model the rotational and fine structure of two nearly degenerate electronic states of an open-shell molecule. In addition to the rotational Hamiltonian for an asymmetric top, this spectroscopic model includes the energy separation between the two states due to difference potential and zero-point energy difference, as well as the spin-orbit (SO), Coriolis, and electron spin-molecular rotation (SR) interactions. Hamiltonian matrices are computed using orbitally and fully symmetrized case (a) and case (b) basis sets. Intensity formulae and selection rules for rotational transitions between a pair of nearly degenerate states and a nondegenerate state have also been derived using all four basis sets. It is demonstrated using real examples of free radicals that the fine structure of a single electronic state can be simulated with either a SR tensor or a combination of SO and Coriolis constants. The related molecular constants can be determined precisely only when all interacting levels are simulated simultaneously. The present study suggests that analysis of rotational and fine structure can provide quantitative insights into vibronic interactions and related effects.

Countering Extremism: An Understanding of the Problem, the Process and Some Solutions

DTIC Science & Technology

2015-06-01

Radicalization into Terrorism.” 20 extremist movement “could not be developed , evolved or sustained over time and place” without the support of...efforts to research, develop , and implement a variety of methods and models to prevent and counter violent extremism (CVE). Despite these efforts...but how to better understand the radicalization process in order to develop effective strategies to prevent radicalization from occurring. Faced

Photodissociation dynamics of CH{sub 3}C(O)SH in argon matrix: A QM/MM nonadiabatic dynamics simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xia, Shu-Hua; Liu, Xiang-Yang; Fang, Qiu

2015-11-21

In this work, we have first employed the combined quantum mechanics/molecular mechanics (QM/MM) method to study the photodissociation mechanism of thioacetic acid CH{sub 3}C(O)SH in the S{sub 1}, T{sub 1}, and S{sub 0} states in argon matrix. CH{sub 3}C(O)SH is treated quantum mechanically using the complete active space self-consistent field and complete active space second-order perturbation theory methods; argon matrix is described classically using Lennard-Jones potentials. We find that the C-S bond fission is predominant due to its small barriers of ca. 3.0 and 1.0 kcal/mol in the S{sub 1} and T{sub 1} states. It completely suppresses the nearby C—Cmore » bond fission. After the bond fission, the S{sub 1} radical pair of CH{sub 3}CO and SH can decay to the S{sub 0} and T{sub 1} states via internal conversion and intersystem crossing, respectively. In the S{sub 0} state, the radical pair can either recombine to form CH{sub 3}C(O)SH or proceed to form molecular products of CH{sub 2}CO and H{sub 2}S. We have further employed our recently developed QM/MM generalized trajectory-based surface-hopping method to simulate the photodissociation dynamics of CH{sub 3}C(O)SH. In 1 ps dynamics simulation, 56% trajectories stay at the Franck-Condon region; the S{sub 1} C—S bond fission takes place in the remaining 44% trajectories. Among all nonadiabatic transitions, the S{sub 1} → S{sub 0} internal conversion is major (55%) but the S{sub 1} → T{sub 1} intersystem crossing is still comparable and cannot be ignored, which accounts for 28%. Finally, we have found a radical channel generating the molecular products of CH{sub 2}CO and H{sub 2}S, which is complementary to the concerted molecular channel. The present work sets the stage for simulating photodissociation dynamics of similar thio-carbonyl systems in matrix.« less

Photogenerated radical intermediates of vitamin K 1: a time-resolved resonance Raman study

NASA Astrophysics Data System (ADS)

Balakrishnan, G.; Umapathy, S.

1999-01-01

Quinones play a vital role in the process of electron transfer in bacterial photosynthetic reaction centers. It is of interest to investigate the photochemical reactions involving quinones with a view to elucidating the structure-function relationships in the biological processes. Resonance Raman spectra of radical anions and the time-resolved resonance Raman spectra of vitamin K 1 (model compound for Q A in Rhodopseudomonas viridis, a bacterial photosynthetic reception center) are presented. The photochemical intermediates of vitamin K 1, viz. radical anion, ketyl radical and o-quinone methide have been identified. The vibrational assignments of all these intermediates are made on the basis of comparison with our earlier TR3 studies on radical anions of naphthoquinone and menaquinone.

Convolutional neural networks for prostate cancer recurrence prediction

NASA Astrophysics Data System (ADS)

Kumar, Neeraj; Verma, Ruchika; Arora, Ashish; Kumar, Abhay; Gupta, Sanchit; Sethi, Amit; Gann, Peter H.

2017-03-01

Accurate prediction of the treatment outcome is important for cancer treatment planning. We present an approach to predict prostate cancer (PCa) recurrence after radical prostatectomy using tissue images. We used a cohort whose case vs. control (recurrent vs. non-recurrent) status had been determined using post-treatment follow up. Further, to aid the development of novel biomarkers of PCa recurrence, cases and controls were paired based on matching of other predictive clinical variables such as Gleason grade, stage, age, and race. For this cohort, tissue resection microarray with up to four cores per patient was available. The proposed approach is based on deep learning, and its novelty lies in the use of two separate convolutional neural networks (CNNs) - one to detect individual nuclei even in the crowded areas, and the other to classify them. To detect nuclear centers in an image, the first CNN predicts distance transform of the underlying (but unknown) multi-nuclear map from the input HE image. The second CNN classifies the patches centered at nuclear centers into those belonging to cases or controls. Voting across patches extracted from image(s) of a patient yields the probability of recurrence for the patient. The proposed approach gave 0.81 AUC for a sample of 30 recurrent cases and 30 non-recurrent controls, after being trained on an independent set of 80 case-controls pairs. If validated further, such an approach might help in choosing between a combination of treatment options such as active surveillance, radical prostatectomy, radiation, and hormone therapy. It can also generalize to the prediction of treatment outcomes in other cancers.

Generation of radicals in hard biological tissues under the action of laser radiation

NASA Astrophysics Data System (ADS)

Sviridov, Alexander P.; Bagratashvili, Victor N.; Sobol, Emil N.; Omelchenko, Alexander I.; Lunina, Elena V.; Zhitnev, Yurii N.; Markaryan, Galina L.; Lunin, Valerii V.

2002-07-01

The formation of radicals upon UV and IR laser irradiation of some biological tissues and their components was studied by the EPR technique. The radical decay kinetics in body tissue specimens after their irradiation with UV light were described by various models. By the spin trapping technique, it was shown that radicals were not produced during IR laser irradiation of cartilaginous tissue. A change in optical absorption spectra and the dynamics of optical density of cartilaginous tissue, fish scale, and a collagen film under exposure to laser radiation in an air, oxygen, and nitrogen atmosphere was studied.

A complex of antioxidant vitamins effectively inhibits free-radical oxidation of LDL phospholipids in blood plasma and membrane structures of the liver and myocardium.

PubMed

Konovalova, G G; Lisina, M O; Tikhaze, A K; Lankin, V Z

2003-02-01

Antioxidant effect of a complex preparation including antioxidant vitamins C, E, provitamin A and selenium was studied on the model of Cu(2+)-initiated free-radical oxidation of LDL isolated from human blood plasma. The antioxidant effect of combined administration of alpha-tocopherol+ascorbic acid and alpha-tocopherol+beta-carotene is far more pronounced that the antioxidant effect of individual components of these cocktails. Moreover, in the model system the combined action of all antioxidant components completely inhibited free-radical oxidation of LDL. A 30-day course of peroral administration of antioxidant vitamin cocktail and selenium to rats pronouncedly enhanced the antioxidant potential of liver and completely suppressed free-radical processes in the myocardium. It is suggested that preparations containing antioxidant vitamins and selenium can be perspective for prevention and complex therapy of atherosclerosis.

Isolation and characterization of charge-tagged phenylperoxyl radicals in the gas phase: direct evidence for products and pathways in low temperature benzene oxidation.

PubMed

Kirk, Benjamin B; Harman, David G; Kenttämaa, Hilkka I; Trevitt, Adam J; Blanksby, Stephen J

2012-12-28

The phenylperoxyl radical has long been accepted as a critical intermediate in the oxidation of benzene and an archetype for arylperoxyl radicals in combustion and atmospheric chemistry. Despite being central to many contemporary mechanisms underpinning these chemistries, reports of the direct detection or isolation of phenylperoxyl radicals are rare and there is little experimental evidence connecting this intermediate with expected product channels. We have prepared and isolated two charge-tagged phenyl radical models in the gas phase [i.e., 4-(N,N,N-trimethylammonium)phenyl radical cation and 4-carboxylatophenyl radical anion] and observed their reactions with dioxygen by ion-trap mass spectrometry. Measured reaction rates show good agreement with prior reports for the neutral system (k(2)[(Me(3)N(+))C(6)H(4)˙ + O(2)] = 2.8 × 10(-11) cm(3) molecule(-1) s(-1), Φ = 4.9%; k(2)[((-)O(2)C)C(6)H(4)˙ + O(2)] = 5.4 × 10(-11) cm(3) molecule(-1) s(-1), Φ = 9.2%) and the resulting mass spectra provide unequivocal evidence for the formation of phenylperoxyl radicals. Collisional activation of isolated phenylperoxyl radicals reveals unimolecular decomposition by three pathways: (i) loss of dioxygen to reform the initial phenyl radical; (ii) loss of atomic oxygen yielding a phenoxyl radical; and (iii) ejection of the formyl radical to give cyclopentadienone. Stable isotope labeling confirms these assignments. Quantum chemical calculations for both charge-tagged and neutral phenylperoxyl radicals confirm that loss of formyl radical is accessible both thermodynamically and entropically and competitive with direct loss of both hydrogen atom and carbon dioxide.

Dynamics of Polarons in Organic Conjugated Polymers with Side Radicals.

PubMed

Liu, J J; Wei, Z J; Zhang, Y L; Meng, Y; Di, B

2017-03-16

Based on the one-dimensional tight-binding Su-Schrieffer-Heeger (SSH) model, and using the molecular dynamics method, we discuss the dynamics of electron and hole polarons propagating along a polymer chain, as a function of the distance between side radicals and the magnitude of the transfer integrals between the main chain and the side radicals. We first discuss the average velocities of electron and hole polarons as a function of the distance between side radicals. It is found that the average velocities of the electron polarons remain almost unchanged, while the average velocities of hole polarons decrease significantly when the radical distance is comparable to the polaron width. Second, we have found that the average velocities of electron polarons decrease with increasing transfer integral, but the average velocities of hole polarons increase. These results may provide a theoretical basis for understanding carriers transport properties in polymers chain with side radicals.

Rate constant for reaction of vitamin C with protein radicals in γ-irradiated aqueous albumin solution at 295 K

NASA Astrophysics Data System (ADS)

Miyazaki, Tetsuo; Yoshimura, Toru; Mita, Kazuya; Suzuki, Keiji; Watanabe, Masami

1995-02-01

When an aqueous solution of albumin (0.1 kg dm -3) is irradiated by γ-rays at 295 K, albumin radicals with a long lifetime are observed by ESR. The reaction of vitamin C with the albumin radicals has been studied at 295 K in the albumin solution, which is considered as a model of cells. The rate constant for the reaction of vitamin C with the albumin radicals was measured as 0.014 dm 3 mol -1 s -1, which is much smaller than the reported rate constants (10 6-10 10 dm 3 mol -1 s -1) for the reaction of vitamin C with radicals in a dilute aqueous solution. The small rate constant for the reaction of vitamin C is ascribed to the reaction in polymer coils in the albumin solution, since vitamin C and albumin radicals diffuse very slowly in the coils.

Investigation of the oxidation of methyl vinyl ketone (MVK) by OH radicals in the atmospheric simulation chamber SAPHIR

NASA Astrophysics Data System (ADS)

Fuchs, Hendrik; Albrecht, Sascha; Acir, Ismail-Hakki; Bohn, Birger; Breitenlechner, Martin; Dorn, Hans-Peter; Gkatzelis, Georgios I.; Hofzumahaus, Andreas; Holland, Frank; Kaminski, Martin; Keutsch, Frank N.; Novelli, Anna; Reimer, David; Rohrer, Franz; Tillmann, Ralf; Vereecken, Luc; Wegener, Robert; Zaytsev, Alexander; Kiendler-Scharr, Astrid; Wahner, Andreas

2018-06-01

The photooxidation of methyl vinyl ketone (MVK) was investigated in the atmospheric simulation chamber SAPHIR for conditions at which organic peroxy radicals (RO2) mainly reacted with NO (high NO case) and for conditions at which other reaction channels could compete (low NO case). Measurements of trace gas concentrations were compared to calculated concentration time series applying the Master Chemical Mechanism (MCM version 3.3.1). Product yields of methylglyoxal and glycolaldehyde were determined from measurements. For the high NO case, the methylglyoxal yield was (19 ± 3) % and the glycolaldehyde yield was (65 ± 14) %, consistent with recent literature studies. For the low NO case, the methylglyoxal yield reduced to (5 ± 2) % because other RO2 reaction channels that do not form methylglyoxal became important. Consistent with literature data, the glycolaldehyde yield of (37 ± 9) % determined in the experiment was not reduced as much as implemented in the MCM, suggesting additional reaction channels producing glycolaldehyde. At the same time, direct quantification of OH radicals in the experiments shows the need for an enhanced OH radical production at low NO conditions similar to previous studies investigating the oxidation of the parent VOC isoprene and methacrolein, the second major oxidation product of isoprene. For MVK the model-measurement discrepancy was up to a factor of 2. Product yields and OH observations were consistent with assumptions of additional RO2 plus HO2 reaction channels as proposed in literature for the major RO2 species formed from the reaction of MVK with OH. However, this study shows that also HO2 radical concentrations are underestimated by the model, suggesting that additional OH is not directly produced from RO2 radical reactions, but indirectly via increased HO2. Quantum chemical calculations show that HO2 could be produced from a fast 1,4-H shift of the second most important MVK derived RO2 species (reaction rate constant 0.003 s-1). However, additional HO2 from this reaction was not sufficiently large to bring modelled HO2 radical concentrations into agreement with measurements due to the small yield of this RO2 species. An additional reaction channel of the major RO2 species with a reaction rate constant of (0.006 ± 0.004) s-1 would be required that produces concurrently HO2 radicals and glycolaldehyde to achieve model-measurement agreement. A unimolecular reaction similar to the 1,5-H shift reaction that was proposed in literature for RO2 radicals from MVK would not explain product yields for conditions of experiments in this study. A set of H-migration reactions for the main RO2 radicals were investigated by quantum chemical and theoretical kinetic methodologies, but did not reveal a contributing route to HO2 radicals or glycolaldehyde.

Hydrogen exchange equilibria in thiols.

PubMed

Hofstetter, Dustin; Thalmann, Basil; Nauser, Thomas; Koppenol, Willem H

2012-09-17

Cysteine, cysteinyl-glycine, glutathione, phenylalanyl-cysteinyl-glycine, and histidyl-cysteinyl-glycine were dissolved in acidic and neutral D(2)O in the presence of the radical generator 2,2'-azobis(2-methylpropionamidine) dihydrochloride and radical mediator compounds (benzyl alcohol and 2-propanol). An exchange of H-atoms by D-atoms took place in these peptides due to intramolecular H-abstraction equilibria. NMR measurements allow one to follow the extent of H-D exchanges and to identify the sites where these exchanges take place. Significant exchanges occur in acidic media in GSH at positions Glu-β and Glu-γ, in Phe-Cys-Gly at positions Phe ortho, Phe-β, Cys-α, Cys-β, and Gly-α, and in His-Cys-Gly at positions His H1, His H2, His β, Cys β, and Gly α. In neutral media, exchanges occur in Cys-Gly at position Cys β and in GSH at position Cys α. Phe-Cys-Gly and His-Cys-Gly were not examined in neutral media. Sites participating in the radical exchange equilibria are highly dependent on structure and pH; the availability of electron density in the form of lone pairs appears to increase the extent of exchange. Interestingly, and unexpectedly, 2D NMR experiments show that GSH rearranges itself in acidic solution: the signals shift, but their patterns do not change. The formation of a thiolactone from Gly and Cys residues matches the changes observed.

Ferromagnetic interactions in Ru(III)-nitronyl nitroxide radical complex: a potential 2p4d building block for molecular magnets.

PubMed

Pointillart, Fabrice; Bernot, Kevin; Sorace, Lorenzo; Sessoli, Roberta; Gatteschi, Dante

2007-07-07

The reaction between [Ru(salen)(PPh3)Cl] and the 4-pyridyl-substituted nitronyl nitroxide radical (NITpPy) leads to the [Ru(salen)(PPh3)(NITpPy)](ClO4)(H2O)2 complex while the reaction with the azido anion (N3-) leads to the [Ru(salen)(PPh3)(N3)] complex 2 (where salen2- = N,N'-ethan-1,2-diylbis(salicylidenamine) and PPh3 = triphenylphosphine). Both compounds have been characterized by single crystal X-ray diffraction. The two crystal structures are composed by a [Ru(III)(salen)(PPh3)]+ unit where the Ru(III) ion is coordinated to a salen2- ligand and one PPh3 ligand in axial position. In 1 the Ru(III) ion is coordinated to the 4-pyridyl-substituted nitronyl nitroxide radical whereas in 2 the second axial position is occupied by the azido ligand. In both complexes the Ru(III) ions are in the same environment RuO2N3P, in a tetragonally elongated octhaedral geometry. The crystal packing of 1 reveals pi-stacking in pairs. While antiferromagnetic intermolecular interaction (J2 = 5.0 cm(-1)) dominates at low temperatures, ferromagnetic intramolecular interaction (J1 = -9.0 cm(-1)) have been found between the Ru(III) ion and the coordinated NITpPy.

In Vitro Antioxidant-Activity Evaluation of Gallic-Acid-Grafted Chitosan Conjugate Synthesized by Free-Radical-Induced Grafting Method.

