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Sample records for radical cation formation

  1. Formation and Dissociation of Phosphorylated Peptide Radical Cations

    NASA Astrophysics Data System (ADS)

    Kong, Ricky P. W.; Quan, Quan; Hao, Qiang; Lai, Cheuk-Kuen; Siu, Chi-Kit; Chu, Ivan K.

    2012-12-01

    In this study, we generated phosphoserine- and phosphothreonine-containing peptide radical cations through low-energy collision-induced dissociation (CID) of the ternary metal-ligand phosphorylated peptide complexes [CuII(terpy) p M]·2+ and [CoIII(salen) p M]·+ [ p M: phosphorylated angiotensin III derivative; terpy: 2,2':6',2''-terpyridine; salen: N, N '-ethylenebis(salicylideneiminato)]. Subsequent CID of the phosphorylated peptide radical cations ( p M·+) revealed fascinating gas-phase radical chemistry, yielding (1) charge-directed b- and y-type product ions, (2) radical-driven product ions through cleavages of peptide backbones and side chains, and (3) different degrees of formation of [M - H3PO4]·+ species through phosphate ester bond cleavage. The CID spectra of the p M·+ species and their non-phosphorylated analogues featured fragment ions of similar sequence, suggesting that the phosphoryl group did not play a significant role in the fragmentation of the peptide backbone or side chain. The extent of neutral H3PO4 loss was influenced by the peptide sequence and the initial sites of the charge and radical. A preliminary density functional theory study, at the B3LYP 6-311++G(d,p) level of theory, of the neutral loss of H3PO4 from a prototypical model— N-acetylphosphorylserine methylamide—revealed several factors governing the elimination of neutral phosphoryl groups through charge- and radical-induced mechanisms.

  2. Quantum chemical insights in energy dissipation and carotenoid radical cation formation in light harvesting complexes.

    PubMed

    Wormit, Michael; Dreuw, Andreas

    2007-06-21

    Light harvesting complexes (LHCs) have been identified in all photosynthetic organisms. To understand their function in light harvesting and energy dissipation, detailed knowledge about possible excitation energy transfer (EET) and electron transfer (ET) processes in these pigment proteins is of prime importance. This again requires the study of electronically excited states of the involved pigment molecules, in LHCs of chlorophylls and carotenoids. This paper represents a critical review of recent quantum chemical calculations on EET and ET processes between pigment pairs relevant for the major LHCs of green plants (LHC-II) and of purple bacteria (LH2). The theoretical methodology for a meaningful investigation of such processes is described in detail, and benefits and limitations of standard methods are discussed. The current status of excited state calculations on chlorophylls and carotenoids is outlined. It is focused on the possibility of EET and ET in the context of chlorophyll fluorescence quenching in LHC-II and carotenoid radical cation formation in LH2. In the context of non-photochemical quenching of green plants, it is shown that replacement of the carotenoid violaxanthin by zeaxanthin in its binding pocket of LHC-II can not result in efficient quenching. In LH2, our computational results give strong evidence that the S(1) states of the carotenoids are involved in carotenoid cation formation. By comparison of theoretical findings with recent experimental data, a general mechanism for carotenoid radical cation formation is suggested.

  3. Zeaxanthin Radical Cation Formation in Minor Light-Harvesting Complexes of Higher Plant Antenna

    SciTech Connect

    Avenson, Thomas H.; Ahn, Tae Kyu; Zigmantas, Donatas; Niyogi, Krishna K.; Li, Zhirong; Ballottari, Matteo; Bassi, Roberto; Fleming, Graham R.

    2008-01-31

    Previous work on intact thylakoid membranes showed that transient formation of a zeaxanthin radical cation was correlated with regulation of photosynthetic light-harvesting via energy-dependent quenching. A molecular mechanism for such quenching was proposed to involve charge transfer within a chlorophyll-zeaxanthin heterodimer. Using near infrared (880-1100 nm) transient absorption spectroscopy, we demonstrate that carotenoid (mainly zeaxanthin) radical cation generation occurs solely in isolated minor light-harvesting complexes that bind zeaxanthin, consistent with the engagement of charge transfer quenching therein. We estimated that less than 0.5percent of the isolated minor complexes undergo charge transfer quenching in vitro, whereas the fraction of minor complexes estimated to be engaged in charge transfer quenching in isolated thylakoids was more than 80 times higher. We conclude that minor complexes which bind zeaxanthin are sites of charge transfer quenching in vivo and that they can assume Non-quenching and Quenching conformations, the equilibrium LHC(N)<--> LHC(Q) of which is modulated by the transthylakoid pH gradient, the PsbS protein, and protein-protein interactions.

  4. Geometrical isomerization of carotenoids mediated by cation radical/dication formation

    SciTech Connect

    Gao, G.; Wei, C.C.; Jeevarajan, A.S.; Kispert, L.D.

    1996-03-28

    Electrochemical oxidation of all-trans-canthaxanthin and {beta}-carotene in dichloromethane leads to significant trans-to-cis isomerization, with cis isomers accounting for about 40% of the products formed. The electrochemically generated isomers were separated by reverse-phase high-performance liquid chromatography and identified as 9-cis, 13-cis, 15-cis, and 9,13-di-cis isomers of the carotenoids by {sup 1}H-NMR spectroscopy and optical spectroscopy (Q ratio). The results of simultaneous bulk electrolysis and optical absorption spectroscopy indicate the following isomerization mechanism: the all-trans cation radicals and/or dications formed by electrochemical oxidation of all-trans-carotenoids can easily undergo geometrical isomerization to form cis cation radicals and/or dications. The latter are converted by the comproportionation equilibrium to cation radicals which are then transformed to neutral cis-carotenoids by exchanging one electron with neutral carotenoids. AM1 molecular orbital calculations, which show that the energy barriers of configurational transformation from trans to cis are much lower in the cation radical and dication species than in the neutral molecule, strongly support the first step of this mechanism. 36 refs., 5 figs., 2 tabs.

  5. Formation, isomerization, and dissociation of alpha-carbon-centered and pi-centered glycylglycyltryptophan radical cations

    SciTech Connect

    Ng, Dominic C.; Song, Tao; Siu, Shiu On; Siu, Chi-Kit; Laskin, Julia; Chu, Ivan K.

    2010-02-11

    Gas phase fragmentations of two isomeric radical cationic tripeptides of glycylglycyltryptophan-G•GW+ and [GGW]•+—with well-defined initial radical sites at the α-carbon atom and the 3-methylindole ring, respectively, have been studied using collision-induced dissociation (CID), density functional theory (DFT), and Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Substantially different low-energy CID spectra were obtained for these two isomeric GGW structures, suggesting that they did not interconvert on the time scale of these experiments. DFT and RRKM calculations were used to investigate the influence of the kinetics, stabilities, and locations of the radicals on the competition between the isomerization and dissociation channels. The calculated isomerization barrier between the GGW radical cations (>35.4 kcal/mol) was slightly higher than the barrier for competitive dissociation of these species (<30.5 kcal/mol); the corresponding microcanonical rate constants for isomerization obtained from RRKM calculations were all considerably lower than the dissociation rates at all internal energies. Thus, interconversion between the GGW isomers examined in this study cannot compete with their fragmentations.

  6. The standard enthalpies of formation of 1- and 2-Adamantyl cations and radicals. An ab initio study

    NASA Astrophysics Data System (ADS)

    Abboud, J.-L. M.; Castaño, O.; Dávalos, J. Z.; Gomperts, R.

    2001-04-01

    The results of a G2(MP2) computational study involving 1- and 2-Adamantyl cations ( 1+, 2+) as well as 1- and 2-Adamantyl radicals ( 1rad , 2rad ) are presented. They provide purely computational thermodynamic data for the following processes: (i) Ionization of 1rad and 2rad , (ii) Exchange of hydrogen atoms or hydride anions between Adamantyl radicals or cations and alkyl radicals or cations, respectively. These data, once combined with the experimental enthalpies of formation of iso -C3H7 rad ,iso -C3H7 + ,tert -C4H9 rad and tert -C4H9 + , allowed us to screen the available experimental data and to define a self-consistent set of experimentally-based standard enthalpies of formation, Δ fH 0 m, for Adamantyl species, namely: Δ fH 0 m( 1+, g)=162.0±2.0 ; Δ fH 0 m( 2+, g)=171.9±2.0 ; Δ fH 0 m( 1rad , g)=17.9±2.1 , Δ fH 0 m( 2rad , g)=16.6±2.0 kcal mol -1.

  7. Halogenated silanes, radicals, and cations

    NASA Astrophysics Data System (ADS)

    Wang, Liming; He, Yi-Liang

    2008-09-01

    Quantum chemistry study has been carried out on the structure and energetics of halogenated silanes, radicals, and cations (SiHxXy0,+1, X = F, Cl, Br; x + y = 1-4). The geometries are optimized at B3LYP/6-31+G(2df,p) level. The adiabatic ionization energiess (IEas), relative energetics of cations, proton affinities (PAs) of silanes, and the enthalpies of formation are predicted using G3(CC) model chemistry. Non-classical ion complex structures are found for hydrogenated cations and transition states connecting classical and non-classical structures are also located. The most stable cations for silylene and silyl radicals have their classical divalent and trivalent structures, and those for silanes have non-classical structures except for SiH3Br+ and SiH2Br2+. The non-classical structures for halosilane cations imply difficulty in experimentally measurement of the adiabatic ionization energies using photoionization or photoelectron studies. For SiH3X, SiH2X2, and SiHX3, the G3(CC) adiabatic IEas to classical ionic structures closest to their neutrals agree better with the photoelectron spectroscopic measurements. The transition states between classical and non-classical structures also hamper the photoionization determination of the appearance energies for silylene cations from silanes. The G3(CC) results for SiHx0,+1 agree excellently with the photoionization mass spectrometric study, and the results for fluorinated and chlorinated species also agree with the previous theoretical predictions at correlation levels from BAC-MP4 to CCSD(T)/CBS. The predicted enthalpy differences between SiH2Cl+, SiHCl2+, and SiCl3+ are also in accordance with previous kinetics study. The G3(CC) results show large discrepancies to the collision-induced charge transfer and/or dissociation reactions involving SiFx+ and SiClx+ ions, for which the G3(CC) enthalpies of formation are also significantly differed from the previous theoretical predictions, especially on SiFx+ (x = 2-4). The G3

  8. Formation of environmentally persistent free radical (EPFR) in iron(III) cation-exchanged smectite clay.

    PubMed

    Nwosu, Ugwumsinachi G; Roy, Amitava; dela Cruz, Albert Leo N; Dellinger, Barry; Cook, Robert

    2016-01-01

    Environmentally persistent free radicals (EPFRs) have been found at a number of Superfund sites, with EPFRs being formed via a proposed redox process at ambient environmental conditions. The possibility of such a redox process taking place at ambient environmental conditions is studied utilizing a surrogate soil system of phenol and iron(III)-exchanged calcium montmorillonite clay, Fe(III)CaM. Sorption of phenol by the Fe(III)CaM is demonstrated by Fourier-transformed infra-red (FT-IR) spectroscopy, as evidenced by the peaks between 1345 cm(-1) and 1595 cm(-1), and at lower frequencies between 694 cm(-1) and 806 cm(-1), as well as X-ray diffraction (XRD) spectroscopy, as shown by an increase in interlayer spacing within Fe(III)CaM. The formation and characterization of the EPFRs is determined by electron paramagnetic resonance (EPR) spectroscopy, showing phenoxyl-type radical with a g-factor of 2.0034 and ΔHP-P of 6.1 G at an average concentration of 7.5 × 10(17) spins per g. EPFRs lifetime data are indicative of oxygen and water molecules being responsible for EPFR decay. The change in the oxidation state of the iron redox center is studied by X-ray absorption near-edge structure (XANES) spectroscopy, showing that 23% of the Fe(III) is reduced to Fe(II). X-ray photoemission spectroscopy (XPS) results confirm the XANES results. These findings, when combined with the EPFR concentration data, demonstrate that the stoichiometry of the EPFR formation under the conditions of this study is 1.5 × 10(-2) spins per Fe(II) atom.

  9. Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: DFT and FTIR studies

    PubMed Central

    Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.

    2011-01-01

    Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769

  10. Radical cation cyclization of 1,5-hexadiene to cyclohexene via the cyclohexane-2,5-diyl radical cation intermediate

    SciTech Connect

    Guo, Q.X.; Qin, X.Z.; Wang, J.T.; Williams, F.

    1988-03-16

    The classical example of a neutral carbon-centered radical cyclization reaction is the regioselective 1,5-ring closure (exocyclization) of the 5-hexenyl radical to the cyclopentylcarbinyl radical. Here the authors report the title reaction, a comparable addition process whereby an ..cap alpha.., omega-diene radical cation reacts by endocyclization and hydrogen shift(s) to produce a cycloolefin radical cation.

  11. Electronic spectrum of 9-methylanthracenium radical cation

    NASA Astrophysics Data System (ADS)

    O'Connor, Gerard D.; Sanelli, Julian A.; Dryza, Vik; Bieske, Evan J.; Schmidt, Timothy W.

    2016-04-01

    The predissociation spectrum of the cold, argon-tagged, 9-methylanthracenium radical cation is reported from 8000 cm-1 to 44 500 cm-1. The reported spectrum contains bands corresponding to at least eight electronic transitions ranging from the near infrared to the ultraviolet. These electronic transitions are assigned through comparison with ab initio energies and intensities. The infrared D1←D0 transitions exhibit significant vibronic activity, which is assigned through comparison with TD-B3LYP excited state frequencies and intensities, as well as modelled vibronic interactions. Dissociation of 9-methylanthracenium is also observed at high visible-photon energies, resulting in the loss of either CH2 or CH3. The relevance of these spectra, and the spectra of other polycyclic aromatic hydrocarbon radical cations, to the largely unassigned diffuse interstellar bands, is discussed.

  12. Surface hopping investigation of the relaxation dynamics in radical cations

    NASA Astrophysics Data System (ADS)

    Assmann, Mariana; Weinacht, Thomas; Matsika, Spiridoula

    2016-01-01

    Ionization processes can lead to the formation of radical cations with population in several ionic states. In this study, we examine the dynamics of three radical cations starting from an excited ionic state using trajectory surface hopping dynamics in combination with multiconfigurational electronic structure methods. The efficiency of relaxation to the ground state is examined in an effort to understand better whether fragmentation of cations is likely to occur directly on excited states or after relaxation to the ground state. The results on cyclohexadiene, hexatriene, and uracil indicate that relaxation to the ground ionic state is very fast in these systems, while fragmentation before relaxation is rare. Ultrafast relaxation is facilitated by the close proximity of electronic states and the presence of two- and three-state conical intersections. Examining the properties of the systems in the Franck-Condon region can give some insight into the subsequent dynamics.

  13. Fragmentation Pathways in the Uracil Radical Cation

    SciTech Connect

    Zhou, Congyi; Matsika, Spiridoula; Kotur, Marija; Weinacht, Thomas C.

    2012-08-24

    We investigate pathways for fragmentation in the uracil radical cation using ab initio electronic structure calculations. We focus on the main fragments produced in pump–probe dissociative ionization experiments. These are fragments with mass to charge ratios (m/z) of 69, 28, 41, and 42. Barriers to dissociation along the ground ionic surface are reported, which provide an estimate of the energetic requirements for the production of the main fragments. Finally, direct and sequential fragmentation mechanisms have been analyzed, and it is concluded that sequential fragmentation after production of fragment with m/z 69 is the dominant mechanism for the production of the smaller fragments.

  14. Elementary radical formation and conversion processes in. gamma. -irradiated polyvinylchloride

    SciTech Connect

    Torikai, A.; Adachi, T.; Fueki, K.

    1981-11-01

    Elementary processes of ..gamma..-irradiated polyvinylchloride (PVC) have been investigated by both electron spin resonance (ESR) and optical absorption measurements. On irradiating PVC film with ..gamma.. rays at -196/sup 0/C, alkyl-type radicals are produced. When the PVC film is warmed to room temperature, the radicals convert to polyenyl type. ..gamma.. irradiation of PVC film containing biphenyl (Ph/sub 2/) or pyrene (Py) at -196/sup 0/C yields the corresponding radical cation. The relative ESR peak heights of the radicals decrease and the G values for the formation of cation radicals increase with increasing additive concentrations. These facts indicate that energy is transferred from the precursor of the radicals to the additive. In the case of PVC film containing Py, the Py cation radical decreases the cyclohexadienyl-type radical from Py is produced by thermal annealing. A possible mechanism for radical formation and conversion is proposed.

  15. Fragmentation of peptide radical cations containing a tyrosine or tryptophan residue: structural features that favor formation of [x(n-1) + H]˙⁺ and [z(n-1) + H]˙⁺ ions.

    PubMed

    Mädler, Stefanie; Lau, Justin Kai-Chi; Williams, Declan; Wang, Yating; Saminathan, Irine S; Zhao, Junfang; Siu, K W Michael; Hopkinson, Alan C

    2014-06-12

    Peptide radical cations A(n)Y(•+) (where n = 3, 4, or 5) and A5W(•+) have been generated by collision-induced dissociation (CID) of [Cu(II)(tpy)(peptide)](•2+) complexes. Apart from the charge-driven fragmentation at the N-Cα bond of the hetero residue producing either [c + 2H](+) or [z - H](•+) ions and radical-driven fragmentation at the Cα-C bond to give a(+) ions, unusual product ions [x + H](•+) and [z + H](•+) are abundant in the CID spectra of the peptides with the hetero residue in the second or third position of the chain. The formation of these ions requires that both the charge and radical be located on the peptide backbone. Energy-resolved spectra established that the [z + H](•+) ion can be produced either directly from the peptide radical cation or via the fragment ion [x + H](•+). Additionally, backbone dissociation by loss of the C-terminal amino acid giving [b(n-1) - H](•+) increases in abundance with the length of the peptides. Mechanisms by which peptide radical cations dissociate have been modeled using density functional theory (B3LYP/6-31++G** level) on tetrapeptides AYAG(•+), AAYG(•+), and AWAG(•+).

  16. The pi-Cation Radical of Chlorophyll a.

    PubMed

    Borg, D C; Fajer, J; Felton, R H; Dolphin, D

    1970-10-01

    Chlorophyll a undergoes reversible one-electron oxidation in dichloromethane and butyronitrile. Removal of the electron by controlled potential electrolysis or by stoichiometric charge transfer to a known cation radical yields a radical (epr line width = 9 gauss, g = 2.0025 +/- 0.0001) whose optical spectrum is bleached relative to that of chlorophyll. Upon electrophoresis this bleached species behaves as a cation. By comparison with the known properties of pi-cation radicals of porphyrins and chlorins, the chlorophyll radical is also identified as a pi-cation. Further correlation of optical and epr properties with published studies on photosynthesis leads to the conclusion that oxidized P700, the first photochemical product of photosystem I in green plants, contains a pi-cation radical of the chlorin component of chlorophyll a. This radical is the likely source of the rapidly-decaying, narrow epr signal of photosynthesis.

  17. Transition-Metal Hydride Radical Cations.

    PubMed

    Hu, Yue; Shaw, Anthony P; Estes, Deven P; Norton, Jack R

    2016-08-10

    Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described.

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

    PubMed

    Bietti, Massimo; Capone, Alberto

    2004-01-23

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

  19. Notable effects of the metal salts on the formation and decay reactions of α-tocopheroxyl radical in acetonitrile solution. The complex formation between α-tocopheroxyl and metal cations.

    PubMed

    Kohno, Yutaro; Fujii, Miyabi; Matsuoka, Chihiro; Hashimoto, Haruka; Ouchi, Aya; Nagaoka, Shin-ichi; Mukai, Kazuo

    2011-08-18

    The measurement of the UV-vis absorption spectrum of α-tocopheroxyl (α-Toc(•)) radical was performed by reacting aroxyl (ArO(•)) radical with α-tocopherol (α-TocH) in acetonitrile solution including four kinds of alkali and alkaline earth metal salts (MX or MX(2)) (LiClO(4), LiI, NaClO(4), and Mg(ClO(4))(2)), using stopped-flow spectrophotometry. The maximum wavelength (λ(max)) of the absorption spectrum of the α-Toc(•) at 425.0 nm increased with increasing concentration of metal salts (0-0.500 M) in acetonitrile, and it approached constant values, suggesting an [α-Toc(•)-M(+) (or M(2+))] complex formation. The stability constants (K) were determined to be 9.2, 2.8, and 45 M(-1) for LiClO(4), NaClO(4), and Mg(ClO(4))(2), respectively. By reacting ArO(•) with α-TocH in acetonitrile, the absorption of ArO(•) disappeared rapidly, while that of α-Toc(•) appeared and then decreased gradually as a result of the bimolecular self-reaction of α-Toc(•) after passing through the maximum. The second-order rate constants (k(s)) obtained for the reaction of α-TocH with ArO(•) increased linearly with an increasing concentration of metal salts. The results indicate that the hydrogen transfer reaction of α-TocH proceeds via an electron transfer intermediate from α-TocH to ArO(•) radicals followed by proton transfer. Both the coordination of metal cations to the one-electron reduced anions of ArO(•) (ArO:(-)) and the coordination of counteranions to the one-electron oxidized cations of α-TocH (α-TocH(•)(+)) may stabilize the intermediate, resulting in the acceleration of electron transfer. A remarkable effect of metal salts on the rate of bimolecular self-reaction (2k(d)) of the α-Toc(•) radical was also observed. The rate constant (2k(d)) decreased rapidly with increasing concentrations of the metal salts. The 2k(d) value decreased at the same concentration of the metal salts in the following order: no metal salt > NaClO(4) > LiClO(4) > Mg

  20. Mechanistic aspects of hydration of guanine radical cations in DNA.

    PubMed

    Rokhlenko, Yekaterina; Cadet, Jean; Geacintov, Nicholas E; Shafirovich, Vladimir

    2014-04-23

    The mechanistic aspects of hydration of guanine radical cations, G(•+) in double- and single-stranded oligonucleotides were investigated by direct time-resolved spectroscopic monitoring methods. The G(•+) radical one-electron oxidation products were generated by SO4(•-) radical anions derived from the photolysis of S2O8(2-) anions by 308 nm laser pulses. In neutral aqueous solutions (pH 7.0), after the complete decay of SO4(•-) radicals (∼5 μs after the actinic laser flash) the transient absorbance of neutral guanine radicals, G(-H)(•) with maximum at 312 nm, is dominant. The kinetics of decay of G(-H)(•) radicals depend strongly on the DNA secondary structure. In double-stranded DNA, the G(-H)(•) decay is biphasic with one component decaying with a lifetime of ∼2.2 ms and the other with a lifetime of ∼0.18 s. By contrast, in single-stranded DNA the G(-H)(•) radicals decay monophasically with a ∼ 0.28 s lifetime. The ms decay component in double-stranded DNA is correlated with the enhancement of 8-oxo-7,8-dihydroguanine (8-oxoG) yields which are ∼7 greater than in single-stranded DNA. In double-stranded DNA, it is proposed that the G(-H)(•) radicals retain radical cation character by sharing the N1-proton with the N3-site of C in the [G(•+):C] base pair. This [G(-H)(•):H(+)C ⇆ G(•+):C] equilibrium allows for the hydration of G(•+) followed by formation of 8-oxoG. By contrast, in single-stranded DNA, deprotonation of G(•+) and the irreversible escape of the proton into the aqueous phase competes more effectively with the hydration mechanism, thus diminishing the yield of 8-oxoG, as observed experimentally.

  1. UVA-visible photo-excitation of guanine radical cations produces sugar radicals in DNA and model structures

    PubMed Central

    Adhikary, Amitava; Malkhasian, Aramice Y. S.; Collins, Sean; Koppen, Jessica; Becker, David; Sevilla, Michael D.

    2005-01-01

    This work presents evidence that photo-excitation of guanine radical cations results in high yields of deoxyribose sugar radicals in DNA, guanine deoxyribonucleosides and deoxyribonucleotides. In dsDNA at low temperatures, formation of C1′• is observed from photo-excitation of G•+ in the 310–480 nm range with no C1′• formation observed ≥520 nm. Illumination of guanine radical cations in 2′dG, 3′-dGMP and 5′-dGMP in aqueous LiCl glasses at 143 K is found to result in remarkably high yields (∼85–95%) of sugar radicals, namely C1′•, C3′• and C5′•. The amount of each of the sugar radicals formed varies dramatically with compound structure and temperature of illumination. Radical assignments were confirmed using selective deuteration at C5′ or C3′ in 2′-dG and at C8 in all the guanine nucleosides/tides. Studies of the effect of temperature, pH, and wavelength of excitation provide important information about the mechanism of formation of these sugar radicals. Time-dependent density functional theory calculations verify that specific excited states in G•+ show considerable hole delocalization into the sugar structure, in accord with our proposed mechanism of action, namely deprotonation from the sugar moiety of the excited molecular radical cation. PMID:16204456

  2. The Prowess of Photogenerated Amine Radical Cations in Cascade Reactions: From Carbocycles to Heterocycles.

    PubMed

    Morris, Scott A; Wang, Jiang; Zheng, Nan

    2016-09-20

    Cascade reactions represent a class of ideal organic reactions because they empower efficiency, elegance, and novelty. However, development of cascade reactions remains a daunting task for synthetic chemists. Radicals are known to be well suited for cascade reactions. Compared with widely used carbon-based radicals, nitrogen-based radicals, such as neutral aminyl radicals and protonated aminyl radicals (amine radical cations), are underutilized, although they are behind some notable synthetic methods such as the Hofmann-Löffler-Freytag reaction. The constraint on their usage is generally attributed to the limited number of available stable precursors. Since amine radical cations offer increased reactivity and selectivity in chemical transformations compared with neutral aminyl radicals, their generation is of utmost importance. Recently, a surge of reports has been revealed using visible light photoredox catalysis. It has been demonstrated that amines can act as an electron donor in a reductive quenching cycle while the amine itself is oxidized to the amine radical cation. Although a number of methods exist to generate amine radical cations, the photochemical formation of these species offers many practical advantages. In this Account, we discuss our journey to the development of annulation reactions with various π-bonds and electrophilic addition reactions to alkenes using photogenerated amine radical cations. Various carbocycles and heterocycles are produced by these reactions. In our annulation work, we first show that single electron photooxidation of cyclopropylanilines to the amine radical cations triggers ring opening of the strained carbocycle, producing distonic radical cations. These odd-electron species are shown to react with alkenes and alkynes to yield the corresponding cyclopentanes and cyclopentenes in an overall redox neutral process. Further development of this annulation reaction allows us to achieve the [4 + 2] annulation of cyclobutylanilines

  3. Fragmentation of alpha-Radical Cations of Arginine-Containing Peptides

    SciTech Connect

    Laskin, Julia; Yang, Zhibo; Ng, Dominic C.; Chu, Ivan K.

    2010-04-01

    Fragmentation pathways of peptide radical cations, M+, with well-defined initial location of the radical site were explored using collision-induced dissociation (CID) experiments. Peptide radical cations were produced by gas-phase fragmentation of CoIII(salen)-peptide complexes [salen = N,N´-ethylenebis (salicylideneaminato)]. Subsequent hydrogen abstraction from the -carbon of the side chain followed by Ca-C bond cleavage results in the loss of a neutral side chain and formation of an a-radical cation with the radical site localized on the a-carbon of the backbone. Similar CID spectra dominated by radical-driven dissociation products were obtained for a number of a-radicals when the basic arginine side chain was present in the sequence. In contrast, proton-driven fragmentation dominates CID spectra of a-radicals produced via the loss of the arginine side chain. Our results suggest that in most cases radical migration precedes fragmentation of large peptide radical cations.

  4. Magnetic Resonance Studies of Proton Loss from Carotenoid Radical Cations

    SciTech Connect

    Kispert, Lowell D; Focsan, A Ligia; Konovalova, Tatyana A; Lawrence, Jesse; Bowman, Michael K; Dixon, David A; Molnar, Peter; Deli, Jozsef

    2007-06-11

    Carotenoids, intrinsic components of reaction centers and pigment-protein complexes in photosynthetic membranes, play a photoprotective role and serve as a secondary electron donor. Before optimum use of carotenoids can be made in artificial photosynthetic systems, their robust nature in living materials requires extensive characterization of their electron transfer, radical trapping ability, stability, structure in and on various hosts, and photochemical behavior. Pulsed ENDOR and 2D-HYSCORE studies combined with DFT calculations reveal that photo-oxidation of natural zeaxanthin (I) and violaxanthin (II) on silica-alumina produces not only the carotenoid radical cations (Car•+) but also neutral radicals (#Car•) by proton loss from the methyl groups at positions 5 or 5', and possibly 9 or 9' and 13 or 13'. Notably, the proton loss favored in I at the 5 position by DFT calculations, is unfavorable in II due to the epoxide at the 5, 6 position. DFT calculations predict the isotropic methyl proton couplings of 8-10 MHz for Car•+ which agree with the ENDOR for carotenoid α-conjugated radical cations. Large α-proton hyperfine coupling constants (>10 MHz) determined from HYSCORE are assigned from the DFT calculations to neutral carotenoid radicals. Proton loss upon photolysis was also examined as a function of carotenoid polarity [Lycopene (III) versus 8'-apo-β-caroten-8'-al (IV)]; hydrogen bonding [Lutein (V) versus III]; host [silica-alumina versus MCM-41 molecular sieve]; and substituted metal in MCM-41. Loss of H+ from the 5(5'), 9(9') or 13(13') methyl positions has importance in photoprotection. Photoprotection involves nonphotochemical quenching (NPQ) in which 1Ch1* decays via energy transfer to the carotenoid which returns to the ground state by thermal dissipation; or via electron transfer to form a charge transfer state (I •+…Chl•-), lower in energy than 1Chl*. Formation of I •+ results in bond lengthening, a mechanism for nonradiative energy

  5. Carotenoid cation formation and the regulation of photosynthetic light harvesting.

    PubMed

    Holt, Nancy E; Zigmantas, Donatas; Valkunas, Leonas; Li, Xiao-Ping; Niyogi, Krishna K; Fleming, Graham R

    2005-01-21

    Photosynthetic light harvesting in excess light is regulated by a process known as feedback deexcitation. Femtosecond transient absorption measurements on thylakoid membranes show selective formation of a carotenoid radical cation upon excitation of chlorophyll under conditions of maximum, steady-state feedback deexcitation. Studies on transgenic Arabidopsis thaliana plants confirmed that this carotenoid radical cation formation is correlated with feedback deexcitation and requires the presence of zeaxanthin, the specific carotenoid synthesized during high light exposure. These results indicate that energy transfer from chlorophyll molecules to a chlorophyllzeaxanthin heterodimer, which then undergoes charge separation, is the mechanism for excess energy dissipation during feedback deexcitation.

  6. Fourier transform infrared spectrum of the radical cation of beta-carotene photoinduced in photosystem II.

    PubMed

    Noguchi, T; Mitsuka, T; Inoue, Y

    1994-12-19

    A Fourier-transform infrared (FTIR) spectrum of the radical cation of beta-carotene photoinduced in photosystem II (PSII) membranes was obtained at 80K under oxidizing conditions, by utilizing the light-induced FTIR difference technique. Formation of the beta-carotene cation was monitored with the electronic absorption band at 993 nm. An FTIR spectrum of a chemically-generated beta-carotene cation in chloroform was also measured and compared with the spectrum of PSII. Since the FTIR bands of carotenoid cation have characteristic features with strong intensities, they can be useful markers in studying the reaction of carotenoid in PSII.

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

    NASA Technical Reports Server (NTRS)

    Jackson, William M.

    1992-01-01

    Two theoretical models for the formation of radicals from ice grains are examined to determine if this can explain the jets in comets. It is shown that the production rates for these radicals by the photolysis of molecules in the icy grains are not high enough to explain the jets. A new mechanism is proposed involving the release of cations and anions in the gas phase as the icy mantle surrounding the grains is evaporated. Solar visible radiation can then form radicals by photodetachment of the electrons from these anions. The production rate of radicals formed in this manner is in accord with the production rates of the observed radicals.

  8. Pyridine radical cation and its fluorine substituted derivatives

    USGS Publications Warehouse

    Bondybey, V.E.; English, J.H.; Shiley, R.H.

    1982-01-01

    The spectra and relaxation of the pyridine cation and of several of its fluorinated derivatives are studied in low temperature Ne matrices. The ions are generated by direct photoionization of the parent compounds. Of the compounds studied, laser induced → and → fluorescence is observed only for the 2, 6‐difluoropyridine cation. The analysis of the spectrum indicates that the ion is planar both in the and states. The large variety in the spectroscopic and relaxation behavior of fluoropyridine radical cations is explained in terms of their electronic structure and of the differential shifts of the individual electronic states caused by the fluorine substitution.

  9. Carotenoid cation radicals: electrochemical, optical, and EPR study

    SciTech Connect

    Grant, J.L.; Kramer, V.J.; Ding, R.; Kispert, L.D.

    1988-03-30

    The general aim of this investigation is to determine whether carotenoid cation radicals can be produced, and stabilized, electrochemically. Hence, the authors have undertaken a detailed study of the electrooxidation of various carotenoids (..beta..-carotene (I), ..beta..-apo-8'-carotenal (II), and canthaxanthin (III) using the techniques of cyclic voltammetry, controlled-potential electrolysis (cpe) in conjunction with optical spectroscopy, and EPR spectroscopy coupled with in situ electrolysis. They report the successful generation of carotenoid cation radicals via electrochemical oxidation and, furthermore, the stabilization of these radicals for several minutes in CH/sub 2/Cl/sub 2/ and C/sub 2/H/sub 4/Cl/sub 2/ solvents.

  10. Absorption and electroabsorption spectra of carotenoid cation radical and dication

    NASA Astrophysics Data System (ADS)

    Krawczyk, Stanisław

    1998-05-01

    Radical cations and dications of two carotenoids astaxanthin and canthaxanthin were prepared by oxidation with FeCl 3 in fluorinated alcohols at room temperature. Absorption and electroabsorption (Stark effect) spectra were recorded for astaxanthin cations in mixed frozen matrices at temperatures about 160 K. The D 0→D 2 transition in cation radical is at 835 nm. The electroabsorption spectrum for the D 0→D 2 transition exhibits a negative change of molecular polarizability, Δ α=-1.2·10 -38 C·m 2/V (-105 A 3), which seems to originate from the change in bond order alternation in the ground state rather than from the electric field-induced interaction of D 1 and D 2 excited states. Absorption spectrum of astaxanthin dication is located at 715-717 nm, between those of D 0→D 2 in cation radical and S 0→S 2 in neutral carotenoid. Its shape reflects a short vibronic progression and strong inhomogeneous broadening. The polarizability change on electronic excitation, Δ α=2.89·10 -38 C·m 2/V (260 A 3), is five times smaller than in neutral astaxanthin. This value reflects the larger energetic distance from the lowest excited state to the higher excited states than in the neutral molecule.

  11. Oxoferryl porphyrin cation radicals in model systems: Evidence for variable metal-radical spin coupling

    NASA Astrophysics Data System (ADS)

    Bill, E.; Bominaar, E. L.; Ding, X.-Q.; Trautwein, A. X.; Winkler, H.; Mandon, D.; Weiss, R.; Gold, A.; Jayaraj, K.; Toney, G. E.

    1990-07-01

    Magnetic properties of frozen solutions of highly oxidized iron porphyrin complexes were investigated by EPR and Mössbauer spectroscopy. The Mössbauer spectra, recorded at low temperatures in various magnetic fields, were analyzed on the basis of spin Hamiltonian simulations. Spin coupling between ferryl iron (FeIV) and porphyrin cation radical was taken into account explicitly. Hyperfine and spin-coupling parameters are given for several complexes, together with zero-field parameters. One of the complexes exhibits weak spin coupling, it is the first model system exhibiting properties comparable to those of the oxoferryl cation radical enzyme Horse Radish Peroxidase I.

  12. Tuning aryl, hydrazine radical cation electronic interactions using substituent effects.

    PubMed

    Valverde-Aguilar, Guadalupe; Wang, Xianghuai; Plummer, Edward; Lockard, Jenny V; Zink, Jeffrey I; Luo, Yun; Weaver, Michael N; Nelsen, Stephen F

    2008-08-14

    Absorption spectra for 2,3-diaryl-2,3-diazabicyclo[2.2.2]octane radical cations (2(X)(*+)) and for their monoaryl analogues 2-tert-butyl-3-aryl-2,3-diazabicyclo[2.2.2]octane radical cations (1(X)(*+)) having para chloro, bromo, iodo, cyano, phenyl, and nitro substituents are reported and compared with those for the previously reported 1- and 2(H)(*+) and 1- and 2(OMe)(*+). The calculated geometries and optical absorption spectra for 2(Cl)(*+) demonstrate that p-C6H4Cl lies between p-C6H4OMe and C6H5 in its ability to stabilize the lowest energy optical transition of the radical cation, which involves electron donation from the aryl groups toward the pi*(NN)(+)-centered singly occupied molecular orbital of 2(X)(*+). Resonance Raman spectral determination of the reorganization energy for their lowest energy transitions (lambda(v)(sym)) increase in the same order, having values of 1420, 5300, and 6000 cm(-1) for X = H, Cl, and OMe, respectively. A neighboring orbital analysis using Koopmans-based calculations of relative orbital energies indicates that the diabatic aryl pi-centered molecular orbital that interacts with the dinitrogen pi system lies closest in energy to the bonding pi(NN)-centered orbital and has an electronic coupling with it of about 9200 +/- 600 cm(-1), which does not vary regularly with electron donating power of the X substituent.

  13. Nature of the lowest excited states of neutral polyenyl radicals and polyene radical cations

    NASA Astrophysics Data System (ADS)

    Starcke, Jan Hendrik; Wormit, Michael; Dreuw, Andreas

    2009-10-01

    Due to the close relation of the polyenyl radicals C2n+1H2n+3• and polyene radical cations C2nH2n+2•+ to the neutral linear polyenes, one may suspect their excited states to possess substantial double excitation character, similar to the famous S1 state of neutral polyenes and thus to be equally problematic for simple excited state theories. Using the recently developed unrestricted algebraic-diagrammatic construction scheme of second order perturbation theory and the equation-of-motion coupled-cluster method, the vertical excitation energies, their corresponding oscillator strengths, and the nature of the wave functions of the lowest excited electronic states of the radicals are calculated and analyzed in detail. For the polyenyl radicals two one-photon allowed states are found as D1 and D4 states, with two symmetry-forbidden D2 and D3 states in between, while in the polyene radical cations D1 and D2 are allowed and D3 is forbidden. The order of the states is conserved with increasing chain length. It is found that all low-lying excited states exhibit a significant but similar amount of doubly excited configuration in their wave functions of 15%-20%. Using extrapolation, predictions for the excitation energies of the five lowest excited states of the polyene radical cations are made for longer chain lengths.

  14. Kinetics for Tautomerizations and Dissociations of Triglycine Radical Cations

    SciTech Connect

    Siu, Chi-Kit; Zhao, Junfang; Laskin, Julia; Chu, Ivan K.; Hopkinson, Alan C.; Siu , K W Michael

    2009-06-01

    Fragmentations of tautomers of the α-centered radical triglycine radical cation, [GGG*]+, [GG*G]+, and [G*GG]+, are charge-driven, giving b-type ions; these are processes that are facilitated by a mobile proton, as in the fragmentation of protonated triglycine (Rodriquez, C.F. et al. J. Am. Chem. Soc. 2001, 123, 3006 - 3012). By contrast, radical centers are less mobile. Two mechanisms have been examined theoretically utilizing density functional theory and Rice-Ramsperger-Kassel-Marcus modeling: (1) a direct hydrogen-atom migration between two α-carbons, and (2) a two-step proton migration involving a canonical [GGG]*+ as an intermediate. Predictions employing the latter mechanism are in good agreement with results of recent CID experiments (Chu, I.K. et al. J. Am. Chem. Soc. 2008, 130, 7862 - 7872).