PubMed

Hu, Qiaobin; Wang, Taoran; Zhou, Mingyong; Xue, Jingyi; Luo, Yangchao

2016-07-27

The major objective of this work was to develop a green and facile process to prepare gallic acid-chitosan conjugate and comprehensively evaluate the physicochemical properties and biological activities of an as-prepared water-soluble chitosan derivative. A free-radical-induced grafting approach using an ascorbic acid-hydrogen peroxide redox pair was adopted. The obtained conjugate was characterized by Fourier transform infrared spectroscopy, UV-vis, X-ray diffraction, and pKa analysis. The antioxidant activities were evaluated by 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2'-azino-bis(3-ethylbenzothiazoline-6)-sulphonic acid (ABTS), reducing power, and oxygen-radical antioxidant-capacity assays. The results showed that the mass ratio of gallic acid to chitosan played a vital role in determining the grafting degree and ζ potential of the conjugates, with the ratio of 0.5:1 being the optimal ratio that resulted in the highest grafting degree. The antioxidant assays demonstrated that conjugation significantly improved the antioxidant activities, being dramatically higher than that of free chitosan. It was notable that the DPPH- and ABTS-scavenging activities of conjugate at 0.4 mg/mL reached the same level as the free gallic acid at the equivalent concentration. Our study demonstrated a green and facile synthesis approach to preparing a novel water-soluble chitosan derivative that may have promising potentials in the food industry.

Prognostic value of transformer 2β expression in prostate cancer.

PubMed

Diao, Yan; Wu, Dong; Dai, Zhijun; Kang, Huafeng; Wang, Ziming; Wang, Xijing

2015-01-01

Deregulation of transformer 2β (Tra2β) has been implicated in several cancers. However, the role of Tra2β expression in prostate cancer (PCa) is unclear. Therefore, this study was to investigate the expression of Tra2β in PCa and evaluated its association with clinicopathological variables and prognosis. Thirty paired fresh PCa samples were analyzed for Tra2β expression by Western blot analysis. Immunohistochemistry (IHC) assay was performed in 160 PCa samples after radical prostatectomy and adjacent non-cancerous tissues. Tra2β protein expression was divided into high expression group and low expression group by IHC. We also investigated the association of Tra2β expression with clinical and pathologic parameters. Kaplan-Meier plots and Cox proportional hazards regression model were used to analyze the association between Tra2β protein expression and prognosis of PCa patients. Our results showed that Tra2β was significantly upregulated in PCa tissues by western blot and IHC. Our data indicated that high expression of Tra2β was significantly associated with lymph node metastasis (P=0.002), clinical stage (P=0.015), preoperative prostate-specific antigen (P=0.003), Gleason score (P=0.001), and biochemical recurrence (P=0.021). High Tra2β expression was a significant predictor of poor biochemical recurrence free survival and overall survival both in univariate and multivariate analysis. We show that Tra2β was significantly upregulated in PCa patients after radical prostatectomy, and multivariate analysis confirmed Tra2β as an independent prognostic factor.

Photoinduced electron transfer interaction of anthraquinones with aniline quenchers: Influence of methyl substitution in aniline donors

NASA Astrophysics Data System (ADS)

Sivakumar, V.; Ponnamma, Deepalekshmi; Hussein, Yasser H. A.

2017-02-01

Photoinduced electron transfer between triplet state of 9,10-anthraquinone (AQ) and its two derivatives: 2-chloro-9,10-anthraquinone (CAQ) and sodium anthraquinone-2-sulfonate (AQS) and ground state aniline (AN) and its dimethyl substitutions: 2,3-dimethylaniline (2,3-DMA), 2,6-dimethylaniline (2,6-DMA), 3,5-dimethylaniline (3,5-DMA) and N,N-dimethylaniline (N,N-DMA) is studied using nanosecond laser flash photolysis at room temperature. Detection of radical bands of quinone anions and aniline cations along with their formation and/or decay kinetics are used to confirm the electron transfer (ET) process. In MeCN medium, AN quenches the triplet state of CAQ (CAQT) but not the triplets AQT or AQST. However in aqueous medium, AN quenches AQST and forms radical ion pair. All the DMAs can react through ET with all the triplet quinones at different degrees of efficiency in MeCN medium. Noticeably, the ring substituted DMAs are less efficient in electron donation to AQT or AQST while the N,N-DMA shows high efficiency in donating electron to all triplet quinones in MeCN medium. Charge distribution of donor molecules, in MeCN medium is calculated using density functional theory (DFT), and shows an enhancement of electron density of the ring of N,N-DMA, making it an ideal electron donor for ET studies compared to other DMAs. This systematic selection and usage of anilines with electrochemically tunable quinones can be viewed as a working model of donor-acceptor system that can be utilized in photoinduced ET applications.

Solution phase and membrane immobilized iron-based free radical reactions: Fundamentals and applications for water treatment

NASA Astrophysics Data System (ADS)

Lewis, Scott Romak

Membrane-based separation processes have been used extensively for drinking water purification, wastewater treatment, and numerous other applications. Reactive membranes synthesized through functionalization of the membrane pores offer enhanced reactivity due to increased surface area at the polymer-solution interface and low diffusion limitations. Oxidative techniques utilizing free radicals have proven effective for both the destruction of toxic organics and non-environmental applications. Most previous work focuses on reactions in the homogeneous phase; however, the immobilization of reactants in membrane pores offers several advantages. The use of polyanions immobilized in a membrane or chelates in solution prevents ferric hydroxide precipitation at near-neutral pH, a common limitation of iron(Fe(II/III))-catalyzed hydrogen peroxide (H 2O2) decomposition. The objectives of this research are to develop a membrane-based platform for the generation of free radicals, degrade toxic organic compounds using this and similar solution-based reactions, degrade toxic organic compounds in droplet form, quantify hydroxyl radical production in these reactions, and develop kinetic models for both processes. In this study, a functionalized membrane containing poly(acrylic acid) (PAA) was used to immobilize iron ions and conduct free radical reactions by permeating H2O2 through the membrane. The membrane's responsive behavior to pH and divalent cations was investigated and modeled. The conversion of Fe(II) to Fe(III) in the membrane and its effect on the decomposition of hydrogen peroxide were monitored and used to develop kinetic models for predicting H2O2 decomposition in these systems. The rate of hydroxyl radical production, and hence contaminant degradation can be varied by changing the residence time, H2O2 concentration, and/or iron loading. Using these membrane-immobilized systems, successful removal of toxic organic compounds, such as pentachlorophenol (PCP), from water was demonstrated. Another toxic organic compound of interest for water treatment applications is trichloroethylene (TCE). Due to its limited solubility in water, a majority of the TCE is often present in the form of droplets. In this study, effective TCE droplet degradation using chelate-modified, iron-catalyzed free radical reactions at near-neutral pH was demonstrated. In order to predict the degradation of aqueous and non-aqueous phase TCE for these reactions, a mathematical model was constructed through the use of droplet mass transfer correlations and free radical reaction kinetics. KEYWORDS: Functionalized membrane, free radical, hydrogen peroxide, chelate-modified, membrane reactor

Prosthetic mesh hernioplasty during laparoscopic radical prostatectomy.

PubMed

Teber, Dogu; Erdogru, Tibet; Zukosky, Derek; Frede, Thomas; Rassweiler, Jens

2005-06-01

To evaluate the role of simultaneous laparoscopic mesh prosthetic hernioplasty during laparoscopic radical prostatectomy (LRP), because 5% to 10% of candidates for radical prostatectomy present with a detectable inguinal hernia at their preoperative physical examination. Moreover, data have suggested a greater incidence of inguinal hernia after open radical prostatectomy. During 1035 LRP procedures, 50 laparoscopic mesh prosthetic hernioplasty procedures were performed in 37 patients (3.6%) for 13 bilateral and 24 unilateral inguinal hernias. We compared the outcome of LRP with simultaneous laparoscopic inguinal hernioplasty (group 1) with that of 37 match-paired patients treated by LRP alone (group 2). Both groups were matched according to age, prostate-specific antigen level, prostate volume, pathologic stage, and Gleason score. Perioperative parameters (ie, operative time, analgesic requirements) and postoperative results were analyzed. The patient age was 64.1 +/- 6.4 years versus 62.8 +/- 4.9 years old and had a body mass of 26.5 +/- 3.0 versus 27.4 +/- 3.2 kg/m2 in groups 1 and 2 (with and without laparoscopic hernioplasty), respectively. The mean operating time (221.9 versus 191.2 minutes, P = 0.011) and the total amount of narcotic analgesic requirements (26.8 mg versus 17.5 mg, P = 0.026) was significantly increased in the patients who underwent simultaneous laparoscopic inguinal hernia mesh repair. No statistically significant difference was found in the complication rate (4% versus 2%), median catheter time (7 days), and positive surgical margins (21.8%). Simultaneous repair of inguinal hernia during LRP using prosthetic mesh is feasible without adverse effects on surgical and functional parameters. Neither the transperitoneal nor extraperitoneal approach is associated with an increase in complications or morbidity. However, an extraperitoneal access allows an easier repair without the refixation of the peritoneum.

EPR investigation of gamma irradiated single crystal guaifenesin: A combined experimental and computational study

NASA Astrophysics Data System (ADS)

Tasdemir, Halil Ugur; Sayin, Ulku; Türkkan, Ercan; Ozmen, Ayhan

2016-04-01

Gamma irradiated single crystal of Guaifenesin (Glyceryl Guaiacolate), an important expectorant drug, were investigated with Electron Paramagnetic Resonance (EPR) spectroscopy between 123 and 333 K temperature at different orientations in the magnetic field. Considering the chemical structure and the experimental spectra of the gamma irradiated single crystal of guaifenesin sample, we assumed that alkoxy or alkyl-type paramagnetic species may be produced by irradiation. Depending on this assumption, eight possible alkoxy and alkyl-type radicals were modeled and EPR parameters of these modeled radicals were calculated using the B3LYP/6-311++G(d,p)-level of density functional theory (DFT). Theoretically calculated values of alkyl-type modeled radical(R3) are in good agreement with experimentally determined EPR parameters of single crystal. Furthermore, simulation spectra which are obtained by using the theoretical initial values are well matched with the experimental spectra. It was determined that a stable Cα •H2αCβHβCγH2γ (R3) alkyl radical was produced in the host crystal as a result of gamma irradiation.

Laparoscopic radical prostatectomy in the canine model.

PubMed

Price, D T; Chari, R S; Neighbors, J D; Eubanks, S; Schuessler, W W; Preminger, G M

1996-12-01

The purpose of this study was to determine the feasibility of performing laparoscopic radical prostatectomy in a canine model. Laparoscopic radical prostatectomy was performed on six adult male canines. A new endoscopic needle driver was used to construct a secure vesicourethral anastomosis. Average operative time required to complete the procedure was 304 min (range 270-345 min). Dissection of the prostate gland took an average of 67 min (range 35-90 min), and construction of the vesicourethral anastomosis took 154 min (rage 80-240 min). There were no intraoperative complications and only one postoperative complication (anastomotic leak). Five of the six animals recovered uneventfully from the procedure, and their foley catheters were removed 10-14 days postoperatively after a retrograde cystourethrogram demonstrated an intact vesicourethral anastomosis. Four (80%) of the surviving animals were clinically continent within 10 days after catheter removal. Post mortem examination confirmed that the vesicourethral anastomosis was intact with no evidence of urine extravasation. These data demonstrate the feasibility of laparoscopic radical prostatectomy in a canine model, and suggest that additional work with this technique should be continued to develop its potential clinical application.

Reduction of protein radicals by GSH and ascorbate: potential biological significance.

PubMed

Gebicki, Janusz M; Nauser, Thomas; Domazou, Anastasia; Steinmann, Daniel; Bounds, Patricia L; Koppenol, Willem H

2010-11-01

The oxidation of proteins and other macromolecules by radical species under conditions of oxidative stress can be modulated by antioxidant compounds. Decreased levels of the antioxidants glutathione and ascorbate have been documented in oxidative stress-related diseases. A radical generated on the surface of a protein can: (1) be immediately and fully repaired by direct reaction with an antioxidant; (2) react with dioxygen to form the corresponding peroxyl radical; or (3) undergo intramolecular long range electron transfer to relocate the free electron to another amino acid residue. In pulse radiolysis studies, in vitro production of the initial radical on a protein is conveniently made at a tryptophan residue, and electron transfer often leads ultimately to residence of the unpaired electron on a tyrosine residue. We review here the kinetics data for reactions of the antioxidants glutathione, selenocysteine, and ascorbate with tryptophanyl and tyrosyl radicals as free amino acids in model compounds and proteins. Glutathione repairs a tryptophanyl radical in lysozyme with a rate constant of (1.05±0.05)×10(5) M(-1) s(-1), while ascorbate repairs tryptophanyl and tyrosyl radicals ca. 3 orders of magnitude faster. The in vitro reaction of glutathione with these radicals is too slow to prevent formation of peroxyl radicals, which become reduced by glutathione to hydroperoxides; the resulting glutathione thiyl radical is capable of further radical generation by hydrogen abstraction. Although physiologically not significant, selenoglutathione reduces tyrosyl radicals as fast as ascorbate. The reaction of protein radicals formed on insulin, β-lactoglobulin, pepsin, chymotrypsin and bovine serum albumin with ascorbate is relatively rapid, competes with the reaction with dioxygen, and the relatively innocuous ascorbyl radical is formed. On the basis of these kinetics data, we suggest that reductive repair of protein radicals may contribute to the well-documented depletion of ascorbate in living organisms subjected to oxidative stress.

High-level theoretical characterization of the vinoxy radical (•CH2CHO) + O2 reaction

NASA Astrophysics Data System (ADS)

Weidman, Jared D.; Allen, Ryan T.; Moore, Kevin B.; Schaefer, Henry F.

2018-05-01

Numerous processes in atmospheric and combustion chemistry produce the vinoxy radical (•CH2CHO). To understand the fate of this radical and to provide reliable energies needed for kinetic modeling of such processes, we have examined its reaction with O2 using highly reliable theoretical methods. Utilizing the focal point approach, the energetics of this reaction and subsequent reactions were obtained using coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)] extrapolated to the complete basis set limit. These extrapolated energies were appended with several corrections including a treatment of full triples and connected quadruple excitations, i.e., CCSDT(Q). In addition, this study models the initial vinoxy radical + O2 reaction for the first time with multireference methods. We predict a barrier for this reaction of approximately 0.4 kcal mol-1. This result agrees with experimental findings but is in disagreement with previous theoretical studies. The vinoxy radical + O2 reaction produces a 2-oxoethylperoxy radical which can undergo a number of unimolecular reactions. Abstraction of a β-hydrogen (a 1,4-hydrogen shift) and dissociation back to reactants are predicted to be competitive to each other due to their similar barriers of 21.2 and 22.3 kcal mol-1, respectively. The minimum-energy β-hydrogen abstraction pathway produces a hydroperoxy radical (QOOH) that eventually decomposes to formaldehyde, CO, and •OH. Two other unimolecular reactions of the peroxy radical are α-hydrogen abstraction (38.7 kcal mol-1 barrier) and HO2• elimination (43.5 kcal mol-1 barrier). These pathways lead to glyoxal + •OH and ketene + HO2• formation, respectively, but they are expected to be uncompetitive due to their high barriers.

Magnetic field effect corroborated with docking study to explore photoinduced electron transfer in drug-protein interaction.

PubMed

Chakraborty, Brotati; Roy, Atanu Singha; Dasgupta, Swagata; Basu, Samita

2010-12-30

Conventional spectroscopic tools such as absorption, fluorescence, and circular dichroism spectroscopy used in the study of photoinduced drug-protein interactions can yield useful information about ground-state and excited-state phenomena. However, photoinduced electron transfer (PET) may be a possible phenomenon in the drug-protein interaction, which may go unnoticed if only conventional spectroscopic observations are taken into account. Laser flash photolysis coupled with an external magnetic field can be utilized to confirm the occurrence of PET and authenticate the spin states of the radicals/radical ions formed. In the study of interaction of the model protein human serum albumin (HSA) with acridine derivatives, acridine yellow (AY) and proflavin (PF(+)), conventional spectroscopic tools along with docking study have been used to decipher the binding mechanism, and laser flash photolysis technique with an associated magnetic field (MF) has been used to explore PET. The results of fluorescence study indicate that fluorescence resonance energy transfer takes place from the protein to the acridine-based drugs. Docking study unveils the crucial role of Ser 232 residue of HSA in explaining the differential behavior of the two drugs towards the model protein. Laser flash photolysis experiments help to identify the radicals/radical ions formed in the due course of PET (PF(•), AY(•-), TrpH(•+), Trp(•)), and the application of an external MF has been used to characterize their initial spin-state. Owing to its distance dependence, MF effect gives an idea about the proximity of the radicals/radical ions during interaction in the system and also helps to elucidate the reaction mechanisms. A prominent MF effect is observed in homogeneous buffer medium owing to the pseudoconfinement of the radicals/radical ions provided by the complex structure of the protein.

Simple model of inhibition of chain-branching combustion processes

NASA Astrophysics Data System (ADS)

Babushok, Valeri I.; Gubernov, Vladimir V.; Minaev, Sergei S.; Miroshnichenko, Taisia P.

2017-11-01

A simple kinetic model has been suggested to describe the inhibition and extinction of flame propagation in reaction systems with chain-branching reactions typical for hydrocarbon systems. The model is based on the generalised model of the combustion process with chain-branching reaction combined with the one-stage reaction describing the thermal mode of flame propagation with the addition of inhibition reaction steps. Inhibitor addition suppresses the radical overshoot in flame and leads to the change of reaction mode from the chain-branching reaction to a thermal mode of flame propagation. With the increase of inhibitor the transition of chain-branching mode of reaction to the reaction with straight-chains (non-branching chain reaction) is observed. The inhibition part of the model includes a block of three reactions to describe the influence of the inhibitor. The heat losses are incorporated into the model via Newton cooling. The flame extinction is the result of the decreased heat release of inhibited reaction processes and the suppression of radical overshoot with the further decrease of the reaction rate due to the temperature decrease and mixture dilution. A comparison of the results of modelling laminar premixed methane/air flames inhibited by potassium bicarbonate (gas phase model, detailed kinetic model) with the results obtained using the suggested simple model is presented. The calculations with the detailed kinetic model demonstrate the following modes of combustion process: (1) flame propagation with chain-branching reaction (with radical overshoot, inhibitor addition decreases the radical overshoot down to the equilibrium level); (2) saturation of chemical influence of inhibitor, and (3) transition to thermal mode of flame propagation (non-branching chain mode of reaction). The suggested simple kinetic model qualitatively reproduces the modes of flame propagation with the addition of the inhibitor observed using detailed kinetic models.