  15. Dynamics of radical cations of poly(4-hydroxystyrene) in the presence and absence of triphenylsulfonium triflate as determined by pulse radiolysis of its highly concentrated solution

    NASA Astrophysics Data System (ADS)

    Okamoto, Kazumasa; Ishida, Takuya; Yamamoto, Hiroki; Kozawa, Takahiro; Fujiyoshi, Ryoko; Umegaki, Kikuo

    2016-07-01

    Pulse radiolysis of highly concentrated poly(4-hydroxystyrene) (PHS) solutions in cyclohexanone and p-dioxane was performed both with and without an onium-type photoacid generator (PAG). With increasing PHS concentration, the rate constant of deprotonation of PHS radical cations was found to decrease. In the presence of PAG, the yield of the multimer radical cation of PHS was shown to decrease. We found that pairing between the anions produced by the attachment of dissociative electrons of PAGs and the monomer PHS radical cations restrict local molecular motions, leading to the formation of the multimer PHS radical cations.

  16. Multi-State Vibronic Interactions in Fluorinated Benzene Radical Cations.

    NASA Astrophysics Data System (ADS)

    Faraji, S.; Köppel, H.

    2009-06-01

    Conical intersections of potential energy surfaces have emerged as paradigms for signalling strong nonadiabatic coupling effects. An important class of systems where some of these effects have been analyzed in the literature, are the benzene and benzenoid cations, where the electronic structure, spectroscopy, and dynamics have received great attention in the literature. In the present work a brief overview is given over our theoretical treatments of multi-mode and multi-state vibronic interactions in the benzene radical cation and some of its fluorinated derivatives. The fluorobenzene derivatives are of systematic interest for at least two different reasons. (1) The reduction of symmetry by incomplete fluorination leads to a disappearance of the Jahn-Teller effect present in the parent cation. (2) A specific, more chemical effect of fluorination consists in the energetic increase of the lowest σ-type electronic states of the radical cations. The multi-mode multi-state vibronic interactions between the five lowest electronic states of the fluorobenzene radical cations are investigated theoretically, based on ab initio electronic structure data, and employing the well-established linear vibronic coupling model, augmented by quadratic coupling terms for the totally symmetric vibrational modes. Low-energy conical intersections, and strong vibronic couplings are found to prevail within the set of tilde{X}-tilde{A} and tilde{B}-tilde{C}-tilde{D} cationic states, while the interactions between these two sets of states are found to be weaker and depend on the particular isomer. This is attributed to the different location of the minima of the various conical intersections occurring in these systems. Wave-packet dynamical simulations for these coupled potential energy surfaces, utilizing the powerful multi-configuration time-dependent Hartree method are performed. Ultrafast internal conversion processes and the analysis of the MATI and photo-electron spectra shed new light

  17. Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical

    SciTech Connect

    Peter R. Craig; Miller, John R.; Havlas, Zdenek; Trujillo, Marianela; Rempala, Pawel; Kirby, James P.; Noll, Bruce C.; Michl, Josef

    2016-05-02

    In this study, properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative 1a have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF4 anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and 1a have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical, whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by ~0.1 V upon going from 1 to 1a

  18. Theoretical studies on the dimerization of substituted paraphenylenediamine radical cations

    NASA Astrophysics Data System (ADS)

    Punyain, Kraiwan; Kelterer, Anne-Marie; Grampp, Günter

    2011-12-01

    Organic radical cations form dicationic dimers in solution, observed experimentally as diamagnetic species in temperature-dependent EPR and low temperature UV/Vis spectroscopy. Dimerization of paraphenylenediamine, N,N-dimethyl-paraphenylenediamine and 2,3,5,6-tetramethyl-paraphenylenediamine radical cation in ethanol/diethylether mixture was investigated theoretically according to geometry, energetics and UV/Vis spectroscopy. Density Functional Theory including dispersion correction describes stable dimers after geometry optimization with conductor-like screening model of solvation and inclusion of the counter-ion. Energy corrections were done on double-hybrid Density Functional Theory with perturbative second-order correlation (B2PLYP-D) including basis set superposition error (BSSE), and multireference Møller-Plesset second-order perturbation theory method (MRMP2) based on complete active space method (CASSCF(2,2)) single point calculation, respectively. All three dication π-dimers exhibit long multicenter π-bonds around 2.9 ± 0.1 Å with strongly interacting orbitals. Substitution with methyl groups does not influence the dimerization process substantially. Dispersion interaction and electrostatic attraction from counter-ion play an important role to stabilize the dication dimers in solution. Dispersion-corrected double hybrid functional B2PLYP-D and CASSCF(2,2) can describe the interaction energetics properly. Vertical excitations were computed with Tamm-Dancoff approximation for time-dependent Density Functional Theory (TDA-DFT) at the B3LYP level with the cc-pVTZ basis set including ethanol solvent molecules explicitly. A strong interaction of the counter-ion and the solvent ethanol with the monomeric species is observed, whereas in the dimers the strong interaction of both radical cation species is the dominating factor for the additional peak in UV/Vis spectra.

  19. Structure and Reactivity of the N-Acetyl-Cysteine Radical Cation and Anion: Does Radical Migration Occur?

    NASA Astrophysics Data System (ADS)

    Osburn, Sandra; Berden, Giel; Oomens, Jos; O'Hair, Richard A. J.; Ryzhov, Victor

    2011-10-01

    The structure and reactivity of the N-acetyl-cysteine radical cation and anion were studied using ion-molecule reactions, infrared multi-photon dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations. The radical cation was generated by first nitrosylating the thiol of N-acetyl-cysteine followed by the homolytic cleavage of the S-NO bond in the gas phase. IRMPD spectroscopy coupled with DFT calculations revealed that for the radical cation the radical migrates from its initial position on the sulfur atom to the α-carbon position, which is 2.5 kJ mol-1 lower in energy. The radical migration was confirmed by time-resolved ion-molecule reactions. These results are in contrast with our previous study on cysteine methyl ester radical cation (Osburn et al., Chem. Eur. J. 2011, 17, 873-879) and the study by Sinha et al. for cysteine radical cation ( Phys. Chem. Chem. Phys. 2010, 12, 9794-9800) where the radical was found to stay on the sulfur atom as formed. A similar approach allowed us to form a hydrogen-deficient radical anion of N-acetyl-cysteine, (M - 2H) •- . IRMPD studies and ion-molecule reactions performed on the radical anion showed that the radical remains on the sulfur, which is the initial and more stable (by 63.6 kJ mol-1) position, and does not rearrange.

  20. A Photo Touch on Amines: New Synthetic Adventures of Nitrogen Radical Cations

    PubMed Central

    Maity, Soumitira; Zheng, Nan

    2013-01-01

    Amines have been used as sacrificial electron donors to reduce photoexcited Ru(II) or Ir(III) complexes, during which they are oxidized to nitrogen radical cations. Recently, the synthetic potential of these nitrogen radical cations have caught synthetic organic chemists’ attention. They have been exploited in various transformations yielding a number of elegant methods for amine synthesis. This article highlights recent developments on nitrogen radical cation chemistry under visible-light photocatalysis. PMID:23419975

  1. Electrochemical and electron paramagnetic resonance studies of a carotenoid cation radicals and dications: Effect of deuteration

    SciTech Connect

    Khaled, M.; Hadjipetrou, A.; Kispert, L. )

    1990-06-14

    The oxidation process involving the transfer of two electrons for {beta}-carotene is confirmed by bulk electrolysis in a CH{sub 2}Cl{sub 2} solvent and the observation of {Delta}E = 42 mV from cyclic voltammetric measurements. A similar process is also found to occur for {beta}-apo-8{prime}-carotenal and canthaxanthin. An additional cathodic peak between 0.2 0.5 relative to SCE is shown to be dependent on the initial formation of dications followed by the loss of H{sup +} as evidenced by a large isotope effect and most likely due to the reduction of a carotenoid cation. EPR evidence exists for the formation of radical cations by the reaction of diffusing carotenoid dictations with neutral carotenoids. The rate of formation is consistent with the differences in the diffusion coefficients of the carotenoids deduced by chronocoulometric measurements, being fastest for canthaxanthin.

  2. Carotenoid radical cations as a probe for the molecular mechanism of nonphotochemical quenching in oxygenic photosynthesis.

    PubMed

    Amarie, Sergiu; Standfuss, Jörg; Barros, Tiago; Kühlbrandt, Werner; Dreuw, Andreas; Wachtveitl, Josef

    2007-04-05

    Nonphotochemical quenching (NPQ) is a fundamental mechanism in photosynthesis which protects plants against excess excitation energy and is of crucial importance for their survival and fitness. Recently, carotenoid radical cation (Car*+) formation has been discovered to be a key step for the feedback deexcitation quenching mechanism (qE), a component of NPQ, of which the molecular mechanism and location is still unknown. We have generated and characterized carotenoid radical cations by means of resonant two color, two photon ionization (R2C2PI) spectroscopy. The Car*+ bands have maxima located at 830 nm (violaxanthin), 880 nm (lutein), 900 nm (zeaxanthin), and 920 nm (beta-carotene). The positions of these maxima depend strongly on solution conditions, the number of conjugated C=C bonds, and molecular structure. Furthermore, R2C2PI measurements on the light-harvesting complex of photosystem II (LHC II) samples with or without zeaxanthin (Zea) reveal the violaxanthin (Vio) radical cation (Vio*+) band at 909 nm and the Zea*+ band at 983 nm. The replacement of Vio by Zea in the light-harvesting complex II (LHC II) has no influence on the Chl excitation lifetime, and by exciting the Chls lowest excited state, no additional rise and decay corresponding to the Car*+ signal observed previously during qE was detected in the spectral range investigated (800-1050 nm). On the basis of our findings, the mechanism of qE involving the simple replacement of Vio with Zea in LHC II needs to be reconsidered.

  3. Reactions and structural investigation of chlorpromazine radical cation

    NASA Astrophysics Data System (ADS)

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

    2008-10-01

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

  4. Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical

    DOE PAGES

    Peter R. Craig; Miller, John R.; Havlas, Zdenek; ...

    2016-05-02

    In this study, properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative 1a have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF–4 anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and 1a have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical,more » whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by ~0.1 V upon going from 1 to 1a« less

  5. Are the Radical Centers in Peptide Radical Cations Mobile? The Generation, Tautomerism, and Dissociation of Isomeric α-Carbon-Centered Triglycine Radical Cations in the Gas Phase

    SciTech Connect

    Chu, Ivan K.; Zhao, Junfang; Xu, Minjie; Siu, Shiu On; Hopkinson, Alan C.; Siu , K W Michael

    2008-05-31

    The mobility of the radical center in three isomeric triglycine radical cationss[G•GG]+, [GG•G]+, and [GGG•]+shas been investigated theoretically via density functional theory (DFT) and experimentally via tandem mass spectrometry. These radical cations were generated by collision-induced dissociations (CIDs) of Cu(II)-containing ternary complexes that contain the tripeptides YGG, GYG, and GGY, respectively (G and Y are the glycine and tyrosine residues, respectively). Dissociative electron transfer within the complexes led to observation of [Y•GG]+, [GY•G]+, and [GGY•]+; CID resulted in cleavage of the tyrosine side chain as p-quinomethide, yielding [G•GG]+, [GG•G]+, and [GGG•]+, respectively. Interconversions between these isomeric triglycine radical cations have relatively high barriers (g44.7 kcal/mol), in support of the thesis that isomerically pure [G•GG]+, [GG•G]+, and [GGG•]+ can be experimentally produced. This is to be contrasted with barriers < 17 kcal/mol that were encountered in the tautomerism of protonated triglycine [Rodriquez C. F. et al. J. Am. Chem. Soc. 2001, 123, 3006-3012]. The CID spectra of [G•GG]+, [GG•G]+, and [GGG•]+ were substantially different, providing experimental proof that initially these ions have distinct structures. DFT calculations showed that direct dissociations are competitive with interconversions followed by dissociation.

  6. The chemistry of amine radical cations produced by visible light photoredox catalysis

    PubMed Central

    Hu, Jie; Wang, Jiang; Nguyen, Theresa H

    2013-01-01

    Summary Amine radical cations are highly useful reactive intermediates in amine synthesis. They have displayed several modes of reactivity leading to some highly sought-after synthetic intermediates including iminium ions, α-amino radicals, and distonic ions. One appealing method to access amine radical cations is through one-electron oxidation of the corresponding amines under visible light photoredox conditions. This approach and subsequent chemistries are emerging as a powerful tool in amine synthesis. This article reviews synthetic applications of amine radical cations produced by visible light photocatalysis. PMID:24204409

  7. Halogenated benzene radical cations and ground state degeneracy splitting by asymmetric substitution

    USGS Publications Warehouse

    Bondybey, V.E.; Vaughn, C.R.; Miller, T.A.; English, J.H.; Shiley, R.H.

    1981-01-01

    The absorption and laser induced fluorescence of several halogenated benzene radical cations were studied in solid Ne matrices. The spectra of 1,2,4-trifluorobenzene, l,3-dichloro-5-fluorobenzene, and l-chloro-3,5- difluorobenzene radical cations are observed and analyzed. Studies of fluorescence polarization and a photoselection technique were used to examine the splitting of the degeneracy of the benzene cation ground state by asymmetric subsitution. ?? 1981 American Institute of Physics.

  8. Formation of free radicals during phacoemulsification.

    PubMed

    Holst, A; Rolfsen, W; Svensson, B; Ollinger, K; Lundgren, B

    1993-04-01

    During phacoemulsification cavitation bubbles are formed. These bubbles are believed to be one source of damage to corneal endothelium seen after phacoemulsification. Free radicals are induced whenever cavitation bubbles implode. The aim of this study was to confirm the initiation of free radicals by phacoemulsification and to correlate the power of ultrasound in the phacoemulsification process to the amount of free radicals formed, using both in vitro and in vivo techniques. The formation of free radicals was determined by adding luminol to a buffer and measuring the chemoluminescence in vitro and in rabbit eyes (Lumacounter 2080 or a single-photon-counting apparatus) during phacoemulsification. The data obtained show that free radicals are formed during phacoemulsification and that the amount of free radicals correlates with the power of ultrasound. Furthermore, the radical formation could be inhibited by the radical scavengers SOD, Healon and Healon GV. These results were achieved both in vitro in the test tube and in vivo in rabbit eyes. By showing that the addition of SOD to the irrigation buffer during phacoemulsification decreases the corneal endothelial cell damage, we show that free radicals could have a role in postoperative complications seen clinically.

  9. Radiation-induced polymerisation of 2,3-dihydrofuran: free-radical or cationic mechanism?

    NASA Astrophysics Data System (ADS)

    Janovský, Igor; Naumov, Sergej; Knolle, Wolfgang; Mehnert, Reiner

    2005-02-01

    Concentrated (10 mol%) solutions of 2,3-dihydrofuran in CFCl 2CF 2Cl matrix were irradiated at 77 K and several intermediates (dimer radical cation, dihydrofuryl radical, and polymer radicals) were observed by low-temperature EPR spectroscopy. The irradiated solutions yielded after melting a polymeric product, which was characterised by IR spectroscopy and gel permeation chromatography. The polydisperse polymer is assumed to be formed mainly by a cationic process initiated by a dimer carbocation. The free-radical mechanism via the dihydrofuryl radical leads to low molecular weight oligomers only. Quantum chemical calculations support the interpretation of the experimental results.

  10. High-level ab initio predictions for the ionization energy, electron affinity, and heats of formation of cyclopentadienyl radical, cation, and anion, C5H5/C5H5+/C5H5-.

    PubMed

    Lo, Po-Kam; Lau, Kai-Chung

    2014-04-03

    The ionization energy (IE), electron affinity (EA), and heats of formation (ΔH°f0/ΔH°f298) for cyclopentadienyl radical, cation, and anion, C5H5/C5H5(+)/C5H5(-), have been calculated by wave function-based ab initio CCSDT/CBS approach, which involves approximation to complete basis set (CBS) limit at coupled-cluster level with up to full triple excitations (CCSDT). The zero-point vibrational energy correction, core-valence electronic correction, scalar relativistic effect, and higher-order corrections beyond the CCSD(T) wave function are included in these calculations. The allylic [C5H5((2)A2)] and dienylic [C5H5((2)B1)] forms of cyclopentadienyl radical are considered: the ground state structure exists in the dienyl form and it is about 30 meV more stable than the allylic structure. Both structures are lying closely and are interconvertible along the normal mode of b2 in-plane vibration. The CCSDT/CBS predictions (in eV) for IE[C5H5(+)((3)A1')←C5H5((2)B1)] = 8.443, IE[C5H5(+)((1)A1)←C5H5((2)B1)] = 8.634 and EA[C5H5(-)((1)A1')←C5H5((2)B1)] = 1.785 are consistent with the respective experimental values of 8.4268 ± 0.0005, 8.6170 ± 0.0005, and 1.808 ± 0.006, obtained from photoelectron spectroscopic measurements. The ΔH°f0/ΔH°f298's (in kJ/mol) for C5H5/C5H5(+)/C5H5(-) have also been predicted by the CCSDT/CBS method: ΔH°f0/ΔH°f298[C5H5((2)B1)] = 283.6/272.0, ΔH°f0/ΔH°f298[C5H5(+)((3)A1')] = 1098.2/1086.9, ΔH°f0/ΔH°f298[C5H5(+)((1)A1)] = 1116.6/1106.0, and ΔH°f0/ΔH°f298[C5H5(-)((1)A1')] = 111.4/100.0. The comparisons between the CCSDT/CBS predictions and the experimental values suggest that the CCSDT/CBS procedure is capable of predicting reliable IE(C5H5)'s and EA(C5H5) with uncertainties of ± 17 and ± 23 meV, respectively.

  11. The role of the position of the basic residue in the generation and fragmentation of peptide radical cations

    NASA Astrophysics Data System (ADS)

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

    2006-03-01

    Using simple di- and tripeptides GX, GGX, GXG, XG and XGG, the influence of the position of the basic residue, X (X = R, K and H), on the formation of peptide radical cations (M+) from [CuII(tpy)M]2+ complexes (where tpy = 2,2':6',2''-terpyridine) was probed. It was found that M+ is formed with greatest abundance when the basic residue is at the C-terminus. For arginine containing peptides, this may be due to further fragmentation of GRG+, RG+ and RGG+ at the MS2 stage. For lysine and histidine containing peptides, when the basic residue is not located at the C-terminus, competing fragmentation pathways that lead to peptide backbone cleavage are more facile than M+ formation. In order to gain some insights into the binding modes of these peptides to [CuII(tpy)]2+, the formation and fragmentation of copper(II) complexes of tripeptides protected as their carboxy methyl/ethyl esters (M-OR', R' = Me/Et) were also probed. The products of the competing fragmentation pathways of [CuII(tpy)M]2+, as well as the formation and fragmentation of [CuII(tpy)(M-OR')]2+, suggest that the unprotected peptides, M, mainly bind as zwitterions to [CuII(tpy)]2+. The fragmentation reactions of the radical cations (M+) were also studied. Radical driven side chain fragmentation reactions of M+ are dependent on both the position of the residue as well as the identity of other residues present in the peptide radical cations. GR and RG, which undergo rearrangement to form a mixed anhydride in their protonated forms, do not undergo the same rearrangement in their radical cation forms.

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

    NASA Astrophysics Data System (ADS)

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

    2006-01-01

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

  13. Generation of oxoiron (IV) tetramesitylporphyrin pi-cation radical complexes by m-CPBA oxidation of ferric tetramesitylporphyrin derivatives in butyronitrile at - 78 degrees C. Evidence for the formation of six-coordinate oxoiron (IV) tetramesitylporphyrin pi-cation radical complexes FeIV = O(tmp*)X (X = Cl-, Br-), by Mössbauer and X-ray absorption spectroscopy.

    PubMed

    Wolter, T; Meyer-Klaucke, W; Müther, M; Mandon, D; Winkler, H; Trautwein, A X; Weiss, R

    2000-01-30

    The generation of six-coordinate oxoiron (IV) tetramesitylporphyrin pi-caption radical complexes by m-CPBA (meta-chloroperbenzoic acid) oxidation of ferric tetramesitylporphyrin derivatives in butyronitrile at - 78 degrees C was investigated. UV-Vis and EPR spectroscopies indicate that the axial ligand present in the ferric starting derivatives is retained in the high-valent iron complexes. Indirect evidence for the formation of six-coordinate oxoiron (IV) tetramesitylporphyrin complexes FeIV = O(tmp*)X (X=Cl-, Br-) by m-CPBA oxidation of FeX(tmp) (X=Cl-, Br-) in butyronitrile at - 78 degrees C was also obtained by Mössbauer spectroscopy. Direct confirmation of the presence of a halide ion as second axial ligand of iron in these high-valent iron species was obtained by X-ray absorption spectroscopy. The EXAFS spectra of the samples obtained by m-CPBA oxidation of FeX(tmp) (X=Cl-, Br-) were refined using two different coordination models including both four porphyrinato-nitrogens and the axial oxo group. The two models include (model I) or exclude (model II) the axial halogen. The statistical tests indicate the presence of a halide ion as second axial ligand of iron in both derivatives. The refinements led to the following bond distances: FeIV=O(tmp*)Cl(3):Fe-O=1.66(1),Fe-Cl=2.39(2) and Fe-Np=1.99(1) A;FeIV=O(tmp*)Br(4):Fe-O=1.65(1),Fe-Br=2.93(2), Fe-Np=2.02(1) A. The lengthening of the Fe-X(X=Cl-, Br-) distances relative to those occurring in the ferric precursor porphyrins is, most probably, related to the strong trans influence of the oxoiron(IV) fragment present in 3 or 4.

  14. Reactivity and acid-base behavior of ring-methoxylated arylalkanoic acid radical cations and radical zwitterions in aqueous solution. Influence of structural effects and pH on the benzylic C-H deprotonation pathway.

    PubMed

    Bietti, Massimo; Capone, Alberto

    2006-07-07

    A product and time-resolved kinetic study of the one-electron oxidation of ring-methoxylated phenylpropanoic and phenylbutanoic acids (Ar(CH2)nCO2H, n = 2, 3) has been carried out at different pH values. Oxidation leads to the formation of aromatic radical cations (Ar.+(CH2)nCO2H) or radical zwitterions (Ar.+(CH2)nCO2-) depending on pH, and pKa values for the corresponding acid-base equilibria have been measured. In the radical cation, the acidity of the carboxylic proton decreases by increasing the number of methoxy ring substituents and by increasing the distance between the carboxylic group and the aromatic ring. At pH 1.7 or 6.7, the radical cations or radical zwitterions undergo benzylic C-H deprotonation as the exclusive side-chain fragmentation pathway, as clearly shown by product analysis results. At pH 1.7, the first-order deprotonation rate constants measured for the ring-methoxylated arylalkanoic acid radical cations are similar to those measured previously in acidic aqueous solution for the alpha-C-H deprotonation of structurally related ring-methoxylated alkylaromatic radical cations. In basic solution, the second-order rate constants for reaction of the radical zwitterions with (-)OH (k-OH)) have been obtained. These values are similar to those obtained previously for the (-)OH-induced alpha-C-H deprotonation of structurally related ring-methoxylated alkylaromatic radical cations, indicating that under these conditions the radical zwitterions undergo benzylic C-H deprotonation. Very interestingly, with 3,4-dimethoxyphenylethanoic acid radical zwitterion, that was previously observed to undergo exclusive decarboxylation up to pH 10, competition between decarboxylation and benzylic C-H deprotonation is observed above pH 11.

  15. UV/Vis Action Spectroscopy and Structures of Tyrosine Peptide Cation Radicals in the Gas Phase.

    PubMed

    Viglino, Emilie; Shaffer, Christopher J; Tureček, František

    2016-06-20

    We report the first application of UV/Vis photodissociation action spectroscopy for the structure elucidation of tyrosine peptide cation radicals produced by oxidative intramolecular electron transfer in gas-phase metal complexes. Oxidation of Tyr-Ala-Ala-Ala-Arg (YAAAR) produces Tyr-O radicals by combined electron and proton transfer involving the phenol and carboxyl groups. Oxidation of Ala-Ala-Ala-Tyr-Arg (AAAYR) produces a mixture of cation radicals involving electron abstraction from the Tyr phenol ring and N-terminal amino group in combination with hydrogen-atom transfer from the Cα positions of the peptide backbone.

  16. Radical cations of sulfides and disulfides: An ESR study

    SciTech Connect

    Bonazzola, L.; Michaut, J.P.; Roncin, J.

    1985-09-15

    Exposure of dilute solutions of dimethylsulfide, methanethiol, tetrahydrothiophene, terbutyl and diterbutyl-sulfides, dimethyl-disulfide, and diterbutyldisulfide, in freon at 77 K to /sup 60/Co ..gamma.. rays gave the corresponding cations. From the reported ESR spectra, g tensors were obtained. It was found that both sulfide and disulfide cations exhibit the same g tensor: (g/sub max/ = 2.034 +- 0.002, g/sub int/ = 2.017 +- 0.001, g/sub min/ = 2.001 +- 0.005). From this result it has been shown that the disulfide cation is planar. This finding was supported by fully optimized geometry ab initio calculations.

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

    NASA Astrophysics Data System (ADS)

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

    2004-05-01

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

  18. EPR and DFT Study of the Polycyclic Aromatic Radical Cations from Friedel-Crafts Alkylation Reactions

    NASA Astrophysics Data System (ADS)

    Wang, Tao; Wu, An-an; Gao, Li-guo; Wang, Han-qing

    2009-02-01

    Electron paramagnetic resonance and electron-nuclear double resonance methods were used to study the polycyclic aromatic radical cations produced in a Friedel-Crafts alkylating system, with m-xylene, or p-xylene and alkyl chloride. The results indicate that the observed electron paramagnetic resonance spectra are due to polycyclic aromatic radicals formed from the parent hydrocarbons. It is suggested that benzyl halides produced in the Friedel-Crafts alkylation reactions undergo Scholl self-condensation to give polycyclic aromatic hydrocarbons, which are converted into corresponding polycyclic aromatic radical cations in the presence of AlCl3. The identification of observed two radicals 2,6-dimethylanthracene and 1,4,5,8-tetramethylanthracene were supported by density functional theory calculations using the B3LYP/6-31G(d,p)//B3LYP/6-31G(d) approach. The theoretical coupling constants support the experimental assignment of the observed radicals.

  19. Theoretical study of second-order hyperpolarizability for nitrogen radical cation

    NASA Astrophysics Data System (ADS)

    Tarazkar, Maryam; Romanov, Dmitri A.; Levis, Robert J.

    2015-05-01

    We report calculations of the static and dynamic hyperpolarizabilities of the nitrogen radical cation in doublet state. The electronic contributions were computed analytically using density functional theory and multi-configurational self-consistent field method with extended basis sets for non-resonant excitation. The open-shell electronic system of nitrogen radical cation provides negative second-order optical nonlinearity, suggesting that the hyperpolarizability coefficient, {{γ }(2)}, in the non-resonant regime is mainly composed of combinations of virtual one-photon transitions rather than two-photon transitions. The second-order optical properties of nitrogen radical cation have been calculated as a function of bond length starting with the neutral molecular geometry (S0 minimum) and stretching the N-N triple bond, reaching the ionic D0 relaxed geometry all the way toward dissociation limit, to investigate the effect of internuclear bond distance on second-order hyperpolarizability.

  20. [Spectral-kinetic characteristics of the cation-radical of pheophytin a].

    PubMed

    Evstigneev, V B

    1977-01-01

    The photochemical generation of pheophytin a cation-radical in acidulated ethanol and aceto nitril has been studied by the method of flash-photolysis. The bands with maxima at 450, 580 and 800 nm correspond to pheophytin a cation-radical in the differential absorption spectra. The efficient rate constants of pheophytin a triplet state desactivation in ethanol, acetonitril, aceton have the following values: 1.5.10(4), 9.10(3), 8.7.10(3) sec(-1) correspondingly. The rate constant of electron transfer from pheophytin a to p-benzoqui-none in ethanol solutions is 7.8.10(9) l/m.sec. The recombination constants of pheophytin a cation-radical with Q-in acetonitril, and with quinone neutral (QH) in acidulated ethanol have the following values: 5.10(9) and 2.10(9) l/m.sec correspondingly.

  1. Fingerprinting DNA oxidation processes: IR characterization of the 5-methyl-2'-deoxycytidine radical cation.

    PubMed

    Bucher, Dominik B; Pilles, Bert M; Pfaffeneder, Toni; Carell, Thomas; Zinth, Wolfgang

    2014-02-24

    Methylated cytidine plays an important role as an epigenetic signal in gene regulation. Its oxidation products are assumed to be involved in active demethylation processes but also in damaging DNA. Here, we report the photochemical production of the 5-methyl-2'-deoxycytidine radical cation via a two-photon ionization process. The radical cation is detected by time-resolved IR spectroscopy and identified by band assignment using density functional theory calculations. Two final oxidation products are characterized with liquid chromatography coupled to mass spectrometry.

  2. Lifetimes and reaction pathways of guanine radical cations and neutral guanine radicals in an oligonucleotide in aqueous solutions.

    PubMed

    Rokhlenko, Yekaterina; Geacintov, Nicholas E; Shafirovich, Vladimir

    2012-03-14

    The exposure of guanine in the oligonucleotide 5'-d(TCGCT) to one-electron oxidants leads initially to the formation of the guanine radical cation G(•+), its deptotonation product G(-H)(•), and, ultimately, various two- and four-electron oxidation products via pathways that depend on the oxidants and reaction conditions. We utilized single or successive multiple laser pulses (308 nm, 1 Hz rate) to generate the oxidants CO(3)(•-) and SO(4)(•-) (via the photolysis of S(2)O(8)(2-) in aqueous solutions in the presence and absence of bicarbonate, respectively) at concentrations/pulse that were ∼20-fold lower than the concentration of 5'-d(TCGCT). Time-resolved absorption spectroscopy measurements following single-pulse excitation show that the G(•+) radical (pK(a) = 3.9) can be observed only at low pH and is hydrated within 3 ms at pH 2.5, thus forming the two-electron oxidation product 8-oxo-7,8-dihydroguanosine (8-oxoG). At neutral pH, and single pulse excitation, the principal reactive intermediate is G(-H)(•), which, at best, reacts only slowly with H(2)O and lives for ∼70 ms in the absence of oxidants/other radicals to form base sequence-dependent intrastrand cross-links via the nucleophilic addition of N3-thymidine to C8-guanine (5'-G*CT* and 5'-T*CG*). Alternatively, G(-H)(•) can be oxidized further by reaction with CO(3)(•-), generating the two-electron oxidation products 8-oxoG (C8 addition) and 5-carboxamido-5-formamido-2-iminohydantoin (2Ih, by C5 addition). The four-electron oxidation products, guanidinohydantoin (Gh) and spiroiminodihydantoin (Sp), appear only after a second (or more) laser pulse. The levels of all products, except 8-oxoG, which remains at a low constant value, increase with the number of laser pulses.

  3. Formation of Carotenoid Neutral Radicals in Photosystem II

    PubMed Central

    Gao, Yunlong; Shinopoulos, Katherine E.; Tracewell, Cara A.; Focsan, A. Ligia; Brudvig, Gary W.; Kispert, Lowell D.

    2010-01-01

    β-carotene radicals produced in the hexagonal pores of the molecular sieve Cu(II)-MCM-41 were studied by ENDOR and visible/near IR spectroscopies. ENDOR studies showed that neutral radicals of β-carotene were produced in humid air under ambient fluorescent light. The maximum absorption wavelengths of the neutral radicals were measured and were additionally predicted by using time-dependent density functional theory (TD-DFT) calculations. An absorption peak at 750 nm, assigned to the neutral radical with a proton loss from the 4(4') position of the β-carotene radical cation in Cu(II)-MCM-41, was also observed in photosystem II (PS II) samples using near-IR spectroscopy after illumination at 20 K. This peak was previously unassigned in PS II samples. The intensity of the absorption peak at 750 nm relative to the absorption of chlorophyll radical cations and β-carotene radical cations increased with increasing pH of the PS II sample, providing further evidence that the absorption peak is due to the deprotonation of the β-carotene radical cation. Based on a consideration of possible proton acceptors that are adjacent to β-carotene molecules in photosystem II, as modeled in the X-ray crystal structure of Guskov et al. Nat. Struct. Mol. Biol. 2009, 16, 334-342, an electron-transfer pathway from a β-carotene molecule with an adjacent proton acceptor to P680•+ is proposed. PMID:19552399

  4. Cationic and radical intermediates in the acid photorelease from aryl sulfonates and phosphates.

    PubMed

    Terpolilli, Marco; Merli, Daniele; Protti, Stefano; Dichiarante, Valentina; Fagnoni, Maurizio; Albini, Angelo

    2011-01-01

    The irradiation of a series of phenyl sulfonates and phosphates leads to the quantitative release of acidity with a reasonable quantum yield (≈0.2). Products characterization, ion chromatography analysis and potentiometric titration are consistent with the intervening of two different paths in this reaction, viz. cationic with phosphates and (mainly) radical with sulfonates.

  5. Isomerization of 4-vinylcyclohexene radical cation. A tandem mass spectrometry study

    SciTech Connect

    Vollmer, D.; Rempel, D.L.; Gross, M. L. ); Williams, F. )

    1995-02-08

    Investigation by matrix-isolation ESR has shown that 4-vinylcyclohexene, 1, surprisingly undergoes isomerization to the bicyclo[3.2.1]oct-2-ene ion, 3. Here we demonstrate the occurrence of this isomerization in the gas phase by use of tandem (MS/MS) sector and Fourier transform (FT) mass spectrometries. The radical cations of 4-vinylcyclohexene (IE = 8.93 eV) or bicyclo[3.2.1]oct-2-ene (approximately 14 kcal/mol more stable than that of 4-vinylcyclohexene) were formed, in separate trials, in a chemical ionization (CI) source by electron ionization (EI). The radical cations were then studied by obtaining their collisionally activated decomposition (CAD) spectra. The CAD spectra are similar, indicating that the isomerization has occurred. Both the sector and the FT mass spectrometer results reflect those obtained in the matrix-isolation ESR investigation. That is isomerizes to 3 at high internal energy, but is stable at low internal energy. Two mechanisms explain this rearrangement. The second mechanism is questionable because the most stable olefin radical cation formed from 5 is that of bicyclo[2.2.2]-2-octene, which gives different ESR and CAD spectra than those of 1 or 3. The CAD spectrum of bicyclo[2.2.2]-2-octene radical cation indicates that the retro-Diels-Alder loss of ethylene is more facile than that from 1 or 3. 18 refs., 3 figs.

  6. Spectroscopy and decay dynamics of several methyl-and fluorine-substituted benzene radical cations

    USGS Publications Warehouse

    Bondybey, V.E.; Vaughn, C.; Miller, T.A.; English, J.H.; Shiley, R.H.

    1981-01-01

    Spectra of several fluorobenzene cation radicals containing 1-3 methyl substituents were observed in solid Ne matrix and analyzed. Comparisons between these compounds and other fluorobenzenes studied previously as well as comparisons between the B?? state lifetimes in the gas phase and in the matrix are used to gain a deeper insight into the B?? state decay dynamics. ?? 1981 American Chemical Society.

  7. Chronoamperometric study of the films formed by 4,4'-bipyridyl cation radical salts on mercury in the presence of iodide ions: consecutive two-dimensional phase transitions.

    PubMed

    Gómez, L; Ruiz, J J; Camacho, L; Rodríguez-Amaro, R

    2005-01-04

    This paper reports a new mathematical model for consecutive two-dimensional phase transitions that accounts for the chronoamperometric behavior observed in the formation of electrochemical phases by 4,4'-bipyridyl cation radical (BpyH(2)(*)(+)) on mercury in aqueous iodide solutions. Also, a new interpretation for the induction time is proposed.

  8. Spectral properties and reactivity of diarylmethanol radical cations in aqueous solution. Evidence for intramolecular charge resonance.

    PubMed

    Bietti, Massimo; Lanzalunga, Osvaldo

    2002-04-19

    Spectral properties and reactivities of ring-methoxylated diarylmethane and diarylmethanol radical cations, generated in aqueous solution by pulse and gamma-radiolysis and by the one-electron chemical oxidant potassium 12-tungstocobalt(III)ate, have been studied. The radical cations display three bands in the UV, visible, and vis-NIR regions of the spectrum. The vis-NIR band is assigned to an intramolecular charge resonance interaction (CR) between the neutral donor and charged acceptor rings, as indicated by the observation that the relative intensity of the vis-NIR band compared to that of the UV and visible bands does not increase with increasing substrate concentration and that the position and intensity of this band is influenced by the ring-substitution pattern. In acidic solution (pH = 4), monomethoxylated diarylmethanol radical cations 1a.(+ -)1e.(+) decay by C(alpha)-H deprotonation [k = (1.7-1.9) x 10(4)s(-1)] through the intermediacy of a ketyl radical, which is further oxidized in the reaction medium to give the corresponding benzophenones, as evidenced by both time-resolved spectroscopic and product studies. With the dimethoxylated radical cation 2.(+), C(alpha)-H deprotonation is instead significantly slower (k = 6.7 x 10(2)s(-1)). In basic solution, 1a.(+)-1e.(+) undergo (-)OH-induced deprotonation from the alpha-OH group with k(OH.)approximately equal to 1.4 x 10(10)M(-1)s(-1), leading to a ketyl radical anion, which is oxidized in the reaction medium to the corresponding benzophenone.

  9. Spectral and Kinetic Properties of Radical Cations Derived from Oxoisoaporphines: Relevance to Electron-Transfer Processes Involving Phytoalexins.