Development of the radical-stable Coprinus cinereus peroxidase (CiP) by blocking the radical attack.

PubMed

Kim, Su Jin; Joo, Jeong Chan; Kim, Han Sang; Kwon, Inchan; Song, Bong Keun; Yoo, Young Je; Kim, Yong Hwan

2014-11-10

Despite the potential use of peroxidases as industrial biocatalysts, their practical application is often impeded due to suicide inactivation by radicals generated in oxidative reactions. Using a peroxidase from Coprinus cinereus (CiP) as a model enzyme, we revealed a dominant factor for peroxidase inactivation during phenol oxidation, and we engineered radical-stable mutants by site-directed mutagenesis of an amino acid residue susceptible to modification by phenoxyl radical. Mass spectrometry analysis of inactivated CiP identified an adduct between F230 and a phenoxyl radical, and subsequently, the F230 residue was mutated to amino acids that resisted radical coupling. Of the F230 mutants, the F230A mutant showed the highest stability against radical inactivation, retaining 80% of its initial activity, while the wild-type protein was almost completely inactivated. The F230A mutant also exhibited a 16-fold higher turnover of the phenol substrate compared with the wild-type enzyme. Furthermore, the F230A mutant was stable during the oxidation of other phenolic compounds, including m-cresol and 3-methoxyphenol. No structural changes were observed by UV-vis and CD spectra of CiP after radical coupling, implying that the F230-phenol radical adduct inactivated CiP by blocking substrate access to the active site. Our novel strategy can be used to improve the stability of other peroxidases inactivated by radicals. Copyright © 2014 Elsevier B.V. All rights reserved.

Lipid-derived free radical production in superantigen-induced interstitial pneumonia

PubMed Central

Miyakawa, Hisako; Mason, Ronald P.; Jiang, JinJie; Kadiiska, Maria B.

2009-01-01

We studied the free radical generation involved in the development of interstitial pneumonia (IP) in an animal model of autoimmune disease. We observed an electron spin resonance (ESR) spectrum of α-(4-pyridyl-1-oxide)-N-tert-butylnitrone (POBN) radical adducts detected in the lipid extract of lungs in autoimmune-prone mice after intratracheal instillation of staphylococcal enterotoxin B. The POBN adducts detected by ESR were paralleled by infiltration of macrophages and neutrophils in the bronchoalveolar lavage fluid. To further investigate the mechanism of free radical generation, mice were pretreated with the macrophage toxicant gadolinium chloride, which significantly suppressed the radical generation. Free radical generation was also decreased by pretreatment with the xanthine oxidase (XO) inhibitor allopurinol, the iron chelator Desferal, and the inducible nitric oxide synthase (iNOS) inhibitor 1400W. Histopathologically, these drugs significantly reduced both the cell infiltration to alveolar septal walls and the synthesis of pulmonary collagen fibers. Experiments with NADPH oxidase knockout mice showed that NADPH oxidase did not contribute to lipid radical generation. These results suggest that lipid-derived carbon-centered free radical production is important in the manifestation of IP and that a macrophage toxicant, an XO inhibitor, an iron chelator, and an iNOS inhibitor protect against both radical generation and the manifestation of IP. PMID:19376221

Quantification of OH and HO2 radicals during the low-temperature oxidation of hydrocarbons by Fluorescence Assay by Gas Expansion technique

PubMed Central

Blocquet, Marion; Schoemaecker, Coralie; Amedro, Damien; Herbinet, Olivier; Battin-Leclerc, Frédérique; Fittschen, Christa

2013-01-01

•OH and •HO2 radicals are known to be the key species in the development of ignition. A direct measurement of these radicals under low-temperature oxidation conditions (T = 550–1,000 K) has been achieved by coupling a technique named fluorescence assay by gas expansion, an experimental technique designed for the quantification of these radicals in the free atmosphere, to a jet-stirred reactor, an experimental device designed for the study of low-temperature combustion chemistry. Calibration allows conversion of relative fluorescence signals to absolute mole fractions. Such radical mole fraction profiles will serve as a benchmark for testing chemical models developed to improve the understanding of combustion processes. PMID:24277836

The Expanding Role of Oxygen Free Radicals in Clinical Medicine

PubMed Central

Katz, Murray A.

1986-01-01

In 1969 McCord and Fridovich discovered superoxide dismutase, which converts the oxygen free radical O2- to hydrogen peroxide H2O2. In the presence of excess O2-, H2O2 may then undergo further reduction to the highly toxic hydroxyl radical, OH•. Since the description of this enzymatic process, there has been explosive growth in related biochemical research, which has now percolated through to clinical investigation. The hypoxanthine-xanthine oxidase system originally used as a radical production model has a close counterpart in the ischemia-reperfusion phenomenon purported to cause diseases of heart, brain and gastrointestinal tract, and free radicals are now known to have a critical role in postphagocytic bacterial killing. Prototypic deficiency diseases such as chronic granulomatous disease are now recognized. Some evidence indicates that excess states such as perhaps Batten's disease also occur, and environmental influences such as selenium and vitamin E deficiency may augment free radical levels. Many disorders including microvasculopathies, noncardiogenic pulmonary edema, glomerulopathies and radiation damage may owe part of their proximate pathogenesis to free radicals. Control of tissue free radical levels is now pharmacologically feasible and perhaps justified for specific diseases. PMID:3521094

Microscopic progression in the free radical addition reaction: modeling, geometry, energy, and kinetics.

PubMed

Zhang, Yun; Huang, Hong; Liang, Zhiling; Liu, Houhe; Yi, Ling; Zhang, Jinhong; Zhang, Zhiqiang; Zhong, Cheng; Huang, Yugang; Ye, Guodong

2017-03-01

The free radical addition reaction is very important in UV curing. The benzoyl radical is the most commonly observed radical. In the addition process, the benzoyl radical adds to an acrylate monomer, forming a primary radical that has great value for subsequent research. In this article, a quantum chemical method was used to study the microscopic progression from the reactive complex to the saddle point. The reactions of three monomers (amylene, allyl methyl ether and methyl acrylate) with a benzoyl radical were evaluated in terms of geometry and energy. The results were also interpreted with an expanded version of the Polanyi rules and the interaction/deformation theory. The deformation energy of methyl acrylate was found to be the smallest, and the bond formation index showed that the transition state in the methyl acrylate system forms early, and can easily reach the saddle point. The activity of the monomer was ascertained by charge analysis and was further confirmed by the reaction rate. Mayer bond order curves depicted the constantly changing chemical bonds during formation and dissociation. Reduced density gradient analysis showed a weak interaction between the monomer and the benzoyl radical.

Free Radical Scavenging Activity of Drops and Spray Containing Propolis-An EPR Examination.

PubMed

Olczyk, Pawel; Komosinska-Vassev, Katarzyna; Ramos, Pawel; Mencner, Lukasz; Olczyk, Krystyna; Pilawa, Barbara

2017-01-13

The influence of heating at a temperature of 50 °C and UV-irradiation of propolis drops and spray on their free radical scavenging activity was determined. The kinetics of interactions of the propolis samples with DPPH free radicals was analyzed. Interactions of propolis drops and propolis spray with free radicals were examined by electron paramagnetic resonance spectroscopy. A spectrometer generating microwaves of 9.3 GHz frequency was used. The EPR spectra of the model DPPH free radicals were compared with the EPR spectra of DPPH in contact with the tested propolis samples. The antioxidative activity of propolis drops and propolis spray decreased after heating at the temperature of 50 °C. A UV-irradiated sample of propolis drops more weakly scavenged free radicals than an untreated sample. The antioxidative activity of propolis spray increased after UV-irradiation. The sample of propolis drops heated at the temperature of 50 °C quenched free radicals faster than the unheated sample. UV-irradiation weakly changed the kinetics of propolis drops or spray interactions with free radicals. EPR analysis indicated that propolis drops and spray should not be stored at a temperature of 50 °C. Propolis drops should not be exposed to UV-irradiation.

Robots drive the German radical prostatectomy market: a total population analysis from 2006 to 2013.

PubMed

Groeben, C; Koch, R; Baunacke, M; Wirth, M P; Huber, J

2016-12-01

To assess trends in the distribution of patients for radical prostatectomy in Germany from 2006 to 2013 and the impact of robotic surgery on annual caseloads. We hypothesized that the advent of robotics and the establishment of certified prostate cancer centers caused centralization in the German radical prostatectomy market. Using remote data processing we analyzed the nationwide German billing data from 2006 to 2013. We supplemented this database with additional hospital characteristics like the prostate cancer center certification status. Inclusion criteria were a prostate cancer diagnosis combined with radical prostatectomy. Hospitals with certification or a surgical robot in 2009 were defined as 'early' group. Linear covariant-analytic models were applied to describe trends over time. Annual radical prostatectomy numbers declined from 28 374 (2006) to 21 850 (2013). High-volume hospitals (⩾100 cases) decreased from 87 (22.0%) in 2006 to 43 (10.4%) in 2013. Low-volume hospitals (<50 cases) increased from 193 (48.7%) to 280 (67.4%). Mean radical prostatectomy caseloads of hospitals with early vs without certification declined from 155 to 130 vs 77 to 39 (P=0.021 for trend comparison). Early robotic hospitals maintained their volume >200 cases per year contrary to the overall trend (P<0.001 for trend comparison). A multivariate model for caseload numbers of 2013 indicated a robotic system to be the most important factor for higher caseloads (multiplication factor 7.3; 95% confidence interval: 6.6-8.0). A prostate cancer center certification (multiplication factor 1.6; 95% confidence interval: 1.50-1.59) had a much smaller impact. We found decentralization of radical prostatectomy in Germany. The driving force for this development might consist in the overall decline of radical prostatectomy numbers. The most important factor for achieving higher caseloads was the presence of a robotic system. In order to optimize outcomes of radical prostatectomy additional health policy measures might be necessary.

Radiation Sensitization in Cancer Therapy.

ERIC Educational Resources Information Center

Greenstock, Clive L.

1981-01-01

Discusses various aspects of radiation damage to biological material, including free radical mechanisms, radiation sensitization and protection, tumor hypoxia, mechanism of hypoxic cell radiosensitization, redox model for radiation modification, sensitizer probes of cellular radiation targets, pulse radiolysis studies of free radical kinetics,…

Laboratory evidence for a key intermediate in the Venus atmosphere: Peroxychloroformyl radical

PubMed Central

Pernice, Holger; Garcia, Placido; Willner, Helge; Francisco, Joseph S.; Mills, Franklin P.; Allen, Mark; Yung, Yuk L.

2004-01-01

For two decades, the peroxychloroformyl radical, ClC(O)OO, has played a central role in models of the chemical stability of the Venus atmosphere. No confirmation, however, has been possible in the absence of laboratory measurements for ClC(O)OO. We report the isolation of ClC(O)OO in a cryogenic matrix and its infrared and ultraviolet spectral signatures. These experiments show that ClC(O)OO is thermally and photolytically stable in the Venus atmosphere. These experimental discoveries validate the existence of ClC(O)OO, confirm several longstanding model assumptions, and provide a basis for the astronomical search for this important radical species. PMID:15375212

Laboratory Evidence for a Key Intermediate in the Venus Atmosphere: Peroxychloroformyl Radical

NASA Technical Reports Server (NTRS)

Pernice, Holger; Garcia, Placido; Willner, Helge; Francisco, Joseph S.; Mills, Franklin P.; Allen, Mark; Yung, Yuk L.

2004-01-01

For two decades, the peroxychloroformyl radical, ClC(O)OO, has played a central role in models of the chemical stability of the Venus atmosphere. No confirmation, however, has been possible in the absence of laboratory measurements for ClC(O)OO. We report the isolation of ClC(O)OO in a cryogenic matrix and its infrared and ultraviolet spectral signatures. These experiments show that ClC(O)OO is thermally and photolytically stable in the Venus atmosphere. These experimental discoveries validate the existence of ClC(O)OO, confirm several longstanding model assumptions, and provide a basis for the astronomical search for this important radical species.

Demonstration of free radical generation in the "stunned" myocardium in the conscious dog and identification of major differences between conscious and open-chest dogs.

PubMed Central

Li, X Y; McCay, P B; Zughaib, M; Jeroudi, M O; Triana, J F; Bolli, R

1993-01-01

Conscious dogs undergoing a 15-min coronary occlusion were given alpha-phenyl N-tert-butyl nitrone (PBN) and the local coronary venous plasma was analyzed by electron paramagnetic resonance spectroscopy. A prolonged myocardial release of PBN radical adducts was observed, which exhibited a burst in the initial minutes of reflow (peaking at 3 min) and then abated but continued for 1-3 h after reperfusion. Computer simulation revealed the presence of at least two PBN adducts (aN = 15.2 G and a beta H = 6.0 G; aN = 14.6 G and a beta H = 3.0 G), both consistent with the trapping of secondary carbon-centered radicals. No appreciable PBN adduct production was observed when collateral flow exceeded 30-40% of nonischemic flow, indicating that a flow reduction of at least 60% is necessary to trigger free radical reactions. There was a direct relationship between the magnitude of PBN adduct production and the severity of contractile dysfunction (r = 0.77), suggesting that the radicals generated upon reperfusion play a causal role in the subsequent stunning. The total release of PBN adducts after 3 h of reperfusion following a 15-min coronary occlusion was found to be approximately five times greater in open-chest compared with conscious dogs; at the same time, the recovery of wall thickening was markedly less in open-chest dogs. This study represents the first application of spin trapping to a conscious animal model of myocardial ischemia. The results demonstrate (a) that free radicals are generated in the stunned myocardium in the absence of the artificial or abnormal conditions associated with previously used models (isolated hearts, open-chest preparations), and (b) that both the severity of postischemic dysfunction and the magnitude of the attendant free radical production are greatly exaggerated in the open-chest dog, implying that previous conclusions derived from this model may not be applicable to conscious animals or to humans. This investigation also provides a method to measure free radicals in awake animals. PMID:8394382

Beneficial effects of Lagenaria siceraria (Mol.) Standley fruit epicarp in animal models.

PubMed

Deshpande, J R; Choudhari, A A; Mishra, M R; Meghre, V S; Wadodkar, S G; Dorle, A K

2008-04-01

Lagenaria siceraria (Mol.) Standley fruit (bottle gourd), a commonly used vegetable in India is described as cardiotonic and as a general tonic in Ayurveda. Keeping in view the presence of free radical scavenging activity in L. siceraria and involvement of free radicals in the development of various disorders, present studies were designed to evaluate the ethanolic extract of L. siceraria fruit against the disorders where free radicals play a major role in pathogenesis. The extract was found effective as hepatoprotective, antioxidant, antihyperglycemic, immunomodulatory, antihyperlipidemic and cardiotonic agent. The results showed that the radical scavenging capacity of L. siceraria fruit may be responsible for various biological activities studied.

Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide

DOE PAGES

Richards-Henderson, Nicole K.; Goldstein, Allen H.; Wilson, Kevin R.

2015-10-27

In this paper we report an unexpectedly large acceleration in the effective heterogeneous OH reaction rate in the presence of NO. This 10–50 fold acceleration originates from free radical chain reactions, propagated by alkoxy radicals that form inside the aerosol by the reaction of NO with peroxy radicals, which do not appear to produce chain terminating products (e.g., alkyl nitrates), unlike gas phase mechanisms. Lastly, a kinetic model, constrained by experiments, suggests that in polluted regions heterogeneous oxidation plays a much more prominent role in the daily chemical evolution of organic aerosol than previously believed.

Free energy gap laws for the pulse-induced and stationary fluorescence quenching by reversible charge transfer in polar solutions.

PubMed

Khokhlova, Svetlana S; Burshtein, Anatoly I

2011-01-21

The Stern-Volmer constants for either pulse-induced or stationary fluorescence being quenched by a contact charge transfer are calculated and their free energy dependencies (the free energy gap laws) are specified. The reversibility of charge transfer is taken into account as well as spin conversion in radical ion pairs, followed by their recombination in either singlet or triplet neutral products. The natural decay of triplets as well as their impurity quenching by ionization are accounted for when estimating the fluorescence quantum yield and its free energy dependence.

Search for beyond standard model physics (non-SUSY) in final states with photons at the Tevatron

DOE Office of Scientific and Technical Information (OSTI.GOV)

Palencia, Jose Enrique; /Fermilab

2009-01-01

We present the results of searches for non-standard model phenomena in photon final states. These searches use data from integrated luminosities of {approx} 1-4 fb{sup -1} of p{bar p} collisions at {radical}s = 1.96 TeV, collected with the CDF and D0 detectors at the Fermilab Tevatron. No significant excess in data has been observed. We report limits on the parameters of several BSM models (excluding SUSY) for events containing photons.

Radical-driven carbonyl-to-acid conversion and acid degradation in tropospheric aqueous systems studied by CAPRAM

NASA Astrophysics Data System (ADS)

Tilgner, A.; Herrmann, H.

2010-12-01

Model studies on the aqueous phase radical-driven processing of carbonyl compounds and acids in clouds and deliquescent particles were performed. The model exposed that aqueous radical conversions of carbonyl compounds and its oxidation products can contribute potentially to the formation of functionalised organic acids. The main identified C 2-C 4 organic gas phase precursors are ethylene glycol, glycolaldehyde, glyoxal, methylglyoxal and 1,4-butenedial. The aqueous phase is shown to contribute significantly with about 93%/63%, 47%/8%, 31%/4%, 7%/4%, 36%/8% to the multiphase oxidative fate of these compounds under remote/urban conditions. Interestingly, the studies revealed that aqueous chemical processing is not only limited to in-cloud conditions but also proceeds in deliquescent particle phase with significant fluxes. Oxalic acid is shown to be formed preferably in deliquescent particles subsequent to the in-cloud oxidations. Mean aqueous phase oxalate formation fluxes of about 12, 42 and 0.4 ng m -3 h -1 in the remote, urban and maritime scenario, respectively. Additionally, the turnovers of the oxidation of organics such as methylglyoxal by NO 3 radical reactions are identified to be competitive to their OH pendants. At the current state of CAPRAM, mean C 2-C 4 in-cloud oxidation fluxes of about 0.12 and 0.5 μg m -3 h -1 are modelled under the idealised remote and urban cloud conditions. Finally, turnovers from radical oxidations were compared with those of thermal reactions. It is demonstrated that, based on the sparse kinetic data available organic accretion reaction might be of interest in just a few cases for cloud droplets and aqueous particles but generally do not reach the oxidative conversion rates of the main radical oxidants OH and NO 3. Interestingly, oxidation reactions of H 2O 2 are shown to be competitive to the OH radical conversions in cases when H 2O 2 is not readily used up by the S(IV) oxidation.

Abnormal brain aging as a radical-related disease: A new target for nuclear medicine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fujibayashi, Y.; Yamamoto, S.; Waki, A.

DNA damages caused by endogenously produced radicals are closely correlated with aging. Among them, mitochondrial DNA (mtDNA) deletions have been reported as a memory of DNA damage by oxygen radicals. In fact, clinical as well as experimental studies indicated the accumulation of deleted mtDNA in the brain, myocardium and son on, in aged subjects. In our previous work, radioiodinated radical trapping agent, p-iodophenyl-N-t-butylnitrone, and hypoxia imaging agent, Cu-62 diacetyl-bis-N-4-methyl-thiosemicarbazone have been developed for the diagnosis of radical-related diseases, such as ischemic, inflammation, cancer or aging. The aim of the present work was to evaluate these agents for brain aging studies.more » In our university, an unique animal model, a senescence accelerated model mouse (SAM), has been established. Among the various substrains, SAMP8 showing memory deterioration in its young age ({approximately}3 month) was basically evaluated as an abnormal brain aging model with mtDNA deletion. As controls, SAMR1 showing normal aging and ddY mice were used. MtDNA deletion n the brain was analyzed with polymerase-chain reaction (PCR) method, and relationship between mtDNA deletion and brain uptake of IPBN or Cu-62-ATSM was studied. In 1-3 month old SAMP8 brain, multiple mtDNa deletions were already found and their content was significantly higher than that of SAMR1 or age-matched ddY control. Thus, it was cleared that SAMP8 brain has high tendency to be attacked by endogenously produced oxygen radicals, possibly from its birth. Both IPBN and Cu-ATSM showed significantly higher accumulation in the SAMP8 brain than in the SAMR1 brain, indicating that these agents have high possibility for the early detection of abnormal brain aging as a radical-related disease.« less

Modeling the gas-phase thermochemistry of organosulfur compounds.

PubMed

Vandeputte, Aäron G; Sabbe, Maarten K; Reyniers, Marie-Françoise; Marin, Guy B

2011-06-27

Key to understanding the involvement of organosulfur compounds in a variety of radical chemistries, such as atmospheric chemistry, polymerization, pyrolysis, and so forth, is knowledge of their thermochemical properties. For organosulfur compounds and radicals, thermochemical data are, however, much less well documented than for hydrocarbons. The traditional recourse to the Benson group additivity method offers no solace since only a very limited number of group additivity values (GAVs) is available. In this work, CBS-QB3 calculations augmented with 1D hindered rotor corrections for 122 organosulfur compounds and 45 organosulfur radicals were used to derive 93 Benson group additivity values, 18 ring-strain corrections, 2 non-nearest-neighbor interactions, and 3 resonance corrections for standard enthalpies of formation, standard molar entropies, and heat capacities for organosulfur compounds and organosulfur radicals. The reported GAVs are consistent with previously reported GAVs for hydrocarbons and hydrocarbon radicals and include 77 contributions, among which 26 radical contributions, which, to the best of our knowledge, have not been reported before. The GAVs allow one to estimate the standard enthalpies of formation at 298 K, the standard entropies at 298 K, and standard heat capacities in the temperature range 300-1500 K for a large set of organosulfur compounds, that is, thiols, thioketons, polysulfides, alkylsulfides, thials, dithioates, and cyclic sulfur compounds. For a validation set of 26 organosulfur compounds, the mean absolute deviation between experimental and group additively modeled enthalpies of formation amounts to 1.9  kJ  mol(-1). For an additional set of 14 organosulfur compounds, it was shown that the mean absolute deviations between calculated and group additively modeled standard entropies and heat capacities are restricted to 4 and 2 J  mol(-1)  K(-1), respectively. As an alternative to Benson GAVs, 26 new hydrogen-bond increments are reported, which can also be useful for the prediction of radical thermochemistry. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diffusive confinement of free radical intermediates in the OH radical oxidation of semisolid aerosols

DOE PAGES

Wiegel, Aaron A.; Liu, Matthew J.; Hinsberg, William D.; ...

2017-02-07

Multiphase chemical reactions (gas + solid/liquid) involve a complex interplay between bulk and interface chemistry, diffusion, evaporation, and condensation. Reactions of atmospheric aerosols are an important example of this type of chemistry: the rich array of particle phase states and multiphase transformation pathways produce diverse but poorly understood interactions between chemistry and transport. Their chemistry is of intrinsic interest because of their role in controlling climate. Their characteristics also make them useful models for the study of principles of reactivity of condensed materials under confined conditions. Previously, we have reported a computational study of the oxidation chemistry of a liquidmore » aliphatic aerosol. In this study, we extend the calculations to investigate nearly the same reactions at a semisolid gas-aerosol interface. A reaction-diffusion model for heterogeneous oxidation of triacontane by hydroxyl radicals (OH) is described, and its predictions are compared to measurements of aerosol size and composition, which evolve continuously during oxidation. Our results are also explicitly compared to those obtained for the corresponding liquid system, squalane, to pinpoint salient elements controlling reactivity. The diffusive confinement of the free radical intermediates at the interface results in enhanced importance of a few specific chemical processes such as the involvement of aldehydes in fragmentation and evaporation, and a significant role of radical-radical reactions in product formation. The simulations show that under typical laboratory conditions semisolid aerosols have highly oxidized nanometer-scale interfaces that encapsulate an unreacted core and may confer distinct optical properties and enhanced hygroscopicity. This highly oxidized layer dynamically evolves with reaction, which we propose to result in plasticization. The validated model is used to predict chemistry under atmospheric conditions, where the OH radical concentration is much lower. The oxidation reactions are more strongly influenced by diffusion in the particle, resulting in a more liquid-like character.« less

Effect of Fibonacci modulation on superconductivity

NASA Astrophysics Data System (ADS)

Gupta, Sanjay; Sil, Shreekantha; Bhattacharyya, Bibhas

2006-02-01

We have studied finite-sized single band models with short-range pairing interactions between electrons in the presence of diagonal Fibonacci modulation in one dimension. Two models, namely the attractive Hubbard model and the Penson-Kolb model, have been investigated at half-filling at zero temperature by solving the Bogoliubov-de Gennes equations in real space within a mean-field approximation. The competition between 'disorder' and the pairing interaction leads to a suppression of superconductivity (of usual pairs with zero centre-of-mass momenta) in the strong-coupling limit while an enhancement of the pairing correlation is observed in the weak-coupling regime for both models. However, the dissimilarity of the pairing mechanisms in these two models brings about notable differences in the results. The extent to which the bond-ordered wave and the η-paired (of pairs with centre-of-mass momenta = π) phases of the Penson-Kolb model are affected by the disorder has also been studied in the present calculation. Some finite size effects are also identified.

Reactions of nitroxide radicals in aqueous solutions exposed to non-thermal plasma: limitations of spin trapping of the plasma induced species

NASA Astrophysics Data System (ADS)

Gorbanev, Yury; Stehling, Nicola; O'Connell, Deborah; Chechik, Victor

2016-10-01

Low temperature (‘cold’) atmospheric pressure plasmas have gained much attention in recent years due to their biomedical effects achieved through the interactions of plasma-induced species with the biological substrate. Monitoring of the radical species in an aqueous biological milieu is usually performed via electron paramagnetic resonance (EPR) spectroscopy using various nitrone spin traps, which form persistent radical adducts with the short-lived radicals. However, the stability of these nitroxide radical adducts in the plasma-specific environment is not well known. In this work, chemical transformations of nitroxide radicals in aqueous solutions using a model nitroxide 4-oxo-TEMPO were studied using EPR and LC-MS. The kinetics of the nitroxide decay when the solution was exposed to plasma were assessed, and the reactive pathways proposed. The use of different scavengers enabled identification of the types of reactive species which cause the decay, indicating the predominant nitroxide group reduction in oxygen-free plasmas. The 2H adduct of the PBN spin trap (PBN-D) was shown to decay similarly to the model molecule 4-oxo-TEMPO. The decay of the spin adducts in plasma-treated solutions must be considered to avoid rendering the spin trapping results unreliable. In particular, the selectivity of the decay indicated the limitations of the PTIO/PTI nitroxide system in the detection of nitric oxide.

π vs σ-Radical States of One-Electron Oxidized DNA/RNA Bases: A Density Functional Theory Study

PubMed Central

Kumar, Anil; Sevilla, Michael D.

2013-01-01

As a result of their inherent planarity, DNA base radicals generated by one electron oxidation/reduction or bond cleavage form π- or σ-radicals. While most DNA base systems form π-radicals there are a number of nucleobase analogs such as one-electron oxidized 6-azauraci1, 6-azacytosine, and 2-thiothymine or one-electron reduced 5-bromouracil that form more reactive σ-radicals. Elucidating the availability of these states within DNA, base radical electronic structure is important to the understanding of the reactivity of DNA base radicals in different environments. In this work, we address this question by the calculation of the relative energies of π- and σ-radical states in DNA/RNA bases and their analogs. We used density functional theory B3LYP/6-31++G** method to optimize the geometries of π- and σ-radicals in Cs symmetry (i.e., planar) in the gas phase and in solution using the polarized continuum model (PCM). The calculations predict that σ- and π-radical states in one electron oxidized bases of thymine, T(N3-H)•, and uracil, U(N3-H)• are very close in energy, i.e., the π-radical is only ca. 4 kcal/mol more stable than the σ-radical. For the one electron oxidized radicals of cytosine, C•+, C(N4-H)•, adenine, A•+, A(N6-H)•, and guanine, G•+, G(N2-H)•, G(N1-H)• the π-radicals are ca. 16 to 41 kcal/mol more stable than their corresponding σ-radicals. Inclusion of solvent (PCM) is found to stabilize the π- over σ-radical of each of the systems. U(N3-H)• with three discrete water molecules in the gas phase, is found to form a three-electron σ bond between N3 atom of uracil and O atom of a water molecule but on inclusion of full solvation and discrete hydration the π-radical remains most stable.. PMID:24000793

π- vs σ-radical states of one-electron-oxidized DNA/RNA bases: a density functional theory study.

PubMed

Kumar, Anil; Sevilla, Michael D

2013-10-03

As a result of their inherent planarity, DNA base radicals generated by one-electron oxidation/reduction or bond cleavage form π- or σ-radicals. While most DNA base systems form π-radicals, there are a number of nucleobase analogues such as one-electron-oxidized 6-azauraci1, 6-azacytosine, and 2-thiothymine or one-electron reduced 5-bromouracil that form more reactive σ-radicals. Elucidating the availability of these states within DNA, base radical electronic structure is important to the understanding of the reactivity of DNA base radicals in different environments. In this work, we address this question by the calculation of the relative energies of π- and σ-radical states in DNA/RNA bases and their analogues. We used density functional theory B3LYP/6-31++G** method to optimize the geometries of π- and σ-radicals in Cs symmetry (i.e., planar) in the gas phase and in solution using the polarized continuum model (PCM). The calculations predict that σ- and π-radical states in one-electron-oxidized bases of thymine, T(N3-H)(•), and uracil, U(N3-H)(•), are very close in energy; i.e., the π-radical is only ca. 4 kcal/mol more stable than the σ-radical. For the one-electron-oxidized radicals of cytosine, C(•+), C(N4-H)(•), adenine, A(•+), A(N6-H)(•), and guanine, G(•+), G(N2-H)(•), G(N1-H)(•), the π-radicals are ca. 16-41 kcal/mol more stable than their corresponding σ-radicals. Inclusion of solvent (PCM) is found to stabilize the π- over σ-radical of each of the systems. U(N3-H)(•) with three discrete water molecules in the gas phase is found to form a three-electron σ bond between the N3 atom of uracil and the O atom of a water molecule, but on inclusion of full solvation and discrete hydration, the π-radical remains most stable.

Role of ascorbic acid in stratum corneum lipid models exposed to UV irradiation.

PubMed

Trommer, Hagen; Böttcher, Roif; Pöppl, Andreas; Hoentsch, Joachim; Wartewig, Siegfried; Neubert, Reinhard H H

2002-07-01

The effects of ascorbic acid on Stratum corneum lipid models following ultraviolet irradiation were studied adding iron ions as transition metal catalysts. Lipid peroxidation was quantified by the thiobarbituric acid assay. The qualitative changes were studied on a molecular level by mass spectrometry. To elucidate the nature of free radical involvement we carried out electron paramagnetic resonance studies. The influence of ascorbic acid on the concentration of hydroxyl radicals was examined using the spin trapping technique. Moreover, we checked the vitamin's ability to react with stable radicals. Ascorbic acid was found to have prooxidative effects in all lipid systems in a concentration dependent manner. The degradation products of ascorbic acid after its prooxidative action were detected. The concentration of the hydroxyl radicals in the Fenton assay was decreased by ascorbic acid. The quantification assay of 2,2-diphenyl-1-picrylhydrazyl hydrate showed reduced concentration levels of the stable radical caused by ascorbic acid. Considering human skin and its constant exposure to UV light and oxygen, an increased pool of iron ions in irradiated skin and the depletion of co-antioxidants, the administration of ascorbic acid in cosmetic formulations or in sunscreens could unfold adverse effects among the Stratum corneum lipids.

Hydroxyl and Hydroperoxy Radical Chemistry during the MCMA-2006 Field Campaign: Measurement and Model Comparison

NASA Astrophysics Data System (ADS)

Dusanter, S.; Vimal, D.; Stevens, P. S.; Volkamer, R.; Molina, L. T.

2007-12-01

The Mexico City Metropolitan Area (MCMA) field campaign, held in March 2006, was a unique opportunity to collect data in one of the most polluted megacities in the world. Such environments exhibit a complex oxidation chemistry involving a strong coupling between odd hydrogen radicals (HOX=OH+HO2) and nitrogen oxides species (NOX=NO+NO2). High levels of volatile organic compounds (VOCs) and NOX control the HOX budget and lead to elevated tropospheric ozone formation. The HOX-NOX coupling can be investigated by comparing measured and model-predicted HOx concentrations. Atmospheric HOX concentrations were measured by the Indiana University laser-induced fluorescence instrument and data were collected at the Instituto Mexicano del Petroleo between 14 and 31 March. Measured hydroxyl radical (OH) concentrations are comparable to that measured in less polluted urban environments and suggest that the OH concentrations are highly buffered under high NOX conditions. In contrast, hydroperoxy radical (HO2) concentrations are more sensitive to the NOX levels and are highly variable between different urban sites. Enhanced levels of OH and HO2 radicals were observed on several days between 9h30-11h00 AM and suggest an additional HOX source for the morning hours and/or a fast HOX cycling under the high NOX conditions of the MCMA. A preliminary investigation of the HOX chemistry occurring in the MCMA urban atmosphere was performed using a photochemical box model based on the Regional Atmospheric Chemistry Mechanism (RACM). Model comparisons will be presented and the agreement between measured and predicted HOX concentrations will be discussed.

Potential of EPR spin-trapping to investigate in situ free radicals generation from skin allergens in reconstructed human epidermis: cumene hydroperoxide as proof of concept.

PubMed

Kuresepi, Salen; Vileno, Bertrand; Turek, Philippe; Lepoittevin, Jean-Pierre; Giménez-Arnau, Elena

2018-02-01

The first step in the development of skin sensitisation to a chemical, and in the elicitation of further allergic contact dermatitis (ACD), is the binding of the allergen to skin proteins after penetrating into the epidermis. The so-formed antigenic adduct is then recognised by the immune system as foreign to the body. Sensitising organic hydroperoxides derived from autoxidation of natural terpenes are believed to form antigens through radical-mediated mechanisms, although this has not yet been established. So far, in vitro investigations on reactive radical intermediates derived from these skin sensitisers have been conducted in solution, yet with experimental conditions being far away from real-life sensitisation. Herein, we report for the first time, the potential use of EPR spin-trapping to study the in situ generation of free radicals derived from cumene hydroperoxide CumOOH in a 3D reconstructed human epidermis (RHE) model, thus much closer to what may happen in vivo. Among the undesirable effects associated with dermal exposure to CumOOH, it is described to cause allergic and irritant dermatitis, being reported as a significant sensitiser. We considered exploiting the usage of spin-trap DEPMPO as an extensive view of all sort of radicals derived from CumOOH were observed all at once in solution. We showed that in the Episkin TM RHE model, both by incubating in the assay medium and by topical application, carbon radicals are mainly formed by redox reactions suggesting the key role of CumOOH-derived carbon radicals in the antigen formation process.

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

Inhibition effects of flavonoids on 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline and 2-amino-3,7,8-trimethylimidazo[4,5-f]quinoxaline formation and alkoxy radical scavenging capabilities of flavonoids in a model system.

PubMed

Shao, Zeping; Han, Zhonghui; Zhang, Jinhui; Zhang, Yan; Wang, Shuo

2018-06-01

Heterocyclic aromatic amines (HAAs) have been considered as carcinogenic and mutagenic chemicals generated during thermal processing of protein-rich foods that can be inhibited by some flavonoids. Free radical scavenging is a major characteristic of flavonoids. The half-maximal inhibitory concentration (IC 50 ) values of nine flavonoids were determined by evaluating their capacity to inhibit 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) and 2-amino-3,7,8-trimethylimidazo[4,5-f]quinoxaline (7,8-DiMeIQx) formation in a model system. The results of the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) test validated that MeIQx and 7,8-DiMeIQx formed via a free radical pathway. Electron spin resonance (ESR) spectroscopic analysis with spin trapping (α-(4-pyridyl N-oxide)-N-tert-butylnitrone (POBN) spin adduct, a N  = 15.2 G and a H  = 2.7 G) revealed that an alkoxy radical was the generated intermediate. The scavenging capacities of the nine flavonoids on alkoxy radicals were then evaluated based on the ESR spectra of the POBN spin adducts. The weak correlation between the alkoxy radical scavenging capacities and IC 50 of the flavonoids suggested that their inhibitory activity against MeIQx and 7,8-DiMeIQx formation operates by a more complex mechanism than simply scavenging alkoxy radicals. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Prevention of acetic acid-induced colitis by desferrithiocin analogs in a rat model.