    PubMed

    De la Fuente, Julio R; Kciuk, Gabriel; Aliaga, Christian; Bobrowski, Krzysztof

    2014-05-16

    The thermally induced intermolecular electron transfer reaction in acetonitrile between the tetracyanoethylene (TCNE), a π-electron acceptor with a large electron affinity, and six oxoisoaporphines (2,3-dihydro-7H-dibenzo[de,h]quinolin-7-one, 5-methoxy-2,3-dihydro-7H-dibenzo[de,h]quinolin-7-one, 1-azabenzo[de]anthracen-7-one, 5-methoxy-1-azabenzo[de]anthracen-7-one, 7H-benzo[e]perimidin-7-one, and 2-methyl-7h-benzo[e]perimidin-7-one) is reported. Spectral and kinetic characteristics are presented for radical cations derived from these six oxoisoaporphines either generated by a thermal reaction or generated radiolytically in argon-saturated 1,2-dichloroethane, oxygen-saturated acetone, and acetonitrile. The radical cations of oxoisoaporphines are insensitive to oxygen and are mostly characterized by absorption maxima of their most intense bands located at λmax = 400-410 nm, except of the radical cations derived from 2,3-dihydrooxoisoaporphines. For the latter compounds, the absorption maxima of the most intense absorption bands are located at λmax = 290-295 nm. Their locations are independent of the presence of functional groups and the solvents used. They are formed in bimolecular processes with pseudo-first-order rate constants ranging from 2.1 × 10(5) to 1.5 × 10(6) s(-1) (in solutions containing 10(-4) M of the substrate), depending on the derivative and the solvent used. They are stable either when formed via the electron-transfer reaction with TCNE or when generated in isolation in pulse radiolysis of Ar-saturated 1,2-dichloroethane. In acetone and acetonitrile they decay predominantly by first-order kinetics with the first-order rate constants ranging from 2.3 × 10(4) to 5.1 × 10(4) s(-1). Formation of dimeric radical cations for all of the oxoisoaporphines studied was observed in acetonitrile solutions, and for azaoxoisoaporphines also in acetone solutions. The experimental spectra show a reasonably good agreement with the ZINDO/S semiempirical

  10. A combined EPR and DFT study of the overcrowded aromatic radical cations from Friedel-Crafts alkylation reactions

    NASA Astrophysics Data System (ADS)

    Wang, Tao; Tang, Fu Ming; Wu, Yi Fang

    2011-09-01

    Electron paramagnetic resonance and electron-nuclear double resonance methods were used to study the polycyclic aromatic radical cations produced in a Friedel-Crafts alkylating system, and the following radical cations were indentified: 3,6,11,14-tetramethyl dibenzo (a, c) triphylene and 2,6-dimethyl-9,10-di(p-methylbenzyl) anthracene radical cations. The results indicate that the observed electron paramagnetic resonance spectra are due to overcrowded polycyclic aromatic radical cations formed from the parent hydrocarbons. It is suggested that benzyl halides produced in the Friedel-Crafts alkylation reactions undergo Scholl condensation to give polycyclic aromatic hydrocarbons, which are converted into corresponding polycyclic aromatic radical cations in the presence of AlCl 3. We carried out the theoretical calculation of the isotropic 1H hyperfine coupling constants for studied both PAHs radical cations. The results indicate that the IEFPCM-DFT calculation at B3LYP level with 6-31++G(d,p), EPRII and EPRIII basis sets could well support the experimental hfcc assignment of the observed radicals. Optimized geometry indicates that the aromatic rings in both PAHs radical cations twisted significantly out of co-planarity.

  11. Multi-mode vibronic interactions in the five lowest electronic states of the fluorobenzene radical cation

    NASA Astrophysics Data System (ADS)

    Bâldea, Ioan; Franz, Jan; Szalay, Péter G.; Köppel, Horst

    2006-10-01

    The multi-mode vibronic interactions between the five lowest electronic states of the fluorobenzene radical cation are investigated theoretically, based on ab initio electronic structure data, and employing the linear vibronic coupling model. Low-energy conical intersections, and strong vibronic couplings are found to prevail within the set of X˜-A˜ and B˜-C˜-D˜ cationic states, while the interactions between these two sets of states are found to be rather weak (owing to high-energy conical intersections). The overall intensity distribution of the experimental photoelectron spectrum, as well as the line positions observed in the MATI spectrum, are well reproduced. The vibronic interactions in the X˜-A˜ states are found to be a replica of the multi-mode dynamical Jahn-Teller effect in the parent system, the XE ground state of the benzene radical cation. Ultrafast internal conversion processes within the electronic manifolds in question demonstrate the strength of the nonadiabatic coupling effects and complement the analogous findings for the electronic spectra. The implications for the fluorescence dynamics of the fluorobenzene radical cation are discussed.

  12. The first BETS radical cation salts with dicyanamide anion: Crystal growth, structure and conductivity study

    SciTech Connect

    Kushch, N.D.; Buravov, L.I.; Chekhlov, A.N.; Spitsina, N.G.; Kushch, P.P.; Yagubskii, E.B.; Herdtweck, E.; Kobayashi, A.

    2011-11-15

    Electrochemical oxidation of bis(ethylenedithio)tetraselenafulvalene (BETS) has been investigated. Simple and complex dicyanamides of transition metals (Mn{sup 2+}, Ni{sup 2+} and Fe{sup 2+}) were used as electrolytes. The correlation between composition of prepared radical cation salts and metal nature in electrolytes was established. Manganese dicyanamides provide the formation of BETS salts with the {l_brace}Mn[N(CN){sub 2}]{sub 3}{r_brace}- and [N(CN){sub 2}]-XH{sub 2}O anions. When Ni- or Fe-containing electrolytes were used only metalless BETS salts, {alpha}''-BETS{sub 2}[N(CN){sub 2}].2H{sub 2}O (I) and {theta}-BETS{sub 2}[N(CN){sub 2}].3.6H{sub 2}O (II), formed. Structures and conducting properties of these salts were analyzed. Both salts exhibit layered structure. Conducting radical cation layers have {alpha}'' (I)- or {theta}-type (II). Anion sheets appear as two-dimensional polymer networks of different types. These networks are formed by [N(CN)]{sub 2}{sup -} anions and water molecules interlinked by hydrogen bonds. Salt I is a semiconductor and II demonstrates resistance drop down to150 K at normal pressure and down to 72 K at {approx}0.4 kbar pressure. - Graphical abstract: We studied electrochemical oxidation of BETS donor in the presence of simple and/or complex dicyanamides of transition metals (Ni, Fe, Mn) as electrolytes. New conducting salts {alpha}''-BETS{sub 2}[N(CN){sub 2}].2H{sub 2}O and {theta}-BETS{sub 2}[N(CN){sub 2}].3.8H{sub 2}O have been synthesized and characterized. Highlights: > We studied electrochemical oxidation of BETS donor. > Dicyanamides of transition metals (Ni, Fe, Mn) were used as electrolytes. > We found a well-reproducible synthesis of magnetic superconductor BETS{sub 2}Mn[N(CN){sub 2}]{sub 3}. > Two new metalless BETS salts form when Ni and Fe electrolytes were used. > Their structure and conductivity were investigated.

  13. Photo-excitation of adenine cation radical [A•+] in the near UV-vis region produces sugar radicals in Adenosine and in its nucleotides

    PubMed Central

    Adhikary, Amitava; Khanduri, Deepti; Kumar, Anil; Sevilla, Michael D.

    2011-01-01

    In this study, we report the formation of ribose sugar radicals in high yields (85 – 100%) via photo-excitation of adenine cation radical (A•+) in Ado and its ribonucleotides. Photo-excitation of A•+ at low temperatures in homogenous aqueous glassy samples of Ado, 2′-AMP, 3′-AMP and 5′-AMP forms sugar radicals predominantly at C5′- and also at C3′-sites. The C5′• and C3′• sugar radicals were identified employing Ado deuterated at specific carbon sites: C1′, C2′, and at C5′. Phosphate substitution is found to deactivate sugar radical formation at the site of substitution. Thus, in 5′-AMP, C3′• is observed to be the main radical formed via photo-excitation at ca. 143 K whereas in 3′-AMP, C5′• is the only species found. These results were supported by results obtained employing 5′-AMP with specific deuteration at C5′-site (i.e., 5′,5′-D,D-5′-AMP). Moreover, contrary to the C5′• observed in 3′-dAMP, we find that C5′• in 3′-AMP shows a clear pH dependent conformational change as evidenced by a large increase in the C4′ β–hyperfine coupling on increasing the pH from 6 to 9. Calculations performed employing DFT (B3LYP/6-31G*) for C5′• in 3′-AMP show that the two conformations of C5′• result from strong hydrogen bond formation between the O5′-H and the 3′-phosphate dianion at higher pHs. Employing time-dependent density functional theory [TD-DFT, B3LYP/6-31G(d)] we show that in the excited state, the hole transfers to the sugar moiety and has significant hole localization at the C5′-site in a number of allowed transitions. This hole localization is proposed to lead to the formation of the neutral C5′-radical (C5′•) via deprotonation. PMID:19367991

  14. Self-assembly of three-dimensional supramolecular polymers through cooperative tetrathiafulvalene radical cation dimerization.

    PubMed

    Tian, Jia; Ding, Yu-Di; Zhou, Tian-You; Zhang, Kang-Da; Zhao, Xin; Wang, Hui; Zhang, Dan-Wei; Liu, Yi; Li, Zhan-Ting

    2014-01-07

    The self-assembly of a new type of three-dimensional (3D) supramolecular polymers from tetrahedral monomers in both organic and aqueous media is described. We have designed and synthesized two tetraphenylmethane derivatives T1 and T2, both of which bear four tetrathiafulvalene (TTF) units. When the TTF units were oxidized to the radical cation TTF(.+) , their pre-organized tetrahedral arrangement remarkably enhanced their intermolecular dimerization, leading to the formation of new 3D spherical supramolecular polymers. The structure of the supramolecular polymers has been inferred on the basis of UV/Vis absorption, electron paramagnetic resonance, cyclic voltammetry, and dynamic light scattering (DLS) analysis, as well as by comparing these properties with those of the self-assembled structures of mono-, di-, and tritopic control compounds. DLS experiments revealed that the spherical supramolecular polymers had hydrodynamic diameters of 68 nm for T1 (75 μM) in acetonitrile and 105 nm for T2 (75 μM) in water/acetonitrile (1:1). The 3D spherical structures of the supramolecular polymers formed in different solvents were also supported by SEM and AFM experiments.

  15. (Iso)pagodane radical cations in liquid hydrocarbons: `Time-resolved fluorescence-detected magnetic resonance` study of valence isomeric radical cations

    SciTech Connect

    Trifunac, A.D.; Werst, D.W.; Herges, R.; Neumann, H.; Prinzbach, H.; Etzkorn, M.

    1996-10-02

    The `tight` (T), cyclobutanoid, and the `extended` (E), {pi}-complex-like, four-centred-three-electron radical cations (4c/3e) derived from (iso)pagodanes and from the valence isomeric (iso)dienes can be viewed as well-separated stationary points on the reaction coordinate for the ethylene/ethylene radical cation [2+1]cycloaddition. So far, experimentally verified examples (ESR, CV, PE) are the extended [1.1.1.1](2{sup .+}) and iso-[2.2.1.1](4{sup .+})ions, persistent in fluid solution at room temperature, and the tight iso-[1.1.1.1]{sup .+} and [2.2.1.1]{sup .+} ions, observable only in Freon matrix (CFCl{sub 3}, {gamma}-rays, 77K). According to calculations, these are the thermodynamically more stable ones of the respective pairs of valence isomers. In this communication the direct observation of tight 1{sup .+} and the activation barrier for its isomerization into extended 2{sup .+} are reported. 16 refs., 3 figs., 1 tab.

  16. Efficient scavenging of β-carotene radical cations by antiinflammatory salicylates.

    PubMed

    Cheng, Hong; Liang, Ran; Han, Rui-Min; Zhang, Jian-Ping; Skibsted, Leif H

    2014-02-01

    The radical cation generated during photobleaching of β-carotene is scavenged efficiently by the anion of methyl salicylate from wintergreen oil in a second-order reaction approaching the diffusion limit with k2 = 3.2 × 10(9) L mol(-1) s(-1) in 9 : 1 v/v chloroform-methanol at 23 °C, less efficiently by the anion of salicylic acid with 2.2 × 10(8) L mol(-1) s(-1), but still of possible importance for light-exposed tissue. Surprisingly, acetylsalicylate, the aspirin anion, reacts with an intermediate rate in a reaction assigned to the anion of the mixed acetic-salicylic acid anhydride formed through base induced rearrangements. The relative scavenging rate of the β-carotene radical cation by the three salicylates is supported by DFT-calculations.

  17. The role of organic solvent radical cations in separations ligand degradation

    DOE PAGES

    Mezyk, Stephen P.; Mincher, Bruce J.; Dhiman, Surajdevprakash B.; ...

    2015-11-04

    The dodecane radical cation reaction rate constant with CMPO was measured using ps electron pulse radiolysis/absorption spectroscopy as k = (1.30 ± 0.11) x 1010 M-1 s-1 in dodecane/0.10 M CH2Cl2 solution. No reactivity increase occurred when these solutions were pre-contacted with nitric acid, similar to the behavior observed for TODGA. To corroborate these kinetic data with steady-state radiolysis measurements, where acid pre contacted CMPO showed significantly less degradation, it is proposed that the dodecane radical cation always reacts directly with TODGA, but for CMPO the charge-transfer occurs with the CMPO•HNO3 complex formed in the acid contacted solvent.

  18. The role of organic solvent radical cations in separations ligand degradation

    SciTech Connect

    Mezyk, Stephen P.; Mincher, Bruce J.; Dhiman, Surajdevprakash B.; Layne, Bobby; Wishart, James F.

    2015-11-04

    The dodecane radical cation reaction rate constant with CMPO was measured using ps electron pulse radiolysis/absorption spectroscopy as k = (1.30 ± 0.11) x 1010 M-1 s-1 in dodecane/0.10 M CH2Cl2 solution. No reactivity increase occurred when these solutions were pre-contacted with nitric acid, similar to the behavior observed for TODGA. To corroborate these kinetic data with steady-state radiolysis measurements, where acid pre contacted CMPO showed significantly less degradation, it is proposed that the dodecane radical cation always reacts directly with TODGA, but for CMPO the charge-transfer occurs with the CMPO•HNO3 complex formed in the acid contacted solvent.

  19. Compounds I of catalase and horse radish peroxidase: pi-cation radicals.

    PubMed

    Dolphin, D; Forman, A; Borg, D C; Fajer, J; Felton, R H

    1971-03-01

    Two-electron oxidation of cobaltous octaethylporphyrin [Co(II)(Et)(8)P] yields a stable pi-cation radical [Co(III)(Et)(8)P](2+.), the optical spectrum of which exhibits spectral changes dependent upon the nature of the counterion. Comparison of these spectra with those of Compounds I of horseradish peroxidase and catalase leads us to propose that these Compounds I contain a pi-cation radical of the heme prosthetic group. This proposal explains the oxidation level, optical spectra, and stability of the primary compounds without recourse to properties such as stoichiometric mixtures of special porphyrins, stable Fe(V) porphyrins, or unique conformers of heme porphyrins. Explanations are advanced to account for the missing electron spin resonance signal of Compound I of horseradish peroxidase.

  20. Intramolecular Electron Transfer in Bis(tetraalkyl Hydrazine) and Bis(hydrazyl) Radical Cations.

    NASA Astrophysics Data System (ADS)

    Chang, Hao

    A series of multicyclic bis(hydrazine) and bis(diazenium) compounds connected by relatively rigid hydrocarbon frameworks were prepared for the study of intramolecular electron transfer. The thermodynamics of electron removal of these compounds was investigated by cyclic voltammetry. The difference between the first and second oxidation potentials for the 4 sigma-bonded species was found to be larger for the bis(hydrazyl) radical systems than for the bis(hydrazines) by ca. 0.2 V (4.6 kcal/mol). This indicates a greater degree of interaction between the two nitrogen moieties for the hydrazyl systems, which is consistent with a greater degree of electronic coupling (H _{rm AB}) in these systems. The ESR spectra of the 4 sigma -bonded bis(hydrazine) radical cations indicate localized radical cations, which corresponds to slow intramolecular electron transfer on the ESR timescale. Conversely, the ESR spectra of the corresponding bis(hydrazyl) radical cation systems show nitrogen hyperfine splittings of a(4N) of ca. 4.5 G. This indicates that intramolecular electron transfer between the two nitrogen moieties is fast on the ESR timescale; the rate of exchange, k_ {rm ex} was estimated to be well above 1.9 times 10^8 s^{-1}. The contrast in exchange rates is consistent with the large geometry change upon oxidation which is characteristic of hydrazines. The hydrazyls undergo a smaller geometry change upon oxidation, and thus are expected to exhibit smaller inner-sphere reorganization energies. The optical spectra of these radical species was investigated in hopes of observing absorption bands corresponding to intramolecular electron transfer, as predicted by Hush theory. A broad absorption band was observed in the near IR region for the saturated bis(hydrazyl) radical cation system at 1060 nm (9420 cm^{-1} ) in acetonitrile at room temperature, and was accompanied by a narrower band at 1430 nm (6993 cm^ {-1}). The width of this band was estimated to be 545 nm (6496 cm^{-1

  1. The radical cation of syn-tricyclooctadiene and its rearrangement products

    PubMed

    Bally; Bernhard; Matzinger; Roulin; Sastry; Truttmann; Zhu; Marcinek; Adamus; Kaminski; Gebicki; Williams; Chen; Fulscher

    2000-03-03

    The syn dimer of cyclobutadiene (tricyclo[4.2.0.0(2.5)]octa-3,7-diene, TOD) is subjected to ionization under different conditions and the resulting species are probed by optical and ESR spectroscopy. By means of quantum chemical modelling of the potential energy surfaces and the optical spectra, it is possible to assign the different products that arise spontaneously after ionization or after subsequent warming or illumination of the samples. Based on these findings, we propose a mechanistic scheme which involves a partitioning of the incipient radical cation of TOD between two electronic states. These two states engage in (near) activation-less decay to the more stable valence isomers, cyclooctatetraene (COT*+) and a bis-cyclobutenylium radical cation BCB*+. The latter product undergoes further rearrangement, first to tetracyclo[4.2.0.0(2,4).0(3,5]oct-7-ene (TCO*+) and eventually to bicyclo[4.2.0]octa-2,4,7-triene (BOT*+) which can also be generated photochemically from BCB*+ or TCO*+. The surprising departure of syn-TOD*+ from the least-motion reaction path leading to BOT*+ can be traced to strong vibronic interactions (second-order Jahn-Teller effects) which prevail in both possible ground states of syn-TOD*+. Such effects seem to be more important in determining the intramolecular reactivity of radical cations than orbital or state symmetry rules.

  2. The lightest organic radical cation for charge storage in redox flow batteries

    SciTech Connect

    Huang, Jinhua; Pan, Baofei; Duan, Wentao; Wei, Xiaoliang; Assary, Rajeev S.; Su, Liang; Brushett, Fikile; Cheng, Lei; Liao, Chen; Ferrandon, Magali S.; Wang, Wei; Zhang, Zhengcheng; Burrell, Anthony K.; Curtiss, Larry A.; Shkrob, Ilya A.; Moore, Jeffrey S.; Zhang, Lu

    2016-08-25

    Electrochemically reversible fluids of high energy density are promising materials for capturing the electrical energy generated from intermittent sources like solar and wind. To meet this technological challenge there is a need to understand the fundamental limits and interplay of electrochemical potential, stability and solubility in “lean” derivatives of redox-active molecules. Here we describe the process of molecular pruning, illustrated for 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene, a molecule known to produce a persistently stable, high-potential radical cation. By systematically shedding molecular fragments considered important for radical cation steric stabilization, we discovered a minimalistic structure that retains long-term stability in its oxidized form. Interestingly, we find the tert-butyl groups are unnecessary; high stability of the radical cation and high solubility are both realized in derivatives having appropriately positioned arene methyl groups. These stability trends are rationalized by mechanistic considerations of the postulated decomposition pathways. We suggest that the molecular pruning approach will uncover lean redox active derivatives for electrochemical energy storage leading to materials with long-term stability and high intrinsic capacity.

  3. β-carotene radical cation addition to green tea polyphenols. Mechanism of antioxidant antagonism in peroxidizing liposomes.

    PubMed

    Song, Lin-Lin; Liang, Ran; Li, Dan-Dan; Xing, Ya-Dong; Han, Rui-Min; Zhang, Jian-Ping; Skibsted, Leif H

    2011-12-14

    Green tea polyphenols, (-)-epicatechin (EC), (-)-epigallocatechin (EGC), (-)-epicatechin gallate (ECG), and (-)-epigallocatechin gallate (EGCG), all showed antioxidative effect in liposomes for lipid oxidation initiated in the lipid phase (antioxidant efficiency EC > EGCG > ECG > EGC) or in the aqueous phase (EC ≫ EGC > EGCG > ECG) as monitored by the formation of conjugated dienes. For initiation in the lipid phase, β-carotene, itself active as an antioxidant, showed antagonism with the polyphenols (EC > ECG > EGCG > EGC). The Trolox equivalent antioxidant capacity (TEAC EGC > EGCG > ECG > EC) correlates with the lowest phenol O-H bond dissociation enthalpy (BDE) as calculated by density functional theory (DFT). Surface-enhanced Raman spectroscopy (SERS) was used to assess the reducing power of the phenolic hydroxyls in corroboration with DFT calculations. For homogeneous (1:9 v/v methanol/chloroform) solution, the β-carotene radical cation reacted readily with each of the polyphenol monoanions (but not with the neutral polyphenols) with a rate approaching the diffusion limit for EC as studied by laser flash photolysis at 25 °C monitoring the radical cation at 950 nm. The rate constant did not correlate with polyphenol HOMO/LUMO energy gap (DFT calculations), and β-carotene was not regenerated by an electron transfer reaction (monitored at 500 nm). It is suggested that the β-carotene radical cation is rather reacting with the tea polyphenols through addition, as further evidenced by steady-state absorption spectroscopy and liquid chromatography-mass spectroscopy (LC-MS), in effect preventing regeneration of β-carotene as an active lipid phase antioxidant and leading to the observed antagonism.

  4. Mechanistic examination of Cβ-Cγ bond cleavages of tryptophan residues during dissociations of molecular peptide radical cations.

    PubMed

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

    2013-02-14

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

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

    SciTech Connect

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

    2013-02-14

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

  6. The radical cation of naphthalene: First correct analysis of its ESR spectrum

    NASA Astrophysics Data System (ADS)

    Gerson, Fabian; Qin, Xue-Zhi

    1988-12-01

    The radical cations of naphthalene ( 1) and its 1,4-dideutero derivative ( 1- d2), generated from the corresponding neutral compounds by γ-rays in a CFCl 3 matrix at 77 K, have been studied by ESR and ENDOR spectroscopy. At 140 K, the hyperfineanisotropy tensors of the protons in 1+• appear to be quasi-axial, presumably as a consequence of the fast rotation about the twofold symmetry axis perpendicular to the molecular plane. The isotropic coupling constants are -0.74±0.01 and -0.187 ± 0.014 mT for the two sets of four equivalent protons in the 1,4,5,8- and 2,3,6,7-positions, respectively. The relative increase in the coupling constant of the 1,4,5,8-protons on going from the radical anion 1-• (-0.495 mT) to the radical cation 1+• (-0.74 mT) is similar to that found for the 1,4-protons in the corresponding radical ions ( 2-• and 2+•) of s-trans-buta-1,3-diene ( 2).

  7. Solvent effects on the resonance Raman spectra of bacteriochlorophyll a cation radical

    NASA Astrophysics Data System (ADS)

    Misono, Yasuhito; Nishizawa, Ei-ichi; Limantara, Leenawaty; Koyama, Yasushi; Itoh, Koichi

    1995-04-01

    Resonance Raman (RR) spectra were measured for the cation radical of bacteriochlorophyll a in acetone, methanol, dichloromethane and mixed solvents of acetone and methanol. The ring-breathing (C a-C m stretching) frequency of the radical (abbreviated as vr+) was observed at 1601 cm -1 in acetone (forming a penta-coordinated monomer), at 1587 cm -1 in a methanol (forming a hexa-coordinated monomer) and at 1600 cm -1 in dichloromethane (forming a penta-coordinated aggregate). The RR spectrum of the radical in dichloromethane is almost identical to the transient RR spectrum ascribed to 'the aggregated T 1 species of Bchl a' formed in the particular solvent by Nishizawa, Limantara, Nanjou, Nagae, Kakuno and Koyama, indicating that their interpretation needs to be revised.

  8. High-field EPR study of carotenoid and chlorophyll cation radicals in photosystem II.

    SciTech Connect

    Lakshmi, K. V.; Reifler, M. J.; Brudvig, G. W.; Poluektov, O. G.; Wagner, A. M.; Thurnuaer, M. C.; Chemistry; Yale Univ.

    2000-11-16

    In photosystem II (PS II), chlorophyll, {beta}-carotene, and cytochrome b{sub 559} are alternate electron donors that may be involved in a photoprotection mechanism. The present study describes the use of high-field EPR spectroscopy to characterize the low-temperature photooxidation of Chl{sub z} and Car cofactors in PS II. The EPR signals of the individual species, previously not resolved at X-band frequency (9 GHz), are resolved at higher D-band frequency (130 GHz) in deuterated Synechococcus lividus PS II. Deuteration of PS II results in significant narrowing of the EPR lines, yielding well-resolved EPR spectra of the Car{sup +} and Chl{sub z}{sup +} radicals at 130 GHz. The g tensors of the individual species were determined by EPR spectral simulations. The g tensor determined for the Car{sup +} radical (g{sub xx} = 2.00335, g{sub yy} = 2.00251, g{sub zz} = 2.00227) is similar to that previously observed for a canthaxanthin cation radical but with a slightly rhombic tensor. The Chl{sub z}{sup +} g tensor (g{sub xx} = 2.00312, g{sub yy} = 2.00263, g{sub zz} = 2.00202) is similar to that of a chlorophyll a cation radical. This study shows that both the carotenoid and chlorophyll radicals are generated in PS II by illumination at temperatures from 6 to 190 K and that there is no interconversion of Car{sup +} and Chl{sub z}{sup +} radicals upon dark annealing at temperatures up to 160 K. This study also establishes the feasibility of using deuteration and high-field EPR to resolve previously unresolvable cofactor signals in PS II.

  9. Lipopolysaccharide Neutralization by Cationic-Amphiphilic Polymers through Pseudoaggregate Formation.

    PubMed

    Uppu, Divakara S S M; Haldar, Jayanta

    2016-03-14

    Synthetic polymers incorporating the cationic charge and hydrophobicity to mimic the function of antimicrobial peptides (AMPs) have been developed. These cationic-amphiphilic polymers bind to bacterial membranes that generally contain negatively charged phospholipids and cause membrane disintegration resulting in cell death; however, cationic-amphiphilic antibacterial polymers with endotoxin neutralization properties, to the best of our knowledge, have not been reported. Bacterial endotoxins such as lipopolysaccharide (LPS) cause sepsis that is responsible for a great amount of mortality worldwide. These cationic-amphiphilic polymers can also bind to negatively charged and hydrophobic LPS and cause detoxification. Hence, we envisaged that cationic-amphiphilic polymers can have both antibacterial as well as LPS binding properties. Here we report synthetic amphiphilic polymers with both antibacterial as well as endotoxin neutralizing properties. Levels of proinflammatory cytokines in human monocytes caused by LPS stimulation were inhibited by >80% when coincubated with these polymers. These reductions were found to be dependent on concentration and, more importantly, on the side-chain chemical structure due to variations in the hydrophobicity profiles of these polymers. These cationic-amphiphilic polymers bind and cause LPS neutralization and detoxification. Investigations of polymer interaction with LPS using fluorescence spectroscopy and dynamic light scattering (DLS) showed that these polymers bind but neither dissociate nor promote LPS aggregation. We show that polymer binding to LPS leads to sort of a pseudoaggregate formation resulting in LPS neutralization/detoxification. These findings provide an unusual mechanism of LPS neutralization using novel synthetic cationic-amphiphilic polymers.

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

    PubMed

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

    2010-07-02

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

  11. Enhancement of a Lewis acid-base interaction via solvation: ammonia molecules and the benzene radical cation.

    PubMed

    Chiang, Chi-Tung; Freindorf, Marek; Furlani, Thomas; DeLeon, Robert L; Richard, John P; Garvey, James F

    2007-07-12

    The interaction between ammonia and the benzene radical cation has been investigated by gas-phase studies of mass selected ion clusters {C(6)H(6)-(NH(3))(n=0-8)}(+) via tandem quadrupole mass spectrometry and through calculations. Experiments show a special stability for the cluster ion that contains four ammonias: {C(6)H(6)(NH(3))(4)}(+). Calculations provide evidence that the first ammonia forms a weak dative bond to the cyclohexadienyl radical cation, {C(6)H(6)-NH(3)}(+), where there is a transfer of electrons from ammonia to benzene. Additional solvating ammonia molecules form stabilizing hydrogen bonds to the ring-bound ammonia {C(6)H(6)-NH(3)}(+).(NH(3))(n), which cause cooperative changes in the structure of the cluster complex. Free ammonia is a weak hydrogen bond donor, but electron transfer from NH(3) to the benzene ring that strengthens the dative bond will increase the hydrogen acidity and the strength of the cluster hydrogen bonds to the added ammonia. A progressive "tightening" of this dative bond is observed upon addition of the first, second, and third ammonia to give a cluster stabilized by three N-(+)H x N hydrogen bonds. This shows that the energetic cost of tightening the dative bond is recovered with dividends in the formation of stable cluster hydrogen bonds.

  12. Electron transfer from aromatic amino acids to guanine and adenine radical cations in pi stacked and T-shaped complexes.

    PubMed

    Butchosa, Cristina; Simon, Sílvia; Voityuk, Alexander A

    2010-04-21

    Similar redox properties of the natural nucleobases and aromatic amino acids make it possible for electron transfer (ET) to occur between these sites in protein-nucleic acid complexes. Using DFT calculations, we estimate the ET rate from aromatic amino acid X (X = Phe, His, Tyr and Trp) to radical cations of guanine (G) and adenine (A) in dimers G-X and A-X with different arrangement of the subunits. We show that irrespective of the mutual orientation of the aromatic rings, the electronic interaction in the systems is strong enough to ensure effective ET from X to G(+) or A(+). Surprisingly, relatively high ET rates are found in T-shaped dimers. This suggests that pi stacking of nucleobases and aromatic amino acids is not required for feasible ET. In most complexes [G-X](+) and [A-X](+), we find the excess charge to be confined to a single site, either the nucleobase or amino acid X. Then, conformational changes may initiate migration of the radical cation state from the nucleobase to X and back. The ET process from Trp and Tyr to G(+) is found to be faster than deprotonation of G(+). Because the last reaction may lead to the formation of highly mutagenic species, the efficient repair of G(+) may play an important role in the protection of genomic DNA from oxidative damage.

  13. In vitro antioxidant and radical-scavenging capacities of Citrullus colocynthes (L) and Artemisia absinthium extracts using promethazine hydrochloride radical cation and contemporary assays.

    PubMed

    Asghar, M Nadeem; Khan, I Ullah; Bano, N

    2011-10-01

    A new, quick and economical decolorization assay based upon the generation of a radical cation made from promethazine hydrochloride (PMZH) is described for screening of antioxidant activity of plants/herbal extracts. PMZH radical cations, produced through a reaction between PMZH and potassium persulfate (K(2)S(2)O(8)) in phosphoric acid medium, have maximum absorption at 515 nm in their first-order derivative spectrum. Theconcentrations of chromagen and K(2)S(2)O(8) were optimized (final concentration of PMZH and K₂S₂O₈ were 0.166 mM and 0.11 mM, respectively) for better stability and sensitivity of the radical cation produced. Agood linear correlation was found between the percentage inhibition and the increasing amounts of standard antioxidants, with correlation coefficients ranging from 0.989 to 0.999. The newly developed assay was employed to evaluate the antioxidant capacity of Citrullus colocynthes L. and Artemisia absinthium extracts. The proposed assay involved a more stable radical cation and required only 1 h for preparation of a working solution in comparison to the 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical cation decolorizaion assay, which was reported to be less sensitive at low pH and almost 12-16 h were required for preparation of a working ABTS solution. Other assays employed to evaluate the antioxidant potential andradical-scavenging capacities of the extracts were the ferric-reducing antioxidant power, 2,2'-diphenyl-1-picrylhydrazyl radical scavenging, total phenolic contents assay, total flavonoid contents and metal-chelating activity assays, and the lipid peroxidation value in linoleic acid emulsion systems. The results indicate that boththe plants have potent free radical-scavenging activity and the ability to prevent lipid peroxidation and radical chain reactions.

  14. Near-UV Photodissociation of Tryptic Peptide Cation Radicals. Scope and Effects of Amino Acid Residues and Radical Sites

    NASA Astrophysics Data System (ADS)

    Nguyen, Huong T. H.; Tureček, František

    2017-02-01

    Peptide cation-radical fragment ions of the z-type, [●AXAR+], [●AXAK+], and [●XAR+], where X = A, C, D, E, F, G, H, K, L, M, N, P, Y, and W, were generated by electron transfer dissociation of peptide dications and investigated by MS3-near-ultraviolet photodissociation (UVPD) at 355 nm. Laser-pulse dependence measurements indicated that the ion populations were homogeneous for most X residues except phenylalanine. UVPD resulted in dissociations of backbone CO-NH bonds that were accompanied by hydrogen atom transfer, producing fragment ions of the [yn]+ type. Compared with collision-induced dissociation, UVPD yielded less side-chain dissociations even for residues that are sensitive to radical-induced side-chain bond cleavages. The backbone dissociations are triggered by transitions to second (B) excited electronic states in the peptide ion R-CH●-CONH- chromophores that are resonant with the 355-nm photon energy. Electron promotion increases the polarity of the B excited states, R-CH+-C●(O-)NH-, and steers the reaction to proceed by transfer of protons from proximate acidic Cα and amide nitrogen positions.

  15. External electric field promotes proton transfer in the radical cation of adenine-thymine

    NASA Astrophysics Data System (ADS)

    Zhang, Guiqing; Xie, Shijie

    2016-07-01

    According to pKa measurements, it has been predicted that proton transfer would not occur in the radical cation of adenine-thymine (A:T). However, recent theoretical calculations indicate that proton transfer takes place in the base pair in water below the room temperature. We have performed simulations of proton transfer in the cation of B-DNA stack composed of 10 A:T base pairs in water from 20 K to 300 K. Proton transfer occurs below the room temperature, meanwhile it could also be observed at the room temperature under the external electric field. Another case that interests us is that proton transfer bounces back after ˜300 fs from the appearance of proton transfer at low temperatures.

  16. Calmodulin Methionine Residues are Targets For One-Electron Oxidation by Hydroxyl Radicals: Formation of S therefore N three-electron bonded Radical Complexes

    SciTech Connect

    Nauser, Thomas; Jacoby, Michael E.; Koppenol, Willem H.; Squier, Thomas C.; Schoneich, Christian

    2005-02-01

    The one-electron (1e) oxidation of organic sulfides and methionine (Met) constitutes an important reaction mechanism in vivo.1,2 Evidence for a Cu(II)-catalyzed oxidation of Met35 in the Alzheimer's disease -amyloid peptide was obtained,3 and, based on theoretical studies, Met radical cations were proposed as intermediates.4 In the structure of -amyloid peptide, the formation of Met radical cations appears to be facilitated by a preexisting close sulfur-oxygen (S-O) interaction between the Met35 sulfur and the carbonyl oxygen of the peptide bond C-terminal to Ile31.5 Substitution of Ile31 with Pro31 abolishes this S-O interaction,5 significantly reducing the ability of -amyloid to reduce Cu(II), and converts the neurotoxic wild-type -amyloid into a non-toxic peptide.6 The preexisting S-O bond characterized for wild-type -amyloid suggests that electron transfer from Met35 to Cu(II) is supported through stabilization of the Met radical cation by the electron-rich carbonyl oxygen, generating an SO-bonded7 sulfide radical cation (Scheme 1, reaction 1).5

  17. The radical cation of anti-tricyclooctadiene and its rearrangement products

    PubMed

    Bally; Bernhard; Matzinger; Truttmann; Zhu; Roulin; Marcinek; Gebicki; Williams; Chen; Roth; Herbertz

    2000-03-03

    The anti dimer of cyclobutadiene (anti-tricyclo[4.2.0.0(2.5)]octa-3,7-diene, TOD) is subjected to ionization by gamma-irradiation in Freon matrices, pulse radiolysis in hydrocarbon matrices, and photoinduced electron transfer in solution. The resulting species are probed by optical and ESR spectroscopy (solid phase) as well as by CIDNP spectroscopy (solution). Thereby it is found that ionization of anti-TOD invariably leads to spontaneous decay to two products, that is bicyclo[4.2.0]octa-2,4,7-triene (BOT) and 1,4-dihydropentalene (1,4-DHP), whose relative yield strongly depends on the conditions of the experiment. Exploration of the C8H8*+ potential energy surface by the B3LYP/6-31G* density functional method leads to a mechanistic hypothesis for the observed rearrangements which involves a bifurcation between a pathway leading to the simple valence isomer, BOT*+, and another one leading to an unprecedented other valence isomer, the anti form of the bicyclo[3.3.0]octa-2,6-diene-4,8-diyl radical cation (anti-BOD*+). The latter product undergoes a very facile H-shift to yield the radical cation of 1,3a-dihydropentalene (1,3a-DHP*+) which ultimately rearrranges by a further H-shift to the observed product, 1,4-DHP*+.

  18. Multistate vibronic interactions in difluorobenzene radical cations. II. Quantum dynamical simulations.

    PubMed

    Faraji, Shirin; Meyer, H-D; Köppel, Horst

    2008-08-21

    The multistate vibronic dynamics in the X-D electronic states of all three difluorobenzene radical cations are investigated theoretically by an ab initio quantum dynamical approach. The vibronic coupling scheme and the ab initio values of the system parameters are adopted from Paper I [S. Faraji and H. Koppel, J. Chem. Phys. 129, 074310 (2008)]. Extensive calculations by wave-packet propagation have been performed with the aid of the multiconfiguration time-dependent Hartree method. Five coupled electronic potential energy surfaces and 10 (11 in the case of the orthoisomer) vibrational degrees of freedom have been included in these calculations. The nonadiabatic interactions lead to the restructuring of the photoelectron spectral envelopes. Ultrafast internal conversion processes within the electronic manifolds in question demonstrate the strength of the nonadiabatic coupling effects and complement the analogous findings for the electronic spectra. The internal conversion dynamics is characterized by a stepwise transfer of the electronic population to the lowest electronic state on a time scale of femtoseconds to picoseconds. A difference between the three isomers is found to be related to the weaker interaction between the sets of X-A and B-C-D states (with high-energy conical intersections) in the meta isomer, as compared to the other isomers. The implications of these findings for the qualitative understanding of the fluorescence dynamics of fluorinated benzene radical cations are discussed.

  19. Controlling the dissociation dynamics of acetophenone radical cation through excitation of ground and excited state wavepackets

    NASA Astrophysics Data System (ADS)

    Moore Tibbetts, Katharine; Tarazkar, Maryam; Bohinski, Timothy; Romanov, Dmitri A.; Matsika, Spiridoula; Levis, Robert J.

    2015-08-01

    Time-resolved measurements of the acetophenone radical cation prepared via adiabatic ionization with strong field 1270 nm excitation reveal coupled wavepacket dynamics that depend on the intensity of the 790 nm probe pulse. At probe intensities below 7× {10}11 W cm-2, out of phase oscillations between the parent molecular ion and the benzoyl fragment ion are shown to arise from a one-photon excitation from the ground D0 ionic surface to the D1 and/or D2 excited surfaces by the probe pulse. At higher probe intensities, a second set of wavepacket dynamics are observed that couple the benzoyl ion to the phenyl, butadienyl, and acylium fragment ions. Equation of motion coupled cluster calculations of the ten lowest lying ionic surfaces and the dipole couplings between the ground ionic surface D0 and the nine excited states enable elucidation of the dissociation pathways and deduction of potential dissociation mechanisms. The results can lead to improved control schemes for selective dissociation of the acetophenone radical cation.

  20. Hydroxyl radical-induced formation of highly oxidized organic compounds

    NASA Astrophysics Data System (ADS)

    Berndt, Torsten; Richters, Stefanie; Jokinen, Tuija; Hyttinen, Noora; Kurtén, Theo; Otkjær, Rasmus V.; Kjaergaard, Henrik G.; Stratmann, Frank; Herrmann, Hartmut; Sipilä, Mikko; Kulmala, Markku; Ehn, Mikael

    2016-12-01

    Explaining the formation of secondary organic aerosol is an intriguing question in atmospheric sciences because of its importance for Earth's radiation budget and the associated effects on health and ecosystems. A breakthrough was recently achieved in the understanding of secondary organic aerosol formation from ozone reactions of biogenic emissions by the rapid formation of highly oxidized multifunctional organic compounds via autoxidation. However, the important daytime hydroxyl radical reactions have been considered to be less important in this process. Here we report measurements on the reaction of hydroxyl radicals with α- and β-pinene applying improved mass spectrometric methods. Our laboratory results prove that the formation of highly oxidized products from hydroxyl radical reactions proceeds with considerably higher yields than previously reported. Field measurements support these findings. Our results allow for a better description of the diurnal behaviour of the highly oxidized product formation and subsequent secondary organic aerosol formation in the atmosphere.