PubMed

Bergeron, Raymond J; Wiegand, Jan; Weimar, William R; Nguyen, John Nhut; Sninsky, Charles A

2003-02-01

Iron contributes significantly to the formation of reactive oxygen species via the Fenton reaction. Therefore, we assessed whether a series of desferrithiocin analogs, both carboxylic acids and hydroxamates, could (1) either promote or diminish the iron-mediated oxidation of ascorbate, (2) quench a model radical species, 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS+), and (3) when applied topically, prevent acetic acid-induced colitis in rats. Surprisingly, most of the desferrithiocin analogs inhibited the Fenton reaction to an approximately equivalent degree; however, substantial differences were observed in the capacity of the analogs to scavenge the model radical cation. Four carboxylic acid desferrithiocin analogs and their respective N-methylhydroxamates were tested along with desferrioxamine and Rowasa, a currently accepted topical therapeutic agent for inflammatory bowel disease (IBD), in a rodent model of acetic acid-induced colitis. The colonic damage was quantitated by two independent measurements. Although neither radical scavenging nor prevention of Fenton chemistry was a definitive predictor of in vivo efficacy, the overall trend is that desferrithiocin analogs substituted with an N-methylhydroxamate in the place of the carboxylic acid are both better free radical scavengers and more active against acetic acid-induced colitis. These results represent an intriguing alternative avenue to the development of improved IBD therapeutic agents.

Health-related quality of life following radical prostatectomy: long-term outcomes.

PubMed

Matthew, Andrew G; Alibhai, Shabbir M H; Davidson, Tal; Currie, Kristen L; Jiang, Haiyan; Krahn, Murray; Fleshner, Neil E; Kalnin, Robin; Louis, Alyssa S; Davison, B Joyce; Trachtenberg, John

2014-10-01

To identify the health-related quality of life (HRQoL) domains that radical prostatectomy (RP) impacts most negatively and to define the recovery of these domains over 30 months of observation. A total of 1,200 RP patients completed the Patient-Oriented Prostate Utility Scale-Psychometric (PORPUS-P; range 0-100, higher is better), a prostate cancer-specific HRQoL measure, prior to RP and at 0-3 (T1), 3-9 (T2), 9-18 (T3) and 18-30 (T4) months post-RP. HRQoL changes were examined using paired t tests and a mixed-effect growth curve model. Multivariable analyses were performed to investigate demographic and treatment factors predicting the change in HRQoL. Mean baseline PORPUS-P score, 83.1, fell to 66.5 (p < 0.001) at T1. Over time HRQoL improved but did not return to baseline (T4 mean 76.4, p < 0.001). Domain analysis revealed that sexual function (p < 0.001), sexual drive (p < 0.001), energy (p = 0.001) and bladder control (p < 0.001) failed to return to baseline at T4. Sexual function demonstrated the greatest impairment overall. The multivariable model revealed Black men experienced greater losses in global HRQoL compared with White men (coefficient -2.77, 95% CI -5.00 to -0.54, p = 0.015). High baseline HRQoL, pro-erectile aid use and bilateral nerve-sparing were significantly associated with smaller reductions in HRQoL post-RP. Overall HRQoL, sexual drive, sexual function, energy and bladder control do not return to preoperative levels within 30 months post-RP. Black patients experience the greatest reductions in HRQoL. HRQoL losses may be ameliorated by use of pro-erectile aids. These findings help to identify at-risk patient populations and inform survivorship programs.

Photoelectrocatalytic degradation of methylene blue using F doped TiO2 photoelectrode under visible light irradiation.

PubMed

Liu, Dong; Tian, Renwen; Wang, Jianqiao; Nie, Er; Piao, Xianqing; Li, Xin; Sun, Zhuo

2017-10-01

Photoelectrocatalysis (PEC) has attracted great interest due to cost effectiveness and high efficiency in water treatment. In this study, F doped TiO 2 (F-TiO 2 ) photoelectrodes with honeycomb like morphology were prepared, and the PEC performance was investigated. F-TiO 2 particles that showed enhanced absorption of visible light were synthesized via a sol-gel method. F-TiO 2 particles were anchored onto the surface of F-doped SnO 2 glass by a screen-printing method to prepare the F-TiO 2 photoelectrodes. The PEC performance of the F-TiO 2 photoelectrodes was investigated via the degradation of methylene blue (MB) under visible light irradiation. The results show that the F-TiO 2 photoelectrodes exhibited an excellent PEC performance that was affected by the F doping content, applied bias and solution pH. A maximum decolorization percentage of 97.8% was achieved by the FT-15 photoelectrode, with a 1.4 V bias at pH 9.94 after 4.0 h of visible light irradiation. The high PEC performance of the F-TiO 2 photoelectrodes is mainly ascribed to the efficient separation of electron-hole (e - -h + ) pairs and the creation of active radicals such as hydroxyl radicals (OH). The PEC decolorization kinetic data were analyzed using the first-order kinetic model and the Langmuir-Hinshelwood (L-H) model. The data indicates that the PEC degradation of MB molecules mainly occurred on the surface of the F-TiO 2 photoelectrodes, and the MB molecules were discolored mainly by h + (41.5%) and OH (46.5%). In addition, 8.2% of the MB molecules were discolored by other oxidative species, and 3.8% of the MB molecules were discolored by self-sensitized oxidation. Copyright © 2017 Elsevier Ltd. All rights reserved.

A unifying view of the broad-spectrum antiviral activity of RSAD2 (viperin) based on its radical-SAM chemistry.

PubMed

Honarmand Ebrahimi, Kourosh

2018-04-25

RSAD2 (cig-5), also known as viperin (virus inhibitory protein, endoplasmic reticulum associated, interferon inducible), is a member of the radical S-adenosylmethionine (SAM) superfamily of enzymes. Since the discovery of this enzyme more than a decade ago, numerous studies have shown that it exhibits antiviral activity against a wide range of viruses. However, there is no clear picture demonstrating the mechanism by which RSAD2 restricts the replication process of different viruses, largely because there is no direct evidence describing its in vivo enzymatic activity. As a result, a multifunctionality model has emerged. According to this model the mechanism by which RSAD2 restricts replication of different viruses varies and in many cases is not dependent on the radical-SAM chemistry of RSAD2. If the radical-SAM activity of RSAD2 is not required for its antiviral function, the question worth asking is: why does the cellular defence mechanism induce the expression of the radical-SAM enzyme RSAD2, which is metabolically expensive due to the requirement for a [4Fe-4S] cluster and usage of SAM? Here, in contrast to the multifunctionality view, I put forward a unifying model. I postulate that the radical-SAM activity of RSAD2 modulates cellular metabolic pathways essential for viral replication and/or cell proliferation and survival. As a result, its catalytic activity restricts the replication of a wide range of viruses via a common cellular function. This view is based on recent discoveries hinting towards possible substrates of RSAD2, re-evaluation of previous studies regarding the antiviral activity of RSAD2, and accumulating evidence suggesting a role of human RSAD2 in the metabolic reprogramming of cells.

Ab initio study of the structural properties of ascorbic acid (vitamin C)

NASA Astrophysics Data System (ADS)

Allen, Reeshemah N.; Shukla, M. K.; Reed, Demarcio; Leszczynski, Jerzy

Geometries of the neutral and ionic tautomeric species of ascorbic acid were optimized at the density functional theory (DFT) level using the B3LYP functional. The radical species were evaluated using the unrestricted B3LYP method. Single-point energy calculations were also performed using the Møller-Plesset (MP2) and unrestricted MP2 (UMP2) methods for the closed-shell and open-shell systems, respectively. The effects of aqueous solution were evaluated using the conducting polarized continuum model (CPCM) and polarized continuum model (PCM). The geometries of most stable radicals in the respective groups were also optimized in the water solution using the CPCM model at the UB3LYP level. All calculation were performed using the 6-311++G(d,p) basis set. The nature of stationary points on the gas phase potential energy surfaces (PESs) was evaluated using vibrational frequency calculations; all geometries characterize local minima. The species obtained by the deprotonation of the O3 site is the most stable monoanion of ascorbic acid. For the radical species, the structure obtained by the dehydrogenation of the O3 site is the most stable monoradical. Among the radical anions, the species obtained by the deprotonation of the O3 site and subsequent dehydrogenation of the O2 site is the most stable in the gas phase and in an aqueous medium. The computed isotropic hyperfine coupling constants of this species were found to be in good agreement with the experimental data. Our investigation also supports the earlier findings that the oxidized species of ascorbic acid in water solution by the OH? radical is radical anion of the AAO?3O-2 form. The spin densities and molecular electrostatic potentials are also discussed.

On the complex •OH/•O--induced free radical chemistry of arylalkylamines with special emphasis on the contribution of the alkylamine side chain.

PubMed

Szabó, László; Mile, Viktória; Tóth, Tünde; Balogh, György T; Földes, Tamás; Takács, Erzsébet; Wojnárovits, László

2017-02-01

A full account of the • OH-induced free radical chemistry of an arylalkylamine is given taking all the possible reaction pathways quantitatively into consideration. Such knowledge is indispensable when the alkylamine side chain plays a crucial role in biological activity. The fundamental reactions are investigated on the model compound N-methyl-3-phenypropylamine (MPPA), and extended to its biologically active analog, to the antidepressant fluoxetine (FLX). Pulse radiolysis techniques were applied including redox titration and transient spectral analysis supplemented with DFT calculations. The contribution of the amine moiety to the free radical-induced oxidation mechanism appeared to be appreciable. • O - was used to observe hydrogen atom abstraction events at pH 14 giving rise to the strongly reducing α-aminoalkyl radicals (∼38% of the radical yield) and to benzyl (∼4%), β-aminoalkyl (∼24%), and aminyl radicals (∼31%) of MPPA. One-electron transfer was also observed yielding aminium radicals with low efficiency (∼3%). In the • OH-induced oxidation protonated α-aminoalkyl (∼49%), β-aminoalkyl (∼27%), benzyl radicals (∼4%), and aminium radicals (∼5%) are initially generated on the side chain of MPPA at pH 6, whereas hydroxycyclohexadienyl radicals (∼15%) were also produced. These initial events are followed by complex protonation-deprotonation reactions establishing acid-base equilibria; however, these processes are limited by the transient nature of the radicals and the kinetics of the ongoing reactions. The contribution of the radicals from the side chain alkylamine substituent of FLX totals up to ∼54% of the initially available oxidant yield.

Formation and implications of alpha-synuclein radical in Maneb- and paraquat-induced models of Parkinson’s disease

PubMed Central

Kumar, Ashutosh; Leinisch, Fabian; Kadiiska, Maria B.; Corbett, Jean; Mason, Ronald P.

2015-01-01

Parkinson’s disease (PD) is a debilitating, progressive, neurodegenerative disorder characterized by progressive loss of dopaminergic neurons and motor deficits. Alpha-synuclein-containing aggregates represent a feature of a variety of neurodegenerative disorders, including PD; however, the mechanism that initiates and promotes intraneuronal alpha-synuclein aggregation remains unknown. We hypothesized protein radical formation as an initiating mechanism for alpha-synuclein aggregation. Therefore, we used the highly sensitive immuno-spin trapping technique to investigate protein radical formation as a possible mechanism of alpha-synuclein aggregation as well as to investigate the source of protein radical formation in the midbrains of Maneb and paraquat coexposed mice. Coexposure to Maneb and paraquat for 6 weeks resulted in active microgliosis, NADPH oxidase activation, and inducible nitric oxide synthase (iNOS) induction, which culminated in protein radical formation in the midbrains of mice. Results obtained with immuno-spin trapping and immunoprecipitation experiments confirmed formation of alpha-synuclein radicals in dopaminergic neurons of exposed mice. Free radical formation requires NADPH oxidase and iNOS, as indicated by decreased protein radical formation in knockout mice (P47phox−/− and iNOS−/−) and in mice treated with inhibitors such as FeTPPS (a peroxynitrite decomposition catalyst), 1400W (an iNOS inhibitor), or apocynin (a NADPH oxidase inhibitor). Concurrence of protein radical formation with dopaminergic neuronal death indicated a link between protein radicals and disease progression. Taken together, these results show for the first time the formation and detection of the alpha-synuclein radical and suggest that NADPH oxidase and iNOS play roles in peroxynitrite-mediated protein radical formation and subsequent neuronal death in the midbrains of Maneb and paraquat coexposed mice. PMID:25952542

Strategies for generating peptide radical cations via ion/ion reactions.

PubMed

Gilbert, Joshua D; Fisher, Christine M; Bu, Jiexun; Prentice, Boone M; Redwine, James G; McLuckey, Scott A

2015-02-01

Several approaches for the generation of peptide radical cations using ion/ion reactions coupled with either collision induced dissociation (CID) or ultraviolet photo dissociation (UVPD) are described here. Ion/ion reactions are used to generate electrostatic or covalent complexes comprised of a peptide and a radical reagent. The radical site of the reagent can be generated multiple ways. Reagents containing a carbon-iodine (C-I) bond are subjected to UVPD with 266-nm photons, which selectively cleaves the C-I bond homolytically. Alternatively, reagents containing azo functionalities are collisionally activated to yield radical sites on either side of the azo group. Both of these methods generate an initial radical site on the reagent, which then abstracts a hydrogen from the peptide while the peptide and reagent are held together by either electrostatic interactions or a covalent linkage. These methods are demonstrated via ion/ion reactions between the model peptide RARARAA (doubly protonated) and various distonic anionic radical reagents. The radical site abstracts a hydrogen atom from the peptide, while the charge site abstracts a proton. The net result is the conversion of a doubly protonated peptide to a peptide radical cation. The peptide radical cations have been fragmented via CID and the resulting product ion mass spectra are compared to the control CID spectrum of the singly protonated, even-electron species. This work is then extended to bradykinin, a more broadly studied peptide, for comparison with other radical peptide generation methods. The work presented here provides novel methods for generating peptide radical cations in the gas phase through ion/ion reaction complexes that do not require modification of the peptide in solution or generation of non-covalent complexes in the electrospray process. Copyright © 2015 John Wiley & Sons, Ltd.

The cost-effectiveness of active surveillance compared to watchful waiting and radical prostatectomy for low risk localised prostate cancer.

PubMed

Lao, Chunhuan; Edlin, Richard; Rouse, Paul; Brown, Charis; Holmes, Michael; Gilling, Peter; Lawrenson, Ross

2017-08-08

Radical prostatectomy is the most common treatment for localised prostate cancer in New Zealand. Active surveillance was introduced to prevent overtreatment and reduce costs while preserving the option of radical prostatectomy. This study aims to evaluate the cost-effectiveness of active surveillance compared to watchful waiting and radical prostatectomy. Markov models were constructed to estimate the life-time cost-effectiveness of active surveillance compared to watchful waiting and radical prostatectomy for low risk localised prostate cancer patients aged 45-70 years, using national datasets in New Zealand and published studies including the SPCG-4 study. This study was from the perspective of the Ministry of Health in New Zealand. Radical prostatectomy is less costly than active surveillance in men aged 45-55 years with low risk localised prostate cancer, but more costly for men aged 60-70 years. Scenario analyses demonstrated significant uncertainty as to the most cost-effective option in all age groups because of the unavailability of good quality of life data for men under active surveillance. Uncertainties around the likelihood of having radical prostatectomy when managed with active surveillance also affect the cost-effectiveness of active surveillance against radical prostatectomy. Active surveillance is less likely to be cost-effective compared to radical prostatectomy for younger men diagnosed with low risk localised prostate cancer. The cost-effectiveness of active surveillance compared to radical prostatectomy is critically dependent on the 'trigger' for radical prostatectomy and the quality of life in men on active surveillance. Research on the latter would be beneficial.

Exploration of the kinetic and thermochemical abilities for the free radical scavenging of two quercetin conformers

NASA Astrophysics Data System (ADS)

Mendoza-Wilson, Ana María; Sotelo-Mundo, Rogerio R.; Balandrán-Quintana, René R.; Glossman-Mitnik, Daniel; Sántiz-gómez, Marco a.; García-orozco, karina D.

2010-09-01

Quercetin has a great antioxidant potential due to its large capacity for free radical scavenging. Although it has been found that conformational changes have a profound effect on its chemical properties, there are few studies where conformation is associated with the antioxidant activity. The aim of this investigation was to explore the kinetic and the thermochemical abilities of two quercetin conformers for the free radical scavenging. Quercetin unhydrate (QUH) and quercetin dihydrate (QDH) conformers were studied employing 2,2-diphenyl-1-picrylhydrazyl (DPPH rad ) as in vitro radical model, and catechol and 4-hexyl-resorcinol as reference systems, for identifying the oxidation products. QDH showed to be most effective under conditions of free radical excess, while QUH was most effective when the flavonoid far exceeds the concentration of free radical. It was found, by means of experimental and computational methods, that 4'-OH, 3-OH and 3'-OH are the main reactive sites of both conformers.

Free Radical Chemistry of Disinfection Byproducts 2: Rate Constants and Degradation Mechanism of Trichloronitromethane (Chloropicrin)

DOE Office of Scientific and Technical Information (OSTI.GOV)

B. J. Mincher; S. K. Cole; W. J. Cooper

2007-02-01

Absolute rate constants for the free-radical-induced degradation of trichloronitromethane (TCNM, chloropicrin) were determined using electron pulse radiolysis and transient absorption spectroscopy. Rate constants for hydroxyl radical, OH, and hydrated electron, eaq-, reactions were (4.97 ± 0.28) × 107 M-1 s-1 and (2.13 ± 0.03) × 1010 M-1 s-1, respectively. It appears that the OH adds to the nitro-group, while the eaq- reacts via dissociative electron attachment to give two carbon centered radicals. The mechanisms of these free radical reactions with TCNM were investigated, using 60Co gamma irradiation at various absorbed doses, measuring the disappearance of TCNM and the appearance ofmore » the product nitrate and chloride ions. The rate constants and mechanistic data were combined in a kinetic computer model that was used to describe the major free radical pathways for the destruction of TCNM in solution. These data are applicable to other advanced oxidation/reduction processes.« less

Influence of oxygen on the chemical stage of radiobiological mechanism

NASA Astrophysics Data System (ADS)

Barilla, Jiří; Lokajíček, Miloš V.; Pisaková, Hana; Simr, Pavel

2016-07-01

The simulation of the chemical stage of radiobiological mechanism may be very helpful in studying the radiobiological effect of ionizing radiation when the water radical clusters formed by the densely ionizing ends of primary or secondary charged particle may form DSBs damaging DNA molecules in living cells. It is possible to study not only the efficiency of individual radicals but also the influence of other species or radiomodifiers (mainly oxygen) being present in water medium during irradiation. The mathematical model based on Continuous Petri nets (proposed by us recently) will be described. It makes it possible to analyze two main processes running at the same time: chemical radical reactions and the diffusion of radical clusters formed during energy transfer. One may study the time change of radical concentrations due to the chemical reactions running during diffusion process. Some orientation results concerning the efficiency of individual radicals in DSB formation (in the case of Co60 radiation) will be presented; the influence of oxygen present in water medium during irradiation will be shown, too.