  1. Hydroxyl radical-induced formation of highly oxidized organic compounds

    PubMed Central

    Berndt, Torsten; Richters, Stefanie; Jokinen, Tuija; Hyttinen, Noora; Kurtén, Theo; Otkjær, Rasmus V.; Kjaergaard, Henrik G.; Stratmann, Frank; Herrmann, Hartmut; Sipilä, Mikko; Kulmala, Markku; Ehn, Mikael

    2016-01-01

    Explaining the formation of secondary organic aerosol is an intriguing question in atmospheric sciences because of its importance for Earth's radiation budget and the associated effects on health and ecosystems. A breakthrough was recently achieved in the understanding of secondary organic aerosol formation from ozone reactions of biogenic emissions by the rapid formation of highly oxidized multifunctional organic compounds via autoxidation. However, the important daytime hydroxyl radical reactions have been considered to be less important in this process. Here we report measurements on the reaction of hydroxyl radicals with α- and β-pinene applying improved mass spectrometric methods. Our laboratory results prove that the formation of highly oxidized products from hydroxyl radical reactions proceeds with considerably higher yields than previously reported. Field measurements support these findings. Our results allow for a better description of the diurnal behaviour of the highly oxidized product formation and subsequent secondary organic aerosol formation in the atmosphere. PMID:27910849

  2. The Effect of the Secondary Structure on Dissociation of Peptide Radical Cations: Fragmentation of Angiotensin III and Its Analogues

    SciTech Connect

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

    2008-09-28

    Fragmentation of protonated RVYIHPF and RVYIHPF-OMe and the corresponding radical cations was studied using time- and collision energy-resolved surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially equipped to perform SID experiments. Peptide radical cations were produced by gas-phase fragmentation of CoIII(salen)-peptide complexes. Both the energetics and mechanisms of dissociation of even-electron and odd-electron angiotensin III ions are quite different. Protonated molecules are much more stable towards fragmentation than the corresponding radical cations. RRKM modeling of the experimental data suggests that this stability is largely attributed to differences in threshold energies for dissociation while activation entropies are very similar. Detailed analysis of the experimental data obtained for radical cations demonstrated the presence of two distinct structures separated by a high free-energy barrier. The two families of structures were ascribed to the canonical and zwitterionic forms of the radical cations produced in our experiments.

  3. Bivalent cation binding effect on formation of the peptide bond

    NASA Astrophysics Data System (ADS)

    Remko, Milan; Rode, Bernd Michael

    2000-01-01

    The reactions between formic acid (or glycine) and ammonia, without and with Mg 2+, Ni 2+ and Cu 2+ cations as catalysts, have been studied as model reactions for peptide bond formation using the Becke3LYP functional and 6-311+G(d,p) basis set of DFT theory. Enthalpies and free energies for the stationary points of each reaction have been calculated to determine the thermodynamics of reactions investigated. A substantial decrease in reaction enthalpies and free energies was found for formic acid-ammonia and glycine-ammonia reactions catalysed by Mg 2+, Ni 2+ and Cu 2+ ions compared with those of the uncatalysed amide bond formation. The catalytic effect of the transition metal ions Ni 2+ and Cu 2+ is of similar strength and more pronounced than that of the Mg 2+ cation.

  4. Hydration of the pyrimidine radical cation and stepwise solvation of protonated pyrimidine with water, methanol, and acetonitrile

    NASA Astrophysics Data System (ADS)

    Hamid, Ahmed M.; Sharma, Pramod; Samy El-Shall, M.; Hilal, Rifaat; Elroby, Shaaban; Aziz, Saadullah G.; Alyoubi, Abdulrahman O.

    2013-08-01

    Equilibrium thermochemical measurements using an ion mobility drift cell technique have been utilized to investigate the binding energies and entropy changes associated with the stepwise hydration of the biologically significant ions pyrimidine radical cation and protonated pyrimidine. The binding energy of the hydrated pyrimidine radical cation is weaker than that of the proton-bound dimer pyrimidineH+(H2O) consistent with the formation of a weak carbon-based CHδ+..OH2 hydrogen bond (11.9 kcal/mol) and a stronger NH+..OH2 hydrogen bond (15.6 kcal/mol), respectively. Other proton-bound dimers such as pyrimidineH+(CH3OH) and pyrimidineH+(CH3CN) exhibit higher binding energies (18.2 kcal/mol and 22.8 kcal/mol, respectively) due to the higher proton affinities and dipole moments of acetonitrile and methanol as compared to water. The measured collisional cross sections of the proton-bound dimers provide experimental-based support for the DFT calculated structures at the M06-2x/6-311++G (d,p) level. The calculations show that the hydrated pyrimidine radical cation clusters form internally solvated structures in which the water molecules are bonded to the C4N2H4•+ ion by weak CHδ+..OH2 hydrogen bonds. The hydrated protonated pyrimidine clusters form externally solvated structures where the water molecules are bonded to each other and the ion is external to the water cluster. Dissociative proton transfer reactions C4N2H4•+(H2O)n-1 + H2O → C4N2H3• + (H2O)nH+ and C4N2H5+(H2O)n-1 + H2O → C4N2H4 + (H2O)nH+ are observed for n ≥ 4 where the reactions become thermoneutral or exothermic. The absence of the dissociative proton transfer reaction within the C4N2H5+(CH3CN)n clusters results from the inability of acetonitrile molecules to form extended hydrogen bonding structures such as those formed by water and methanol due to the presence of the methyl groups which block the extension of hydrogen bonding networks.

  5. Hydration of the pyrimidine radical cation and stepwise solvation of protonated pyrimidine with water, methanol, and acetonitrile.

    PubMed

    Hamid, Ahmed M; Sharma, Pramod; El-Shall, M Samy; Hilal, Rifaat; Elroby, Shaaban; Aziz, Saadullah G; Alyoubi, Abdulrahman O

    2013-08-28

    Equilibrium thermochemical measurements using an ion mobility drift cell technique have been utilized to investigate the binding energies and entropy changes associated with the stepwise hydration of the biologically significant ions pyrimidine radical cation and protonated pyrimidine. The binding energy of the hydrated pyrimidine radical cation is weaker than that of the proton-bound dimer pyrimidineH(+)(H2O) consistent with the formation of a weak carbon-based CH(δ+)··OH2 hydrogen bond (11.9 kcal/mol) and a stronger NH(+)··OH2 hydrogen bond (15.6 kcal/mol), respectively. Other proton-bound dimers such as pyrimidineH(+)(CH3OH) and pyrimidineH(+)(CH3CN) exhibit higher binding energies (18.2 kcal/mol and 22.8 kcal/mol, respectively) due to the higher proton affinities and dipole moments of acetonitrile and methanol as compared to water. The measured collisional cross sections of the proton-bound dimers provide experimental-based support for the DFT calculated structures at the M06-2x/6-311++G (d,p) level. The calculations show that the hydrated pyrimidine radical cation clusters form internally solvated structures in which the water molecules are bonded to the C4N2H4(●+) ion by weak CH(δ+)··OH2 hydrogen bonds. The hydrated protonated pyrimidine clusters form externally solvated structures where the water molecules are bonded to each other and the ion is external to the water cluster. Dissociative proton transfer reactions C4N2H4(●+)(H2O)(n-1) + H2O → C4N2H3(●) + (H2O)(n)H(+) and C4N2H5(+)(H2O)(n-1) + H2O → C4N2H4 + (H2O)(n)H(+) are observed for n ≥ 4 where the reactions become thermoneutral or exothermic. The absence of the dissociative proton transfer reaction within the C4N2H5(+)(CH3CN)n clusters results from the inability of acetonitrile molecules to form extended hydrogen bonding structures such as those formed by water and methanol due to the presence of the methyl groups which block the extension of hydrogen bonding networks.

  6. COMPUTATIONAL STUDY OF INTERSTELLAR GLYCINE FORMATION OCCURRING AT RADICAL SURFACES OF WATER-ICE DUST PARTICLES

    SciTech Connect

    Rimola, Albert; Sodupe, Mariona; Ugliengo, Piero

    2012-07-20

    Glycine is the simplest amino acid, and due to the significant astrobiological implications that suppose its detection, the search for it in the interstellar medium (ISM), meteorites, and comets is intensively investigated. In the present work, quantum mechanical calculations based on density functional theory have been used to model the glycine formation on water-ice clusters present in the ISM. The removal of either one H atom or one electron from the water-ice cluster has been considered to simulate the effect of photolytic radiation and of ionizing particles, respectively, which lead to the formation of OH{sup .} radical and H{sub 3}O{sup +} surface defects. The coupling of incoming CO molecules with the surface OH{sup .} radicals on the ice clusters yields the formation of the COOH{sup .} radicals via ZPE-corrected energy barriers and reaction energies of about 4-5 kcal mol{sup -1} and -22 kcal mol{sup -1}, respectively. The COOH{sup .} radicals couple with incoming NH=CH{sub 2} molecules (experimentally detected in the ISM) to form the NHCH{sub 2}COOH{sup .} radical glycine through energy barriers of 12 kcal mol{sup -1}, exceedingly high at ISM cryogenic temperatures. Nonetheless, when H{sub 3}O{sup +} is present, one proton may be barrierless transferred to NH=CH{sub 2} to give NH{sub 2}=CH{sub 2}{sup +}. This latter may react with the COOH{sup .} radical to give the NH{sub 2}CH{sub 2}COOH{sup +.} glycine radical cation which can then be transformed into the NH{sub 2}CHC(OH){sub 2}{sup +.} species (the most stable form of glycine in its radical cation state) or into the NH{sub 2}CHCOOH{sup .} neutral radical glycine. Estimated rate constants of these events suggest that they are kinetically feasible at temperatures of 100-200 K, which indicate that their occurrence may take place in hot molecular cores or in comets exposed to warmer regions of solar systems. Present results provide quantum chemical evidence that defects formed on water ices due to the harsh

  7. Facile Smiles-type rearrangement in radical cations of N-acyl arylsulfonamides and analogs

    PubMed Central

    Irikura, Karl K.; Todua, Nino G.

    2016-01-01

    RATIONALE N-Alkylation of sulfonylbenzamides was reported recently to cause a dramatic and surprising change in electron ionization mass spectrometry (EIMS), leading to a closed-shell base peak. Only an incomplete, speculative mechanism was available at that time. The fragmentation mechanism is determined in the present work and set in the context of related compounds. METHODS Candidate reaction mechanisms were evaluated theoretically using modest density-functional calculations. The fragmentation mechanism with the lowest barriers was identified and one of its implications tested successfully by experimental 18O-isotopic substitution. RESULTS The amide oxygen atom attacks the arylsulfonyl group at the ipso position (Smiles-type rearrangement), displacing a molecule of SO2. The resulting carboximidate radical cation has a weak C–O bond that breaks easily. The incipient aryloxyl radical abstracts a proton from the amide nitrogen to form the dominant product ion, but if the molecule is N-alkylated this cannot occur. Instead, the neutral aryloxyl radical is lost and a closed-shell, N-alkyl nitrilium ion is the major product. CONCLUSIONS The Smiles-type ion fragmentation mechanism is facile for the title compounds, despite the necessity for carbonyl oxygen to serve as a nucleophile. This rearrangement probably occurs in many of the mass spectra reported for structurally similar compounds, in which the nucleophile may be a thione, arylthio, imine, methylene, or methine moiety. PMID:24573815

  8. The role of aspartate-235 in the binding of cations to an artificial cavity at the radical site of cytochrome c peroxidase.

    PubMed

    Fitzgerald, M M; Trester, M L; Jensen, G M; McRee, D E; Goodin, D B

    1995-09-01

    The activated state of cytochrome c peroxidase, compound ES, contains a cation radical on the Trp-191 side chain. We recently reported that replacing this tryptophan with glycine creates a buried cavity at the active site that contains ordered solvent and that will specifically bind substituted imidazoles in their protonated cationic forms (Fitzgerald MM, Churchill MJ, McRee DE, Goodin DB, 1994, Biochemistry 33:3807-3818). Proposals that a nearby carboxylate, Asp-235, and competing monovalent cations should modulate the affinity of the W191G cavity for ligand binding are addressed in this study. Competitive binding titrations of the imidazolium ion to W191G as a function of [K+] show that potassium competes weakly with the binding of imidazoles. The dissociation constant observed for potassium binding (18 mM) is more than 3,000-fold higher than that for 1,2-dimethylimidazole (5.5 microM) in the absence of competing cations. Significantly, the W191G-D235N double mutant shows no evidence for binding imidazoles in their cationic or neutral forms, even though the structure of the cavity remains largely unperturbed by replacement of the carboxylate. Refined crystallographic B-values of solvent positions indicate that the weakly bound potassium in W191G is significantly depopulated in the double mutant. These results demonstrate that the buried negative charge of Asp-235 is an essential feature of the cation binding determinant and indicate that this carboxylate plays a critical role in stabilizing the formation of the Trp-191 radical cation.

  9. The role of aspartate-235 in the binding of cations to an artificial cavity at the radical site of cytochrome c peroxidase.

    PubMed Central

    Fitzgerald, M. M.; Trester, M. L.; Jensen, G. M.; McRee, D. E.; Goodin, D. B.

    1995-01-01

    The activated state of cytochrome c peroxidase, compound ES, contains a cation radical on the Trp-191 side chain. We recently reported that replacing this tryptophan with glycine creates a buried cavity at the active site that contains ordered solvent and that will specifically bind substituted imidazoles in their protonated cationic forms (Fitzgerald MM, Churchill MJ, McRee DE, Goodin DB, 1994, Biochemistry 33:3807-3818). Proposals that a nearby carboxylate, Asp-235, and competing monovalent cations should modulate the affinity of the W191G cavity for ligand binding are addressed in this study. Competitive binding titrations of the imidazolium ion to W191G as a function of [K+] show that potassium competes weakly with the binding of imidazoles. The dissociation constant observed for potassium binding (18 mM) is more than 3,000-fold higher than that for 1,2-dimethylimidazole (5.5 microM) in the absence of competing cations. Significantly, the W191G-D235N double mutant shows no evidence for binding imidazoles in their cationic or neutral forms, even though the structure of the cavity remains largely unperturbed by replacement of the carboxylate. Refined crystallographic B-values of solvent positions indicate that the weakly bound potassium in W191G is significantly depopulated in the double mutant. These results demonstrate that the buried negative charge of Asp-235 is an essential feature of the cation binding determinant and indicate that this carboxylate plays a critical role in stabilizing the formation of the Trp-191 radical cation. PMID:8528082

  10. Single-Crystal X-ray Structures of conductive π-Stacking Dimers of Tetrakis(alkylthio)benzene Radical Cations

    PubMed Central

    Chen, Xiaoyu; Gao, Feng; Yang, Wuqin

    2016-01-01

    Salts containing radical cations of 1,2,4,5-tetrakis(isopropylthio)benzene (TPB) and 1,2,4,5-tetrakis(ethylthio) benzene (TEB) have been successfully synthesized with . These newly synthesized salts have been characterized by UV-Vis absorption, EPR spectroscopy, conductivity measurement, single crystal X-ray diffraction analysis as well as DFT calculation. This study raises the first crystal structure of conductive π-stacking radical cation with single phenyl ring and reveals their conductivity has relationship with the stack structure which affected by the substituent. PMID:27403720

  11. Carotenoid cation radicals produced by the interaction of carotenoids with iodine

    SciTech Connect

    Ding, R.; Grant, J.L.; Metzger, R.M.; Kispert, L.D.

    1988-08-11

    Electron paramagnetic resonance (EPR) and optical absorption spectra of 1,2-dichloroethane and dichloromethane solutions of ..beta..-carotene (C/sub 40/H/sub 56/) and iodine have been studied. EPR studies showed that ..beta..-carotene cation radicals are formed. These radicals form complexes at 77 K, in highly concentrated (0.1 M) iodine solutions, with higher order polyiodide anions, I/sub 5//sup -/, I/sub 7//sup -/, I/sub 9//sup -/ (as evidenced by g value shifts and line-width increases), while at room temperature and in dilute (10/sup -4/-10/sup -5/ M) solutions of iodine only I/sub 3//sup -/ counterions are involved. In dilute solutions (total molar concentratino = 2 x 10/sup -4/ M), a Job plot showed the stoichiometry to be 2:3, indicating the reaction 2C/sub 40/H/sub 56/ + 31/sub 2/ /r equilibrium/ 2C/sub 40/H/sub 56//sup .+/ + 2I/sub 3//sup -/. The radical fraction (EPR) is /approximately/ 2% at 77 K and 0.4% at 300 K (for a 2 mM ..beta..-carotene/0.1 M I/sub 2/ solution); it increases at lower ..beta..-carotene concentrations. Dimers and trimers of ..beta..-carotene cation radicals are formed in dilute solution (I/sub 2/ < 10/sup -4/ M) if (I/sub 2/)/(..beta..-carotene) < 1, and an intense absorption band occurs at lambda/sub max/ /approximately/ 1030 nm. Canthaxanthin and ..beta..-apo-8'-carotenal with I/sub 2/ produce new absorption bands with lambda/sub max/ < 1000 nm; the g values are independent of iodine concentration, suggesting a poorer ability to form complexes with the polyiodide anions. All three carotenoids react with other electron acceptors (7,7,8,8-tetracyanoquinodimethane (TCNQ), tetrachloro-1,4-benzoquinone (chloranil), and Br/sub 2/) according to the electron affinity of the acceptor used.

  12. Density Functional Theory and Mass Spectrometry of Phthalate Fragmentations Mechanisms: Modeling Hyperconjugated Carbocation and Radical Cation Complexes with Neutral Molecules

    NASA Astrophysics Data System (ADS)

    Jeilani, Yassin A.; Cardelino, Beatriz H.; Ibeanusi, Victor M.

    2011-11-01

    This is the first ab initio study of the energetics of the fragmentation mechanisms of phthalate, by mass spectrometry, leading to protonated phthalic anhydride ( m/z 149). Phthalates fragment by two major pathways; namely, the McLafferty + 1 rearrangement and the loss of alkoxy. Both pathways involve a carbonyl oxygen attack to the ortho-carbonyl carbon leading to structures with tetrahedral carbon intermediates that eventually give m/z 149. These pathways were studied by collision induced dissociation (CID) using triple quadrupole mass spectrometry. The proposed McLafferty + 1 pathway proceeds through a distonic M•+, leading to the loss of an allylic-stabilized alkene radical. The McLafferty rearrangement step proceeds through a six-membered ring transition state with a small activation energy ranging 0.4-6.2 kcal/mol; the transfer of a second H from the distonic ion of the rearrangement step proceeds through a radical cation molecule complex. Based on quantum chemical modeling of the cation molecule complexes, two kinds of cation molecule complexes were identified as radical cation molecule complex and hyperconjugated cation molecule complex. This distinction is based on the cation and simplifies future modeling of similar complexes. Optimization of important fragments in these pathways showed cyclized and hydrogen-bonded structures to be favored. An exception was the optimized structure of the protonated phthalic anhydride ( m/z 149) that showed a structure with an open anhydride ring.

  13. Synthesis, Physical Properties and Reactivity of Stable Antiaromatic 1,4-DIHYDROPYRAZINES and Their Associated Radical Cations

    NASA Astrophysics Data System (ADS)

    Brook, David James Rawsthorne

    oxidation resulted in cleavage of the pyrazine ring and in trifluoroacetic acid only the DDTTA radical cation was observed as an oxidation product. With iron carbonyls, HTTA produced an unstable pi coordinated intermediate, detected by NMR spectroscopy. This decomposed to give an insoluble iron carbonyl with stoichiometry Fe_{5 }(CO)_{8}. With cobalt and manganese carbonyls, reaction resulted in the formation of 4.9, probably through metal-hydrido intermediates. Reaction of DDTTA with tetracyanoquinodimathane (TCNQ) results in three phases of composition DDTTA(TCNQ)_ {2}, two of which were characterised by single crystal X-ray diffraction, the third by X-ray powder diffraction. The materials are semiconductors with infinite TCNQ stacks. HTTA also gave a TCNQ salt of composition HTTAcdotTCNQcdotCH _{3}CN with the TCNQ molecules arranged in discrete dimers. Magnetic properties of the TCNQ salts along with the trifluoracetate and tetraphenyl borate salts of DDTTA^{+} were investigated. These suggest that the hydrogen bonded arrangement of DDTTA cations within the P1 form of DDTTA(TCNQ) _{2} give rise to short range ferromagnetic interactions between cations.

  14. Multistate vibronic interactions in difluorobenzene radical cations. I. Electronic structure calculations.

    PubMed

    Faraji, Shirin; Köppel, Horst

    2008-08-21

    The multimode multistate vibronic interactions between the five lowest electronic states of all three isomers of the difluorobenzene radical cation are investigated theoretically, based on ab initio electronic structure data, and employing a well-established vibronic coupling model. The approach rests on the linear vibronic coupling scheme, augmented by quadratic coupling terms for the totally symmetric modes. The underlying ionization potentials and coupling constants are obtained from ab initio coupled-cluster calculations. Low-energy conical intersections and strong vibronic couplings are found to prevail within the sets of X-A and B-C-D cationic states, while the interactions between these two sets of states are found to be weaker and depend on the isomer. The inclusion of the aforementioned quadratic couplings is found to be essential to correctly reproduce the lowest-energy conical intersections between the two different sets of electronic states. Differences between the three isomers regarding these quantities are pointed out. The results will be used as basis for multidimensional wave-packet dynamical simulations for these coupled potential energy surfaces to be presented in the following paper (Paper II).

  15. Influence of pH on the decay of β-carotene radical cation in aqueous Triton X-100: A laser flash photolysis study.

    PubMed

    El-Agamey, Ali; El-Hagrasy, Maha A; Suenobu, Tomoyoshi; Fukuzumi, Shunichi

    2015-05-01

    The identification of the spectral information of carotenoid neutral radicals is essential for studying their reactivities towards O2 and thereby evaluating their role in the antioxidant-prooxidant properties of the corresponding carotenoid. Recently, it was reported that β-carotene neutral radical (β-CAR) has an absorption maximum at 750 nm. This contradicts the results of many reports that show carotenoid neutral radicals (CAR) absorb in the same or near to the spectral region as their parent carotenoids. In this manuscript, the influence of pH on the decay of β-carotene radical cation (β-CAR-H(+)), generated in an aqueous solution of 2% Triton X-100 (TX-100), was investigated, employing laser flash photolysis (LFP) coupled with kinetic absorption spectroscopy, to identify the absorption bands of the β-carotene neutral radicals. By increasing the pH value of the solution, the decay of β-CAR-H(+) is enhanced and this enhancement is not associated with the formation of any positive absorption bands over the range 550-900 nm. By comparing these results with the literature, it can be concluded that β-carotene neutral radicals most probably absorb within the same spectral range as that of β-carotene. The reaction pathways of the reaction of β-CAR-H(+) with (-)OH have been discussed.

  16. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  18. Review: Formation of Peptide Radical Ions Through Dissociative Electron Transfer in Ternary Metal-Ligand-Peptide Complexes

    SciTech Connect

    Chu, Ivan K.; Laskin, Julia

    2011-12-31

    The formation and fragmentation of odd-electron ions of peptides and proteins is of interest to applications in biological mass spectrometry. Gas-phase redox chemistry occurring during collision-induced dissociation of ternary metal-ligand-peptide complexes enables the formation of a variety of peptide radicals including the canonical radical cations, M{sup +{sm_bullet}}, radical dications, [M{sup +}H]{sup 2+{sm_bullet}}, radical anions, [M-2H]{sup -{sm_bullet}}. In addition, odd-electron peptide ions with well-defined initial location of the radical site are produced through side chain losses from the radical ions. Subsequent fragmentation of these species provides information on the role of charge and the location of the radical site on the competition between radical-induced and proton-driven fragmentation of odd-electron peptide ions. This account summarizes current understanding of the factors that control the efficiency of the intramolecular electron transfer (ET) in ternary metal-ligand-peptide complexes resulting in formation of odd-electron peptide ions. Specifically, we discuss the effect of the metal center, the ligand and the peptide structure on the competition between the ET, proton transfer (PT), and loss of neutral peptide and neutral peptide fragments from the complex. Fundamental studies of the structures, stabilities, and the energetics and dynamics of fragmentation of such complexes are also important for detailed molecular-level understanding of photosynthesis and respiration in biological systems.

  19. Synthesis of the iron phthalocyaninate radical cation μ-nitrido dimer and its interaction with hydrogen peroxide

    NASA Astrophysics Data System (ADS)

    Grishina, E. S.; Makarova, A. S.; Kudrik, E. V.; Makarov, S. V.; Koifman, O. I.

    2016-03-01

    The iron phthalocyaninate μ-nitrido dimer radical cation, as well as the μ-nitrido dimer complexes of iron phthalocyaninate, was found to have high catalytic activity in the oxidation of organic compounds. It was concluded that this compound is of interest as a model of active intermediates—catalase and oxidase enzymes.

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

    PubMed

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

    2011-09-07

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

  1. Photoinduced electron-transfer reactions of 2(3H)-furanones and bis(benzofuranones). Spectral and kinetic behavior of radicals and radical cations

    SciTech Connect

    Davis, H.F.; Lohray, B.B.; Gopidas, K.R.; Kumar, C.V.; Das, P.K.; George, M.V.

    1985-10-04

    The spectral and kinetic behaviors of radical cations produced under efficient electron-transfer quenching of 1,4-dicyanonaphthalene or 9,10-dicyanoanthracene singlet by a number of 2(3H)-furanones and bis(benzo-furanones) have been examined by nanosecond laser flash photolysis (337.1 and 425 nm). The efficiencies of net electron transfer in the course of quenching processes are moderately high (0.2-0.6) in acetonitrile. The radical cations from bis(benzofuranones) several 2(3H)-furanones containing a benzyl group at the 3-position undergo fragmentation to benzofuranoxy and furanoxy radicals (+ benzyl or benzofuranoyl carbocations) with rate constants of 0.3 x 10W s . The long-lived furanoxy radicals, independently generated via hydrogen abstraction by tert-butoxy radicals from 2(5H)-furanones and 3-phenyl-2(3H)-benzofuranone, as well as via direct photolysis of 3-benzoyl-3,5-diphenyl-2(3H)-furanone, are characterized by sharply structured absorption spectra and relatively slow second-order decay kinetics (6-8 x 10Y M s in 1:2 benzene-di-tert butyl peroxide, v/v). 28 references, 7 figures, 3 tables.

  2. Reactions of 5-methylcytosine cation radicals in DNA and model systems: thermal deprotonation from the 5-methyl group vs. excited state deprotonation from sugar

    PubMed Central

    Adhikary, Amitava; Kumar, Anil; Palmer, Brian J.; Todd, Andrew D.; Heizer, Alicia N.; Sevilla, Michael D.

    2014-01-01

    Purpose To study the formation and subsequent reactions of the 5-methyl-2′-deoxycytidine cation radical (5-Me-2′-dC•+) in nucleosides and DNA-oligomers and compare to one electron oxidized thymidine. Materials and methods Employing electron spin resonance (ESR), cation radical formation and its reactions were investigated in 5-Me-2′-dC, thymidine (Thd) and their derivatives, in fully double stranded (ds) d[GC*GC*GC*GC*]2 and in the 5-Me-C/A mismatched, d[GGAC*AAGC:CCTAATCG], where C* = 5-Me-C. Results We report 5-Me-2′-dC•+ production by one-electron oxidation of 5-Me-2′-dC by Cl2•− via annealing in the dark at 155 K. Progressive annealing of 5-Me-2′-dC•+ at 155 K produces the allylic radical (C-CH2•). However, photoexcitation of 5-Me-2′-dC•+ by 405 nm laser or by photoflood lamp leads to only C3′• formation. Photoexcitation of N3-deprotonated thyminyl radical in Thd and its 5′-nucleotides leads to C3′• formation but not in 3′-TMP which resulted in the allylic radical (U-CH2•) and C5′• production. For excited 5-Me-2′,3′-ddC•+, absence of the 3′-OH group does not prevent C3′• formation. For d[GC*GC*GC*GC*]2 and d[GGAC*AAGC:CCTAATCG], intra-base paired proton transferred form of G cation radical (G(N1-H)•:C(+H+)) is found with no observable 5-Me-2′-dC•+ formation. Photoexcitation of (G(N1-H)•:C(+H+)) in d[GC*GC*GC*GC*]2 produced only C1′• and not the expected photoproducts from 5-Me-2′-dC•+. However, photoexcitation of (G(N1-H)•:C(+H+)) in d[GGAC*AAGC:CCTAATCG] led to C5′• and C1′• formation. Conclusions C-CH2• formation from 5-Me-2′-dC•+ occurs via ground state deprotonation from C5-methyl group on the base. In the excited 5-Me-2′-dC•+ and 5-Me-2′,3′-ddC•+, spin and charge localization at C3′ followed by deprotonation leads to C3′• formation. Thus, deprotonation from C3′ in the excited cation radical is kinetically controlled and sugar C-H bond energies are

  3. Vanadium promotes hydroxyl radical formation by activated human neutrophils.

    PubMed

    Fickl, Heidi; Theron, Annette J; Grimmer, Heidi; Oommen, Joyce; Ramafi, Grace J; Steel, Helen C; Visser, Susanna S; Anderson, Ronald

    2006-01-01

    This study was undertaken to investigate the effects of vanadium in the +2, +3, +4, and +5 valence states on superoxide generation, myeloperoxidase (MPO) activity, and hydroxyl radical formation by activated human neutrophils in vitro, using lucigenin-enhanced chemiluminescence (LECL), autoiodination, and electron spin resonance with 5,5-dimethyl-l-pyrroline N-oxide as the spin trap, respectively. At concentrations of up to 25 microM, vanadium, in the four different valence states used, did not affect the LECL responses of neutrophils activated with either the chemoattractant, N-formyl-l-methionyl-l-leucyl-l-phenylalanine (1 microM), or the phorbol ester, phorbol 12-myristate 12-acetate (25 ng/ml). However, exposure to vanadium in the +2, +3, and +4, but not the +5, valence states was accompanied by significant augmentation of hydroxyl radical formation by activated neutrophils and attenuation of MPO-mediated iodination. With respect to hydroxyl radical formation, similar effects were observed using cell-free systems containing either hydrogen peroxide (100 microM) or xanthine/xanthine oxidase together with vanadium (+2, +3, +4), while the activity of purified MPO was inhibited by the metal in these valence states. These results demonstrate that vanadium in the +2, +3, and +4 valence states interacts prooxidatively with human neutrophils, competing effectively with MPO for hydrogen peroxide to promote formation of the highly toxic hydroxyl radical.

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

    PubMed

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

    2016-06-21

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

  5. Iron corrolates: unambiguous chloroiron(III) (corrolate)(2-.) pi-cation radicals.

    PubMed

    Walker, F Ann; Licoccia, Silvia; Paolesse, Roberto

    2006-04-01

    The structures, electron configurations, magnetic susceptibilities, spectroscopic properties, molecular orbital energies and spin density distributions, redox properties and reactivities of iron corrolates having chloride, phenyl, pyridine, NO and other ligands are reviewed. It is shown that with one very strong donor ligand such as phenyl anion the electron configuration of the metal is d(4)S=1 Fe(IV) coordinated to a (corrolate)(3-) anion, while with one weaker donor ligand such as chloride or other halide, the electron configuration is d(5)S=3/2 Fe(III) coordinated to a (corrolate)(2-.) pi-cation radical, with antiferromagnetic coupling between the metal and corrolate radical electron. Many of these complexes have been studied by electrochemical techniques and have rich redox reactivity, in most cases involving two 1-electron oxidations and two 1-electron reductions, and it is not possible to tell, from the shapes of cyclic voltammetric waves, whether the electron is added or removed from the metal or the macrocycle; often infrared, UV-Vis, or EPR spectroscopy can provide this information. (1)H and (13)C NMR spectroscopic methods are most useful in delineating the spin state and pattern of spin density distribution of the complexes listed above, as would also be expected to be the case for the recently-reported formal Fe(V)O corrolate, if this complex were stable enough for characterization by NMR spectroscopy. Iron, manganese and chromium corrolates can be oxidized by iodosylbenzene and other common oxidants used previously with metalloporphyrinates to effect efficient oxidation of substrates. Whether the "resting state" form of these complexes, most generally in the case of iron [FeCl(Corr)], actually has the electron configuration Fe(IV)(Corr)(3-) or Fe(III)(Corr)(2-.) is not relevant to the high-valent reactivity of the complex.

  6. Assigning structures to gas-phase peptide cations and cation-radicals. An infrared multiphoton dissociation, ion mobility, electron transfer, and computational study of a histidine peptide ion.

    PubMed

    Moss, Christopher L; Chamot-Rooke, Julia; Nicol, Edith; Brown, Jeffery; Campuzano, Iain; Richardson, Keith; Williams, Jonathan P; Bush, Matthew F; Bythell, Benjamin; Paizs, Bela; Turecek, Frantisek

    2012-03-15

    Infrared multiphoton dissociation (IRMPD) spectroscopy, using a free-electron laser, and ion mobility measurements, using both drift-cell and traveling-wave instruments, were used to investigate the structure of gas-phase peptide (AAHAL + 2H)(2+) ions produced by electrospray ionization. The experimental data from the IRMPD spectra and collisional cross section (Ω) measurements were consistent with the respective infrared spectra and Ω calculated for the lowest-energy peptide ion conformer obtained by extensive molecular dynamics searches and combined density functional theory and ab initio geometry optimizations and energy calculations. Traveling-wave ion mobility measurements were employed to obtain the Ω of charge-reduced peptide cation-radicals, (AAHAL + 2H)(+●), and the c(3), c(4), z(3), and z(4) fragments from electron-transfer dissociation (ETD) of (AAHAL + 2H)(2+). The experimental Ω for the ETD charge-reduced and fragment ions were consistent with the values calculated for fully optimized ion structures and indicated that the ions retained specific hydrogen bonding motifs from the precursor ion. In particular, the Ω for the doubly protonated ions and charge-reduced cation-radicals were nearly identical, indicating negligible unfolding and small secondary structure changes upon electron transfer. The experimental Ω for the (AAHAL + 2H)(+●) cation-radicals were compatible with both zwitterionic and histidine radical structures formed by electron attachment to different sites in the precursor ion, but did not allow their distinction. The best agreement with the experimental Ω was found for ion structures fully optimized with M06-2X/6-31+G(d,p) and using both projection approximation and trajectory methods to calculate the theoretical Ω values.

  7. Prevention of cancer by agents that suppress oxygen radical formation.

    PubMed

    Troll, W

    1991-01-01

    The prevention of cancer by agents in our diet has led to the concept that oxygen radicals are a necessary component of a variety of human cancers including breast, colon and prostatic cancer. These cancers are putatively promoted by estradiol, bile acids and androgens. Epidemiological studies have shown that these cancers are suppressed in vegetarian populations. Vegetable components that may be responsible for this cancer prevention are Vitamin A, retinoids and protease inhibitors (PIs). These agents have been shown to suppress the formation of hydrogen peroxide in promoter-induced neutrophils. They also have been shown to block two-stage carcinogenesis and breast cancer when fed to animals. PIs also suppress experimentally-induced colon cancer and spontaneous liver cancer. Moreover, a new series of cancer-preventive agents, Sarcophytols (isolated by Fujiki and co-workers), are capable of suppressing two-stage carcinogenesis, breast and colon cancers in rodents when given in low concentrations. Sarcophytols were also active suppressors of H2O2 formation of 12-O-tetradecanoyl-phorbol-13-acetate (TPA)-induced neutrophils. These observations point to an essential role of oxygen radicals in carcinogenesis. Suppression of the oxygen radical response of neutrophils in relation to cancer preventive agents is a facile assay of these important substances. The mechanism of action of oxygen radicals in promoting carcinogenesis is a multiple one, including: (1) activation of oncogenes, (2) modification of DNA bases, and (3) formation of single-strand breaks leading to poly(ADP)ribose polymerase activation.

  8. Effects of structural factors on the pi-dimerization and/or disproportionation of the cation radical of extended TTF containing thiophene-based pi-conjugated spacers.

    PubMed

    Frère, Pierre; Allain, Magali; Elandaloussi, El Hadj; Levillain, Eric; Sauvage, François-Xavier; Riou, Amédée; Roncali, Jean

    2002-02-15

    The electrochemical and chemical oxidation of extended TTF 4 and 5 are analysed by cyclic voltammetry, Visible/NIR and ESR spectroscopies, and the X-ray structures of the new salts 5 x BF(4)(CH(2)Cl(2)) and 4 x ClO(4)(THF)(1/2) are presented. The effects of structural factors on the pi-dimerization or the disproportionation reaction of the cation radical are shown. The oxidation of compound 4 presents the successive formation of stable cation radical and dication species both in dichloromethane (DCM) and in a CH(3)CN/THF mixture. In contrast, for compound 5, the stability of the oxidation states strongly depends on the nature of the solvent. In DCM, the oxidation of 5 proceeds by two close one-electron transfers while in CH(3)CN/THF the dication is directly formed via a two-electron process. The X-ray structures of the two salts reveal the formation of pi-dimers of cation radical. While the dimer (5(2))(2+) is due mainly to pi-pi interactions between the conjugating spacer, the multiplication of the sulfur atoms in compound 4 contributes to stabilize the dimer by the combined effects of S-S and pi-pi interactions. Visible/NIR and ESR experiments confirm the higher tendency of 4(+)(.) to dimerize with the occurrence of dimer and monomer in solution, while for 5(+)(.) only the monomer is detected in DCM. On the other hand, by dissolution of 5 x BF(4)(CH(2)Cl(2)) in CH(3)CN, only the neutral and the dicationic states of compounds 5 are observed owing to the disproportionation reaction.

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

    PubMed Central

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

    2015-01-01

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

  10. Accidental degeneracy in the spiropyran radical cation: charge transfer between two orthogonal rings inducing ultra-efficient reactivity.

    PubMed

    Mendive-Tapia, David; Kortekaas, Luuk; Steen, Jorn D; Perrier, Aurélie; Lasorne, Benjamin; Browne, Wesley R; Jacquemin, Denis

    2016-11-16

    Photochromism of the spiropyran radical cation to the corresponding merocyanine form is investigated by a combination of electrochemical oxidation, UV/vis absorption spectroscopy, spectroelectrochemistry and first-principles calculations (TD-DFT, CAS-SCF and CAS-PT2). First, we demonstrate that the ring-opening of mono-spiropyrans occurs upon one-electron oxidation and that it can be driven photochemically as well as thermally, with trapping of the merocyanine by protonation. Second, in order to explain this experimentally observed spectroelectrochemical behaviour we suggest a theoretical mechanism based on the reactivity of the two lowest electronic excited-states, which promotes effective electron transfer from the indoline (nitrogen-ring) to the pyran (oxygen-ring) moieties (and vice versa) through a conical intersection seam of degeneracy. Characterisation of the minimum energy conical intersection on this crossing revealed that it presents a rare diabatic trapping topology. The excited state molecule cannot escape from crossing the intersection seam due to the presence of only one degeneracy-lifting coordinate that efficiently channels into the formation of the merocyanine photoproduct, so giving rise to a "kitchen sink" funnel-like effect. Therefore, assuming rapid relaxation after vertical excitation to a higher electronic state, photoconversion cannot be avoided in the D1 electronic state, which rationalises the remarkably efficient visible light driven excited-state reactivity observed experimentally.

  11. Some Rearrangements of Free Alkyl Radicals and Alkyl Cations in Solutions

    NASA Astrophysics Data System (ADS)

    Reutov, Oleg A.

    1984-03-01

    The results of studies of rearrangement reactions by the author and his co-workers during the last 20 years are described. A rearrangement of the n-propyl free radical in solutions as a result of the hydrogen 1,3-shift has been discovered and its characteristic features have been investigated (using carbon-14, deuterium, and tritium). The reaction involving the formation of organomercury compounds from mercury salts of carboxylic acids and peroxides has been studied and a mechanism has been proposed for it. New skeletal rearrangements in the thermal decomposition of cycloalkyl peroxides in benzene and bromoform have been discovered. It has been shown by the method of double 13C NMR that some of the reactions involve the formation of species which manifest properties intermediate between those of free radicals and carbonium ions. The mechanism of the thermolysis of peroxides is considered. The skeletal rearrangements and hydride shifts in the deamination and solvolysis of alicyclic compounds have been studied and a number of rearrangements with 1,2-migration of the halogen and in particular the isomerisation of acyloxybromopropanes in organic solvents, which takes place particularly readily, have been observed. The bibliography includes 103 references.

  12. Formation and reactivity of pyridylperoxyl radicals in solution

    SciTech Connect

    Alfassi, Z.B.; Khaikin, G.I.; Neta, P.

    1995-03-30

    2-Pyridyl radicals were produced by the reaction of 2-chloro- or 2-bromopyridine with solvated electrons (k approximately 10{sup 10} L mol{sup -1} s{sup -1}) and reacted rapidly with oxygen (k = 2.2 x 10{sup 9} L mol{sup -1} s{sup -1}) to produce the 2-pyridylperoxyl radical. This radical exhibits optical absorption in the visible range, with {lambda}{sub max} at 440 nm. 2-Pyridylperoxyl radical is a fairly strong oxidant, which reacts with 2,2`-azinobis(3-ethylbenzothiazoline-6-sulfonate ion) (ABTS), chlorpromazine, and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox C) by one-electron oxidation. The rate constants k for these reactions, determined from the rate of formation of the one-electron oxidation as a function of substrate concentration, vary between 2 x 10{sup 6} and 2 x 10{sup 9} L mol{sup -1} s{sup -1} in various mixtures. For each substrate, a good correlation was found between log k and the cohesive pressure of the solvent or solvent mixture, as found before for CCI{sub 3}O{sub 2} radical reactions in nearly neat solvents. 3-Bromo, 3-chloro- and 4-chloropyridine also reacted rapidly with solvated electrons, but their radical anions underwent protonation on the nitrogen in competition with the dehalogenation process. Therefore, no pyridylperoxyl radicals were formed from these species in aqueous solutions and only partial yield was found in neat methanol. 20 refs., 4 figs., 1 tab.

  13. Ellagic acid inhibits iron-mediated free radical formation.

    PubMed

    Dalvi, Luana T; Moreira, Daniel C; Andrade, Roberto; Ginani, Janini; Alonso, Antonio; Hermes-Lima, Marcelo

    2017-02-15

    Polyphenols are reported to have some health benefits, which are link to their antioxidant properties. In the case of ellagic acid (EA), there is evidence that it has free radical scavenger properties and that it is able to form complexes with metal ions. However, information on a possible link between the formation of iron-EA complexes and their interference in Haber-Weiss/Fenton reactions was not yet determined. Thus, the present study investigated the in vitro antioxidant mechanism of EA in a system containing ascorbate, Fe(III) and different iron ligands (EDTA, citrate and NTA). Iron-mediated oxidative degradation of 2-deoxyribose was poorly inhibited (by 12%) in the presence of EA (50μM) and EDTA. When citrate or NTA - which form weak iron complexes - were used, the 2-deoxyribose protection increased to 89-97% and 45%, respectively. EA also presented equivalent inhibitory effects on iron-mediated oxygen uptake and ascorbyl radical formation. Spectral analyses of iron-EA complexes show that EA removes Fe(III) from EDTA within hours, and from citrate within 1min. This difference in the rate of iron-EA complex formation may explain the antioxidant effects of EA. Furthermore, the EA antioxidant effectiveness was inversely proportional to the Fe(III) concentration, suggesting a competition with EDTA. In conclusion, the results indicate that EA may prevent in vitro free radical formation when it forms a complex with iron ions.

  14. Ellagic acid inhibits iron-mediated free radical formation

    NASA Astrophysics Data System (ADS)

    Dalvi, Luana T.; Moreira, Daniel C.; Andrade, Roberto; Ginani, Janini; Alonso, Antonio; Hermes-Lima, Marcelo

    2017-02-01

    Polyphenols are reported to have some health benefits, which are link to their antioxidant properties. In the case of ellagic acid (EA), there is evidence that it has free radical scavenger properties and that it is able to form complexes with metal ions. However, information on a possible link between the formation of iron-EA complexes and their interference in Haber-Weiss/Fenton reactions was not yet determined. Thus, the present study investigated the in vitro antioxidant mechanism of EA in a system containing ascorbate, Fe(III) and different iron ligands (EDTA, citrate and NTA). Iron-mediated oxidative degradation of 2-deoxyribose was poorly inhibited (by 12%) in the presence of EA (50 μM) and EDTA. When citrate or NTA - which form weak iron complexes - were used, the 2-deoxyribose protection increased to 89-97% and 45%, respectively. EA also presented equivalent inhibitory effects on iron-mediated oxygen uptake and ascorbyl radical formation. Spectral analyses of iron-EA complexes show that EA removes Fe(III) from EDTA within hours, and from citrate within 1 min. This difference in the rate of iron-EA complex formation may explain the antioxidant effects of EA. Furthermore, the EA antioxidant effectiveness was inversely proportional to the Fe(III) concentration, suggesting a competition with EDTA. In conclusion, the results indicate that EA may prevent in vitro free radical formation when it forms a complex with iron ions.

  15. Role of. pi. -cation radicals in the enzymatic cycles of peroxidases, catalases, and nitrite and sulfite reductases

    SciTech Connect

    Hanson, L K; Chang, C K; Davis, M S; Fajer, J

    1980-01-01

    Charge iterative extended Hueckel calculations, and magnetic and optical results on porphyrins, chlorins, and isobacteriochlorins (1) suggest that the catalytic cycles of the enzymes horseradish peroxidase, catalase, Neurospora crassa catalase, and nitrite and sulfite reductases proceed via ..pi..-cation radicals of their prosthetic groups; (2) offer distinguishing features for the optical and magnetic spectra of these radicals, pertinent to their detection as enzymatic intermediates; (3) reconcile the seemingly contradictory optical and NMR data on Compounds I of horseradish peroxidase; and (4) predict that the axial ligation of the heme differs for horseradish peroxidase and catalase.

  16. Diel peroxy radicals in a semi-industrial coastal area: nighttime formation of free radicals

    NASA Astrophysics Data System (ADS)

    Andrés-Hernández, M. D.; Kartal, D.; Crowley, J. N.; Sinha, V.; Regelin, E.; Martínez-Harder, M.; Nenakhov, V.; Williams, J.; Harder, H.; Bozem, H.; Song, W.; Thieser, J.; Tang, M. J.; Hosaynali Beigi, Z.; Burrows, J. P.

    2013-06-01

    Peroxy radicals were measured by a PeRCA (Peroxy Radical Chemical Amplifier) instrument in the boundary layer during the DOMINO (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) campaign at a coastal, forested site influenced by urban-industrial emissions in southern Spain in late autumn. Total peroxy radicals (RO2* = HO2 + ΣRO2) generally showed a daylight maximum between 10 and 50 pptv at 13:00 UTC, with an average of 18 pptv over the 15 days of measurements. Emissions from the industrial area of Huelva often impacted the measurement site at night during the campaign. The processing of significant levels of anthropogenic organics leads to an intense nocturnal radical chemistry accompanied by formation of organic peroxy radicals at comparable levels to those of summer photochemical conditions with peak events up to 60-80 pptv. The RO2 production initiated by reactions of NO3 with organic trace gases was estimated to be significant, but not sufficient to account for the concentrations of RO2* observed in air masses carrying high pollutant loading. The nocturnal production of peroxy radicals in those periods seems therefore to be dominated by ozonolysis of volatile organic compounds, in particular alkenes of industrial petrochemical origin. RO2* diurnal variations were consistent with HO2 measurements available at the site. HO2/RO2* ratios generally varied between 0.3 and 0.6, though on some occasions this ratio was likely to have been affected by instrumental artifacts (overestimated HO2) associated with high RO2 loads.

  17. Unconventional hydrogen bonding to organic ions in the gas phase: stepwise association of hydrogen cyanide with the pyridine and pyrimidine radical cations and protonated pyridine.

    PubMed

    Hamid, Ahmed M; El-Shall, M Samy; Hilal, Rifaat; Elroby, Shaaban; Aziz, Saadullah G

    2014-08-07

    Equilibrium thermochemical measurements using the ion mobility drift cell technique have been utilized to investigate the binding energies and entropy changes for the stepwise association of HCN molecules with the pyridine and pyrimidine radical cations forming the C5H5N(+·)(HCN)n and C4H4N2 (+·)(HCN)n clusters, respectively, with n = 1-4. For comparison, the binding of 1-4 HCN molecules to the protonated pyridine C5H5NH(+)(HCN)n has also been investigated. The binding energies of HCN to the pyridine and pyrimidine radical cations are nearly equal (11.4 and 12.0 kcal/mol, respectively) but weaker than the HCN binding to the protonated pyridine (14.0 kcal/mol). The pyridine and pyrimidine radical cations form unconventional carbon-based ionic hydrogen bonds with HCN (CH(δ+)⋯NCH). Protonated pyridine forms a stronger ionic hydrogen bond with HCN (NH(+)⋯NCH) which can be extended to a linear chain with the clustering of additional HCN molecules (NH(+)⋯NCH··NCH⋯NCH) leading to a rapid decrease in the bond strength as the length of the chain increases. The lowest energy structures of the pyridine and pyrimidine radical cation clusters containing 3-4 HCN molecules show a strong tendency for the internal solvation of the radical cation by the HCN molecules where bifurcated structures involving multiple hydrogen bonding sites with the ring hydrogen atoms are formed. The unconventional H-bonds (CH(δ+)⋯NCH) formed between the pyridine or the pyrimidine radical cations and HCN molecules (11-12 kcal/mol) are stronger than the similar (CH(δ+)⋯NCH) bonds formed between the benzene radical cation and HCN molecules (9 kcal/mol) indicating that the CH(δ+) centers in the pyridine and pyrimidine radical cations have more effective charges than in the benzene radical cation.

  18. Sulphur-radical control on petroleum formation rates

    USGS Publications Warehouse

    Lewan, M.D.

    1998-01-01

    Most petroleum is formed through the partial decomposition of kerogen (an insoluble sedimentary organic material) in response to thermal stress during subsurface burial in a sedimentary basin. Knowing the mechanisms and kinetics of this process allows the determination of the extent and timing of petroleum formation, which, in turn, are critical for evaluating the potential for petroleum occurrences within a sedimentary basin. Kinetic models of petroleum generation are derived mainly from pyrolysis experiments, in which it is usually assumed that formation rates are controlled by the strength of the bonds within the precursor compounds: this agrees with the observation that petroleum formation rates increase with increasing sulphur content of thermally immature kerogen, C-S bonds being weaker than C-C bonds. However, this explanation fails to account for the overall composition of petroleum. Here I argue, on the basis of pyrolysis experiments, that it is the presence of sulphur radicals, rather than the relative weakness of C-S bonds, that controls petroleum formation rates. My findings suggest that the rate of petroleum formation depends critically on the concentration of sulphur radicals generated during the initial stages of thermal maturation. The proposed mechanism appears to provide a realistic explanation for both the overall composition of petroleum and the observed variation in formation rates.

  19. A search for blues brothers: X-ray crystallographic/spectroscopic characterization of the tetraarylbenzidine cation radical as a product of aging of solid magic blue.

    PubMed

    Talipov, Marat R; Hossain, Mohammad M; Boddeda, Anitha; Thakur, Khushabu; Rathore, Rajendra

    2016-03-14

    Magic blue (MB+˙ SbCl6− salt), i.e. tris-4-bromophenylamminium cation radical, is a routinely employed one-electron oxidant that slowly decomposes in the solid state upon storage to form so called ‘blues brothers’, which often complicate the quantitative analyses of the oxidation processes. Herein, we disclose the identity of the main ‘blues brother’ as the cation radical and dication of tetrakis-(4-bromophenyl)benzidine (TAB) by a combined DFT and experimental approach, including isolation of TAB+˙ SbCl6− and its X-ray crystallography characterization. The formation of TAB in aged magic blue samples occurs by a Scholl-type coupling of a pair of MB followed by a loss of molecular bromine. The recognition of this fact led us to the rational design and synthesis of tris(2-bromo-4-tert-butylphenyl)amine, referred to as ‘blues cousin’ (BC: Eox1 = 0.78 V vs. Fc/Fc+, λmax(BC+˙) = 805 nm, εmax = 9930 cm−1 M−1), whose oxidative dimerization is significantly hampered by positioning the sterically demanding tert-butyl groups at the para-positions of the aryl rings. A ready two-step synthesis of BC from triphenylamine and the high stability of its cation radical (BC+˙) promise that BC will serve as a ready replacement for MB and an oxidant of choice for mechanistic investigations of one-electron transfer processes in organic, inorganic, and organometallic transformations.

  20. Resonance Raman spectra of the anion and cation radicals of bacterial photosynthetic pigments

    SciTech Connect

    Diers, J.R.; Bocian, D.F. )

    1994-12-08

    Resonance Raman (RR) spectra are reported for the radical ions of the bacterial photosynthetic pigments bacteriochlorophyll a (BCh) and its metal-free analog bacteriopheophytin a (BPh). The radical anions, BCh[sup [minus

  1. The formation of singly and doubly cationized oligomers in SIMS

    NASA Astrophysics Data System (ADS)

    Delcorte, A.; Wojciechowski, I.; Gonze, X.; Garrison, B. J.; Bertrand, P.

    2003-01-01

    The cationization of sputtered organic species via metal particle adduction is investigated using poly-4-methylstyrene molecules in combination with Cu, Pd, Ag and Au substrates. Metal-cationization occurs for these four substrates. The cationized molecule yields vary with the considered substrate and they are not correlated with the metal ion yields. In addition, double cationization with two metal particles is observed with a very significant intensity for Cu, Ag and Au supports. We interpret the results with an emission scheme in which excited molecules and metal atoms recombine above the surface and decay via electron emission, thereby locking the complex in the ionic state.

  2. The Influence of Zeolites on Radical Formation During Lignin Pyrolysis.

    PubMed

    Bährle, Christian; Custodis, Victoria; Jeschke, Gunnar; van Bokhoven, Jeroen A; Vogel, Frédéric

    2016-09-08

    Lignin from lignocellulosic biomass is a promising source of energy, fuels, and chemicals. The conversion of the polymeric lignin to fuels and chemicals can be achieved by catalytic and noncatalytic pyrolysis. The influence of nonporous silica and zeolite catalysts, such as silicalite, HZSM5, and HUSY, on the radical and volatile product formation during lignin pyrolysis was studied by in situ high-temperature electron paramagnetic resonance spectroscopy (HTEPR) as well as GC-MS. Higher radical concentrations were observed in the samples containing zeolite compared to the sample containing only lignin, which suggests that there is a stabilizing effect by the inorganic surfaces on the formed radical fragments. This effect was observed for nonporous silica as well as for HUSY, HZSM5, and silicalite zeolite catalysts. However, the effect is far larger for the zeolites owing to their higher specific surface area. The zeolites also showed an effect on the volatile product yield and the product distribution within the volatile phase. Although silicalite showed no effect on the product selectivity, the acidic zeolites such as HZSM5 or HUSY increased the formation of deoxygenated products such as benzene, toluene, xylene (BTX), and naphthalene.

  3. Effects of Hofmeister salt series on gluten network formation: Part I. Cation series.

    PubMed

    Tuhumury, H C D; Small, D M; Day, L

    2016-12-01

    Different cationic salts were used to investigate the effects of the Hofmeister salt series on gluten network formation. The effects of cationic salts on wheat flour dough mixing properties, the rheological and the chemical properties of the gluten extracted from the dough with different respective salts, were investigated. The specific influence of different cationic salts on the gluten structure formation during dough mixing, compared to the sodium ion, were determined. The effects of different cations on dough and gluten of different flours mostly followed the Hofmeister series (NH4(+), K(+), Na(+), Mg(2+) and Ca(2+)). The impacts of cations on gluten structure and dough rheology at levels tested were relatively small. Therefore, the replacement of sodium from a technological standpoint is possible, particularly by monovalent cations such as NH4(+), or K(+). However the levels of replacement need to take into account sensory attributes of the cationic salts.

  4. Role of the hydroxyl radical in soot formation

    NASA Technical Reports Server (NTRS)

    King, Galen B.; Laurendeau, Normand M.

    1983-01-01

    The goal of this project is to determine the role of the hydroxyl radical during formation of soot. Correlations will be sought between OH concentration and (1) the critical equivalence ratio for incipient soot formation and (2) soot yield as a function of higher equivalence ratios. The ultimate aim is the development of a quasi-global kinetic model for the pre-particulate chemistry leading to soot nucleation. Hydroxyl radical concentration profiles are measured directly in both laminar premixed and diffusion flames using the newly developed technique, laser saturated fluorescence (LSF). This method is capable of measuring OH in the presence of soot particles. Aliphatic and aromatic fuels will be used to assess the influence of fuel type on soot formation. The influence of flame temperature on the critical equivalence ratio and soot yield will be related to changes in the OH concentration profiles. LSF measurements will be augmented with auxiliary measurements of soot and PAH concentrations to allow the development of a quasi-global model for soot formation.

  5. Structural evolution and solvation of the OH radical in ionized water radical cations (H2O)n(+), n = 5-8.

    PubMed

    Lu, En-Ping; Pan, Piin-Ruey; Li, Ying-Cheng; Tsai, Ming-Kang; Kuo, Jer-Lai

    2014-09-21

    Structural evolution of ionized water radical cations (H2O)n(+), n = 5-8, is studied by ab intio methods. A structure searching method based on the previous understanding of the hydrogen bond (H-bond) network in neutral and protonated water clusters is found to be effective, covering a wide range of structural isomers of (H2O)n(+). With these local minima, we can analyze both the size and temperature dependence of the structure of (H2O)n(+) and solvation of the OH radical. Agreement between our calculated IR spectra and experimental data in the free OH stretching region confirms that the OH radical preferred to stay on the terminal site of the H-bond network at n = 5 and n = 6. Furthermore, we found that the OH radical began to form H-bonds with water molecules as a H-bond donor at n = 7 and 8. Vibrational signatures of fully solvated OH were found to be located at 3200-3400 cm(-1) coinciding with the additional peaks found in previous experimental data obtained by Mizuse and Fujii.

  6. Characterization of a solvent-separated ion-radical pair in cationized water networks: infrared photodissociation and Ar-attachment experiments for water cluster radical cations (H2O)n+(n = 3-8).

    PubMed

    Mizuse, Kenta; Fujii, Asuka

    2013-02-07

    We present infrared spectra of nominal water cluster radical cations (H(2)O)(n)(+) (n = 3-8), or to be precise, ion-radical complexes H(+)(H(2)O)(n-1)(OH), with and without an Ar tag. These clusters are closely related to the ionizing radiation-induced processes in water and are a good model to characterize solvation structures of the ion-radical pair. The spectra of Ar-tagged species show narrower bandwidths relative to those of the bare clusters due to the reduced internal energy via an Ar-attachment. The observed spectra are analyzed by comparing with those of the similar system, H(+)(H(2)O)(n), and calculated ones. We find that the observed spectra are attributable to ion-radical-separated motifs in n ≥ 5, as reported in the previous study (Mizuse et al. Chem. Sci.2011, 2, 868-876). Beyond the structural trends found in the previous study, we characterize isomeric structures and determine the number of water molecules between the charged site and the OH radical in each cluster size. In all of the characterized cluster structures (n = 5-8), the most favorable position of OH radical is the next neighbor of the charged site (H(3)O(+) or H(5)O(2)(+)). The positions and cluster structures are governed by the balance among the hydrogen-bonding abilities of the charged site, H(2)O, and OH radical. These findings on the ionized water networks lead to understanding of the detailed processes of ionizing radiation-initiated reactions in liquid water and aqueous solutions.

  7. The cyclopropene radical cation: Rovibrational level structure at low energies from high-resolution photoelectron spectra

    SciTech Connect

    Vasilatou, K.; Michaud, J. M.; Baykusheva, D.; Grassi, G.; Merkt, F.

    2014-08-14

    The cyclopropene radical cation (c-C{sub 3}H{sub 4}{sup +}) is an important but poorly characterized three-membered-ring hydrocarbon. We report on a measurement of the high-resolution photoelectron and photoionization spectra of cyclopropene and several deuterated isotopomers, from which we have determined the rovibrational energy level structure of the X{sup ~+} {sup 2}B{sub 2} ground electronic state of c-C{sub 3}H{sub 4}{sup +} at low energies for the first time. The synthesis of the partially deuterated isotopomers always resulted in mixtures of several isotopomers, differing in their number of D atoms and in the location of these atoms, so that the photoelectron spectra of deuterated samples are superpositions of the spectra of several isotopomers. The rotationally resolved spectra indicate a C{sub 2v}-symmetric R{sub 0} structure for the ground electronic state of c-C{sub 3}H{sub 4}{sup +}. Two vibrational modes of c-C{sub 3}H{sub 4}{sup +} are found to have vibrational wave numbers below 300 cm{sup −1}, which is surprising for such a small cyclic hydrocarbon. The analysis of the isotopic shifts of the vibrational levels enabled the assignment of the lowest-frequency mode (fundamental wave number of ≈110 cm{sup −1} in c-C{sub 3}H{sub 4}{sup +}) to the CH{sub 2} torsional mode (ν{sub 8}{sup +}, A{sub 2} symmetry) and of the second-lowest-frequency mode (≈210 cm{sup −1} in c-C{sub 3}H{sub 4}{sup +}) to a mode combining a CH out-of-plane with a CH{sub 2} rocking motion (ν{sub 15}{sup +}, B{sub 2} symmetry). The potential energy along the CH{sub 2} torsional coordinate is flat near the equilibrium structure and leads to a pronounced anharmonicity.

  8. Optical spectra of protected diamine 10-bond-bridged intervalence radical cations related to N,N,N'N'-tetraalkylbenzidine.

    PubMed

    Nelsen, Stephen F; Luo, Yun; Weaver, Michael N; Lockard, Jenny V; Zink, Jeffrey I

    2006-05-26

    The optical absorption spectra of the delocalized intervalence radical cations of seven o,o'-linked benzidine derivatives that have the nitrogens protected as 9-(9-aza-bicyclo[3.3.1]nonan-3-one) derivatives are discussed and compared with that of the p-phenylene radical cation. The linking units are CH2, CH2CH2, NMe, S, SO2, and C=O, and we also studied H,H (the unlinked benzidine). The lowest-energy absorption band is assigned as the transition from the antibonding combination of symmetrical N and aromatic orbitals to the antibonding combination of the antisymmetric N and aromatic orbitals using TD-DFT calculations, and a good correlation between the observed transition energies and those calculated using the simple Koopmans theorem-based "neutral in-cation geometry" calculations on the UB3LYP/6-31G* structures is found. The use of the two-state model that equates the electronic interaction through the bridge between the amino groups with half of the lowest transition energy is seriously incorrect for these and other delocalized intervalence compounds. The problem of extracting the electronic interactions that actually are involved from calculated transition energies is discussed.

  9. The loss of NH2O from the N-hydroxyacetamide radical cation CH3C(O)NHOH+

    NASA Astrophysics Data System (ADS)

    Jobst, Karl J.; Burgers, Peter C.; Ruttink, Paul J. A.; Terlouw, Johan K.

    2006-08-01

    A previous study [Ch. Lifshitz, P.J.A. Ruttink, G. Schaftenaar, J.K. Terlouw, Rapid Commun. Mass Spectrom. 1 (1987) 61] shows that metastable N-hydroxyacetamide ions CH3C(O)NHOH+ (HA-1) do not dissociate into CH3CO+ + NHOH by direct bond cleavage but rather yield CH3CO+ + NH2OE The tandem mass spectrometry based experiments of the present study on the isotopologue CH3C(O)NDOD+ reveal that the majority of the metastable ions lose the NH2O radical as NHDO rather than ND2O. A mechanistic analysis using the CBS-QB3 model chemistry shows that the molecular ions HA-1 rearrange into hydrogen-bridged radical cations [OCC(H2)H...N(H)OH]+ whose acetyl cation component then catalyses the transformation NHOH --> NH2O prior to dissociation. The high barrier for the unassisted 1,2-H shift in the free radical, 43 kcal mol-1, is reduced to a mere 7 kcal mol-1 for the catalysed transformation which can be viewed as a quid-pro-quo reaction involving two proton transfers.

  10. Solution-phase mechanistic study and solid-state structure of a tris(bipyridinium radical cation) inclusion complex.

    PubMed

    Fahrenbach, Albert C; Barnes, Jonathan C; Lanfranchi, Don Antoine; Li, Hao; Coskun, Ali; Gassensmith, Jeremiah J; Liu, Zhichang; Benítez, Diego; Trabolsi, Ali; Goddard, William A; Elhabiri, Mourad; Stoddart, J Fraser

    2012-02-15

    The ability of the diradical dicationic cyclobis(paraquat-p-phenylene) (CBPQT(2(•+))) ring to form inclusion complexes with 1,1'-dialkyl-4,4'-bipyridinium radical cationic (BIPY(•+)) guests has been investigated mechanistically and quantitatively. Two BIPY(•+) radical cations, methyl viologen (MV(•+)) and a dibutynyl derivative (V(•+)), were investigated as guests for the CBPQT(2(•+)) ring. Both guests form trisradical complexes, namely, CBPQT(2(•+))⊂MV(•+) and CBPQT(2(•+))⊂V(•+), respectively. The structural details of the CBPQT(2(•+))⊂MV(•+) complex, which were ascertained by single-crystal X-ray crystallography, reveal that MV(•+) is located inside the cavity of the ring in a centrosymmetric fashion: the 1:1 complexes pack in continuous radical cation stacks. A similar solid-state packing was observed in the case of CBPQT(2(•+)) by itself. Quantum mechanical calculations agree well with the superstructure revealed by X-ray crystallography for CBPQT(2(•+))⊂MV(•+) and further suggest an electronic asymmetry in the SOMO caused by radical-pairing interactions. The electronic asymmetry is maintained in solution. The thermodynamic stability of the CBPQT(2(•+))⊂MV(•+) complex was probed by both isothermal titration calorimetry (ITC) and UV/vis spectroscopy, leading to binding constants of (5.0 ± 0.6) × 10(4) M(-1) and (7.9 ± 5.5) × 10(4) M(-1), respectively. The kinetics of association and dissociation were determined by stopped-flow spectroscopy, yielding a k(f) and k(b) of (2.1 ± 0.3) × 10(6) M(-1) s(-1) and 250 ± 50 s(-1), respectively. The electrochemical mechanistic details were studied by variable scan rate cyclic voltammetry (CV), and the experimental data were compared digitally with simulated data, modeled on the proposed mechanism using the thermodynamic and kinetic parameters obtained from ITC, UV/vis, and stopped-flow spectroscopy. In particular, the electrochemical mechanism of association

  11. Aggregation of Kanamycin A: dimer formation with physiological cations.

    PubMed

    Dieterich, Johannes M; Gerstel, Ulrich; Schröder, Jens-Michael; Hartke, Bernd

    2011-12-01

    Global cluster geometry optimization has focused so far on clusters of atoms or of compact molecules. We are demonstrating here that present-day techniques also allow to globally optimize clusters of extended, flexible molecules, and that such studies have immediate relevance to experiment. For example, recent experimental findings point to production of larger clusters of an aminoglycoside closely related to Kanamycin A (KA), together with certain preferred physiological cations, by Pseudomonas aeruginosa. The present study provides first theoretical support for KA clustering, with a close examination of the monomer, the bare dimer, and dimers with sodium and potassium cations, employing global cluster structure optimization, in conjunction with force fields, semiempirical methods, DFT and ab-initio approaches. Interestingly, already at this stage the theoretical findings support the experimental observation that sodium cations are preferred over potassium cations in KA clusters, due to fundamentally different cationic embedding. Theoretically predicted NMR and IR spectra for these species indicate that it should be possible to experimentally detect the aggregation state and even the cationic embedding mode in such clusters.

  12. A Radical-Mediated Pathway for the Formation of [M + H]+ in Dielectric Barrier Discharge Ionization

    NASA Astrophysics Data System (ADS)

    Wolf, Jan-Christoph; Gyr, Luzia; Mirabelli, Mario F.; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

    2016-09-01

    Active capillary plasma ionization is a highly efficient ambient ionization method. Its general principle of ion formation is closely related to atmospheric pressure chemical ionization (APCI). The method is based on dielectric barrier discharge ionization (DBDI), and can be constructed in the form of a direct flow-through interface to a mass spectrometer. Protonated species ([M + H]+) are predominantly formed, although in some cases radical cations are also observed. We investigated the underlying ionization mechanisms and reaction pathways for the formation of protonated analyte ([M + H]+). We found that ionization occurs in the presence and in the absence of water vapor. Therefore, the mechanism cannot exclusively rely on hydronium clusters, as generally accepted for APCI. Based on isotope labeling experiments, protons were shown to originate from various solvents (other than water) and, to a minor extent, from gaseous impurities and/or self-protonation. By using CO2 instead of air or N2 as plasma gas, additional species like [M + OH]+ and [M - H]+ were observed. These gas-phase reaction products of CO2 with the analyte (tertiary amines) indicate the presence of a radical-mediated ionization pathway, which proceeds by direct reaction of the ionized plasma gas with the analyte. The proposed reaction pathway is supported with density functional theory (DFT) calculations. These findings add a new ionization pathway leading to the protonated species to those currently known for APCI.

  13. Organic conductors and superconductors based on bis(ethylenedithio)tetrathiafulvalene radical cation salts with supramolecular tris(oxalato)metallate anions

    NASA Astrophysics Data System (ADS)

    Prokhorova, T. G.; Yagubskii, E. B.

    2017-02-01

    The results of studies of a family of conductors and superconductors based on bis(ethylenedithio)tetrathiafulvalene radical cation salts with paramagnetic and diamagnetic supramolecular tris(oxalato)metallate anions are collated and analyzed. Methods for the preparation of these salts and various types of packing of conducting layers within the salt structures are considered. The transport properties of crystals of the salts of this family and the effect of guest solvent molecules on these properties are discussed. The contribution of scientists from the Institute of Problems of Chemical Physics, RAS, to the research into organic conductors and superconductors is noted. The bibliography includes 70 references.

  14. Fast regeneration of carotenoids from radical cations by isoflavonoid dianions: importance of the carotenoid keto group for electron transfer.

    PubMed

    Han, Rui-Min; Chen, Chang-Hui; Tian, Yu-Xi; Zhang, Jian-Ping; Skibsted, Leif H

    2010-01-14

    Electron transfer to radical cations of beta-carotene, zeaxanthin, canthaxanthin, and astaxanthin from each of the three acid/base forms of the diphenolic isoflavonoid daidzein and its C-glycoside puerarin, as studied by laser flash photolysis in homogeneous methanol/chloroform (1/9) solution, was found to depend on carotenoid structures and more significantly on the deprotonation degree of the isoflavonoids. None of the carotenoid radical cations reacted with the neutral forms of the isoflavonoids while the monoanionic and dianionic forms of the isoflavonoids regenerated the oxidized carotenoid. Electron transfer to the beta-carotene radical cation from the puerarin dianion followed second order kinetics with the rate constant at 25 degrees C k(2) = 5.5 x 10(9) M(-1) s(-1), zeaxanthin 8.5 x 10(9) M(-1) s(-1), canthaxanthin 6.5 x 10(10) M(-1) s(-1), and astaxanthin 11.1 x 10(10) M(-1) s(-1) approaching the diffusion limit and establishing a linear free energy relationship between rate constants and driving force. Comparable results found for the daidzein dianion indicate that the steric hindrance from the glucoside is not important suggesting the more reducing but less acidic 4'-OH/4'-O(-) as electron donors. On the basis of the rate constants obtained from kinetic analyses, the keto group of carotenoids is concluded to facilitate electron transfer. The driving force was estimated from oxidation potentials, as determined by cyclic-voltametry for puerarin and daidzein in aqueous solutions at varying pH conditions, which led to the standard reduction potentials E degrees = 1.13 and 1.10 V versus NHE corresponding to the uncharged puerarin and daidzein. For pH > pK(a2), the apparent potentials of both puerarin and daidzein became constants and were E degrees = 0.69 and 0.65 V, respectively. Electron transfer from isoflavonoids to the carotenoid radical cation, as formed during oxidative stress, is faster for astaxanthin than for the other carotenoids, which may relate

  15. Protonation switching to the least-basic heteroatom of carbamate through cationic hydrogen bonding promotes the formation of isocyanate cations.

    PubMed

    Kurouchi, Hiroaki; Sumita, Akinari; Otani, Yuko; Ohwada, Tomohiko

    2014-07-07

    We found that phenethylcarbamates that bear ortho-salicylate as an ether group (carbamoyl salicylates) dramatically accelerate OC bond dissociation in strong acid to facilitate generation of isocyanate cation (N-protonated isocyanates), which undergo subsequent intramolecular aromatic electrophilic cyclization to give dihydroisoquinolones. To generate isocyanate cations from carbamates in acidic media as electrophiles for aromatic substitution, protonation at the ether oxygen, the least basic heteroatom, is essential to promote CO bond cleavage. However, the carbonyl oxygen of carbamates, the most basic site, is protonated exclusively in strong acids. We found that the protonation site can be shifted to an alternative basic atom by linking methyl salicylate to the ether oxygen of carbamate. The methyl ester oxygen ortho to the phenolic (ether) oxygen of salicylate is as basic as the carbamate carbonyl oxygen, and we found that monoprotonation at the methyl ester oxygen in strong acid resulted in the formation of an intramolecular cationic hydrogen bond (>CO(+) H⋅⋅⋅O<) with the phenolic ether oxygen. This facilitates OC bond dissociation of phenethylcarbamates, thereby promoting isocyanate cation formation. In contrast, superacid-mediated diprotonation at the methyl ester oxygen of the salicylate and the carbonyl oxygen of the carbamate afforded a rather stable dication, which did not readily undergo CO bond dissociation. This is an unprecedented and unknown case in which the monocation has greater reactivity than the dication.

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

    PubMed Central

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

    2013-01-01

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

  17. Mechanistic and comparative studies of melatonin and classic antioxidants in terms of their interactions with the ABTS cation radical.

    PubMed

    Tan, Dun-xian; Hardeland, Rüdiger; Manchester, Lucien C; Poeggeler, Burkhard; Lopez-Burillo, Silvia; Mayo, Juan C; Sainz, Rosa M; Reiter, Russel J

    2003-05-01

    Melatonin and classic antioxidants possess the capacity to scavenge ABTSb+ with IC50s of 4, 11, 15.5, 15.5, 17 and 21 microm for melatonin, glutathione, vitamin C, trolox, NADH and NADPH, respectively. In terms of scavenging ABTSb+, melatonin exhibits a different profile than that of the classic antioxidants. Classic antioxidants scavenge one or less ABTSb+, while each melatonin molecule can scavenge more than one ABTSb+, probably with a maximum of four. Classic antioxidants do not synergize when combined in terms of scavenging ABTSb+. However, a synergistic action is observed when melatonin is combined with any of the classic antioxidants. Cyclic voltammetry indicates that melatonin donates an electron at the potential of 715 mV. The scavenging mechanism of melatonin on ABTSb+ may involve multiple-electron donations via intermediates through a stepwise process. Intermediates including the melatoninyl cation radical, the melatoninyl neutral radical and cyclic 3-hydroxymelatonin (cyclic 3-OHM) and N1-acetyl-N2-formyl-5-methoxykynuramine (AFMK) seem to participate in these reactions. More interestingly, the pH of the solution dramatically modifies the ABTSb+ scavenging capacity of melatonin while pH changes have no measurable influence on the scavenging activity of classic antioxidants. An acidic pH markedly reduces the ABTSb+ scavenging capacity of melatonin while an increased pH promotes the interaction of melatonin and ABTSb+. The major melatonin metabolites that develop when melatonin interacts with ABTSb+ are cyclic 3-OHM and AFMK. Cyclic 3-OHM is the intermediate between melatonin and AFMK, and cyclic 3-OHM also has the ability to scavenge ABTSb+. Melatonin and the metabolites which are generated via the interaction of melatonin with ABTSb+, i.e. the melatoninyl cation radical, melatoninyl neutral radical and cyclic 3-OHM, all scavenge ABTSb+. This unique cascade action of melatonin, in terms of scavenging, increases its efficiency to neutralized ABTSb+; this

  18. Photochemical formation of hydroxyl radical from effluent organic matter.

    PubMed

    Dong, Mei Mei; Rosario-Ortiz, Fernando L

    2012-04-03

    The photochemical formation of hydroxyl radical (HO•) from effluent organic matter (EfOM) was evaluated using three bulk wastewater samples collected at different treatment facilities under simulated sunlight. For the samples studied, the formation rates of HO•(R(HO•)) were obtained from the formation rate of phenol following the hydroxylation of benzene. The values of R(HO•) ranged from 2.3 to 3.8 × 10(-10) M s(-1) for the samples studied. The formation rate of HO• from nitrate photolysis (R(NO3)(HO•)) was determined to be 3.0 × 10(-7) M(HO)• M(NO3)(-1) s(-1). The HO• production rate from EfOM (R(EfOM)(HO•)) ranged from 0.76 to 1.3 × 10(-10) M s(-1). For the wastewater samples studied, R(EfOM)(HO•) varied from 1.5 to 2.4 × 10(-7) M(HO)• M(C)(-1) (s-1) on molarcarbon basis, which was close to HO• production from nitrate photolysis. The apparent quantum yield for the formation of HO• from nitrate (Φ(NO3-HO•)(a)) was determined as 0.010 ± 0.001 for the wavelength range 290-400 nm in ultrapure water. The apparent quantum yield for HO• formation in EfOM (Φ(EfOM-HO•)(a)) ranged from 6.1 to 9.8 × 10(-5), compared to 2.99 to 4.56 × 10(-5) for organic matter (OM) isolates. The results indicate that wastewater effluents could produce significant concentrations of HO•, as shown by potential higher nitrate levels and relatively higher quantum yields of HO• formation from EfOM.

  19. Formation and reactivity of phenylperoxyl radicals in aqueous solutions

    SciTech Connect

    Alfassi, Z.B.; Marguet, S.; Neta, P. )

    1994-08-18

    The reaction of phenyl radicals with oxygen, to produce phenylperoxyl radicals, and the reactions of several phenylperoxyl radicals with a number of organic compounds in aqueous solutions have been studied by pulse radiolysis. Phenyl radicals were produced by reduction of aryl halides with hydrated electrons. The rate constant for the reaction of 4-carboxyphenyl with O[sub 2] was determined from the rate of buildup of the peroxyl radical absorption at 520 nm as a function of [O[sub 2

  20. Radical formation, chemical processing, and explosion of interstellar grains

    NASA Technical Reports Server (NTRS)

    Greenberg, J. M.