Electrochemiluminescence sensors for scavengers of hydroxyl radical based on its annihilation in CdSe quantum dots film/peroxide system.

PubMed

Jiang, Hui; Ju, Huangxian

2007-09-01

This work elucidated the detailed electrochemiluminescence (ECL) process of the thioglycolic acid-capped CdSe quantum dots (QDs) film/peroxide aqueous system. The QDs were first electrochemically reduced to form electrons-injected QDs approximately -1.1 V, which then reduced hydrogen peroxide to produce OH* radical. The intermediate OH* radical was a key species for producing holes-injected QDs. The ECL emission with a peak at -1.114 V was demonstrated to come from the 1Se-1Sh transition emission. Using thiol compounds as the model molecules to annihilate the OH* radical, their quenching effects on ECL emission were studied. This effect led to a novel strategy for ECL sensing of the scavengers of hydroxyl radical. The detection results of thiol compounds showed high sensitivity, good precision, and acceptable accuracy, suggesting the promising application of the proposed method for quick detection of both scavengers and generators of hydroxyl radical in different fields.

Experimental congruence of interval scale production from paired comparisons and ranking for image evaluation

NASA Astrophysics Data System (ADS)

Handley, John C.; Babcock, Jason S.; Pelz, Jeff B.

2003-12-01

Image evaluation tasks are often conducted using paired comparisons or ranking. To elicit interval scales, both methods rely on Thurstone's Law of Comparative Judgment in which objects closer in psychological space are more often confused in preference comparisons by a putative discriminal random process. It is often debated whether paired comparisons and ranking yield the same interval scales. An experiment was conducted to assess scale production using paired comparisons and ranking. For this experiment a Pioneer Plasma Display and Apple Cinema Display were used for stimulus presentation. Observers performed rank order and paired comparisons tasks on both displays. For each of five scenes, six images were created by manipulating attributes such as lightness, chroma, and hue using six different settings. The intention was to simulate the variability from a set of digital cameras or scanners. Nineteen subjects, (5 females, 14 males) ranging from 19-51 years of age participated in this experiment. Using a paired comparison model and a ranking model, scales were estimated for each display and image combination yielding ten scale pairs, ostensibly measuring the same psychological scale. The Bradley-Terry model was used for the paired comparisons data and the Bradley-Terry-Mallows model was used for the ranking data. Each model was fit using maximum likelihood estimation and assessed using likelihood ratio tests. Approximate 95% confidence intervals were also constructed using likelihood ratios. Model fits for paired comparisons were satisfactory for all scales except those from two image/display pairs; the ranking model fit uniformly well on all data sets. Arguing from overlapping confidence intervals, we conclude that paired comparisons and ranking produce no conflicting decisions regarding ultimate ordering of treatment preferences, but paired comparisons yield greater precision at the expense of lack-of-fit.

Carbon Tetrachloride at Hepatotoxic Levels Blocks Reversibly Gap Junctions between Rat Hepatocytes

NASA Astrophysics Data System (ADS)

Saez, J. C.; Bennett, M. V. L.; Spray, D. C.

1987-05-01

Electrical coupling and dye coupling between pairs of rat hepatocytes were reversibly reduced by brief exposure to halogenated methanes (CBrCl3, CCl4, and CHCl3). The potency of different halomethanes in uncoupling hepatocytes was comparable to their hepatotoxicity in vivo, and the rank order was the same as that of their tendency to form free radicals. The effect of carbon tetrachloride (CCl4) on hepatocytes was substantially reduced by prior treatment with SKF 525A, an inhibitor of cytochrome P-450, and by exposure to the reducing reagent β -mercaptoethanol. Halomethane uncoupling occurred with or without extracellular calcium and did not change intracellular concentrations of calcium and hydrogen ions or the phosphorylation state of the main gap-junctional protein. Thus the uncoupling appears to depend on cytochrome P-450 oxidative metabolism in which free radicals are generated and may result from oxidation of the gap-junctional protein or of a regulatory molecule that leads to closure of gap-junctional channels. Decreases in junctional conductance may be a rapid cellular response to injury that protects healthy cells by uncoupling them from unhealthy ones.

Giant coercivity and high magnetic blocking temperatures for N 2 3- radical-bridged dilanthanide complexes upon ligand dissociation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Demir, Selvan; Gonzalez, Miguel I.; Darago, Lucy E.

Increasing the operating temperatures of single-molecule magnets—molecules that can retain magnetic polarization in the absence of an applied field—has potential implications toward information storage and computing, and may also inform the development of new bulk magnets. Progress toward these goals relies upon the development of synthetic chemistry enabling enhancement of the thermal barrier to reversal of the magnetic moment, while suppressing alternative relaxation processes. Here in this paper, we show that pairing the axial magnetic anisotropy enforced by tetramethylcyclopentadienyl (Cp Me4H) capping ligands with strong magnetic exchange coupling provided by an N 2 3- radical bridging ligand results in amore » series of dilanthanide complexes exhibiting exceptionally large magnetic hysteresis loops that persist to high temperatures. Significantly, reducing the coordination number of the metal centers appears to increase axial magnetic anisotropy, giving rise to larger magnetic relaxation barriers and 100-s magnetic blocking temperatures of up to 20 K, as observed for the complex [K(crypt-222)][(Cp Me4H 2Tb) 2(μ-N∙ 2« less

Mulliken Hush elucidation of the encounter (precursor) complex in intermolecular electron transfer via self-exchange of tetracyanoethylene anion-radical

NASA Astrophysics Data System (ADS)

Rosokha, S. V.; Newton, M. D.; Head-Gordon, M.; Kochi, J. K.

2006-05-01

The paramagnetic [1:1] encounter complex (TCNE)2-rad is established as the important precursor in the kinetics and mechanism of electron-transfer for the self-exchange between tetracyanoethylene acceptor ( TCNE) and its radical-anion as the donor. Spectroscopic observation of the dimeric complex (TCNE)2-rad by its intervalence absorption band at the solvent-dependent wavelength of λIV ˜ 1500 nm facilitates the application of Mulliken-Hush theory which reveals the significant electronic interaction extant between the pair of cofacial TCNE moieties with the sizable coupling of HDA = 1000 cm -1. The transient existence of such an encounter complex provides the critical link in the electron-transfer kinetics by lowering the classical Marcus reorganization barrier by the amount of HDA in this strongly adiabatic system. Ab initio quantum-mechanical methods as applied to independent theoretical computations of both the reorganization energy ( λ) and the electronic coupling element ( HDA) confirm the essential correctness of the Mulliken-Hush formalism for fast electron transfer via strongly coupled donor/acceptor encounter complexes.

Giant coercivity and high magnetic blocking temperatures for N 2 3- radical-bridged dilanthanide complexes upon ligand dissociation

DOE PAGES

Demir, Selvan; Gonzalez, Miguel I.; Darago, Lucy E.; ...

2017-12-15

Increasing the operating temperatures of single-molecule magnets—molecules that can retain magnetic polarization in the absence of an applied field—has potential implications toward information storage and computing, and may also inform the development of new bulk magnets. Progress toward these goals relies upon the development of synthetic chemistry enabling enhancement of the thermal barrier to reversal of the magnetic moment, while suppressing alternative relaxation processes. Here in this paper, we show that pairing the axial magnetic anisotropy enforced by tetramethylcyclopentadienyl (Cp Me4H) capping ligands with strong magnetic exchange coupling provided by an N 2 3- radical bridging ligand results in amore » series of dilanthanide complexes exhibiting exceptionally large magnetic hysteresis loops that persist to high temperatures. Significantly, reducing the coordination number of the metal centers appears to increase axial magnetic anisotropy, giving rise to larger magnetic relaxation barriers and 100-s magnetic blocking temperatures of up to 20 K, as observed for the complex [K(crypt-222)][(Cp Me4H 2Tb) 2(μ-N∙ 2« less

Photon and neutral pion production in Au+Au collisions at {radical}s{sub NN} = 130 GeV

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adams, J.; Adler, C.; Aggarwal, M.M.

2004-01-08

We report the first inclusive photon measurements about mid-rapidity (|y| < 0.5) from {sup 197}Au + {sup 197}Au collisions at {radical}s{sub NN} = 130 GeV at RHIC. Photon pair conversions were reconstructed from electron and positron tracks measured with the Time Projection Chamber (TPC) of the STAR experiment. With this method, an energy resolution of {Delta}E/E {approx} 2% at 0.5 GeV has been achieved. Reconstructed photons have also been used to measure the transverse momentum (p{sub t}) spectra of {pi}{sup 0} mesons about mid-rapidity (|y| < 1) via the {pi}{sup 0} {yields} {gamma}{gamma} decay channel. The fractional contribution of themore » {pi}{sup 0} {yields} {gamma}{gamma} decay to the inclusive photon spectrum decreases by 20% {+-} 5% between p{sub t} = 1.65 GeV/c and p{sub t} = 2.4 GeV/c in the most central events, indicating that relative to {pi}{sup 0} {yields} {gamma}{gamma} decay the contribution of other photon sources is substantially increasing.« less

Cu-modified alkalinized g-C3N4 as photocatalytically assisted heterogeneous Fenton-like catalyst

NASA Astrophysics Data System (ADS)

Dong, Qimei; Chen, Yingying; Wang, Lingli; Ai, Shasha; Ding, Hanming

2017-12-01

Alkalinized graphitic carbon nitride (CNK-OH) has been synthesized by one-step thermal poly-condensation method, and Cu-modified alkalinized g-C3N4 (Cu-CNK-OH) has been prepared by impregnation approach over CNK-OH. These copper species in Cu-CNK-OH are embedded in the frame of CNK-OH mostly via the Cu-N bonds. Cu-CNK-OH has been employed as a heterogeneous Fenton-like catalyst to degrade rhodamine B (RhB). Both the production efficiency of hydroxyl radicals and the transformation rate of Cu(II)/Cu(I) redox pair increase under visible-light irradiation. As a result, Cu-CNK-OH exhibits improved Fenton-like catalytic activity on the degradation of RhB. The synergetic interaction between Fenton-like process and photocatalytic process also contributes such improvement. The hydroxyl radicals and holes are the major reactive species in the photocatalytically assisted Fenton-like process. This study provides a valuable strategy for metal modification of alkalinized g-C3N4 with enhanced Fenton-like catalytic performance for the degradation of organic contaminants.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nikitin, N. V., E-mail: nnikit@mail.cern.ch; Sotnikov, V.P., E-mail: sotnikov@physics.msu.ru; Toms, K. S., E-mail: ktoms@mail.cern.ch

A radically new class of Bell inequalities in Wigner’s form was obtained on the basis of Kolmorov’s axiomatization of probability theory and the hypothesis of locality. These inequalities take explicitly into account the dependence on time (time-dependent Bell inequalities in Wigner’s form). By using these inequalities, one can propose a means for experimentally testing Bohr’ complementarity principle in the relativistic region. The inequalities in question open broad possibilities for studying correlations of nonrelativistic and relativistic quantum systems in external fields. The violation of the time-dependent inequalities in quantum mechanics was studied by considering the behavior of a pair of anticorrelatedmore » spins in a constant external magnetic field and oscillations of neutral pseudoscalar mesons. The decay of a pseudoscalar particle to a fermion–antifermion pair is considered within quantum field theory. In order to test experimentally the inequalities proposed in the present study, it is not necessary to perform dedicated noninvasive measurements required in the Leggett–Garg approach, for example.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li Zhiming; Radboud University/NIKHEF, NL-6525 ED Nijmegen

We report on an entropy analysis using Ma's coincidence method on {pi}+p and K+p collisions at {radical}(s) = 22 GeV. A scaling law and additivity properties of Renyi entropies and their charged-particle multiplicity dependence are investigated. The results are compared with those from the PYTHIA Monte Carlo model.

Open conversion during minimally invasive radical prostatectomy: impact on perioperative complications and predictors from national data.

PubMed

Sharma, Vidit; Meeks, Joshua J

2014-12-01

Despite the increased use of minimally invasive radical prostatectomy, open conversion may occur due to surgical complications, surgeon inexperience or failure to progress. We used nationally representative data to quantify the impact of open conversion compared to nonconverted minimally invasive radical prostatectomy and open radical prostatectomy, and identify predictors of open conversion. Years 2004 to 2010 of the Nationwide Inpatient Sample were queried for patients who underwent radical prostatectomy to analyze the association of open conversion during minimally invasive radical prostatectomy with Clavien complications. Multivariate regression models yielded significant predictors of open conversion. From 2004 to 2010, 134,398 (95% CI 111,509-157,287) minimally invasive radical prostatectomies were performed with a 1.8% (95% CI 1.4-2.1) open conversion rate, translating to 2,360 (95% CI 2,001-2,720) conversions. Open conversion cases had a longer length of stay (4.17 vs 1.71 days, p <0.001) and higher hospital charges ($51,049 vs $37,418, p <0.001) than nonconverted cases. Of open conversion cases 45.2% experienced a complication vs 7.2% and 12.9% of minimally invasive radical prostatectomy and open radical prostatectomy cases, respectively (p <0.001). After adjusting for age and comorbidities, open conversion was associated with significantly increased odds of a Clavien grade 1, 2, 3 and 4 complication compared to nonconverted minimally invasive radical prostatectomy and open radical prostatectomy (OR range 2.913 to 15.670, p <0.001). Significant multivariate predictors of open conversion were obesity (OR 1.916), adhesions (OR 3.060), anemia (OR 5.692) and surgeon volume for minimally invasive radical prostatectomy less than 25 cases per year (OR 7.376) (all p <0.01). Open conversion during minimally invasive radical prostatectomy is associated with a higher than expected increase in complications compared to open radical prostatectomy and minimally invasive radical prostatectomy after adjusting for age and comorbidities. External validation of predictors of open conversion may prove useful in minimizing open conversion during minimally invasive radical prostatectomy. Copyright © 2014 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Scavenging of free-radical metabolites of aniline xenobiotics and drugs by amino acid derivatives: toxicological implications of radical-transfer reactions.

PubMed

Michail, Karim; Baghdasarian, Argishti; Narwaley, Malyaj; Aljuhani, Naif; Siraki, Arno G

2013-12-16

We investigated a novel scavenging mechanism of arylamine free radicals by poly- and monoaminocarboxylates. Free radicals of arylamine xenobiotics and drugs did not react with oxygen in peroxidase-catalyzed reactions; however, they showed marked oxygen uptake in the presence of an aminocarboxylate. These free-radical intermediates were identified using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and electron paramagnetic resonance (EPR) spectrometry. Diethylenetriaminepentaacetic acid (DTPA), a polyaminocarboxylate, caused a concentration-dependent attenuation of N-centered radicals produced by the peroxidative metabolism of arylamines with the subsequent formation of secondary aliphatic carbon-centered radicals stemming from the cosubstrate molecule. Analogously, N,N-dimethylglycine (DMG) and N-methyliminodiacetate (MIDA), but not iminodiacetic acid (IDA), demonstrated a similar scavenging effect of arylamine-derived free radicals in a horseradish peroxidase/H2O2 system. Using human promyelocytic leukemia (HL-60) cell lysate as a model of human neutrophils, DTPA, MIDA, and DMG readily reduced anilinium cation radicals derived from the arylamines and gave rise to the corresponding carbon radicals. The rate of peroxidase-triggered polymerization of aniline was studied as a measure of nitrogen-radical scavenging. Although, IDA had no effect on the rate of aniline polymerization, this was almost nullified in the presence of DTPA and MIDA at half of the molar concentration of the aniline substrate, whereas a 20 molar excess of DMPO caused only a partial inhibition. Furthermore, the yield of formaldehyde, a specific reaction endproduct of the oxidation of aminocarboxylates by aniline free-radical metabolites, was quantitatively determined. Azobenzene, a specific reaction product of peroxidase-catalyzed free-radical dimerization of aniline, was fully abrogated in the presence of DTPA, as confirmed by GC/MS. Under aerobic conditions, a radical-transfer reaction is proposed between aminocarboxylates and arylamine free radicals via the carboxylic group-linked tertiary nitrogen of the deprotonated amino acid derivatives. These findings may have significant implications for the biological fate of arylamine xenobiotic and drug free-radical metabolites.

Measurement of free radicals using electron paramagnetic resonance spectroscopy during open aorto-iliac arterial reconstruction.