    1976-01-01

    The ultraviolet radiation in interstellar space is shown to create a sufficient steady-state density of free radicals in the grain mantle material consisting of oxygen, carbon, nitrogen, and hydrogen to satisfy the critical condition for initiation of chain reactions. The criterion for minimum critical particle size for maintaining the chain reaction is of the order of the larger grain sizes in a distribution satisfying the average extinction and polarization measures. The triggering of the explosion of interstellar grains leading to the ejection of complex interstellar molecules is shown to be most probable where the grains are largest and where radiation is suddenly introduced; i.e., in regions of new star formation. Similar conditions prevail at the boundaries between very dark clouds and H II regions. When the energy released by the chemical activity of the free radicals is inadequate to explode the grain, the resulting mantle material must consist of extremely large organic molecules which are much more resistant to the hostile environment of H II regions than the classical dirty-ice mantles made up of water, methane, and ammonia.

  1. Oxidation of guanine in G, GG, and GGG sequence contexts by aromatic pyrenyl radical cations and carbonate radical anions: relationship between kinetics and distribution of alkali-labile lesions.

    PubMed

    Lee, Young Ae; Durandin, Alexander; Dedon, Peter C; Geacintov, Nicholas E; Shafirovich, Vladimir

    2008-02-14

    Oxidatively generated DNA damage induced by the aromatic radical cation of the pyrene derivative 7,8,9,10-tetrahydroxytetrahydrobenzo[a]pyrene (BPT), and by carbonate radicals anions, was monitored from the initial one-electron transfer, or hole injection step, to the formation of hot alkali-labile chemical end-products monitored by gel electrophoresis. The fractions of BPT molecules bound to double-stranded 20-35-mer oligonucleotides with noncontiguous guanines G and grouped as contiguous GG and GGG sequences were determined by a fluorescence quenching method. Utilizing intense nanosecond 355 nm Nd:YAG laser pulses, the DNA-bound BPT molecules were photoionized to BPT*+ radicals by a consecutive two-photon ionization mechanism. The BPT*+ radicals thus generated within the duplexes selectively oxidize guanine by intraduplex electron-transfer reactions, and the rate constants of these reactions follow the trend 5'-..GGG.. > 5'-..GG.. > 5'-..G... In the case of CO3*- radicals, the oxidation of guanine occurs by intermolecular collision pathways, and the bimolecular rate constants are independent of base sequence context. However, the distributions of the end-products generated by CO3*- radicals, as well as by BPT*+, are base sequence context-dependent and are greater than those in isolated guanines at the 5'-G in 5'-...GG... sequences, and the first two 5'- guanines in the 5'-..GGG sequences. These results help to clarify the conditions that lead to a similar or different base sequence dependence of the initial hole injection step and the final distribution of oxidized, alkali-labile guanine products. In the case of the intermolecular one-electron oxidant CO3*-, the rate constant of hole injection is similar for contiguous and isolated guanines, but the subsequent equilibration of holes by hopping favors trapping and product formation at contiguous guanines, and the sequence dependence of these two phenomena are not correlated. In contrast, in the case of the DNA

  2. Key Role of End-Capping Groups in Optoelectronic Properties of Poly-p-phenylene Cation Radicals

    PubMed Central

    2015-01-01

    Poly-p-phenylenes (PPs) are prototype systems for understanding the charge transport in π-conjugated polymers. In a combined computational and experimental study, we demonstrate that the smooth evolution of redox and optoelectronic properties of PP cation radicals toward the polymeric limit can be significantly altered by electron-donating iso-alkyl and iso-alkoxy end-capping groups. A multiparabolic model (MPM) developed and validated here rationalizes this unexpected effect by interplay of the two modes of hole stabilization: due to the framework of equivalent p-phenylene units and due to the electron-donating end-capping groups. A symmetric, bell-shaped hole in unsubstituted PPs becomes either slightly skewed and shifted toward an end of the molecule in iso-alkyl-capped PPs or highly deformed and concentrated on a terminal unit in PPs with strongly electron-donating iso-alkoxy capping groups. The MPM shows that the observed linear 1/n evolution of the PP cation radical properties toward the polymer limit originates from the hole stabilization due to the growing chain of p-phenylene units, while shifting of the hole toward electron-donating end-capping groups leads to early breakdown of these 1/n dependencies. These insights, along with the readily applicable and flexible multistate parabolic model, can guide studies of complex donor–spacer–acceptor systems and doped molecular wires to aid the design of the next generation materials for long-range charge transport and photovoltaic applications. PMID:25264475

  3. Unconventional hydrogen bonding to organic ions in the gas phase: Stepwise association of hydrogen cyanide with the pyridine and pyrimidine radical cations and protonated pyridine

    SciTech Connect

    Hamid, Ahmed M.; El-Shall, M. Samy; Hilal, Rifaat; Elroby, Shaaban; Aziz, Saadullah G.

    2014-08-07

    Equilibrium thermochemical measurements using the ion mobility drift cell technique have been utilized to investigate the binding energies and entropy changes for the stepwise association of HCN molecules with the pyridine and pyrimidine radical cations forming the C{sub 5}H{sub 5}N{sup +·}(HCN){sub n} and C{sub 4}H{sub 4}N{sub 2}{sup +·}(HCN){sub n} clusters, respectively, with n = 1–4. For comparison, the binding of 1–4 HCN molecules to the protonated pyridine C{sub 5}H{sub 5}NH{sup +}(HCN){sub n} has also been investigated. The binding energies of HCN to the pyridine and pyrimidine radical cations are nearly equal (11.4 and 12.0 kcal/mol, respectively) but weaker than the HCN binding to the protonated pyridine (14.0 kcal/mol). The pyridine and pyrimidine radical cations form unconventional carbon-based ionic hydrogen bonds with HCN (CH{sup δ+}⋯NCH). Protonated pyridine forms a stronger ionic hydrogen bond with HCN (NH{sup +}⋯NCH) which can be extended to a linear chain with the clustering of additional HCN molecules (NH{sup +}⋯NCH··NCH⋯NCH) leading to a rapid decrease in the bond strength as the length of the chain increases. The lowest energy structures of the pyridine and pyrimidine radical cation clusters containing 3-4 HCN molecules show a strong tendency for the internal solvation of the radical cation by the HCN molecules where bifurcated structures involving multiple hydrogen bonding sites with the ring hydrogen atoms are formed. The unconventional H-bonds (CH{sup δ+}⋯NCH) formed between the pyridine or the pyrimidine radical cations and HCN molecules (11–12 kcal/mol) are stronger than the similar (CH{sup δ+}⋯NCH) bonds formed between the benzene radical cation and HCN molecules (9 kcal/mol) indicating that the CH{sup δ+} centers in the pyridine and pyrimidine radical cations have more effective charges than in the benzene radical cation.

  4. Studies of radiation-produced radicals and radical ions

    SciTech Connect

    Williams, T.F.

    1991-01-01

    The radiolytic oxidation of anti-5-methylbicyclo(2.1.0)pentane gives the 1-methylcyclopentene radical cation as the sole rearrangement product H migration whereas oxidation of its syn isomer results in the highly selective formation of the 3-methylcyclopentene radical cation by methyl group migration. Since exactly the same stereoselectivity of olefin formation was observed in corresponding PET (photosensitized electron transfer) studies in the liquid phase, it is concluded that the rearrangement in this case also occurs through the intermediacy of radical cations. Clearly, the radical cation rearrangement must occur very rapidly (10{sup {minus}8}--10{sup {minus}9}s) under liquid-phase conditions at room temperature to compete with back electron transfer, and therefore the hydrogen (or methyl) migration is a fast process under these conditions. An intramolecular cycloaddition reaction was demonstrated in the radical cation rearrangement of 4-vinylcyclohexene to bicyclo(3.2.1)oct-2-ene. ESR studies show that the radiolytic oxidation of quadricyclane in Freon matrices under conditions of high substrate dilution leads to the bicyclo(3.2.0)hepta-2,6-diene radical cation as well as the previously reported norbornadiene radical cation, the former species predominating at sufficiently low concentrations.

  5. Electronic and vibrational spectra of matrix isolated anthracene radical cations - Experimental and theoretical aspects

    NASA Technical Reports Server (NTRS)

    Szczepanski, Jan; Vala, Martin; Talbi, Dahbia; Parisel, Olivier; Ellinger, Yves

    1993-01-01

    The IR vibrational and visible/UV electronic absorption spectra of the anthracene cation, An(+), were studied experimentally, in argon matrices at 12 K, as well as theoretically, using ab initio calculations for the vibrational modes and enhanced semiempirical methods with configuration interaction for the electronic spectra. It was found that both approaches predicted well the observed photoelectron spectrum. The theoretical IR intensities showed some remarkable differences between neutral and ionized species (for example, the CH in-plane bending modes and CC in-plane stretching vibrations were predicted to increase by several orders of magnitude upon ionization). Likewise, estimated experimental IR intensities showed a significant increase in the cation band intensities over the neutrals. The implication of these findings for the hypothesis that polycyclic aromatic hydrocarbon cations are responsible for the unidentified IR emission bands from interstellar space is discussed.

  6. Activation of Methane by the Pyridine Radical Cation and its Substituted Forms in the Gas Phase

    NASA Astrophysics Data System (ADS)

    Wu, Guohua; Stewart, Hamish; Liu, Zeyu; Wang, Yongcheng; Stace, Anthony J.

    2015-08-01

    We present an experimental study of methane activation by pyridine cation and its substituents in the gas phase. Mass spectrometric experiments in an ion trap demonstrate that pyridine cation and some of its substituent cations are able to react with methane. The deuterated methane experiment has confirmed that the hydrogen atom in the ionic product of reaction does come from methane. The collected information about kinetic isotope effects has been used to distinguish the nature of the bond activation as a hydrogen abstraction. Furthermore, experimental results demonstrated that the substituent groups on the pyridine ring can crucially influence their reactivity in methane bond activation processes. Density functional calculation (DFT) was employed to study the electronic structures of the complex and reaction mechanism of CH4+C5H5N+. The calculations confirmed the hypothesis from the experimental observation, namely, the reaction is rapid with no energy barrier.

  7. Detection of Anisotropic Hyperfine Components of Chemically Prepared Carotenoid Radical Cations:1D and 2D ESEEM and Pulsed ENDOR Study

    SciTech Connect

    Konovalova, Tatyana A.; Dikanov, Sergei A.; Bowman, Michael K.; Kispert, Lowell D.

    2001-09-06

    Canthaxanthin and 8'-apo-B-caroten-8'-al radical cations chemically prepared on activated silica-alumina and in CH2CI2 solution containing A1C13 were studied by pulsed EPR and ENDOR spectroscopies. Both the 1D three-pulse ESEEM and the 2D HYSCORE spectra of the carotenoid-A1C13 mixtures exhibited the 27 A1 nuclei peak at 3.75 MHz. This indicates electron-transfer interactions between carotenoids and A1III ions resulting in the formation and stabilization of carotenoid radical cations. Davies ENDOR measurements of the canthaxanthin radical cation on silica-alumina determined the hyperfine couplings of B protons belonging to three different methyl groups with ahI=2.6 MHz, aH2=8.6MHz, and ah3 ca. 13 MHz. The principal components of the proton hyperfine tensors were obtained from HYSCORE spectra in A1C13 solutions and on the solid support. Identification of the protons was made on the basis of isotropic hyperfine couplings determined by RHF-INDO/SP molecular orbital calculations. In frozen A1C13 solution, the C(7, 7')Ha and C(14, 14')-Ha a protons were observed for Canthaxanthin and the C(8 or 14')-Ha, C(15')-Ha were observed for 8'-apo-B-caroten-8'-al. On the silica-alumina support, the C(10, 10')-Ha, C(11, 11')-Ha, and C(15,15')-Ha a protons were measured for Canthaxanthin and the C(12)-Ha and C(15')-Ha were measured for 8' apo-B-caroten-8'-al. Some protons with large isotropic couplings (>10 MHz) determined from HYSCORE analysis could be assigned to B protons, but the principal components of their hyperfine tensors are much more anisotropic than those reported previously for B protons. We suggest that cis/trans isomerization of carotenoids on silica-alumina results in stabilization of di-cis isomers with large isotropic couplings for some a protons which are comparable to those of B protons.

  8. Serine effects on collision-induced dissociation and photodissociation of peptide cation radicals of the z(+•) -type.

    PubMed

    Nguyen, Huong T H; Shaffer, Christopher J; Ledvina, Aaron R; Coon, Joshua J; Tureček, František

    2015-02-15

    The serine residue displays specific effects on the dissociations of peptide fragment cation-radicals of the z(+•) type which are produced by electron transfer dissociation. Energy-resolved collision-induced dissociation (ER-CID), time-resolved infrared multiphoton dissociation (TR-IRMPD), and single-photon UV photodissociation at 355 nm revealed several competitive dissociation pathways consisting of loss of OH radical, water, and backbone cleavages occurring at N-terminal and C-terminal positions relative to the serine residue. The activation modes using slow-heating and UV photon absorption resulted in different relative intensities of fragment ions. This indicated that the dissociations proceeded through several channels with different energy-dependent kinetics. The experimental data were interpreted with the help of electron structure calculations that provided fully optimized structures and relative energies for cis and trans amide isomers of the z4(+•) ions as well as isomerization, dissociation, and transition state energies. UV photon absorption by the z4(+•) ions was due to Cα-radical amide groups created by ETD that provided a new chromophore absorbing at 355 nm.

  9. Serine effects on collision-induced dissociation and photodissociation of peptide cation radicals of the z+•-type

    PubMed Central

    Nguyen, Huong T. H.; Shaffer, Christopher J.; Ledvina, Aaron R.; Coon, Joshua J.

    2014-01-01

    The serine residue displays specific effects on the dissociations of peptide fragment cation-radicals of the z+• type which are produced by electron transfer dissociation. Energy-resolved collision-induced dissociation (ER-CID), time-resolved infrared multiphoton dissociation (TR-IRMPD), and single-photon UV photodissociation at 355 nm revealed several competitive dissociation pathways consisting of loss of OH radical, water, and backbone cleavages occurring at N-terminal and C-terminal positions relative to the serine residue. The activation modes using slow-heating and UV photon absorption resulted in different relative intensities of fragment ions. This indicated that the dissociations proceeded through several channels with different energy-dependent kinetics. The experimental data were interpreted with the help of electron structure calculations that provided fully optimized structures and relative energies for cis and trans amide isomers of the z4+• ions as well as isomerization, dissociation, and transition state energies. UV photon absorption by the z4+• ions was due to Cα-radical amide groups created by ETD that provided a new chromophore absorbing at 355 nm. PMID:26005367

  10. Pathways of arachidonic acid peroxyl radical reactions and product formation with guanine radicals.

    PubMed

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

    2008-02-01

    Peroxyl radicals were derived from the one-electron oxidation of polyunsaturated fatty acids by sulfate radicals that were generated by the photodissociation of peroxodisulfate anions in air-equilibrated aqueous solutions. Reactions of these peroxyl and neutral guanine radicals, also generated by oxidation with sulfate radicals, were investigated by laser kinetic spectroscopy, and the guanine oxidation products were identified by HPLC and mass spectrometry methods. Sulfate radicals rapidly oxidize arachidonic (ArAc), linoleic (LnAc), and palmitoleic (PmAc) acids with similar rate constants, (2-4) x 10 (9) M (-1) s (-1). The C-centered radicals derived from the oxidation of ArAc and LnAc include nonconjugated Rn(.) ( approximately 80%) and conjugated bis-allylic Rba(.) ( approximately 20%) radicals. The latter were detectable in the absence of oxygen by their prominent, narrow absorption band at 280 nm. The Rn(.) radicals of ArAc (containing three bis-allylic sites) transform to the Rba(.) radicals via an intramolecular H-atom abstraction [rate constant (7.5 +/- 0.7) x 10 (4) s (-1)]. In contrast, the Rn(.) radicals of LnAc that contain only one bis-allylic site do not transform intramolecularly to the Rba(.) radicals. In the case of PmAc, which contains only one double bond, the Rba(.) radicals are not observed. The Rn(.) radicals of PmAc rapidly combine with oxygen with a rate constant of (3.8 +/- 0.4) x 10(9) M(-1) s(-1). The Rba(.) radicals of ArAc are less reactive and react with oxygen with a rate constant of (2.2 +/- 0.2) x 10 (8) M (-1) s (-1). The ArAc peroxyl radicals formed spontaneously eliminate superoxide radical anions [rate constant = (3.4 +/- 0.3) x 10 (4) M (-1) s (-1)]. The stable oxidative lesions derived from the 2',3',5'-tri- O-acetylguanosine or 2',3',5'-tri- O-acetyl-8-oxo-7,8-dihydroguanosine radicals and their subsequent reactions with ArAc peroxyl radicals were also investigated. The major products found were the 2,5-diamino-4 H

  11. Rifampin induces hydroxyl radical formation in Mycobacterium tuberculosis.

    PubMed

    Piccaro, Giovanni; Pietraforte, Donatella; Giannoni, Federico; Mustazzolu, Alessandro; Fattorini, Lanfranco

    2014-12-01

    The antituberculosis (anti-TB) drug rifampin (RIF) binds to the beta subunit of the RNA polymerase (RpoB) of Mycobacterium tuberculosis, but the bactericidal responses triggered after target interaction are not known. To evaluate whether RIF induced an oxidative burst, lysates of RIF-treated M. tuberculosis were tested for determination of reactive oxygen species (ROS) by the electron paramagnetic resonance (EPR) technique using 1-hydroxy-3-carboxy-pyrrolidine (CPH) and 5,5-dimethyl-1-pyrrolidine-N-oxide (DMPO) as spin traps. M. tuberculosis killing by RIF stimulated an increase in the rate of formation of the CPH radical (CP·). Lysate pretreatment with the O2·(-) and ·OH scavengers superoxide dismutase (SOD) and thiourea (THIO), respectively, or with the metal chelator diethylene triamine pentaacetic acid (DTPA) inhibited CP· formation, arguing in favor of a metal-catalyzed ROS response. Formation of CP· did not increase following treatment of RIF-resistant strains with RIF, indicating that the ROS were induced after RpoB binding. To identify the ROS formed, lysates of RIF-treated bacilli were incubated with DMPO, a spin trap specific for ·OH and O2·(-), with or without pretreatment with SOD, catalase, THIO, or DTPA. Superoxide dismutase, catalase, and THIO decreased formation of the DMPO-OH adduct, and SOD plus DTPA completely suppressed it, suggesting that RIF activated metal-dependent O2·(-)-mediated mechanisms producing ·OH inside tubercle bacilli. The finding that the metal chelator DTPA reduced the bactericidal activity of RIF supported the possibility that ·OH was generated through these mechanisms and that it participated at least in part in M. tuberculosis killing by the drug.

  12. Theoretical study of electronically excited radical cations of naphthalene and anthracene as archetypal models for astrophysical observations. Part I. Static aspects.

    PubMed

    Ghanta, S; Reddy, V Sivaranjana; Mahapatra, S

    2011-08-28

    Motivated by the recent discovery of new diffuse interstellar bands and results from laboratory experiments, ab initio quantum chemistry calculations are carried out for the lowest six electronic states of naphthalene and anthracene radical cations. The calculated adiabatic electronic energies are utilized to construct suitable diabatic electronic Hamiltonians in order to perform nuclear dynamics studies in Part II. Complex entanglement of the electronic states is established for both the radical cations and the coupling surfaces among them are also derived in accordance with the symmetry selection rules. Critical examination of the coupling parameters of the Hamiltonian suggests that 29 (out of 48) and 31 (out of 66) vibrational modes are relevant in the nuclear dynamics in the six lowest electronic states of naphthalene and anthracene radical cations, respectively.

  13. ENDOR and ESEEM of the 15N labelled radical cations of chlorophyll a and the primary donor P 700 in photosystem I

    NASA Astrophysics Data System (ADS)

    Käβ, H.; Bittersmann-Weidlich, E.; Andréasson, L.-E.; Bönigk, B.; Lubitz, W.

    1995-05-01

    The hyperfine couplings of the nitrogen nuclei in the radical cations of both 15N-labelled chlorophyll a and the primary donor P 700 in Photosystem I of Synechococcus elongatus and spinach ( Spinacea oleracea) in frozen solutions were investigated by ENDOR and, for confirmation, by two-dimensional ESEEM techniques. In addition, 1H ENDOR experiments were performed on these compounds. The experimental 15N hyperfine couplings of the chlorophyll a radical cation are compared with theoretical ones obtained by RHF-INDO/SP calculations and with the respective hyperfine couplings in the closely related 15N-bacteriochlorophyll a radical cation. Based on the observed 15N and 1H hyperfine couplings two possible models are discussed for P 700+: (a) the special pair model with a strongly asymmetric spin density distribution over the dimer halves; (b) the model of a strongly perturbed chlorophyll a monomer.

  14. Structure of radical cations of saturated heterocyclic compounds with two heteroatoms as studied by electron paramagnetic resonance, electron-nuclear double resonance, and density functional theory calculations.

    PubMed

    Nuzhdin, Kirill B; Nesterov, Sergej V; Tyurin, Daniil A; Feldman, Vladimir I; Wei, Liu; Lund, Anders

    2005-07-21

    The radical cations of piperazine, morpholine, thiomorpholine, and thioxane were investigated by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy in a solid Freon matrix. Optimized geometry and magnetic parameters of the radical cations were calculated using a density functional theory (DFT)/Perdew-Burke-Ernzerhof (PBE) method. Both experimental and theoretical results suggest that all the studied species adopt chair (or distorted chair) conformations. No evidence for the boat conformers with intramolecular sigma-bonding between heteroatoms were obtained. In the cases of morpholine and thioxane, the oxygen atoms are characterized by relatively small spin populations, whereas a major part of spin density is located at N and S atoms, respectively. The thiomorpholine radical cation exhibits nearly equal spin population of N and S atoms. In most cases (except for thioxane), the calculated magnetic parameters agree with the experimental data reasonably well.

  15. Hydroxyl radical reaction with trans-resveratrol: initial carbon radical adduct formation followed by rearrangement to phenoxyl radical.

    PubMed

    Li, Dan-Dan; Han, Rui-Min; Liang, Ran; Chen, Chang-Hui; Lai, Wenzhen; Zhang, Jian-Ping; Skibsted, Leif H

    2012-06-21

    In the reaction between trans-resveratrol (resveratrol) and the hydroxyl radical, kinetic product control leads to a short-lived hydroxyl radical adduct with an absorption maximum at 420 nm and a lifetime of 0.21 ± 0.01 μs (anaerobic acetonitrile at 25 °C) as shown by laser flash photolysis using N-hydroxypyridine-2(1H)-thione (N-HPT) as a "photo-Fenton" reagent. The transient spectra of the radical adduct are in agreement with density functional theory (DFT) calculations showing an absorption maximum at 442 or 422 nm for C2 and C6 hydroxyl adducts, respectively, and showing the lowest energy for the transition state leading to the C2 adduct compared to other radical products. From this initial product, the relative long-lived 4'-phenoxyl radical of resveratrol (τ = 9.9 ± 0.9 μs) with an absorption maximum at 390 nm is formed in a process with a time constant (τ = 0.21 ± 0.01 μs) similar to the decay constant for the C2 hydroxyl adduct (or a C2/C6 hydroxyl adduct mixture) and in agreement with thermodynamics identifying this product as the most stable resveratrol radical. The hydroxyl radical adduct to phenoxyl radical conversion with concomitant water dissociation has a rate constant of 5 × 10(6) s(-1) and may occur by intramolecular hydrogen atom transfer or by stepwise proton-assisted electron transfer. Photolysis of N-HPT also leads to a thiyl radical which adds to resveratrol in a parallel reaction forming a sulfur radical adduct with a lifetime of 0.28 ± 0.04 μs and an absorption maximum at 483 nm.

  16. Ne matrix spectra of the sym-C6Br3F3+ radical cation

    USGS Publications Warehouse

    Bondybey, V.E.; Sears, T.J.; Miller, T.A.; Vaughn, C.; English, J.H.; Shiley, R.S.

    1981-01-01

    The electronic absorption and laser excited, wavelength resolved fluorescence spectra of the title cation have been observed in solid Ne matrix and vibrationally analysed. The vibrational structure of the excited B2A2??? state shows close similarity to the parent compound. The X2E??? ground state structure is strongly perturbed and irregular owing to a large Jahn-Teller distortion. The data are analysed in terms of a recently developed, sophisticated multimode Jahn-Teller theoretical model. We have generated the sym-C6Br3F3+ cations in solid Ne matrix and obtained their wavelength resolved emission and absorption spectra. T ground electronic X2E??? state exhibits an irregular and strongly perturbed vibrational structure, which can be successfully modeled using sophisticated multimode Jahn-Teller theory. ?? 1981.

  17. A Visible Light Initiating System for Free Radical Promoted Cationic Polymerization

    DTIC Science & Technology

    1994-02-02

    bis-(4, 4’-dimethylaminoihenyl)methane as the main product and crystal violet, methyl violet, as well as the leuco rorms of these dyes as minor...cation in chain polymerization is reported. The system is based on electron transfer photoreduction of xanthene dye triplets by aromatic amines...Previously, Crivello and Lam 9 had reported attempts to use visible light absorbing dyes to sensitize the decomposition of iodonium salts to initiate

  18. Theoretical study of the electronically excited radical cations of naphthalene and anthracene as archetypal models for astrophysical observations. Part II. Dynamics consequences.

    PubMed

    Ghanta, S; Reddy, V Sivaranjana; Mahapatra, S

    2011-08-28

    Nuclear dynamics is investigated theoretically from first principles by employing the ab initio vibronic models of the prototypical naphthalene and anthracene radical cations developed in Part I. This Part is primarily aimed at corroborating a large amount of available experimental data with a specific final goal to establish an unambiguous link with the current observations in astrophysics and astronomy. The detailed analyses presented here perhaps establish that these two prototypical polycyclic aromatic hydrocarbon radical cations are indeed potential carriers of the observed diffuse interstellar bands.

  19. Evaluation of 2D-ESEEM data of 15N-labeled radical cations of the primary donor P 700 in photosystem I and chlorophyll a

    NASA Astrophysics Data System (ADS)

    Käβ, H.; Lubitz, W.

    1996-03-01

    Hyperfine couplings (hfc's) of the nitrogen nuclei in the 15N-labeled radical cations of chlorophyll a and the primary donor P 700 in photosystem I of spinach were investigated in frozen solution by two-dimensional stimulated echo ESEEM. 15N hfc tensors were evaluated by comparison of the experimental data with simulations of the time domain and frequency domain ESEEM signals. The results are discussed in the framework of a chlorophyll a dimer model for the radical cation of P 700.

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

    PubMed

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

    2014-04-15

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

  1. Cationic cluster formation versus disproportionation of low-valent indium and gallium complexes of 2,2'-bipyridine

    PubMed Central

    Lichtenthaler, Martin R.; Stahl, Florian; Kratzert, Daniel; Heidinger, Lorenz; Schleicher, Erik; Hamann, Julian; Himmel, Daniel; Weber, Stefan; Krossing, Ingo

    2015-01-01

    Group 13 MI compounds often disproportionate into M0 and MIII. Here, however, we show that the reaction of the MI salt of the weakly coordinating alkoxyaluminate [GaI(C6H5F)2]+[Al(ORF)4]− (RF=C(CF3)3) with 2,2'-bipyridine (bipy) yields the paramagnetic and distorted octahedral [Ga(bipy)3]2+•{[Al(ORF)4]−}2 complex salt. While the latter appears to be a GaII compound, both, EPR and DFT investigations assign a ligand-centred [GaIII{(bipy)3}•]2+ radical dication. Surprisingly, the application of the heavier homologue [InI(C6H5F)2]+[Al(ORF)4]− leads to aggregation and formation of the homonuclear cationic triangular and rhombic [In3(bipy)6]3+, [In3(bipy)5]3+ and [In4(bipy)6]4+ metal atom clusters. Typically, such clusters are formed under strongly reductive conditions. Analysing the unexpected redox-neutral cationic cluster formation, DFT studies suggest a stepwise formation of the clusters, possibly via their triplet state and further investigations attribute the overall driving force of the reactions to the strong In−In bonds and the high lattice enthalpies of the resultant ligand stabilized [M3]3+{[Al(ORF)4]−}3 and [M4]4+{[Al(ORF)4]−}4 salts. PMID:26478464

  2. Comparison of the Reactivity of the Three Distonic Isomers of the Pyridine Radical Cation Toward Tetrahydrofuran in Solution and in the Gas Phase

    PubMed Central

    Widjaja, Fanny; Jin, Zhicheng; Nash, John J.; Kenttämaa, Hilkka I.

    2013-01-01

    The reactivity of the three distonic isomers of the pyridine radical cation toward tetrahydrofuran is compared in solution and in the gas phase. In solution, the distonic ions were generated by UV photolysis at 300 nm from iodo-precursors in acidic 50:50 tetrahydrofuran/water solutions. In the gas phase, the ions were generated by collisionally activated dissociation (CAD) of protonated iodo-precursors in an FT-ICR mass spectrometer, as described in the literature. The same major reaction, hydrogen atom abstraction, was observed in solution and in the gas phase. Attempts to cleave the iodine atom from the 2-iodopyridinium cation in the gas phase and in solution yielded the 2-pyridyl cation in addition to the desired 2-dehydropyridinium cation. In the gas phase, this ion was ejected prior to the examination of the desired ion’s chemical properties. This was not possible in solution. This study suggests that solvation effects are not significant for radical reactions of charged radicals. On the other hand, the even-electron ion studied, the 2-pyridyl cation, shows substantial solvation effects. For example, in solution, the 2-pyridyl cation forms a stable adduct with tetrahydrofuran, whereas in the gas phase, only addition/elimination reactions were observed. PMID:23345033

  3. Role of configurational gating in intracomplex electron transfer from cytochrome c to the radical cation in cytochrome c peroxidase.

    PubMed

    Mei, H; Wang, K; Peffer, N; Weatherly, G; Cohen, D S; Miller, M; Pielak, G; Durham, B; Millett, F

    1999-05-25

    Electron transfer within complexes of cytochrome c (Cc) and cytochrome c peroxidase (CcP) was studied to determine whether the reactions are gated by fluctuations in configuration. Electron transfer in the physiological complex of yeast Cc (yCc) and CcP was studied using the Ru-39-Cc derivative, in which the H39C/C102T variant of yeast iso-1-cytochrome c is labeled at the single cysteine residue on the back surface with trisbipyridylruthenium(II). Laser excitation of the 1:1 Ru-39-Cc-CcP compound I complex at low ionic strength results in rapid electron transfer from RuII to heme c FeIII, followed by electron transfer from heme c FeII to the Trp-191 indolyl radical cation with a rate constant keta of 2 x 10(6) s-1 at 20 degrees C. keta is not changed by increasing the viscosity up to 40 cP with glycerol and is independent of temperature. These results suggest that this reaction is not gated by fluctuations in the configuration of the complex, but may represent the elementary electron transfer step. The value of keta is consistent with the efficient pathway for electron transfer in the crystalline yCc-CcP complex, which has a distance of 16 A between the edge of heme c and the Trp-191 indole [Pelletier, H., and Kraut, J. (1992) Science 258, 1748-1755]. Electron transfer in the complex of horse Cc (hCc) and CcP was examined using Ru-27-Cc, in which hCc is labeled with trisbipyridylruthenium(II) at Lys-27. Laser excitation of the Ru-27-Cc-CcP complex results in electron transfer from RuII to heme c FeII with a rate constant k1 of 2.3 x 10(7) s-1, followed by oxidation of the Trp-191 indole to a radical cation by RuIII with a rate constant k3 of 7 x 10(6) s-1. The cycle is completed by electron transfer from heme c FeII to the Trp-191 radical cation with a rate constant k4 of 6.1 x 10(4) s-1. The rate constant k4 decreases to 3.4 x 10(3) s-1 as the viscosity is increased to 84 cP, but the rate constants k1 and k3 remain the same. The results are consistent with a

  4. Formaldehyde mediated proton-transport catalysis in the ketene-water radical cation CH2C(O)OH2+

    NASA Astrophysics Data System (ADS)

    Lee, Richard; Ruttink, Paul J. A.; Burgers, Peter C.; Terlouw, Johan K.

    2006-09-01

    Previous studies have shown that the solitary ketene-water ion CH2C(O)OH2+ (1) does not isomerize into CH2C(OH)2+ (2), its more stable hydrogen shift isomer. Tandem mass spectrometry based collision experiments reveal that this isomerization does take place in the CH2O loss from low-energy 1,3-dihydroxyacetone ions (HOCH2)2CO+. A mechanistic analysis using the CBS-QB3 model chemistry shows that such molecular ions rearrange into hydrogen-bridged radical cations [CH2C(O)O(H)-H...OCH2]+ in which the CH2O molecule catalyzes the transformation 1 --> 2 prior to dissociation. The barrier for the unassisted reaction, 29 kcal mol-1, is reduced to a mere 0.6 kcal mol-1 for the catalysed transformation. Formaldehyde is an efficient catalyst because its proton affinity meets the criterion for facile proton-transport catalysis.

  5. Large excited state two photon absorptions in the near infrared region of surprisingly stable radical cations of (ferrocenyl)indenes.

    PubMed

    Orian, Laura; Scuppa, Stefano; Santi, Saverio; Meneghetti, Moreno

    2013-08-21

    Multiphoton absorptions are important non-linear optical processes which allow us to explore excited states with low energy photons giving rise to new possibilities for photoinduced processes. Among these processes, multiphoton absorptions from excited states are particularly interesting because of the large susceptibilities characteristic of excited states. Here we explore the nonlinear transmission measurements recorded with 9 ns laser pulses at 1064 nm of the radical cations of (2-ferrocenyl)indene and of (2-ferrocenyl)-hexamethylindene, two interesting very stable molecules. The non-linear transmission data can be interpreted with a multiphoton sequence of three photon absorptions, the first being a one photon absorption related to the intramolecular charge transfer and the second a two photon absorption from the excited state created with the first process. The two photon absorption cross section is found to be several orders of magnitude larger than those usually found for two photon absorbing systems excited from the ground state.

  6. Formation and reactivity of vinylperoxyl radicals in aqueous solutions

    SciTech Connect

    Khaikin, G.I.; Neta, P.

    1995-03-30

    Vinyl, carboxyvinyl and dicarboxyvinyl radicals were produced in irradiated aqueous solutions from acetylene and acetylenecarboxylic and acetylenedicarboxylic acid by addition of H atom to the triple bond or by reaction with e{sub aq}{sup -}, followed by protonation. Vinyl and phenylvinyl radicals were produced by reductive dehalogenation of vinyl bromide and {beta}-bromostyrene with e{sub aq}{sup -}. All these vinyl radicals react rapidly with oxygen to produce the corresponding vinylperoxyl radicals. Vinylperoxyl radicals exhibit optical absorptions in the UV ({lambda}{sub max} 250-290 nm) and in the visible range. The peaks in the visible range were at 440 nm for unsubstituted vinylperoxyl radical, between 480 and 520 nm for carboxylated vinylperoxyl, depending on pH and number of carboxyl groups, and at 540 and 690 nm for (2-phenylvinyl)peroxyl. These vinylperoxyl radicals oxidize organic reductants such as 2,2`azinobis(3-ethylbenzothiazoline-6-sulfonate ion) (ABTS), chlorpromazine, ascorbate, and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox C) with rate constants between 4 x 10{sup 5} and 2 x 10{sup 9} L mol{sup -1} s{sup -1}, depending on the radical and the reductant. Vinylperoxyl radicals are more reactive than similarly substituted alkylperoxyl. 20 refs., 5 figs., 1 tab.

  7. Fluorescence of the perylene radical cation and an inaccessible D0/D1 conical intersection: An MMVB, RASSCF, and TD-DFT computational study

    NASA Astrophysics Data System (ADS)

    Tokmachev, Andrei M.; Boggio-Pasqua, Martial; Mendive-Tapia, David; Bearpark, Michael J.; Robb, Michael A.

    2010-01-01

    The photophysics of the perylene radical cation (Pe•+) was studied using the molecular mechanics-valence bond (MMVB) hybrid force field. Potential energy surfaces of the first three electronic states were investigated. Geometry optimizations of critical points—including conical intersections between the relevant electronic states—were performed using the MMVB analytical energy gradient for cations. No accessible planar conical intersection between the D0 and D1 states of Pe•+ was found; this is consistent with the experimentally observed D1 lifetimes and the observation of D1 emission from this cation in the condensed phase. Benchmark RASSCF and TD-DFT calculations support the reliability of the MMVB results.

  8. (Bi)sulfite Oxidation by Copper,Zinc-Superoxide Dismutase: Sulfite-Derived, Radical-Initiated Protein Radical Formation

    PubMed Central

    Ranguelova, Kalina; Bonini, Marcelo G.; Mason, Ronald P.

    2010-01-01

    Background Sulfur dioxide, formed during the combustion of fossil fuels, is a major air pollutant near large cities. Its two ionized forms in aqueous solution, sulfite and (bi)sulfite, are widely used as preservatives and antioxidants to prevent food and beverage spoilage. (Bi)sulfite can be oxidized by peroxidases to form the very reactive sulfur trioxide anion radical (•SO3−). This free radical further reacts with oxygen to form the peroxymonosulfate anion radical (−O3SOO•) and sulfate anion radical (SO4• −). Objective To explore the critical role of these radical intermediates in further oxidizing biomolecules, we examined the ability of copper,zinc-superoxide dismutase (Cu,Zn-SOD) to initiate this radical chain reaction, using human serum albumin (HSA) as a model target. Methods We used electron paramagnetic resonance, optical spectroscopy, oxygen uptake, and immuno-spin trapping to study the protein oxidations driven by sulfite-derived radicals. Results We found that when Cu,Zn-SOD reacted with (bi)sulfite, •SO3− was produced, with the concomitant reduction of SOD-Cu(II) to SOD-Cu(I). Further, we demonstrated that sulfite oxidation mediated by Cu,Zn-SOD induced the formation of radical-derived 5,5-dimethyl-1-pyrroline N-oxide (DMPO) spin-trapped HSA radicals. Conclusions The present study suggests that protein oxidative damage resulting from (bi)sulfite oxidation promoted by Cu,Zn-SOD could be involved in oxidative damage and tissue injury in (bi)sulfite-exacerbated allergic reactions. PMID:20348042

  9. Perinatal manganese exposure and hydroxyl radical formation in rat brain.

    PubMed

    Bałasz, Michał; Szkilnik, Ryszard; Brus, Ryszard; Malinowska-Borowska, Jolanta; Kasperczyk, Sławomir; Nowak, Damian; Kostrzewa, Richard M; Nowak, Przemysław

    2015-01-01

    The present study was designed to investigate the role of pre- and postnatal manganese (Mn) exposure on hydroxyl radical (HO(•)) formation in the brains of dopamine (DA) partially denervated rats (Parkinsonian rats). Wistar rats were given tap water containing 10,000 ppm manganese chloride during the duration of pregnancy and until the time of weaning. Control rat dams consumed tap water without added Mn. Three days after birth, rats of both groups were treated with 6-hydroxydopamine at one of three doses (15, 30, or 67 µg, intraventricular on each side), or saline vehicle. We found that Mn content in the brain, kidney, liver, and bone was significantly elevated in dams exposed to Mn during pregnancy. In neonates, the major organs that accumulated Mn were the femoral bone and liver. However, Mn was not elevated in tissues in adulthood. To determine the possible effect on generation of the reactive species, HO(•) in Mn-induced neurotoxicity, we analyzed the contents of 2.3- and 2.5-dihydroxybenzoic acid (spin trap products of salicylate; HO(•) being an index of in vivo HO(•) generation), as well as antioxidant enzyme activities of superoxide dismutase (SOD) isoenzymes and glutathione S-transferase (GST). 6-OHDA-depletion of DA produced enhanced HO(•) formation in the brain tissue of newborn and adulthood rats that had been exposed to Mn, and the latter effect did not depend on the extent of DA denervation. Additionally, the extraneuronal, microdialysate, content of HO(•) in neostriatum was likewise elevated in 6-OHDA-lesioned rats. Interestingly, there was no difference in extraneuronal HO(•) formation in the neostriatum of Mn-exposed versus control rats. In summary, findings in this study indicate that Mn crosses the placenta but in contrast to other heavy metals, Mn is not deposited long term in tissues. Also, damage to the dopaminergic system acts as a "trigger mechanism," initiating a cascade of adverse events leading to a protracted increase in

  10. Ab Initio Study of Ionized Water Radical Cation (H2O)8(+) in Combination with the Particle Swarm Optimization Method.

    PubMed

    Tang, Mei; Hu, Cui-E; Lv, Zhen-Long; Chen, Xiang-Rong; Cai, Ling-Cang

    2016-12-01

    The structures of cationic water clusters (H2O)8(+) have been globally explored by the particle swarm optimization method in combination with quantum chemical calculations. Geometry optimization and vibrational analysis for the 15 most interesting clusters were computed at the MP2/aug-cc-pVDZ level and infrared spectrum calculation at MPW1K/6-311++G** level. Special attention was paid to the relationships between their configurations and energies. Both MP2 and B3LYP-D3 calculations revealed that the cage-like structure is the most stable, which is different from a five-membered ring lowest energy structure but agrees well with a cage-like structure in the literature. Furthermore, our obtained cage-like structure is more stable by 0.87 and 1.23 kcal/mol than the previously reported structures at MP2 and B3LYP-D3 levels, respectively. Interestingly, on the basis of their relative Gibbs free energies and the temperature dependence of populations, the cage-like structure predominates only at very low temperatures, and the most dominating species transforms into a newfound four-membered ring structure from 100 to 400 K, which can contribute greatly to the experimental infrared spectrum. By topological analysis and reduced density gradient analysis, we also investigated the structural characteristics and bonding strengths of these water cluster radical cations.

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

    NASA Astrophysics Data System (ADS)

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

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

  12. Competitive Hydrogen Atom Migrations Accompanying Cascade Dissociations of Peptide Cation-Radicals of the z(+•) Type.

    PubMed

    Ledvina, Aaron R; Coon, Joshua J; Tureček, František

    2015-02-01

    We report a combined experimental and computational study of energy-resolved collision-induced dissociation (ER-CID) and time-resolved infrared multiphoton dissociation (TR-IRMPD) of z4 ions prepared by electron transfer dissociation of peptide (Ala-Ala-Asn-Ala-Arg + 2H)(2+) ions. The z4 cation-radicals, (•)ANAR(+), undergo competitive dissociations by backbone cleavage and loss of a CONH2 radical from the Asn side chain. The backbone cleavage proceeds by radical-assisted dissociation of the Asn Cα-CO bond, forming an x2 ion intermediate which rapidly dissociates by HNCO elimination to yield a stable z2 fragment ion, (•)AR(+). The ER-CID and TR-IRMPD data were consistent with the consecutive nature of the backbone dissociation but showed different branching ratios for the two major fragmentations. The ER-CID data showed branching ratios 0.6-1.0 for the side-chain and backbone cleavages whereas the TR-IRMPD data showed an earlier onset for the latter dissociation. Computational analysis of the potential energy surface with density functional theory and ab initio calculations was carried out to provide structures and energies for the reactant ions as well as several intermediates, products, and transition states. Dissociation pathways for cis and trans amide conformers were distinguished and their energies were evaluated. The threshold dissociation energies for the backbone and side-chain dissociations were similar in accordance with the experimental ER-CID branching ratio. The TR-IRMPD data were interpreted by different absorbances of intermediates produced by hydrogen atom migrations along the dissociation pathways.

  13. Competitive Hydrogen Atom Migrations Accompanying Cascade Dissociations of Peptide Cation-Radicals of the z+• Type

    PubMed Central

    Ledvina, Aaron R.; Coon, Joshua J.

    2014-01-01

    We report a combined experimental and computational study of energy-resolved collision-induced dissociation (ER-CID) and time-resolved infrared multiphoton dissociation (TR-IRMPD) of z4 ions prepared by electron transfer dissociation of peptide (Ala-Ala-Asn-Ala-Arg + 2H)2+ ions. The z4 cation-radicals, •ANAR+, undergo competitive dissociations by backbone cleavage and loss of a CONH2 radical from the Asn side chain. The backbone cleavage proceeds by radical-assisted dissociation of the Asn Cα—CO bond, forming an x2 ion intermediate which rapidly dissociates by HNCO elimination to yield a stable z2 fragment ion, •AR+. The ER-CID and TR-IRMPD data were consistent with the consecutive nature of the backbone dissociation but showed different branching ratios for the two major fragmentations. The ER-CID data showed branching ratios 0.6-1.0 for the side-chain and backbone cleavages whereas the TR-IRMPD data showed an earlier onset for the latter dissociation. Computational analysis of the potential energy surface with density functional theory and ab initio calculations was carried out to provide structures and energies for the reactant ions as well as several intermediates, products, and transition states. Dissociation pathways for cis and trans amide conformers were distinguished and their energies were evaluated. The threshold dissociation energies for the backbone and side-chain dissociations were similar in accordance with the experimental ER-CID branching ratio. The TR-IRMPD data were interpreted by different absorbances of intermediates produced by hydrogen atom migrations along the dissociation pathways. PMID:25844055

  14. Cymantrene radical cation family: spectral and structural characterization of the half-sandwich analogues of ferrocenium ion.

    PubMed

    Laws, Derek R; Chong, Daesung; Nash, Karen; Rheingold, Arnold L; Geiger, William E

    2008-07-30

    The anodic one-electron oxidation of three members of the half-sandwich family of piano-stool compounds MnCp (gamma)(CO) 3, where Cp (gamma) is a generic cyclopentadienyl ligand, has been studied in a CH 2Cl 2/[NBu 4][TFAB] electrolyte (TFAB = [B(C6F5) 4] (-)). The long-sought 17 e (-) radical cation of the parent complex MnCp(CO) 3 (cymantrene, 1, E 1/2 = 0.92 V vs ferrocene) has been shown to be persistent in solutions that use weakly coordinating anions in place of more nucleophilic traditional electrolyte anions. Spectroscopically characterized for the first time, 1 (+) was shown to absorb in the visible (530 nm), near-IR (2066 nm), and IR (2118, 1934 cm (-1)) regions. It was ESR-active at low temperatures (g parallel = 2.213, g perpendicular = 2.079, A parallel (Mn) = 79.2 G, A perpendicular (Mn) = 50 G) and NMR active at room temperature (delta = 22.4 vs TMS). The radical cations of the Cp-functionalized analogues, Mn(eta (5)-C5H 4NH2)(CO) 3, 2, E 1/2 = 0.62 V, and MnCp*(CO) 3 (Cp*= eta (5)-C 5Me 5, 3), E 1/2 = 0.64 V, were generated electrochemically as well by the chemical oxidant [ReCp(CO) 3] (+). The structures of 2 (+) and 3 (+) were determined by X-ray crystallographic studies of their TFAB salts. Compared to the structures of the corresponding neutral compounds, the cations showed elongated Mn-C(O) bonds and shortened C-O bonds, displaying the effect of diminished metal-to-CO backbonding. The bond-length changes in the Mn(CO) 3 moiety were much larger in 3 (+) (avg changes, Mn-C(O) = + 0.142 A, C-O = -0.063 A) than in 2 (+) (avg changes, Mn-C(O) = + 0.006 A, C-O = -0.003 A). Although there were only minor changes in the metal-to-center ring distances upon oxidation of either 2 or 3, there was decidedly less bending of the C(N) atom out of the cyclopentadienyl plane in 2 (+) compared to 2. The optical, vibrational, and magnetic resonance spectra of radicals 2 (+) and 3 (+) were also observed. The spectral data argue for the SOMOs of the 17-electron

  15. Anion size control of the packing in the metallic versus semiconducting chiral radical cation salts (DM-EDT-TTF)2XF6 (X = P, As, Sb).

    PubMed

    Pop, Flavia; Auban-Senzier, Pascale; Canadell, Enric; Avarvari, Narcis

    2016-10-13

    Control of the structural type in metallic enantiopure and racemic radical cation salts is achieved through hydrogen bonding interactions between the chiral donor DM-EDT-TTF and the XF6 anions (X = P, As, Sb), determined by the anion size and the chiral information.

  16. Theoretical vibrational spectra and thermodynamics of organic semiconductive tetrathiafulvalene and its cation radical.

    PubMed

    Mukherjee, V; Singh, N P

    2014-01-03

    Molecular structure in optimum geometry and vibrational frequencies of pentafulvalene [bicyclopentyliden-2,4,2',4'-tetraene], tetrathiafulvalene [2,2'-bis(1,3-dithiolylidene)] and its cation are calculated. All the calculations are carried out by employing density functional theory incorporated with a suitable basis set. Normal coordinate analysis is also employed to scale the DFT calculated frequencies and to calculate potential energy distributions. The molecular structures and vibrational frequencies are compared for both the pentafulvalene and tetrathiafulvalene molecules. The effect upon geometry and vibrational frequencies of TTF due to charge transfer has also been studied. The vibrational partition function and hence, the thermodynamical properties, such as Helmholtz free energy, entropy, specific heat at constant volume and enthalpy are also calculated and compared for the title molecules. The reason of conductivity of tetrathiafulvalene has been tried to explain on the basis of molecular geometry and normal modes. Study of vibrational partition function exhibits that below 109 K, PFV starts to condense.

  17. Observation of covalent and electrostatic bonds in nitrogen-containing polycyclic ions formed by gas phase reactions of the benzene radical cation with pyrimidine.

    PubMed

    Attah, Isaac Kwame; Soliman, Abdel-Rahman; Platt, Sean P; Meot-Ner Mautner, Michael; Aziz, Saaudallah G; Samy El-Shall, M

    2017-03-01

    Polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic nitrogen heterocyclics (PANHs) are present in ionizing environments, including interstellar clouds and solar nebulae, where their ions can interact with neutral PAH and PANH molecules leading to the formation of a variety of complex organics including large N-containing ions. Herein, we report on the formation of a covalently-bonded (benzene·pyrimidine) radical cation dimer by the gas phase reaction of pyrimidine with the benzene radical cation at room temperature using the mass-selected ion mobility technique. No ligand exchange reactions with benzene and pyrimidine are observed indicating that the binding energy of the (benzene·pyrimidine)˙(+) adduct is significantly higher than both the benzene dimer cation and the proton-bound pyrimidine dimer. The (benzene·pyrimidine)˙(+) adduct shows thermal stability up to 541 K. Thermal dissociation of the (C6D6·C4H4N2)˙(+) adduct at temperatures higher than 500 K produces C4H4N2D(+) (m/z 82) suggesting the transfer of a D atom from the C6D6 moiety to the C4H4N2 moiety before the dissociation of the adduct. Mass-selected ion mobility of the (benzene·pyrimidine)˙(+) dimer reveals the presence of two families of isomers formed by electron impact ionization of the neutral (benzene·pyrimidine) dimer. The slower mobility peak corresponds to a non-covalent family of isomers with larger collision cross sections (76.0 ± 1.8 Å(2)) and the faster peak is consistent with a family of covalent isomers with more compact structures and smaller collision cross sections (67.7 ± 2.2 Å(2)). The mobility measurements at 509 K show only one peak corresponding to the family of stable covalently bonded isomers characterized by smaller collision cross sections (66.9 ± 1.9 Å(2) at 509 K). DFT calculations at the M06-2X/6-311++G** level show that the most stable (benzene·pyrimidine)˙(+) isomer forms a covalent C-N bond with a binding energy of 49.7 kcal mol(-1) and a

  18. 15N electron nuclear double resonance of the primary donor cation radical P+.865 in reaction centers of Rhodopseudomonas sphaeroides: additional evidence for the dimer model.

    PubMed Central

    Lubitz, W; Isaacson, R A; Abresch, E C; Feher, G

    1984-01-01

    Four 15N hyperfine coupling constants, including signs, have been measured by electron nuclear double resonance (ENDOR) and electron nuclear nuclear triple resonance (TRIPLE) for the bacteriochlorophyll a radical cation, BChla+., in vitro and for the light-induced primary donor radical cation, P+.865, in reaction centers of Rhodopseudomonas sphaeroides R-26. A comparison of the data shows that the hyperfine coupling constants have the same sign in both radicals and are, on the average, smaller by a factor of 2 in P+.865. These results provide additional evidence that P+.865 is a bacteriochlorophyll dimer and are in contradiction with the monomer structure of P+.865 recently proposed by O'Malley and Babcock. The reduction factors of the individual 15N couplings, together with the evidence from proton ENDOR data and molecular orbital calculations, indicate a dimer structure in which only two rings (either I and I or III and III) of the bacteriochlorophyll macrocycles overlap. PMID:6096857

  19. Time-resolved fluorescence spectroscopic investigation of cationic polymer/DNA complex formation

    NASA Astrophysics Data System (ADS)

    D'Andrea, Cosimo; Bassi, Andrea; Taroni, Paola; Pezzoli, Daniele; Volonterio, Alessandro; Candiani, Gabriele

    2011-07-01

    Since DNA is not internalized efficiently by cells, the success of gene therapy depends on the availability of carriers to efficiently deliver genetic material into target cells. Gene delivery vectors can be broadly categorized into viral and non-viral ones. Non-viral gene delivery systems are represented by cationic lipids and polymers rely on the basics of supramolecular chemistry termed "self-assembling": at physiological pH, they are cations and spontaneously form lipoplexes (for lipids) and polyplexes (for polymers) complexing nucleic acids. In this scenario, cationic polymers are commonly used as non-viral vehicles. Their effectiveness is strongly related to key parameters including DNA binding ability and stability in different environments. Time-resolved fluorescence spectroscopy of SYBR Green I (DNA dye) was carried out to characterize cationic polymer/DNA complex (polyplex) formation dispersed in aqueous solution. Both fluorescence amplitude and lifetime proved to be very sensitive to the polymer/DNA ratio (N/P ratio, +/-).

  20. Formation and reactivity of carboxyphenyl radicals in aqueous solution

    NASA Astrophysics Data System (ADS)

    Janković, Ivana A.; Josimović, Ljubica R.; Jovanović, Slobodan V.

    1998-03-01

    Carboxyphenyl radicals were generated in aqueous solutions by reacting the solvated electron with ortho-, meta- and para-chlorobenzoate. These radicals were found to add to chlorobenzoates and abstract hydrogen atoms from a H-atom donor. It was concluded that the rate constants for the addition of carboxyphenyl radicals to chlorobenzoate depend on steric hindrance, since ortho-carboxyphenyl radical adds to 2-chlorobenzoate [ kadd=(1.0±0.2)×10 6 dm 3 mol -1 s -1] an order of magnitude slower than para-carboxyphenyl radical to 4-chlorobenzoate [ kadd=(1.0±0.2)×10 7 dm 3 mol -1 s -1]. The products of these addition reactions were detected by GC-MS. All three carboxyphenyl radical isomers abstract a H-atom from 4-methoxybenzen thiol at the same rate [ kH-aps˜1×10 9 dm 3 mol -1 s -1], i.e. the position of the carboxylate group seems not to influence the rate of the H-abstraction reaction.

  1. Radical Formation and Chemical Track Structure in Ion-Beam Irradiated DNA

    NASA Astrophysics Data System (ADS)

    Becker, David; Adhikary, Amitava; Khanduri, Deepti; Sevilla, Michael D.

    2009-12-01

    Ion-beam irradiation of hydrated DNA at 77 K results in formation of at least three base radicals and a variety of radicals on the sugar phosphate backbone that can be observed using Electron Spin Resonance (ESR) spectroscopy. From dose-response curves for these radicals, we have formulated a radiation-chemical model of the track structure for ion-beam irradiated DNA. The model for chemical behavior posits that the base radicals trapped at 77 K are formed almost entirely in the track penumbra. The lower yields observed in ion-beam irradiated samples results from the fact that only a portion of the energy deposited by the ion beam ends up in this γ-like region. The remainder of the energy is deposited in the core in which the proximity of ion-radical formation results in the fast recombination of oppositely charged radicals, so few survive in the core at 77 K. However, a second group of radicals, neutral sugar radicals, are not as susceptible to recombination as are ion radicals, and can survive after formation in the core; these are presumed to form predominantly in the core. They include the sugar radicals, C1'ṡC3'ṡC5'ṡ, formed from oxidative processes, and C3'ṡdephos and phosphorous radicals which are formed after immediate strand breaks. The later species are thought to result from reductive cleavage by low energy electrons (LEE.) The high energy density in the core results in excited state processes that produce additional sugar radicals. The spatial characteristics of the radicals, deduced from PELDOR experiments, indicates that multiply damaged cluster sites (MDS) are formed in the core; these would be biologically significant, if formed in cells.

  2. Where Does the Electron Go? Stable and Metastable Peptide Cation Radicals Formed by Electron Transfer

    NASA Astrophysics Data System (ADS)

    Pepin, Robert; Layton, Erik D.; Liu, Yang; Afonso, Carlos; Tureček, František

    2017-01-01

    Electron transfer to doubly and triply charged heptapeptide ions containing polar residues Arg, Lys, and Asp in combination with nonpolar Gly, Ala, and Pro or Leu generates stable and metastable charge-reduced ions, (M + 2H)+●, in addition to standard electron-transfer dissociation (ETD) fragment ions. The metastable (M + 2H)+● ions spontaneously dissociate upon resonant ejection from the linear ion trap, giving irregularly shaped peaks with offset m/ z values. The fractions of stable and metastable (M + 2H)+● ions and their mass shifts depend on the presence of Pro-4 and Leu-4 residues in the peptides, with the Pro-4 sequences giving larger fractions of the stable ions while showing smaller mass shifts for the metastables. Conversion of the Asp and C-terminal carboxyl groups to methyl esters further lowers the charge-reduced ion stability. Collisional activation and photodissociation at 355 nm of mass-selected (M + 2H)+● results in different dissociations that give sequence specific MS3 spectra. With a single exception of charge-reduced (LKGLADR + 2H)+●, the MS3 spectra do not produce ETD sequence fragments of the c and z type. Hence, these (M + 2H)+● ions are covalent radicals, not ion-molecule complexes, undergoing dramatically different dissociations in the ground and excited electronic states. The increased stability of the Pro-4 containing (M + 2H)+● ions is attributed to radicals formed by opening of the Pro ring and undergoing further stabilization by hydrogen atom migrations. UV-VIS photodissociation action spectroscopy and time-dependent density functional theory calculations are used in a case in point study of the stable (LKGPADR + 2H)+● ion produced by ETD. In contrast to singly-reduced peptide ions, doubly reduced (M + 3H)+ ions are stable only when formed from the Pro-4 precursors and show all characteristics of even electron ions regarding no photon absorption at 355 nm or ion-molecule reactions, and exhibiting proton driven

  3. EPR spectroscopy of chlorpromazine-induced free radical formation in normal human melanocytes.

    PubMed

    Otręba, Michał; Zdybel, Magdalena; Pilawa, Barbara; Beberok, Artur; Wrześniok, Dorota; Rok, Jakub; Buszman, Ewa

    2015-07-01

    The purpose of this study was to estimate the effect of chlorpromazine on free radical concentration in HEMn-DP melanocytes using electron paramagnetic resonance (EPR) spectroscopy. It was found that chlorpromazine at concentrations of 1 × 10(-7) and 1 × 10(-6) M contributed to the formation of free radicals (g values ~2) in a dose-dependent manner. The increase in free radical formation was accompanied by an increase in cytotoxicity, as shown by a tetrazolium assay. Homogeneous broadening of EPR lines, slow spin-lattice relaxation processes, and strong dipolar interactions characterized all the tested cellular samples. The performed examination of free radical formation in cells exposed to different chlorpromazine concentrations confirmed the usefulness of electron paramagnetic resonance spectroscopy to determine the effect of a drug on free radical production in a cellular model system in vitro.

  4. Pressure-induced spectral changes for the special-pair radical cation of the bacterial photosynthetic reaction center.

    PubMed

    Leiger, Kristjan; Freiberg, Arvi; Dahlbom, Mats G; Hush, Noel S; Reimers, Jeffrey R

    2007-06-07

    The effect of pressure up to 6 kbars on the near to mid infrared absorption spectrum (7500-14,300 cm(-1) or 1333-700 nm) of the oxidized reaction center of Rhodobacter sphaeroides is measured and interpreted using density-functional B3LYP, INDO, and PM5 calculations. Two weak electronic transition origins at approximately 8010 and approximately 10,210 cm(-1) are unambiguously identified. The first transition is assigned to a Qy tripdoublet band that involves, in the localized description of the excitation, a triplet absorption on one of the bacteriochlorophyll molecules (PM) in the reaction center's special pair intensified by the presence of a radical cation on the other (PL). While most chlorophyll transition energies decrease significantly with increasing pressure, the tripdoublet band is found to be almost pressure insensitive. This difference is attributed to the additional increase in the tripdoublet-band energy accompanying compression of the pi-stacked special pair. The second band could either be the anticipated second Qy tripdoublet state, a Qx tripdoublet state, or a state involving excitation from a low-lying doubly occupied orbital to the half-occupied cationic orbital. A variety of absorption bands that are also resolved in the 8300-9600 cm(-1) region are assigned as vibrational structure associated with the first tripdoublet absorption. These sidebands are composites that are shown by the calculations to comprise many unresolved individual modes; while the calculated pressure sensitivity of each individual mode is small, the calculated pressure dependence of the combined sideband structure is qualitatively similar to the observed pressure dependence, preventing the positive identification of possible additional electronic transitions in this spectral region.

  5. Pathways for the reaction of the butadiene radical cation, [C{sub 4}H{sub 6}]{sup {sm{underscore}bullet}+}, with ethylene

    SciTech Connect

    Hofmann, M.; Schaefer, H.F. III

    1999-11-04

    The Diels-Alder (DA) reaction, a [4+2] cycloaddition used to build six membered rings, is one of the most valuable cycloadditions in organic chemistry. In cases where the ene does not add to the diene (even with the help of Lewis acids which may reduce the electron density of one reactant by complexation) one electron oxidation (by an oxidizing agent or by photoinduced electron transfer (PET)) may accelerate the reaction. Reaction pathways for the addition of ethylene, 1, to butadiene radical cation, 2, involving H-shifts have been investigated at the coupled cluster UCCSD(T)/DZP//UMP2(fc)/DZP + ZPE level of theory. Activation energies are relatively low for [1,2]- (10.0 kcal mol{sup {minus}1}, TS-4/20) and [1,5]-hydrogen shifts (7.7 kcal mol{sup {minus}1}, TS-4/26) but are relatively high for [1,4]-(33.8 kcal mol{sup {minus}1}, TS-4/14) and [1,3]-H shifts (e.g., 42.2 kcal mol{sup {minus}1}, TS-12/13; 57.2 kcal mol{sup {minus}1}, TS-16/21). Several rearrangement reactions have been found to occur below the energy limit of separated 1 + 2. The cyclopentenyl cation, [C{sub 5}{sub 7}]{sup +}, 18, experimentally observed as reaction product of the butadiene radical cation, 2, and ethylene, 1, in the gas phase may origin from various reaction pathways. The following reaction sequence has been identified as the lowest in energy path from 1 + 2 to 18 with all relative energies ({Delta}E{degree}) of transition structures below that of 1 + 2: (a) ethylene adds to the butadiene radical cation to form an open-chain distonic intermediate, that undergoes a [1,5]-H shift to the 1,4-hexadiene radical cation; (b) intramolecular [2+1] cycloaddition to methyl-cyclopenta-1,3-diyl intermediates, which can interconvert through a bicyclo[2.1.0]pentane radical cation; (c) [1,2]-H shift to the 3-methyl cyclopentene radical cation; (d) methyl radical loss to give cyclopenten-3-yl cation. Along this reaction pathway, {Delta}H{sup 298} is below that of 1 + 2; max. ({Delta}G{sup 298} by

  6. Chlorophyll-quinone photochemistry in liposomes: mechanisms of radical formation and decay

    SciTech Connect

    Hurley, J.K.; Tollin, G.

    1980-01-01

    Laser flash photolysis has been used to investigate the mechanism of formation and decay of the radical species generated by light induced electron transfer from chlorophyll a triplet to quinone in egg phosphatidyl choline bilayer vesicles. Chlorophyll triplet quenching by quinone is controlled by diffusion occurring within the bilayer membrane and reflects bilayer viscosity. Radical formation via separation of the intermediate ion pair is also inhibited by increased bilayer viscosity. Cooperativity is observed in this process due to an enhancement of radical separation by electron transfer from semiquinone anion radical to a neighboring quinone molecule. Two modes of radical decay are observed, a rapid recombination occurring within the bilayer and a much slower recombination occurring across the bilayer. The slow decay is only observed with quinones which are not tightly anchored into the bilayer, and is probably the result of electron transfer from semiquinone anion radical formed within the bilayer to a quinone molecule residing at the bilayer-water interface. With benzoquinone, approximately 60% of the radical decay occurs via the slow mode. Triplet to radical conversion efficiencies in the bilayer systems are comparable to those obtained in fluid solution (approx. 60%). However, radical recombination, at least for the slow decay mechanism, is considerably retarded.

  7. Theoretical study of reactivity of methane, methyl fluoride, and methyl chloride: Interaction with their radical cations and proton donors

    SciTech Connect

    Hess, B.A. Jr. ); Zahradnik, R. )

    1990-07-18

    This work deals with interactions between CH{sub 4} and CH{sub 4}{sup {sm bullet}+}, CH{sub 3}F and CH{sub 3}F{sup {sm bullet}+}, and CH{sub 3}Cl and CH{sub 3}Cl{sup {sm bullet}+}. The calculated {Delta}H{sub 0} values (MP4/6-31G**//MP2/6-31G**, ZPE included) for processes leading to CH{sub 5}{sup +} and CH{sub 3}{sup {sm bullet}}, and to CFH{sub 4} and CH{sub 2}F{sup {sm bullet}} amount to {minus}1.8 and {minus}21.0 kcal/mol, respectively. The {Delta}H{sub 0} leading to CClH{sub 4}{sup +} and CH{sub 2}Cl{sup {sm bullet}} (MP4/6-31G**//SCF/6-31G**, ZPE included) is {minus}2.3 kcal/mol. The calculated reaction heat for the first interaction is significantly closer to experimental values ({minus}4.16 and {minus}6 kcal/mol, respectively) than their previous theoretical estimates. The structures of the radical cations (CH{sub 4}{sup {sm bullet}+}, CH{sub 3}F{sup {sm bullet}+}) possess features of van der Waals associates.

  8. Influence of ionization on the conformational preferences of peptide models. Ramachandran surfaces of N-formyl-glycine amide and N-formyl-alanine amide radical cations.

    PubMed

    Gil, Adrià; Sodupe, Mariona; Bertran, Juan

    2009-09-01

    Ramachandran maps of neutral and ionized HCO-Gly-NH2 and HCO-Ala-NH2 peptide models have been built at the B3LYP/6-31++G(d,p) level of calculation. Direct optimizations using B3LYP and the recently developed MPWB1K functional have also been carried out, as well as single-point calculations at the CCSD(T) level of theory with the 6-311++G(2df,2p) basis set. Results indicate that for both peptide models ionization can cause drastic changes in the shape of the PES in such a way that highly disallowed regions in neutral PES become low-energy regions in the radical cation surface. The structures localized in such regions, epsilonL+* and epsilonD+* are highly stabilized due to the formation of 2-centre-3-electron interactions between the two carbonyl oxygens. Inclusion of solvent effects by the conductor-like polarizable continuum model (CPCM) shows that the solute-solvent interaction energy plays an important role in determining the stability order.

  9. Secondary organic aerosol formation from reaction of tertiary amines with nitrate radical

    NASA Astrophysics Data System (ADS)

    Erupe, M. E.; Price, D. J.; Silva, P. J.; Malloy, Q. G. J.; Qi, L.; Warren, B.; Cocker, D. R., III

    2008-09-01

    Secondary organic aerosol formation from the reaction of tertiary amines with nitrate radical was investigated in an indoor environmental chamber. Particle chemistry was monitored using a high resolution aerosol mass spectrometer while gas-phase species were detected using a proton transfer reaction mass spectrometer. Trimethylamine, triethylamine and tributylamine were studied. Results indicate that tributylamine forms the most aerosol mass followed by trimethylamine and triethylamine respectively. Spectra from the aerosol mass spectrometer indicate the formation of complex non-salt aerosol products. We propose a reaction mechanism that proceeds via abstraction of a proton by nitrate radical followed by RO2 chemistry. Rearrangement of the aminyl alkoxy radical through hydrogen shift leads to the formation of hydroxylated amides, which explain most of the higher mass ions in the mass spectra. These experiments show that oxidation of tertiary amines by nitrate radical may be an important night-time source of secondary organic aerosol.

  10. A valence bond analysis of electronic degeneracies in Jahn-Teller systems: low-lying states of the cyclopentadienyl radical and cation.

    PubMed

    Zilberg, Shmuel; Haas, Yehuda

    2002-09-11

    The lowest doublet electronic state of the cyclopentadienyl radical (CPDR) and the lowest singlet state of the cyclopentadienyl cation (CPDC) are distorted from the highly symmetric D(5h) structure due to the Jahn-Teller effect. A valence bond analysis based on the phase-change rule of Longuet-Higgins reveals that in both cases the distortion is due to the first-order Jahn-Teller effect. It is shown that, while for the radical an isolated Jahn-Teller degeneracy is expected, in the case of the cation the main Jahn-Teller degeneracy is accompanied by five satellite degeneracies. The method offers a chemically oriented way for identifying the distortive coordinates.

  11. Contrasting reactions of hydrated electron and formate radical with 2-thio analogues of cytosine and uracil.

    PubMed

    Prasanthkumar, Kavanal P; Alvarez-Idaboy, Juan R; Kumar, Pavitra V; Singh, Beena G; Priyadarsini, K Indira

    2016-10-19

    2-Thiocytosine (TC) and 2-thiouracil (TU) were subjected to hydrated electron (eaq(-)), formate radical (CO2˙(-)) and 2-hydroxypropan-2-yl radical ((CH3)2˙COH) reactions in aqueous medium. Transients were characterized by absorption spectroscopy and the experimental findings were rationalized by DFT calculations at LC-ωPBE and M06-2X levels using a 6-311+G(d,p) basis set and SMD solvation. In eaq(-) reactions, a ring N-atom protonated radical of TC and an exocyclic O-atom protonated radical of TU were observed via addition of eaq(-) and subsequent protonation by solvent molecules. However, two competing but simultaneous mechanisms are operative in CO2˙(-) reactions with TC and TU. The first one corresponds to formations of N(O)-atom protonated radicals (similar to eaq(-) reactions); the second mechanism led to 2 center-3 electron, sulfur-sulfur bonded neutral dimer radicals, TCdim˙ and TUdim˙. DFT calculations demonstrated that H-abstraction by CO2˙(-) from TC(TU) results in S-centered radical which upon combination with TC(TU) provide the dimer radical. In some cases, DFT energy profiles were further validated by CBS-QB3//M06-2X calculations. This is the first time report for a contradictory behavior in the mechanisms of eaq(-) and CO2˙(-) reactions with any pyrimidines or their thio analogues.

  12. Biotin synthase: insights into radical-mediated carbon-sulfur bond formation.

    PubMed

    Fugate, Corey J; Jarrett, Joseph T

    2012-11-01

    The enzyme cofactor and essential vitamin biotin is biosynthesized in bacteria, fungi, and plants through a pathway that culminates with the addition of a sulfur atom to generate the five-membered thiophane ring. The immediate precursor, dethiobiotin, has methylene and methyl groups at the C6 and C9 positions, respectively, and formation of a thioether bridging these carbon atoms requires cleavage of unactivated CH bonds. Biotin synthase is an S-adenosyl-l-methionine (SAM or AdoMet) radical enzyme that catalyzes reduction of the AdoMet sulfonium to produce 5'-deoxyadenosyl radicals, high-energy carbon radicals that can directly abstract hydrogen atoms from dethiobiotin. The available experimental and structural data suggest that a [2Fe-2S](2+) cluster bound deep within biotin synthase provides a sulfur atom that is added to dethiobiotin in a stepwise reaction, first at the C9 position to generate 9-mercaptodethiobiotin, and then at the C6 position to close the thiophane ring. The formation of sulfur-containing biomolecules through a radical reaction involving an iron-sulfur cluster is an unprecedented reaction in biochemistry; however, recent enzyme discoveries suggest that radical sulfur insertion reactions may be a distinct subgroup within the burgeoning Radical SAM superfamily. This article is part of a Special Issue entitled: Radical SAM enzymes and Radical Enzymology.

  13. A new special pair model comprising meso-di-p-anisylaminoporphyrin: enhancement of visible-light absorptivities and quantification of electronic communication in mixed-valent cation radical.

    PubMed

    Sakamoto, Ryota; Nishikawa, Michihiro; Yamamura, Takeshi; Kume, Shoko; Nishihara, Hiroshi

    2010-03-28

    Slipped cofacial porphyrin dimer 1(2) with di-p-anisylamino groups on the meso-positions shows characteristic photo- and electroproperties making it suitable as a photosynthetic special pair model: more intense and red-shifted absorptivities in the visible region, and electronic communication between the two porphyrins in mixed-valent cation radical 1(2)(+), which is quantified with an IVCT band analysis.

  14. Mode of formation and structural features of DNA-cationic liposome complexes used for transfection.

    PubMed

    Gershon, H; Ghirlando, R; Guttman, S B; Minsky, A

    1993-07-20

    Complexes formed between cationic liposomes and nucleic acids represent a highly efficient vehicle for delivery of DNA and RNA molecules into a large variety of eukaryotic cells. By using fluorescence, gel electrophoresis, and metal-shadowing electron microscopy techniques, the factors that affect the, yet unclear, interactions between DNA and cationic liposomes as well as the structural features of the resulting complexes have been elucidated. A model is suggested according to which cationic liposomes bind initially to DNA molecules to form clusters of aggregated vesicles along the nucleic acids. At a critical liposome density, two processes occur, namely, DNA-induced membrane fusion, indicated by lipid mixing studies, and liposome-induced DNA collapse, pointed out by the marked cooperativity of the encapsulation processes, by their modulations by DNA-condensing agents, and also by their conspicuous independence upon DNA length. The DNA collapse leads to the formation of condensed structures which can be completely encapsulated within the fused lipid bilayers in a fast, highly cooperative process since their exposed surface is substantially smaller than that of extended DNA molecules. The formation of the transfecting DNA-liposome complexes in which the nucleic acids are fully encapsulated within a positively-charged lipid bilayer is proposed, consequently, to be dominated by mutual effects exerted by the DNA and the cationic liposomes, leading to interrelated lipid fusion and DNA collapse.

  15. Spectroscopic and Kinetic Characterization of Peroxidase-Like π-Cation Radical Pinch-Porphyrin-Iron(III) Reaction Intermediate Models of Peroxidase Enzymes.

    PubMed

    Hernández Anzaldo, Samuel; Arroyo Abad, Uriel; León García, Armando; Ramírez Rosales, Daniel; Zamorano Ulloa, Rafael; Reyes Ortega, Yasmi

    2016-06-27

    The spectroscopic and kinetic characterization of two intermediates from the H₂O₂ oxidation of three dimethyl ester [(proto), (meso), (deuteroporphyrinato) (picdien)]Fe(III) complexes ([FePPPic], [FeMPPic] and [FeDPPic], respectively) pinch-porphyrin peroxidase enzyme models, with s = 5/2 and 3/2 Fe(III) quantum mixed spin (qms) ground states is described herein. The kinetic study by UV/Vis at λmax = 465 nm showed two different types of kinetics during the oxidation process in the guaiacol test for peroxidases (1-3 + guaiacol + H₂O₂ → oxidation guaiacol products). The first intermediate was observed during the first 24 s of the reaction. When the reaction conditions were changed to higher concentration of pinch-porphyrins and hydrogen peroxide only one type of kinetics was observed. Next, the reaction was performed only between pinch-porphyrins-Fe(III) and H₂O₂, resulting in only two types of kinetics that were developed during the first 0-4 s. After this time a self-oxidation process was observed. Our hypotheses state that the formation of the π-cation radicals, reaction intermediates of the pinch-porphyrin-Fe(III) family with the ligand picdien [N,N'-bis-pyridin-2-ylmethyl-propane-1,3-diamine], occurred with unique kinetics that are different from the overall process and was involved in the oxidation pathway. UV-Vis, ¹H-NMR and ESR spectra confirmed the formation of such intermediates. The results in this paper highlight the link between different spectroscopic techniques that positively depict the kinetic traits of artificial compounds with enzyme-like activity.

  16. Formation of free radicals during mechanical degradation of elastomers.

    NASA Technical Reports Server (NTRS)

    Devries, K. L.; Williams, M. L.; Roylance, D. K.

    1971-01-01

    Solithane 113 (an amorphous polyurethane elastomer) was prepared by curing equal proportions of castor oil and trifunctional isocyanate for 6 hr 45 min at 170 F. The sample material was mechanically degraded by grinding below and above its glass transition point at liquid nitrogen and room temperatures. The EPR spectra of ground samples were recorded and the number of free radicals were determined by a computer double-integration of the recorded spectra and by a comparison of the values with those of a standard material. Curves of EPR spectra suggest that different molecular mechanisms may be active in degradation of this material below and above its glass transition temperature.

  17. Electronic Characterization of Reaction Intermediates: The Fluorenylium, Phenalenylium, and Benz[f]indenylium Cations and Their Radicals.

    PubMed

    Fulara, Jan; Chakraborty, Arghya; Maier, John P

    2016-03-01

    Three vibrationally resolved absorption systems commencing at 538, 518, and 392 nm were detected in a 6 K neon matrix after mass-selected deposition of C13 H9 (+) ions (m/z=165) produced from fluorene in a hot-cathode discharge ion source. The benz[f]indenylium (BfI(+) : 538 nm), fluorenylium (FL9(+) : 518 nm), and phenalenylium (PHL(+) : 392 nm) cations are the absorbing molecules. Two electronic systems corresponding to neutral species are apparent at 490 and 546 nm after irradiation of the matrix with λ<260 nm photons and were assigned to the FL9 and BfI radicals, respectively. The strongest peak at 518 nm is the origin of the 2 (1) B2 ←X̃ (1) A1 absorption of FL9(+) , and the 490 nm band is the 2 (2) A2 ←X̃ (2) B1 origin of FL9. The electronic systems commencing at 538 nm and 546 nm were assigned to the 1 (1) A1 ←X̃ (1) A1 and 1 (2) A2 ←X̃ (2) A2 transitions of BfI(+) and BfI. The 392 nm band is the 1 (1) E'←X̃ (1) A1 ' transition of PHL(+). The electronic spectra of C13 H9 (+) /C13 H9 were assigned on the basis of the vertical excitation energies calculated with SAC-CI and MS-CASPT2 methods.