PubMed

Majewski, Wacław; Krzyminiewski, Ryszard; Stanisić, Michał; Iskra, Maria; Krasiński, Zbigniew; Nowak, Marek; Dobosz, Bernadeta

2014-11-27

Aortic cross-clamping during abdominal aortic aneurysm (AAA) open repair leads to development of ischemia-reperfusion injury. Electron paramagnetic resonance spectroscopy (EPR) spin-trapping is a valuable method of direct measurement of free radicals. The objective of the study was to evaluate the results of EPR as a direct method of free radical measurement and degree of inflammatory response in open operative treatment of patients with AAA and aorto-iliac occlusive disease (AIOD). The study was performed on a group of 32 patients with AAA and 25 patients with AIOD scheduled for open repair. Peripheral venous blood for EPR spectroscopy and for SOD, GPx, ox-LDL, Il-6, TNF-alfa, CRP, and HO-1 were harvested. Selected parameters were established accordingly to specified EPR and immunohistochemical methods and analyzed between groups by Mann-Whitney U test and Wilcoxon matched-pairs signed-ranks test with Bonferroni correction. Free radicals level was correlated with the time of the aortic cross-clamping after the reperfusion of he first and second leg in AAA (r=0.7; r=0.47). ox-LDL in AAA decreased 5 min after reperfusion of the first leg (32.99 U/L, range: 14.09-77.12) and 5 min after reperfusion of the second leg (26.75 U/L, range: 11.56-82.12) and 24 h after the operation (25.85 U/L, range: 14.29-49.70). HO-1 concentration increased to above the level before intervention 24 h after surgery. The activities of GPx and SOD decreased 5 min after the first-leg reperfusion in AAA. Twenty-four hours after surgery, inflammatory markers increased in AAA to CRP was 14.76 ml/l (0.23-38.55), IL-6 was 141.22 pg/ml (84.3-591.03), TNF-alfa was 6.82 pg/ml (1.76-80.01) and AIOD: CRP was 18.44 mg/l (2.56-33.14), IL-6: 184.1 pg/ml (128.46-448.03), TNF-alfa was 7.74 pg/ml (1.74-74.74). EPR spin-trapping demonstrates temporarily elevated level of free radicals in early phase of reperfusion, leading to decrease antioxidants in AAA. Elevated free radical levels decreased 24 h after surgery due to various endogenous antioxidants and therapies.

Photoreduction of Azoalkanes by Direct Hydrogen Abstraction from 1,4-Cyclohexadiene, Alcohols, Stannanes, and Silanes.

PubMed

Adam, Waldemar; Moorthy, Jarugu N.; Nau, Werner M.; Scaiano, J. C.

1997-11-14

A mechanistic investigation of the photoreduction of the n,pi triplet-excited azo chromophore has been carried out on azoalkanes 1, which exhibit efficient intersystem-crossing quantum yields (ca. 0.5). The azoalkanes 1a and 1b undergo facile photoreduction to the corresponding hydrazines in the presence of a variety of hydrogen donors, which include 2-propanol, benzhydrol, 1,4-cyclohexadiene, tributylstannane, and tris(trimethylsilyl)silane. In contrast, the hydrazine yields derived for the azoalkanes 1c and 1d are significantly lower even at high hydrogen donor concentrations due to their lower triplet yields and shorter triplet lifetimes. A clear dependence of the hydrazine yields on the bond dissociation energies of the hydrogen donors has been observed, which is reflected in the quenching rate constants obtained from time-resolved transient absorption spectroscopy. The absolute rate constants for interaction of the triplet azoalkane 1a with hydrogen donors are generally lower (ca. 10-100-fold) than for benzophenone, in line with the less favorable reaction thermodynamics. The comparison of the rate constants for quenching of the triplet-excited azoalkane 1a and of the singlet-excited state of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) reveals a similar reactivity of excited azoalkanes toward hydrogen donors; differences can be accounted for in terms of variations in the energies of the excited states. The interactions of the excited azoalkanes with tributylstannane and benzhydrol produce the radicals characteristic for hydrogen abstraction from these substrates, namely tributylstannyl and hydroxydiphenylmethyl radicals, which were detected through their transient absorptions at 390 and 550 nm, respectively. Interestingly, compared to the photoreduction of benzophenone with benzhydrol, for which the quantum yield for conversion to radicals is unity, between the azoalkane 1a and benzhydrol this efficiency is only ca. 12%. An associative effect through N.H-O bonding is held responsible, which promotes hydrogen transfer versus diffusion out of the caged radical pair. The quenching of the singlet-excited DBO by toluene was also employed to monitor the formation of benzyl radicals (at 317 nm). The photolysis of DBO in tetrahydrofuran as solvent and quencher produced an absorption at ca. 290 nm, which was tentatively assigned to the corresponding hydrazinyl radical.

Interactions of short-acting, intermediate-acting and pre-mixed human insulins with free radicals--Comparative EPR examination.

PubMed

Olczyk, Paweł; Komosinska-Vassev, Katarzyna; Ramos, Paweł; Mencner, Łukasz; Olczyk, Krystyna; Pilawa, Barbara

2015-07-25

Electron paramagnetic resonance (EPR) spectroscopy was used to examine insulins interactions with free radicals. Human recombinant DNA insulins of three groups were studied: short-acting insulin (Insuman Rapid); intermediate-acting insulins (Humulin N, Insuman Basal), and pre-mixed insulins (Humulin M3, Gensulin M50, Gensulin M40, Gensulin M30). The aim of an X-band (9.3GHz) study was comparative analysis of antioxidative properties of the three groups of human insulins. DPPH was used as a stable free radical model. Amplitudes of EPR lines of DPPH as the paramagnetic free radical reference, and DPPH interacting with the individual tested insulins were compared. For all the examined insulins kinetics of their interactions with free radicals up to 60 min were obtained. The strongest interactions with free radicals were observed for the short-acting insulin - Insuman Rapid. The lowest interactions with free radicals were characteristic for intermediate-acting insulin - Insuman Basal. The pre-mixed insulins i.e. Humulin M3 and Gensulin M50 revealed the fastest interactions with free radicals. The short acting, intermediate acting and premixed insulins have been found to be effective agents in reducing free radical formation in vitro and should be further considered as potential useful tools in attenuation of oxidative stress in diabetic patients. Copyright © 2015 Elsevier B.V. All rights reserved.

Efficient, environmentally-friendly and specific valorization of lignin: promising role of non-radical lignolytic enzymes.

PubMed

Wang, Wenya; Zhang, Chao; Sun, Xinxiao; Su, Sisi; Li, Qiang; Linhardt, Robert J

2017-06-01

Lignin is the second most abundant bio-resource in nature. It is increasingly important to convert lignin into high value-added chemicals to accelerate the development of the lignocellulose biorefinery. Over the past several decades, physical and chemical methods have been widely explored to degrade lignin and convert it into valuable chemicals. Unfortunately, these developments have lagged because of several difficulties, of which high energy consumption and non-specific cleavage of chemical bonds in lignin remain the greatest challenges. A large number of enzymes have been discovered for lignin degradation and these are classified as radical lignolytic enzymes and non-radical lignolytic enzymes. Radical lignolytic enzymes, including laccases, lignin peroxidases, manganese peroxidases and versatile peroxidases, are radical-based bio-catalysts, which degrade lignins through non-specific cleavage of chemical bonds but can also catalyze the radical-based re-polymerization of lignin fragments. In contrast, non-radical lignolytic enzymes selectively cleave chemical bonds in lignin and lignin model compounds and, thus, show promise for use in the preparation of high value-added chemicals. In this mini-review, recent developments on non-radical lignolytic enzymes are discussed. These include recently discovered non-radical lignolytic enzymes, their metabolic pathways for lignin conversion, their recent application in the lignin biorefinery, and the combination of bio-catalysts with physical/chemical methods for industrial development of the lignin refinery.

Confirmed Assignments of Isomeric Dimethylbenzyl Radicals Generated by Corona Discharge

NASA Astrophysics Data System (ADS)

Yoon, Young Wook; Lee, Sang Kuk

2012-06-01

Polymethylbenzyl radicals, multi-methyl-substituted benzyl radicals, have been believed to be an ideal model for understanding the torsional effect of methyl group and substitution effect on electronic transition. These radicals are mainly generated from polymethylbenzenes by electric discharge for spectroscopic observation. However, the existence of several methyl groups on the benzene ring may produce several isomeric polymethylbenzyl radicals by removing one of the C-H bonds of each methyl group at different substitution position, which makes the assignment of spectrum ambiguous. In this work, the controversial vibronic assignments of isomeric dimethylbenzyl radicals were clearly resolved by using different precursors. By using corresponding dimethylbenzyl chlorides as precursors, we identified the origins of the vibronic bands of the dimethylbenzyl radicals generated by corona discharge of precursors 1,2,3- and 1,2,4-trimethylbenzenes. From the analysis of the spectra observed from the dimethylbenzyl chlorides in a corona excited supersonic expansion using a pinhole-type glass nozzle, we revised previous assignments of the 2,6- and 2,3-dimethylbenzyl radicals as well as the 3,4-, 2,4-, and 2,5-dimethylbenzyl radicals. In addition, spectroscopic data of electronic transition and vibrational mode frequencies in the ground electronic state of each isomer were accurately determined by comparing them with those obtained by an ab initio calculation and with the known vibrational data of precursors.

The time-course of lexical activation in Japanese morphographic word recognition: evidence for a character-driven processing model.

PubMed

Miwa, Koji; Libben, Gary; Dijkstra, Ton; Baayen, Harald

2014-01-01

This lexical decision study with eye tracking of Japanese two-kanji-character words investigated the order in which a whole two-character word and its morphographic constituents are activated in the course of lexical access, the relative contributions of the left and the right characters in lexical decision, the depth to which semantic radicals are processed, and how nonlinguistic factors affect lexical processes. Mixed-effects regression analyses of response times and subgaze durations (i.e., first-pass fixation time spent on each of the two characters) revealed joint contributions of morphographic units at all levels of the linguistic structure with the magnitude and the direction of the lexical effects modulated by readers' locus of attention in a left-to-right preferred processing path. During the early time frame, character effects were larger in magnitude and more robust than radical and whole-word effects, regardless of the font size and the type of nonwords. Extending previous radical-based and character-based models, we propose a task/decision-sensitive character-driven processing model with a level-skipping assumption: Connections from the feature level bypass the lower radical level and link up directly to the higher character level.

Radiation damage to DNA in DNA-protein complexes.

PubMed

Spotheim-Maurizot, M; Davídková, M

2011-06-03

The most aggressive product of water radiolysis, the hydroxyl (OH) radical, is responsible for the indirect effect of ionizing radiations on DNA in solution and aerobic conditions. According to radiolytic footprinting experiments, the resulting strand breaks and base modifications are inhomogeneously distributed along the DNA molecule irradiated free or bound to ligands (polyamines, thiols, proteins). A Monte-Carlo based model of simulation of the reaction of OH radicals with the macromolecules, called RADACK, allows calculating the relative probability of damage of each nucleotide of DNA irradiated alone or in complexes with proteins. RADACK calculations require the knowledge of the three dimensional structure of DNA and its complexes (determined by X-ray crystallography, NMR spectroscopy or molecular modeling). The confrontation of the calculated values with the results of the radiolytic footprinting experiments together with molecular modeling calculations show that: (1) the extent and location of the lesions are strongly dependent on the structure of DNA, which in turns is modulated by the base sequence and by the binding of proteins and (2) the regions in contact with the protein can be protected against the attack by the hydroxyl radicals via masking of the binding site and by scavenging of the radicals. 2011 Elsevier B.V. All rights reserved.

Modelling radicalization: how small violent fringe sects develop into large indoctrinated societies

PubMed Central

2017-01-01

We model radicalization in a society consisting of two competing religious, ethnic or political groups. Each of the ‘sects’ is divided into moderate and radical factions, with intra-group transitions occurring either spontaneously or through indoctrination. We also include the possibility of one group violently attacking the other. The intra-group transition rates of one group are modelled to explicitly depend on the actions and characteristics of the other, including violent episodes, effectively coupling the dynamics of the two sects. We use a game theoretic framework and assume that radical factions may tune ‘strategic’ parameters to optimize given utility functions aimed at maximizing their ranks while minimizing the damage inflicted by their rivals. Constraints include limited overall resources that must be optimally allocated between indoctrination and external attacks on the other group. Various scenarios are considered, from symmetric sects whose behaviours mirror each other, to totally asymmetric ones where one sect may have a larger population or a superior resource availability. We discuss under what conditions sects preferentially employ indoctrination or violence, and how allowing sects to readjust their strategies allows for small, violent sects to grow into large, indoctrinated communities. PMID:28879010

Modelling radicalization: how small violent fringe sects develop into large indoctrinated societies

NASA Astrophysics Data System (ADS)

Short, Martin B.; McCalla, Scott G.; D'Orsogna, Maria R.

2017-08-01

We model radicalization in a society consisting of two competing religious, ethnic or political groups. Each of the `sects' is divided into moderate and radical factions, with intra-group transitions occurring either spontaneously or through indoctrination. We also include the possibility of one group violently attacking the other. The intra-group transition rates of one group are modelled to explicitly depend on the actions and characteristics of the other, including violent episodes, effectively coupling the dynamics of the two sects. We use a game theoretic framework and assume that radical factions may tune `strategic' parameters to optimize given utility functions aimed at maximizing their ranks while minimizing the damage inflicted by their rivals. Constraints include limited overall resources that must be optimally allocated between indoctrination and external attacks on the other group. Various scenarios are considered, from symmetric sects whose behaviours mirror each other, to totally asymmetric ones where one sect may have a larger population or a superior resource availability. We discuss under what conditions sects preferentially employ indoctrination or violence, and how allowing sects to readjust their strategies allows for small, violent sects to grow into large, indoctrinated communities.

In silico modelling of thiazolidine derivatives with antioxidant potency: Models quantify the degree of contribution of molecular fragments towards the free radical scavenging ability

NASA Astrophysics Data System (ADS)

De, Biplab; Adhikari, Indrani; Nandy, Ashis; Saha, Achintya; Goswami, Binoy Behari

2017-06-01

Design and development of antioxidant supplements constitute an essential aspect of research in order to derive molecules that would help to combat the free radical invasion to the human body and curb oxidative stress related diseases. The present work deals with the development of in silico models for a series of thiazolidine derivatives having antioxidant potential. The objective of the work is to obtain models that would help to design new thazolidine derivatives based on substituent modification and thereby predict their activity profile. The QSAR model thus developed helps in quantification of the extent of contribution of the various molecular fragments towards the activity of the molecules, while the 3D pharmacophore model provides a brief idea of the essential molecular features that help the molecules to interact with the neighbouring free radicals. Both the models have been extensively validated which ensures their predictive ability as well the potential to search molecular databases for selection of thiazolidine derivatives with potent antioxidant activity. The models can thus be utilised effectively for database searching with the aim to isolate active antioxidants belonging to the thiazolidine group.

Addition and hydrogen abstraction reactions of an OH radical with 8-oxoguanine

NASA Astrophysics Data System (ADS)

Jena, N. R.; Mishra, P. C.

2006-05-01

Addition reaction of an OH radical at the C2, C4, C5 or C8 position of 8-oxoguanine (8OG) and abstraction of its H9 atom by an OH radical were studied using density functional theory (B3LYP) employing 6-31G ∗∗, 6-311++G ∗∗ and AUG-cc-pVDZ basis sets. Solvent effects of aqueous media were treated using the PCM model. It is found that the addition of an OH radical at the C4 position of 8OG would be most favored in both gas phase and aqueous media. These addition and abstraction reactions in aqueous media are both found to be barrierless.

A modified method for studying behavioral paradox of antioxidants and their disproportionate competitive kinetic effect to scavenge the peroxyl radical formation.

PubMed

Masood, Nusrat; Fatima, Kaneez; Luqman, Suaib

2014-01-01

We have described a modified method for evaluating inhibitor of peroxyl radicals, a well-recognized and -documented radical involved in cancer initiation and promotion as well as diseases related to oxidative stress and ageing. We are reporting hydrophilic and lipophilic as well as natural and synthetic forms of antioxidants revealing a diversified behaviour to peroxyl radical in a dose-dependent manner (1 nM-10 μM). A simple kinetic model for the competitive oxidation of an indicator molecule (ABTS) and a various antioxidant by a radical (ROO(•)) is described. The influences of both the concentration of antioxidant and duration of reaction (70 min) on the inhibition of the radical cation absorption are taken into account while determining the activity. The induction time of the reaction was also proposed as a parameter enabling determination of antioxidant content by optimizing and introducing other kinetic parameters in 96-well plate assays. The test evidently improves the original PRTC (peroxyl radical trapping capacity) assay in terms of the amount of chemical used, simultaneous tracking, that is, the generation of the radical taking place continually and the kinetic reduction technique (area under curve, peak value, slope, and Vmax).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Acosta, D.; Affolder, Anthony A.; Albrow, M.G.

The authors have measured the azimuthal angular correlation of b{bar b} production, using 86.5 pb{sup -1} of data collected by Collider Detector at Fermilab (CDF) in p{bar p} collisions at {radical}s = 1.8 TeV during 1994-1995. In high-energy p{bar p} collisions, such as at the Tevatron, b{bar b} production can be schematically categorized into three mechanisms. The leading-order (LO) process is ''flavor creation'', where both b and {bar b} quarks substantially participate in the hard scattering and result in a distinct back-to-back signal in final state. The ''flavor excitation'' and the ''gluon splitting'' processes, which appear at next-leading-order (NLO), aremore » known to make a comparable contribution to total b{bar b} cross section, while providing very different opening angle distributions from the LO process. An azimuthal opening angle between bottom and anti-bottom, {Delta}{phi}, has been used for the correlation measurement to probe the interaction creating b{bar b} pairs. The {Delta}{phi} distribution has been obtained from two different methods. one method measures the {Delta}{phi} between bottom hadrons using events with two reconstructed secondary vertex tags. The other method uses b{bar b} {yields} (J/{psi}X)({ell}X') events, where the charged lepton ({ell}) is an electron (e) or a muon ({mu}), to measure {Delta}{phi} between bottom quarks. The b{bar b} purity is determined as a function of {Delta}{phi} by fitting the decay length of the J/{psi} and the impact parameter of the {ell}. Both methods quantify the contribution from higher-order production mechanisms by the fraction of the b{bar b} pairs produced in the same azimuthal hemisphere, f{sub toward}. The measured f{sub toward} values are consistent with both parton shower Monte Carlo and NLO QCD predictions.« less

Laparoscopic Radical Prostatectomy after Previous Transurethral Resection of the Prostate in Clinical T1a and T1b Prostate Cancer: A Matched-Pair Analysis.

PubMed

Yang, Yi; Luo, Yun; Hou, Guo-Liang; Huang, Qun-Xiong; Lu, Min-Hua; Si-tu, Jie; Gao, Xin

2015-07-01

To analyze and compare surgical, oncological and functional outcomes of laparoscopic radi­cal prostatectomy (LRP) in patients with and without previous transurethral resection of the prostate (TURP). In total, 785 men underwent LRP at our institution from January 2002 to December 2012. TURP had been performed previously in 35 of these patients (TURP group). A matched-pair analysis iden­tified 35 additional men without previous TURP who exhibited equivalent clinicopathological characteristics to serve as a control group. Perioperative complications and surgical, functional, and oncological outcomes were compared between the two groups. The groups were similar in age, body mass index, serum prostate-specific antigen level, and pre- and post-operative Gleason scores. Patients in the TURP group had greater blood loss (231 vs. 139 mL), longer opera­tive times (262 vs. 213 min), a greater probability of transfusion (8.6% vs. 0%), and a higher rate of complications (37.1% vs. 11.4%) compared with the control group. The positive surgical margin rate was higher in the TURP group, but this difference was not statistically significant (P = .179). The continence rates at one year after surgery were similar, but a lower continence rate was identified in the TURP group (42.9% vs. 68.6%) at 3 months. Bio­chemical recurrence developed in 17.1% and 11.4% of the patients in the TURP and control groups, respectively, after a mean follow-up of 57.6 months. LRP is feasible but challenging after TURP. LRP entails longer operating times, greater blood loss, higher complication rates and worse short-term continence outcomes. However, the radical nature of this cancer surgery is not compromised.

Time-resolved luminescence measurements of the magnetic field effect on paramagnetic photosensitizers in photodynamic reactions

NASA Astrophysics Data System (ADS)

Mermut, O.; Bouchard, J.-P.; Cormier, J.-F.; Desroches, P.; Diamond, K. R.; Fortin, M.; Gallant, P.; Leclair, S.; Marois, J.-S.; Noiseux, I.; Morin, J.-F.; Patterson, M. S.; Vernon, M.

2008-02-01

The development of multimodal molecular probes and photosensitizing agents for use in photodynamic therapy (PDT) is vital for optimizing and monitoring cytotoxic responses. We propose a combinatorial approach utilizing photosensitizing molecules that are both paramagnetic and luminescent with multimodal functionality to perturb, control, and monitor molecular-scale reaction pathways in PDT. To this end, a time-domain single photon counting lifetime apparatus with a 400 nm excitation source has been developed and integrated with a variable low field magnet (0- 350mT). The luminescence lifetime decay function was measured in the presence of a sweeping magnetic field for a custom designed photosensitizing molecule in which photoinduced electron transfer was studied The photosensitizer studied was a donor-acceptor complex synthesized using a porphyrin linked to a fullerene molecule. The magneto-optic properties were investigated for the free-base photosensitizer complex as well as those containing either diamagnetic (paired electron) or paramagnetic (unpaired electron) metal centers, Zn(II) and Cu(II). The magnetic field was employed to affect and modify the spin states of radical pairs of the photosensitizing agents via magnetically induced hyperfine and Zeeman effects. Since the Type 1 reaction pathway of an excited triplet state photosensitizer involves the production of radical species, lifetime measurements were conducted at low dissolved oxygen concentration (0.01ppm) to elucidate the dependence of the magnetic perturbation on the photosensitization mechanistic pathway. To optimize the magnetic response, a solvent study was performed examining the dependence of the emission properties on the magnetic field in solutions of varying dielectric constants. Lastly, the cytotoxicity in murine tumor cell suspensions was investigated for the novel porphyrin-fullerene complex by inducing photodynamic treatments and determining the associated cell survival.

The Diurnal Variation of Hydrogen, Nitrogen, and Chlorine Radicals: Implications for the Heterogeneous Production of HNO2

NASA Technical Reports Server (NTRS)

Salawitch, R. J.; Wofsy, S. C.; Wennberg, P. O.; Cohen, R. C.; Anderson, J. G.; Fahey, D. W.; Gao, R. S.; Keim, E. R.; Woodbridge, E. L.; Stimpfle, R. M.;

The diurnal variation of hydrogen, nitrogen, and chlorine radicals: Implications for the heterogeneous production of HNO2

NASA Technical Reports Server (NTRS)

Salawitch, R. J.; Wofsy, S. C.; Wennberg, P. O.; Cohen, R. C.; Anderson, J. G.; Fahey, D. W.; Gao, R. S.; Keim, E. R.; Woodbridge, E. L.; Stimpfle, R. M.

1994-01-01

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained through sunrise and sunset in the lower statosphere during SPADE are compared to results from a photochemical model constrained by observed concentrations of radical precursors and environmental conditions. Models allowing for heteogeneous hydrolysis of N2O5 on sulfate aerosols agree with measured concentrations of NO, NO2, and ClO throughout the day, but fail to account for high concentrations of OH and HO2 observed near sunrise and sunset. The morning burst of (OH) and (HO2) coincides with the rise of (NO) from photolysis of NO2, suggesting a new source of HO(x) that photolyzes in the near UV (350 to 400 nm) spectral region. A model that allow for the heterogeneous production of HNO2 results in an excellent simulation of the diurnal variations of (OH) and (HO2).

Chapter 8: Pyrolysis Mechanisms of Lignin Model Compounds Using a Heated Micro-Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robichaud, David J.; Nimlos, Mark R.; Ellison, G. Barney

2015-10-03

Lignin is an important component of biomass, and the decomposition of its thermal deconstruction products is important in pyrolysis and gasification. In this chapter, we investigate the unimolecular pyrolysis chemistry through the use of singly and doubly substituted benzene molecules that are model compounds representative of lignin and its primary pyrolysis products. These model compounds are decomposed in a heated micro-reactor, and the products, including radicals and unstable intermediates, are measured using photoionization mass spectrometry and matrix isolation infrared spectroscopy. We show that the unimolecular chemistry can yield insight into the initial decomposition of these species. At pyrolysis and gasificationmore » severities, singly substituted benzenes typically undergo bond scission and elimination reactions to form radicals. Some require radical-driven chain reactions. For doubly substituted benzenes, proximity effects of the substituents can change the reaction pathways.« less

Regioselectivity of enzymatic and photochemical single electron transfer promoted carbon-carbon bond fragmentation reactions of tetrameric lignin model compounds.

PubMed

Cho, Dae Won; Latham, John A; Park, Hea Jung; Yoon, Ung Chan; Langan, Paul; Dunaway-Mariano, Debra; Mariano, Patrick S

2011-04-15

New types of tetrameric lignin model compounds, which contain the common β-O-4 and β-1 structural subunits found in natural lignins, have been prepared and carbon-carbon bond fragmentation reactions of their cation radicals, formed by photochemical (9,10-dicyanoanthracene) and enzymatic (lignin peroxidase) SET-promoted methods, have been explored. The results show that cation radical intermediates generated from the tetrameric model compounds undergo highly regioselective C-C bond cleavage in their β-1 subunits. The outcomes of these processes suggest that, independent of positive charge and odd-electron distributions, cation radicals of lignins formed by SET to excited states of sensitizers or heme-iron centers in enzymes degrade selectively through bond cleavage reactions in β-1 vs β-O-4 moieties. In addition, the findings made in the enzymatic studies demonstrate that the sterically large tetrameric lignin model compounds undergo lignin peroxidase-catalyzed cleavage via a mechanism involving preliminary formation of an enzyme-substrate complex.

IMMUNO-SPIN TRAPPING FROM BIOCHEMISTRY TO MEDICINE: advances, challenges, and pitfalls

PubMed Central

Gomez-Mejiba, Sandra E.; Zili, Zhai; Della-Vedova, Maria C.; Muñoz, Marcos D.; Chatterjee, Saurabh; Towner, Rheal A.; Hensley, Kenneth; Floyd, Robert A.; Mason, Ronald P.; Ramirez, Dario C.

2013-01-01

BACKGROUND Immuno-spin trapping (IST) is based on the reaction of a spin trap with a free radical to form a stable nitrone adduct, followed by the use of antibodies, rather than traditional electron paramagnetic resonance spectroscopy, to detect the nitrone adduct. IST has been successfully applied to mechanistic in vitro studies, and recently, macromolecule-centered radicals have been detected in models of drug-induced agranulocytosis, hepatotoxicity, cardiotoxicity, and ischemia/reperfusion, as well as in models of neurological, metabolic and immunological diseases. SCOPE OF THE REVIEW To critically evaluate advances, challenges, and pitfalls as well as the scientific opportunities of IST as applied to the study of protein-centered free radicals generated in stressed organelles, cells, tissues and animal models of disease and exposure. MAJOR CONCLUSIONS Because the spin trap has to be present at high enough concentrations in the microenvironment where the radical is formed, the possible effects of the spin trap on gene expression, metabolism and cell physiology have to be considered in the use of IST and in the interpretation of results. These factors have not yet been thoroughly dealt with in the literature. GENERAL SIGNIFICANCE The identification of radicalized proteins during cell/tissue response to stressors will help define their role in the complex cellular response to stressors and pathogenesis; however, the fidelity of spin trapping/ immuno-detection and the effects of the spin trap on the biological system should be considered. PMID:23644035

HYDROXYL RADICAL/OZONE RATIOS DURING OZONATION PROCESSES. I. THE RCT CONCEPT

EPA Science Inventory

The ozonation of model systems and several natural waters was examined in bench-scale batch experiments. In addition to measuring the concentration of ozone (03), the rate of depletion of an in situ hydroxyl radical probe compound was monitored, thus providing information on the ...

Evidence on the Formation of Singlet Oxygen in the Donor Side Photoinhibition of Photosystem II: EPR Spin-Trapping Study

PubMed Central

Yadav, Deepak Kumar; Pospíšil, Pavel

2012-01-01

When photosystem II (PSII) is exposed to excess light, singlet oxygen (1O2) formed by the interaction of molecular oxygen with triplet chlorophyll. Triplet chlorophyll is formed by the charge recombination of triplet radical pair 3[P680•+Pheo•−] in the acceptor-side photoinhibition of PSII. Here, we provide evidence on the formation of 1O2 in the donor side photoinhibition of PSII. Light-induced 1O2 production in Tris-treated PSII membranes was studied by electron paramagnetic resonance (EPR) spin-trapping spectroscopy, as monitored by TEMPONE EPR signal. Light-induced formation of carbon-centered radicals (R•) was observed by POBN-R adduct EPR signal. Increased oxidation of organic molecules at high pH enhanced the formation of TEMPONE and POBN-R adduct EPR signals in Tris-treated PSII membranes. Interestingly, the scavenging of R• by propyl gallate significantly suppressed 1O2. Based on our results, it is concluded that 1O2 formation correlates with R• formation on the donor side of PSII due to oxidation of organic molecules (lipids and proteins) by long-lived P680•+/TyrZ•. It is proposed here that the Russell mechanism for the recombination of two peroxyl radicals formed by the interaction of R• with molecular oxygen is a plausible mechanism for 1O2 formation in the donor side photoinhibition of PSII. PMID:23049883

Effects of chemical structure on the thermodynamic efficiency of radical chain carriers for organic synthesis.

PubMed

Lin, Ching Yeh; Peh, Jessie; Coote, Michelle L

2011-03-18

The chain carrier index (CCI), defined as the ratio of the bond dissociation free energies (BDFE) of corresponding chain carrier halides and hydrides, is proposed as a measure of the thermodynamic efficiency of chain carriers for radical dehalogenation. The larger this value is relative to the corresponding value of the organic substrate, the more thermodynamically efficient the process. The chloride and bromide CCIs were evaluated at the G3(MP2)-RAD(+) level of theory for 120 different R-groups, covering a broad range of carbon-centered and noncarbon-centered species; the effects of solvent and temperature have also been studied. The broad finding from this work is that successful chain carriers generally maximize the strength of their halide (versus hydride bonds) through charge-shift bonding. As a result, the thermodynamic efficiency of a chain carrier tends to increase down the periodic table, and also with the inclusion of stronger electron donating substituents. The CCIs of carbon-centered species fall into a relatively narrow range so that, even when the CCI is maximized through inclusion of lone pair donor OMe or NMe(2) groups, the thermodynamic driving force for dehalogenation of other organic substrates is modest at best, and the process is likely to be kinetically hampered. Among the noncarbon-centered species studied, bismuth- and borane-centered compounds have some of the highest CCI values and, although their kinetics requires further optimization, these classes of compounds would be worth further investigation as tin-free radical reducing agents.

A comparison of radical retropubic with perineal prostatectomy for localized prostate cancer within the Uniformed Services Urology Research Group.

PubMed

Lance, R S; Freidrichs, P A; Kane, C; Powell, C R; Pulos, E; Moul, J W; McLeod, D G; Cornum, R L; Brantley Thrasher J

2001-01-01

To review and compare the outcome of patients undergoing radical retropubic prostatectomy (RRP) or radical perineal prostatectomy (RPP) for clinically localized prostate cancer. From 1988 to 1997, 1382 men who were treated by RRP and 316 by RPP were identified from databases of the Uniformed Services Urology Research Group. The following variables were assessed; age, race, prostate-specific antigen (PSA) level before surgery, clinical stage, biopsy Gleason sum, estimated blood loss (EBL), margin-positive rate, pathological stage, biochemical recurrence rate, short and long-term complication rates, impotence and incontinence rates. To eliminate selection bias, the analysis was concentrated on pairs of patients matched by race, preoperative PSA level, clinical stage and biopsy Gleason sum. In the 190 matched patients there were no significant differences between the RRP and RPP groups in either organ-confined (57% vs 55%), margin-positive (39% vs 43%), or biochemical recurrence rates (12.9% vs 17.6% at a mean follow-up of 47.1 vs 42.9 months), respectively. The mean EBL was 1575 mL in the RRP group and 802 mL in the RPP group (P < 0.001). The only significant difference in complication rates was a higher incidence of rectal injury in the RPP group (4.9%) than in the RRP group (none, P < 0.05). In similar populations of patients, RPP offers equivalent organ-confined, margin-positive and biochemical recurrence rates to RRP, while causing significantly less blood loss.

Free radicals induced by sunlight in different spectral regions - in vivo versus ex vivo study.

PubMed

Lohan, Silke B; Müller, Robert; Albrecht, Stephanie; Mink, Kathrin; Tscherch, Kathrin; Ismaeel, Fakher; Lademann, Jürgen; Rohn, Sascha; Meinke, Martina C

2016-05-01

Sunlight represents an exogenous factor stimulating formation of free radicals which can induce cell damage. To assess the effect of the different spectral solar regions on the development of free radicals in skin, in vivo electron paramagnetic resonance (EPR) investigations with human volunteers and ex vivo studies on excised human and porcine skin were carried out. For all skin probes, the ultraviolet (UV) spectral region stimulates the most intensive radical formation, followed by the visible (VIS) and the near infrared (NIR) regions. A comparison between the different skin models shows that for UV light, the fastest and highest production of free radicals could be detected in vivo, followed by excised porcine and human skin. The same distribution pattern was found for the VIS/NIR spectral regions, whereby the differences in radical formation between in vivo and ex vivo were less pronounced. An analysis of lipid composition in vivo before and after exposure to UV light clearly showed modifications in several skin lipid components; a decrease of ceramide subclass [AP2] and an increase of ceramide subclass [NP2], sodium cholesterol sulphate and squalene (SQ) were detectable. In contrast, VIS/NIR irradiation led to an increase of ceramides [AP2] and SCS, and a decrease of SQ. These results, which are largely comparable for the different skin models investigated in vivo and ex vivo, indicate that radiation exposure in different spectral regions strongly influences radical production in skin and also results in changes in skin lipid composition, which is essential for barrier function. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

One-electron oxidation reactions of purine and pyrimidine bases in cellular DNA

PubMed Central

Cadet, Jean; Wagner, J. Richard; Shafirovich, Vladimir; Geacintov, Nicholas E.

2014-01-01

Purpose The aim of this survey is to critically review the available information on one-electron oxidation reactions of nucleobases in cellular DNA with emphasis on damage induced through the transient generation of purine and pyrimidine radical cations. Since the indirect effect of ionizing radiation mediated by hydroxyl radical is predominant in cells, efforts have been made to selectively ionize bases using suitable one-electron oxidants that consist among others of high intensity UVC laser pulses. Thus, the main oxidation product in cellular DNA was found to be 8-oxo-7,8-dihydroguanine as a result of direct bi-photonic ionization of guanine bases and indirect formation of guanine radical cations through hole transfer reactions from other base radical cations. The formation of 8-oxo-7,8-dihydroguanine and other purine and pyrimidine degradation products was rationalized in terms of the initial generation of related radical cations followed by either hydration or deprotonation reactions in agreement with mechanistic pathways inferred from detailed mechanistic studies. The guanine radical cation has been shown to be implicated in three other nucleophilic additions that give rise to DNA-protein and DNA-DNA cross-links in model systems. Evidence was recently provided for the occurrence of these three reactions in cellular DNA. Conclusion There is growing evidence that one-electron oxidation reactions of nucleobases whose mechanisms have been characterized in model studies involving aqueous solutions take place in a similar way in cells. It may also be pointed out that the above cross-linked lesions are only produced from the guanine radical cation and may be considered as diagnostic products of the direct effect of ionizing radiation. PMID:24369822

One-electron oxidation reactions of purine and pyrimidine bases in cellular DNA.

PubMed

Cadet, Jean; Wagner, J Richard; Shafirovich, Vladimir; Geacintov, Nicholas E

2014-06-01

The aim of this survey is to critically review the available information on one-electron oxidation reactions of nucleobases in cellular DNA with emphasis on damage induced through the transient generation of purine and pyrimidine radical cations. Since the indirect effect of ionizing radiation mediated by hydroxyl radical is predominant in cells, efforts have been made to selectively ionize bases using suitable one-electron oxidants that consist among others of high intensity UVC laser pulses. Thus, the main oxidation product in cellular DNA was found to be 8-oxo-7,8-dihydroguanine as a result of direct bi-photonic ionization of guanine bases and indirect formation of guanine radical cations through hole transfer reactions from other base radical cations. The formation of 8-oxo-7,8-dihydroguanine and other purine and pyrimidine degradation products was rationalized in terms of the initial generation of related radical cations followed by either hydration or deprotonation reactions in agreement with mechanistic pathways inferred from detailed mechanistic studies. The guanine radical cation has been shown to be implicated in three other nucleophilic additions that give rise to DNA-protein and DNA-DNA cross-links in model systems. Evidence was recently provided for the occurrence of these three reactions in cellular DNA. There is growing evidence that one-electron oxidation reactions of nucleobases whose mechanisms have been characterized in model studies involving aqueous solutions take place in a similar way in cells. It may also be pointed out that the above cross-linked lesions are only produced from the guanine radical cation and may be considered as diagnostic products of the direct effect of ionizing radiation.