  18. Studies with primaquine in vitro: superoxide radical formation and oxidation of haemoglobin.

    PubMed Central

    Summerfield, M; Tudhope, G R

    1978-01-01

    1. The production of superoxide radicals from primaquine diphosphate in aqueous solution has been demonstrated, using as indicator the reduction of cytochrome C with inhibition of the reaction by superoxide dismutase. 2. Primaquine-mediated oxidation of haemoglobin to methaemoglobin was reduced by the addition of catalase and increased by superoxide dismutase. Mannitol, a hydroxyl radical scavenger, abolished the increase in methaemoglobin observed in the presence of superoxide dismutase. EDTA reduced the oxidation of haemoglobin with and without superoxide dismutase. 3. Although the oxidation of haemoglobin in the presence of primaquine includes the effects of hydrogen peroxide, superoxide and hydroxyl radicals and metal ions, the results indicate that hydrogen peroxide, rather than the superoxide radical, is the main oxidizing species. The increase in haemoglobin oxidation occurring with superoxide dismutase may result from the augmented rate of hydrogen peroxide formation from superoxide radicals. PMID:212091

  19. Free radical formation in vivo and hepatotoxicity due to anesthesia with halothane

    SciTech Connect

    Plummer, J.L.; Beckwith, A.L.; Bastin, F.N.; Adams, J.F.; Cousins, M.J.; Hall, P.

    1982-09-01

    In vivo studies were undertaken to determine whether free radical formation in the liver during administration of various halogenated anesthetics is associated with hepatotoxicity of these agents in an animal model. In addition to the anesthetics halothane, enflurane, and isoflurane, carbon tetrachloride was studied as an example of a hepatotoxic halogenated compound acting by a free radical mechanism. Free radicals were trapped in vivo during anesthesia as stable adducts using the spin trap, alpha-phenyl-t-butyl nitrone. These adducts were extracted from the liver and studied by electron spin resonance spectrometry. Free radicals were detected after administration of halothane or carbon tetrachloride, compounds which were hepatotoxic under the conditions of the experiment, but were not found after anesthesia induced with enflurane or isoflurane, anesthetics which were not hepatotoxic under identical conditions. The free radical trapped after alpha-phenyl-t-butyl nitrone treatment of halothane-anesthetized rats appeared to be a metabolic intermediate of halothane.

  20. Picosecond pulse radiolysis of highly concentrated sulfuric acid solutions: evidence for the oxidation reactivity of radical cation H2O(•+).

    PubMed

    Ma, Jun; Schmidhammer, Uli; Mostafavi, Mehran

    2014-06-12

    Aqueous solution of sulfuric acid is used as a suitable system to investigate the reactivity of the short-lived radical cation H2O(•+) which is generated by radiation in water. Ten aqueous solutions containing sulfuric acid with concentration from 1 to 18 mol L(-1) are studied by picosecond pulse radiolysis. The absorbance of the secondary radical SO4(•-) (or HSO4(•)) formed within the 10 ps electron pulse is measured by a pulse-probe method in the visible range. The analysis of the kinetics show that the radicals of sulfuric acid are formed within the picosecond electron pulse via two parallel mechanisms: direct electron detachment by the electron pulse and oxidation by the radical cation of water H2O(•+). In highly concentrated solution when SO4(2-) is in contact with H2O(•+), the electron transfer becomes competitive against proton transfer with another water molecule. Therefore, H2O(•+) may act as an extremely strong oxidant. The maximum radiolytic yield of scavenged H2O(•+) is estimated to be 5.3 ± 0.1 × 10(-7) mol J(-1).

  1. Iron reduction potentiates hydroxyl radical formation only in flavonols.

    PubMed

    Macáková, Kateřina; Mladěnka, Přemysl; Filipský, Tomáš; Říha, Michal; Jahodář, Luděk; Trejtnar, František; Bovicelli, Paolo; Proietti Silvestri, Ilaria; Hrdina, Radomír; Saso, Luciano

    2012-12-15

    Flavonoids, substantial components of the human diet, are generally considered to be beneficial. However, they may possess possible pro-oxidative effects, which could be based on their reducing potential. The aims of this study were to evaluate the ability of 26 flavonoids to reduce ferric ions at relevant pH conditions and to find a possible relationship with potentiation of hydroxyl radical production. A substantial ferric ions reduction was achieved under acidic conditions, particularly by flavonols and flavanols with the catecholic ring B. Apparently corresponding bell-shaped curves displaying the pro-oxidant effect of flavonols quercetin and kaempferol on iron-based Fenton reaction were documented. Several flavonoids were efficient antioxidants at very low concentrations but rather inefficient or pro-oxidative at higher concentrations. Flavonols, morin and rutin were progressively pro-oxidant, while 7-hydroxyflavone and hesperetin were the only flavonoids with dose-dependent inhibition of hydroxyl radical production. Conclusively, administration of flavonoids may lead to unpredictable consequences with few exceptions.

  2. Formation of {beta}-hydroxycarbonyls from the OH radical-initiated reactions of selected alkenes

    SciTech Connect

    Aschmann, S.M.; Arey, J.; Atkinson, R.

    2000-05-01

    {beta}-Hydroxycarbonyls can be formed from the gas-phase reactions of alkenes with the OH radical, both in the presence and in the absence of NO. To date, because of analytical difficulties, few data have been reported for the formation of this class of compound from the reactions of the OH radical with alkenes. The authors have determined that {beta}-hydroxy-ketones can be readily analyzed by gas chromatography, and in this work they have shown that in 1 atm of air the {beta}-hydroxyalkoxy radicals formed in the reactions of the OH radical with trans-2-butene, trans-3-hexene, 1-butene, and {alpha}-pinene in the presence of NO primarily decompose rather than react with O{sub 2}. Rate constant ratios k{sub d}/k{sub 0{sub 2}} (or lower limits thereof), where k{sub d} and k{sub 0{sub 2}} are respectively the rate constants for the decomposition and the reaction with 0{sub 2} of the intermediate {beta}-hydroxyalkoxy radicals, have been obtained for the reactions of the CH{sub 3}CH(O)CH-(OH)CH{sub 3}, CH{sub 3}CH{sub 2}CH(O)CH{sub 2}OH, and CH{sub 3}CH{sub 2}CH(O)CH(OH)CH{sub 2}-CH{sub 3} radicals at 296 {+-} 2 K and atmospheric pressure. Using the O{sub 3} reactions with the alkenes to generate OH radicals, the reactions of the OH radical to generate OH radicals, the reactions of the OH radical with trans-2-butene, trans-3-hexene, and {alpha}-pinene in the absence of NO lead to the formation of the expected {beta}-hydroxycarbonyls and (at least for trans-2-butene) the {alpha},{beta}-diol.

  3. Diastereo-specific conformational properties of neutral, protonated and radical cation forms of (1R,2S)-cis- and (1R,2R)-trans-amino-indanol by gas phase spectroscopy.

    PubMed

    Bouchet, Aude; Klyne, Johanna; Piani, Giovanni; Dopfer, Otto; Zehnacker, Anne

    2015-10-21

    Chirality effects on the intramolecular interactions strongly depend on the charge and protonation states. Here, the influence of chirality on the structure of the neutral, protonated, and radical cation forms of (1R,2S)-cis- and (1R,2R)-trans-1-amino-2-indanol diastereomers, prototypical molecules with two chiral centers, is investigated in a molecular beam by laser spectroscopy coupled with quantum chemical calculations. The neutral systems are structurally characterised by double resonance IR-UV spectroscopy, while IR-induced dissociation spectroscopy is employed for the charged molecules. The sterical constraints due to the cyclic nature of the molecule emphasise the chirality effects, which manifest themselves by the formation of an intramolecular hydrogen bond in neutral or protonated (1R,2S)-cis-amino-indanol. In contrast, this interaction is not possible in (1R,2R)-trans-amino-indanol. In the protonated species, chirality also influences the spectroscopic probes in the NH/OH stretch range by fine-tuning subtle effects such as the hyperconjugation between the σ(OH) orbital and σ* orbitals localised on the alicyclic ring. The radical cation undergoes opening of the alicyclic ring, which results in an ionisation-induced loss of the chirality effects.

  4. Sulfate radical-based water treatment in presence of chloride: formation of chlorate, inter-conversion of sulfate radicals into hydroxyl radicals and influence of bicarbonate.

    PubMed

    Lutze, Holger V; Kerlin, Nils; Schmidt, Torsten C

    2015-04-01

    Sulfate radical (SO4(-)) based oxidation is discussed as a potential water treatment option and is already used in ground water remediation. However, the complex SO4(-) chemistry in various matrices is poorly understood. In that regard, the fast reaction of SO4(-) with Cl(-) is of high importance since Cl(-) belongs to the main constituents in aqueous environments. This reaction yields chlorine atoms (Cl) as primary products. Cl initiate a cascade of subsequent reactions with a pH dependent product pattern. At low pH (<5) formation of chlorine derived oxidation products such as chlorate (ClO3(-)) is favoured. This is undesired because ClO3(-) may reveal adverse effects on the environment and human health. At pH > 5 Cl mainly react with water yielding hydroxyl radicals. Thus, at moderate Cl(-) concentrations (mM range) the SO4(-)-based process may be converted into a conventional (hydroxyl radical -based) advanced oxidation process. The conversion of SO4(-) into OH, however, is interrupted in presence of bicarbonate by scavenging of Cl.

  5. Free-radical Destruction of Sphingolipids Resulting in 2-hexadecenal Formation

    PubMed Central

    Shadyro, Oleg; Lisovskaya, Alexandra; Semenkova, Galina; Edimecheva, Irina; Amaegberi, Nadezda

    2015-01-01

    The action of hypochlorous acid (HOCl) and γ-radiation on aqueous lysosphingolipid dispersions was found to produce 2-hexadecenal (Hex). This process includes the stages of formation of nitrogen-centered radicals from the starting molecules and the subsequent fragmentation of these radicals via the rupture of C–C and O–H bonds. These findings prove the existence of a nonenzymatic pathway of sphingolipid destruction leading to the formation of Hex, which possesses a wide spectrum of biological activity. Analysis of the effect of HOCl on transplantable rat glioma C6 cells and human embryonic kidney 293 cells points to the formation of Hex. This suggests that the described mechanism of free-radical destruction of sphingolipids may be replicated on cell culture under the stress of active chlorine forms. PMID:25861222

  6. HYDROGENATION OF PAH CATIONS: A FIRST STEP TOWARD H{sub 2} FORMATION

    SciTech Connect

    Boschman, L.; Cazaux, S.; Spaans, M.; Reitsma, G.; Schlathoelter, T.; Hoekstra, R.; Gonzalez-Magana, O.

    2012-12-20

    Molecular hydrogen is the most abundant molecule in the universe. A large fraction of H{sub 2} forms by association of hydrogen atoms adsorbed on polycyclic aromatic hydrocarbons (PAHs), where formation rates depend crucially on the H sticking probability. We have experimentally studied PAH hydrogenation by exposing coronene cations, confined in a radio-frequency ion trap, to gas phase atomic hydrogen. A systematic increase of the number of H atoms adsorbed on the coronene with the time of exposure is observed. Odd coronene hydrogenation states dominate the mass spectrum up to 11 H atoms attached. This indicates the presence of a barrier preventing H attachment to these molecular systems. For the second and fourth hydrogenations, barrier heights of 72 {+-} 6 meV and 40 {+-} 10 meV, respectively, are found, which are in good agreement with theoretical predictions for the hydrogenation of neutral PAHs. Our experiments, however, prove that the barrier does not vanish for higher hydrogenation states. These results imply that PAH cations, as their neutral counterparts, exist in highly hydrogenated forms in the interstellar medium. Due to this catalytic activity, PAH cations and neutrals seem to contribute similarly to the formation of H{sub 2}.

  7. Rapid formation of the stable tyrosyl radical in photosystem II.

    PubMed

    Faller, P; Debus, R J; Brettel, K; Sugiura, M; Rutherford, A W; Boussac, A

    2001-12-04

    Two symmetrically positioned redox active tyrosine residues are present in the photosystem II (PSII) reaction center. One of them, TyrZ, is oxidized in the ns-micros time scale by P680+ and reduced rapidly (micros to ms) by electrons from the Mn complex. The other one, TyrD, is stable in its oxidized form and seems to play no direct role in enzyme function. Here, we have studied electron donation from these tyrosines to the chlorophyll cation (P680+) in Mn-depleted PSII from plants and cyanobacteria. In particular, a mutant lacking TyrZ was used to investigate electron donation from TyrD. By using EPR and time-resolved absorption spectroscopy, we show that reduced TyrD is capable of donating an electron to P680+ with t1/2 approximately equal to 190 ns at pH 8.5 in approximately half of the centers. This rate is approximately 10(5) times faster than was previously thought and similar to the TyrZ donation rate in Mn-depleted wild-type PSII (pH 8.5). Some earlier arguments put forward to rationalize the supposedly slow electron donation from TyrD (compared with that from TyrZ) can be reassessed. At pH 6.5, TyrZ (t1/2 = 2-10 micros) donates much faster to P680+ than does TyrD (t1/2 > 150 micros). These different rates may reflect the different fates of the proton released from the respective tyrosines upon oxidation. The rapid rate of electron donation from TyrD requires at least partial localization of P680+ on the chlorophyll (PD2) that is located on the D2 side of the reaction center.

  8. Radical S-adenosylmethionine enzyme catalyzed thioether bond formation in sactipeptide biosynthesis.

    PubMed

    Flühe, Leif; Marahiel, Mohamed A

    2013-08-01

    Sactipeptides represent a new emerging class of ribosomally assembled and posttranslationally modified peptides that show diverse bioactivities. Their common hallmark is an intramolecular thioether bond that crosslink the sulfur atom of a cysteine residue with the α-carbon of an acceptor amino acid. This review summarizes recent achievements concerning the biosynthesis of sactipeptides in general and with special focus on the common enzymatic radical SAM mechanism leading to the thioether linkage formation. In addition this mechanism is compared to the mechanism of thioether bond formation during lanthipeptide biosynthesis and to other radical based thioether bond forming reactions.

  9. [Effects of ascorbic acid on the free radical formations of isoniazid and its metabolites].

    PubMed

    Matsuki, Y; Akazawa, M; Tsuchiya, K; Sakurai, H; Kiwada, H; Goromaru, T

    1991-10-01

    By the use of electron spin resonance (ESR) spectroscopy and of spin-trapping technique, the effects of ascorbic acid on the formation of the free radical intermediates due to isoniazid (INAH) and its metabolites were investigated with a microsomal system. When alpha-(4-pyridyl 1-oxide)-N-tert butylnitrone (4-POBN) was used as a spin trapping agent, the ESR signal due to hydrazine (Hy) was formed to be most intensive among others. Therefore, it was presumed that Hy is a potent intermediate to cause an INAH-induced hepatic injury. In the presence of ascorbic acid (AA), the free radical formation of Hy, INAH and acetyl hydrazine was significantly inhibited, suggesting that AA may affect the INAH-hepatitis. By the addition of inhibitors of cytochrome P-450 like metyrapone and CO, the generation of the radical from Hy decreased, confirming that the radical is formed by the cytochrome P-450 dependent microsome systems. The 4-POBN-trapped radical species generated from Hy was presumed to be the hydrazyl radical by the results of mass spectrometry.

  10. Thermodynamics of cationic lipid-DNA complex formation as studied by isothermal titration calorimetry.

    PubMed

    Pozharski, Edwin; MacDonald, Robert C

    2002-07-01

    The detailed analysis of the cationic lipid-DNA complex formation by means of isothermal titration calorimetry is presented. Most experiments were done using 1,2-dioleyl-sn-glycero-3-ethylphosphocholine (EDOPC), but basic titrations were also done using DOTAP, DOTAP:DOPC, and DOTAP:DOPE mixtures. Complex formation was endothermic with less than 1 kcal absorbed per mole of lipid or DNA charge. This enthalpy change was attributed to DNA-DNA mutual repulsion within the lamellar complex. The exception was DOTAP:DOPE-containing lipoplex for which the enthalpy of formation was exothermic, presumably because of DOPE amine group protonation. Experimental conditions, namely, direction and titration increment as well as concentration of titrant, which dictate the structure of resulting lipoplex (whether lamellar complex or DNA-coated vesicle), were found to affect the apparent thermodynamics of complex formation. The structure, in turn, influences the biological properties of the lipoplex. If the titration of lipid into DNA was carried out in large increments, the DeltaH was larger than when the injection increments were smaller, a finding that is consistent with increased vesicle disruption under large increments and which is expected theoretically. Cationic lipid-DNA binding was weak in high ionic strength solutions, however, the effective binding constant is within micromolar range because of macromolecular nature of the interaction.

  11. Thermodynamics of cationic lipid-DNA complex formation as studied by isothermal titration calorimetry.

    PubMed Central

    Pozharski, Edwin; MacDonald, Robert C

    2002-01-01

    The detailed analysis of the cationic lipid-DNA complex formation by means of isothermal titration calorimetry is presented. Most experiments were done using 1,2-dioleyl-sn-glycero-3-ethylphosphocholine (EDOPC), but basic titrations were also done using DOTAP, DOTAP:DOPC, and DOTAP:DOPE mixtures. Complex formation was endothermic with less than 1 kcal absorbed per mole of lipid or DNA charge. This enthalpy change was attributed to DNA-DNA mutual repulsion within the lamellar complex. The exception was DOTAP:DOPE-containing lipoplex for which the enthalpy of formation was exothermic, presumably because of DOPE amine group protonation. Experimental conditions, namely, direction and titration increment as well as concentration of titrant, which dictate the structure of resulting lipoplex (whether lamellar complex or DNA-coated vesicle), were found to affect the apparent thermodynamics of complex formation. The structure, in turn, influences the biological properties of the lipoplex. If the titration of lipid into DNA was carried out in large increments, the DeltaH was larger than when the injection increments were smaller, a finding that is consistent with increased vesicle disruption under large increments and which is expected theoretically. Cationic lipid-DNA binding was weak in high ionic strength solutions, however, the effective binding constant is within micromolar range because of macromolecular nature of the interaction. PMID:12080142

  12. Erbium-formate frameworks templated by diammonium cations: syntheses, structures, structural transition and magnetic properties.

    PubMed

    Li, Mengyuan; Liu, Bin; Wang, Bingwu; Wang, Zheming; Gao, Song; Kurmoo, Mohamedally

    2011-06-14

    Two structurally different Er-formate frameworks, one NaCl-like [dmenH(2)][Er(HCOO)(4)](2) (1) and the other pillared-layer type [tmenH(2)][Er(HCOO)(4)](2) (2), were obtained when templated by the corresponding protonated N,N'-dimethylethylenediamine (dmenH(2)) and N,N,N',N'-tetramethyl- ethylenediamine (tmenH(2)). The shape and size of the template cations dictate the different coordination geometries of erbium and consequently the framework topologies, though erbium adopts eight coordination in the two compounds. In the NaCl-like structure of 1, erbium is coordinated by eight anti-anti bridging formates in a square antiprism, while in the pillared-layer structure of 2, it is coordinated by six anti-anti bridging formates and one chelating formate in a pentagonal bipyramid. 2 exhibits a structural phase transition around -70 °C which is related to the disorder-order transition of the template cation. Both compounds behave as paramagnets between 2 and 300 K. However, they display field-dependent ac-susceptibilities with complicated field-induced magnetic relaxation processes, and the major slow ones probably results from spin-lattice relaxation.

  13. Nighttime formation of peroxy and hydroxyl radicals during the BERLIOZ campaign: Observations and modeling studies

    NASA Astrophysics Data System (ADS)

    Geyer, Andreas; BäChmann, Kurt; Hofzumahaus, Andreas; Holland, Frank; Konrad, Stefan; Klüpfel, Thomas; PäTz, Hans-Werner; Perner, Dieter; Mihelcic, Djuro; SchäFer, Hans-Jürgen; Volz-Thomas, Andreas; Platt, Ulrich

    2003-02-01

    Traditionally, tropospheric radical chemistry is discussed in terms of the daytime photochemically produced hydroxyl radical (OH). Radicals, however, are also important during nighttime: this is especially true for ozone and the nitrate radical (NO3), which both act as key initiators of the degradation of alkenes such as biogenic monoterpenes. These reactions lead to the formation of peroxy radicals (HO2 and RO2) and hydroxyl radicals at night. We present recent observations of nighttime concentrations of NO3, RO2, HO2, and OH by differential optical absorption spectroscopy (DOAS), matrix isolation electron spin resonance (MIESR), laser-induced fluorescence (LIF), and a chemical amplifier (CA) in the framework of the Berliner Ozonexperiment (BERLIOZ) campaign at Pabstthum, Germany, together with modeling studies of nocturnal radical chemistry. Modeled RO2 mixing ratios reached 40 ppt while the measured ROx level went up to 22 ppt at the same time. Modeled and measured HO2 mixing ratios were up to 6 and 4 ppt, respectively. In the case of OH, a nocturnal concentration of (1.85 ± 0.82) × 105 cm-3 was measured during one night. At this time, the model yielded an OH level of (4.1 ± 0.7) × 105 cm-3. This overestimation by the model could point to a missing nocturnal sink of OH. Nitrate radical reactions with terpenes were found responsible for producing 77% of the RO2 radicals, 53% of the HO2, and 36% of the OH radicals during night. Nighttime ozonolysis formed 12% of the RO2, 47% of the HO2, and 64% of the OH radicals. Another 11% of the RO2 radicals were formed by OH-volatile organic compound (VOC) reactions. A positive linear correlation of RO2 and NO3 was observed and could be reproduced in model calculations originating from the loss of both radicals by reaction with NO and the NO3-initiated RO2 production. The contribution of nighttime OH to the atmosphere's oxidation capacity (oxidation rate of VOCs, CO, and CH4) was found negligible (<0.5%).

  14. Dihydroquercetin (taxifolin) and other flavonoids as inhibitors of free radical formation at key stages of apoptosis.

    PubMed

    Vladimirov, Yu A; Proskurnina, E V; Demin, E M; Matveeva, N S; Lubitskiy, O B; Novikov, A A; Izmailov, D Yu; Osipov, A N; Tikhonov, V P; Kagan, V E

    2009-03-01

    Formation of free radicals in mitochondria plays a key role in the development of apoptosis, which includes formation of superoxide by the respiratory chain, formation of radicals by cytochrome c-cardiolipin complex in the presence of hydrogen peroxide or lipids, and chain lipid peroxidation resulting in cytochrome c release from mitochondria and initiation of the apoptotic cascade. In this work the effect of taxifolin (dihydroquercetin) and some other antioxidants on these three radical-producing reactions was studied. Peroxidase activity of the complex of cytochrome c with dioleyl cardiolipin estimated by chemiluminescence with luminol decreased by 50% with quercetin, taxifolin, rutin, Trolox, and ionol at concentrations 0.7, 0.7, 0.8, 3, and 10 microM, respectively. The lipid radical production detected by coumarin C-525-activated chemiluminescence decreased under the action of rutin and taxifolin in a dose-dependent manner, so that a 50% inhibition of chemiluminescence was observed at the antioxidant concentrations of 3.7 and 10 microM, respectively. Thus, these two radical-producing reactions responsible for apoptosis onset are inhibited by antioxidants at rather low concentrations. Experiments performed on liver slices and mash showed that taxifolin, quercetin, naringenin, and Trolox have low inhibitory effect on the lucigenin-dependent chemiluminescence in the tissue only at concentrations higher than 100 microM.

  15. Formation of stable radicals in catechin/nitrous acid systems: participation of dinitrosocatechin.

    PubMed

    Morina, Filis; Takahama, Umeo; Mojović, Miloš; Popović-Bijelić, Ana; Veljović-Jovanović, Sonja

    2016-03-01

    Catechins are transformed into dinitrosocatechins (diNOcats) and then oxidized to the quinones by salivary nitrite under conditions simulating the stomach. This manuscript deals with formation of stable radicals in the NO group of diNOcat during nitrite-induced oxidation of (+)-catechin and diNOcat at pH 2. We postulated two mechanisms for the stable radical formation; one is nitrous acid-induced oxidation of diNOcat in the A-ring, and the other intermolecular charge transfer from the A-ring of diNOcat and/or diNOcat quinone to the quinone moiety of the B-ring of diNOcat quinone. In addition, an unstable phenoxyl radical, which might be transformed into quinone, was also produced, accompanying the formation of the stable radical on the NO group. Taking the above results into account, we mainly focus on the adverse effects of the radicals and quinone, which may be produced from (+)-catechin in the stomach under the conditions of high salivary nitrite concentrations.

  16. Ion/molecule reactions of 2-chloro- and 2-bromopropene radical cations with methanol and ethanol--FT-ICR spectrometry and DFT calculations

    NASA Astrophysics Data System (ADS)

    Grützmacher, Hans-Friedrich; Büchner, Michael; Zipse, Hendrik

    2005-02-01

    Continuing the studies of ion/molecule reactions of haloalkene radical cations with nucleophiles, the reactions of the radical cations of 2-chloropropene, 1+, and 2-bromopropene. 2+, with methanol and ethanol, respectively, have been investigated by FT-ICR spectrometry and by computational analysis using DFT calculation (BHLYP/6-311 + G(2d,p)//BHLYP/6-31 + G(d) level). Only slow reactions (reaction efficiency <1%) are observed for 1+/methanol and 2+/methanol. Slow proton transfer is the main process for 1+/methanol besides minor addition of methanol to 1+ followed by loss of HCl or Cl. Addition of methanol accompanied by loss of Br is the exclusive process observed for 2+/methanol. In contrast, both 1+ and 2+ react efficiently with ethanol yielding protonated acetaldehyde as the exclusive (1+) or by far dominant (2+) primary reaction product. The computational analysis of these ion/molecule reactions shows that in the case of 1+/methanol and 2+/methanol all processes are either endothermic or blocked by large activation energies. Nonetheless, addition of methanol to the ionized CC double bond of 1+ or 2+ is exothermic, yielding in each case a pair of isomeric [beta]-distonic methoxonium ions. A new reaction mechanism has been found for the HX (X = Cl, Br) elimination from the less stable isomer of the distonic intermediates. Further, an energetically favorable transition state has been detected for hydrogen atom transfer from the [alpha]-CH2 group of alcohol to the halogenoalkene radical cations. These findings lead to a revised mechanism of the oxidation process and provide a plausible explanation for the excessive H/D exchange between 1+ and CD3OH during their slow reaction.

  17. A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

    SciTech Connect

    Solano, Eduardo A.; Mayer, Paul M.

    2015-09-14

    The fragmentation mechanisms of the naphthalene molecular ion to [M–C{sub 4}H{sub 2}]{sup +•}, [M–C{sub 2}H{sub 2}]{sup +•}, [M–H{sub 2}]{sup +•}, and [M–H{sup •}]{sup +} were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)’s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)’s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0–18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Z- and E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H{sub 2} molecule in a two-step fragmentation. H{sup •} loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C{sub 4}H{sub 2}) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%–100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M–C{sub 2}H{sub 2}]{sup +•} structure is the phenylacetylene cation.

  18. A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface.

    PubMed

    Solano, Eduardo A; Mayer, Paul M

    2015-09-14

    The fragmentation mechanisms of the naphthalene molecular ion to [M-C4H2](+•), [M-C2H2](+•), [M-H2](+•), and [M-H(•)](+) were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)'s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)'s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0-18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Z- and E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H2 molecule in a two-step fragmentation. H(•) loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C4H2) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%-100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M-C2H2](+•) structure is the phenylacetylene cation.

  19. A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

    NASA Astrophysics Data System (ADS)

    Solano, Eduardo A.; Mayer, Paul M.

    2015-09-01

    The fragmentation mechanisms of the naphthalene molecular ion to [M-C4H2]+•, [M-C2H2]+•, [M-H2]+•, and [M-H•]+ were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)'s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)'s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0-18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Z- and E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H2 molecule in a two-step fragmentation. H• loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C4H2) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%-100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M-C2H2]+• structure is the phenylacetylene cation.

  20. Hypochlorite-induced damage to nucleosides: formation of chloramines and nitrogen-centered radicals.

    PubMed

    Hawkins, C L; Davies, M J

    2001-08-01

    Stimulated monocytes and neutrophils generate hypochlorite (HOCl) via the release of the enzyme myeloperoxidase and hydrogen peroxide. HOCl is a key bactericidal agent, but can also damage host tissue. As there is a strong link between chronic inflammation and some cancers, we have investigated HOCl damage to DNA bases. We show that reaction of HOCl with the exocyclic -NH(2) groups of cytidine, adenosine, and guanosine, and the ring NH groups of all bases, yields chloramines (RNHCl/RR'NCl). These are the major initial products. Chloramine decay can be accelerated by UV light and metal ions, and these reactions, together with thermal decomposition, give rise to nucleoside-derived nitrogen-centered radicals. Evidence is presented for the rapid addition of pyrimidine-derived nitrogen-centered radicals to another parent molecule to give dimers. Experiments with nucleoside mixtures show that the propensity for radical formation is cytidine > adenosine = guanosine > uridine = thymidine. These data are inconsistent with the selectivity of HOCl attack and the stability of the resulting chloramines, but can be rationalized if chlorine transfer between bases is rapid and yields the most stable chloramine, with such transfer preceding radical formation. Thus, though thymidine is the major initial site of chloramine formation, rapid chlorine atom transfer generates cytidine and adenosine chloramines. These reactions rationalize the preferential formation of chlorinated cytidine and adenosine in DNA.

  1. Photochemical Formation of Hydroxyl Radical in Red-Soil-Polluted Seawater in Okinawa, Japan -Potential Impacts on Marine Organisms

    NASA Astrophysics Data System (ADS)

    Arakaki, T.; Hamdun, A. M.; Okada, K.; Kuroki, Y.; Ikota, H.; Fujimura, H.; Oomori, T.

    2004-12-01

    Development of pineapple farmlands and construction of recreational facilities caused runoff of red soil into coastal ocean (locally termed as red-soil-pollution) in the north of Okinawa Island, Japan. In an attempt to understand the impacts of red soil on oxidizing power of the seawater, we studied formation of hydroxyl radical (OH radical), the most potent oxidant in the environment, in red-soil-polluted seawaters, using 313 nm monochromatic light. Photo-formation rates of OH radical showed a good correlation with dissolved iron concentrations (R = 0.98). The major source of OH radical was found to be the Fenton reaction (a reaction between Fe(II) and HOOH). The un-filtered red-soil-polluted seawater samples exhibited faster OH radical formation rates than the filtered samples, suggesting that iron-bearing red soil particles enhanced formation of OH radical.

  2. Asymmetric catalytic formation of quaternary carbons by iminium ion trapping of radicals

    NASA Astrophysics Data System (ADS)

    Murphy, John J.; Bastida, David; Paria, Suva; Fagnoni, Maurizio; Melchiorre, Paolo

    2016-04-01

    An important goal of modern organic chemistry is to develop new catalytic strategies for enantioselective carbon-carbon bond formation that can be used to generate quaternary stereogenic centres. Whereas considerable advances have been achieved by exploiting polar reactivity, radical transformations have been far less successful. This is despite the fact that open-shell intermediates are intrinsically primed for connecting structurally congested carbons, as their reactivity is only marginally affected by steric factors. Here we show how the combination of photoredox and asymmetric organic catalysis enables enantioselective radical conjugate additions to β,β-disubstituted cyclic enones to obtain quaternary carbon stereocentres with high fidelity. Critical to our success was the design of a chiral organic catalyst, containing a redox-active carbazole moiety, that drives the formation of iminium ions and the stereoselective trapping of photochemically generated carbon-centred radicals by means of an electron-relay mechanism. We demonstrate the generality of this organocatalytic radical-trapping strategy with two sets of open-shell intermediates, formed through unrelated light-triggered pathways from readily available substrates and photoredox catalysts—this method represents the application of iminium ion activation (a successful catalytic strategy for enantioselective polar chemistry) within the realm of radical reactivity.

  3. Oxygen acidity of ring methoxylated 1,1-diarylalkanol radical cations bearing alpha-cyclopropyl groups. The competition between O-neophyl shift and C-cyclopropyl beta-scission in the intermediate 1,1-diarylalkoxyl radicals.

    PubMed

    Bietti, Massimo; Fiorentini, Simone; Pato, Iria Pèrez; Salamone, Michela

    2006-04-14

    A product and time-resolved kinetic study on the reactivity of the radical cations generated from cyclopropyl(4-methoxyphenyl)phenylmethanol (1) and cyclopropyl[bis(4-methoxyphenyl)]methanol (2) has been carried out in aqueous solution. In acidic solution, 1*+ and 2*+ display very low reactivities toward fragmentation, consistent with the presence of groups at Calpha (aryl and cyclopropyl) that after Calpha-Cbeta bond cleavage would produce relatively unstable carbon-centered radicals. In basic solution, 1*+ and 2*+ display oxygen acidity, undergoing -OH-induced deprotonation from the alpha-OH group, leading to the corresponding 1,1-diarylalkoxyl radicals 1r* and 2r*, respectively, as directly observed by time-resolved spectroscopy. The product distributions observed in the reactions of 1*+ and 2*+ under these conditions (cyclopropyl phenyl ketone, cyclopropyl(4-methoxyphenyl) ketone, and 4-methoxybenzophenone from 1*+; cyclopropyl(4-methoxyphenyl) ketone and 4,4'-dimethoxybenzophenone from 2*+) have been rationalized in terms of a water-induced competition between O-neophyl shift and C-cyclopropyl beta-scission in the intermediate 1,1-diarylalkoxyl radicals 1r* and 2r*.

  4. Effects on detection of radical formation in skin due to solar irradiation measured by EPR spectroscopy.

    PubMed

    Albrecht, Stephanie; Ahlberg, Sebastian; Beckers, Ingeborg; Kockott, Dieter; Lademann, Jürgen; Paul, Victoria; Zastrow, Leonhard; Meinke, Martina C

    2016-10-15

    In various research projects, oxidative stress in irradiated skin was investigated by measuring the production of free radical using EPR spectroscopy. However, comparison of the obtained measuring results proved to be difficult as different preparation parameters were used for those measurements. In the present study the influence of the preparation parameters on the detected radical production was methodically investigated. For this purpose, porcine skin was exposed in situ to UV and VIS-NIR radiation, respectively, while being measured in an X band EPR spectrometer. Prior to the measurements, the skin had been treated with the spin trap N-tert-Butyl-α-phenylnitrone (PBN) and the spin marker 3-(Carboxyl)-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (PCA). The two methods were investigated for quantitative comparability, for advantages and disadvantages and for errors potentially affecting the evaluation of the results. A significant influence of the preparation parameters (concentration and amount of substance) on the detected radical formations could be found. This influence had a nonlinear effect on the detected radical production. 120μl of incubated amount for 1M PBN and for PCA at a concentration of 0.6 and 1.5mM were determined to be the optimum parameters. The incubated skin samples were 1cm in diameter and 300μm thick. Between 22 and 37°C the incubation temperature showed no significant influence on the detected radical production. For the first time it could be demonstrated for PCA-incubated skin that the radiation-induced radical production depends exclusively on the irradiation dose, provided the preparation parameters and the spectral region are kept constant. In addition, the radical production in the UVB-UVA and VIS-NIR spectral regions was measured in PCA- and PBN-treated excised porcine skin. It was found that PBN and PCA provide comparable results for the relative quantity and kinetics of radical production.

  5. Generation of free radicals from organic hydroperoxide tumor promoters in isolated mouse keratinocytes. Formation of alkyl and alkoxyl radicals from tert-butyl hydroperoxide and cumene hydroperoxide.

    PubMed

    Taffe, B G; Takahashi, N; Kensler, T W; Mason, R P

    1987-09-05

    The organic hydroperoxides tert-butyl hydroperoxide and cumene hydroperoxide are tumor promoters in the skin of SENCAR mice, and this activity is presumed to be mediated through the activation of the hydroperoxides to free radical species. In this study we have assessed the generation of free radicals from organic hydroperoxides in the target cell (the murine basal keratinocyte) using electron spin resonance. Incubation of primary isolates of keratinocytes from SENCAR mice in the presence of spin traps (5,5-dimethyl-1-pyrroline N-oxide or 2-methyl-2-nitrosopropane) and either tert-butyl hydroperoxide or cumene hydroperoxide resulted in the generation and detection of radical adducts of these spin traps. tert-Butyl alkoxyl and alkyl radical adducts of 5,5-dimethyl-1-pyrroline N-oxide were detected shortly after addition of tert-butyl hydroperoxide, whereas only alkyl radical adducts were observed with cumene hydroperoxide. Spin trapping of the alkyl radicals with 2-methyl-2-nitrosopropane led to the identification of methyl and ethyl radical adducts following both tert-butyl hydroperoxide and cumene hydroperoxide exposures. Prior heating of the cells to 100 degrees C for 30 min prevented radical formation. The radical generating capacity of subcellular fractions of these epidermal cells was examined using 5,5-dimethyl-1-pyrroline N-oxide and cumene hydroperoxide, and this activity was confined to the 105,000 X g supernatant fraction.

  6. Modeling the radical chemistry in an oxidation flow reactor: radical formation and recycling, sensitivities, and the OH exposure estimation equation.

    PubMed

    Li, Rui; Palm, Brett B; Ortega, Amber M; Hlywiak, James; Hu, Weiwei; Peng, Zhe; Day, Douglas A; Knote, Christoph; Brune, William H; de Gouw, Joost A; Jimenez, Jose L

    2015-05-14

    Oxidation flow reactors (OFRs) containing low-pressure mercury (Hg) lamps that emit UV light at both 185 and 254 nm ("OFR185") to generate OH radicals and O3 are used in many areas of atmospheric science and in pollution control devices. The widely used potential aerosol mass (PAM) OFR was designed for studies on the formation and oxidation of secondary organic aerosols (SOA), allowing for a wide range of oxidant exposures and short experiment duration with reduced wall loss effects. Although fundamental photochemical and kinetic data applicable to these reactors are available, the radical chemistry and its sensitivities have not been modeled in detail before; thus, experimental verification of our understanding of this chemistry has been very limited. To better understand the chemistry in the OFR185, a model has been developed to simulate the formation, recycling, and destruction of radicals and to allow the quantification of OH exposure (OHexp) in the reactor and its sensitivities. The model outputs of OHexp were evaluated against laboratory calibration experiments by estimating OHexp from trace gas removal and were shown to agree within a factor of 2. A sensitivity study was performed to characterize the dependence of the OHexp, HO2/OH ratio, and O3 and H2O2 output concentrations on reactor parameters. OHexp is strongly affected by the UV photon flux, absolute humidity, reactor residence time, and the OH reactivity (OHR) of the sampled air, and more weakly by pressure and temperature. OHexp can be strongly suppressed by high OHR, especially under low UV light conditions. A OHexp estimation equation as a function of easily measurable quantities was shown to reproduce model results within 10% (average absolute value of the relative errors) over the whole operating range of the reactor. OHexp from the estimation equation was compared with measurements in several field campaigns and shows agreement within a factor of 3. The improved understanding of the OFR185 and

  7. Free radical mediated formation of 3-monochloropropanediol (3-MCPD) fatty acid diesters.

    PubMed

    Zhang, Xiaowei; Gao, Boyan; Qin, Fang; Shi, Haiming; Jiang, Yuangrong; Xu, Xuebing; Yu, Liangli Lucy

    2013-03-13

    The present study was conducted to test the hypothesis that a free radical was formed and mediated the formation of 3-monochloropropanediol (3-MCPD) fatty acid diesters, a group of food contaminants, from diacylglycerols at high temperature under a low-moisture condition for the first time. The presence of free radicals in a vegetable oil kept at 120 °C for 20 min was demonstrated using an electron spin resonance (ESR) spectroscopy examination with 5,5-dimethylpyrroline-N-oxide (DMPO) as the spin trap agent. ESR investigation also showed an association between thermal treatment degree and the concentration of free radicals. A Fourier transform infrared spectroscopy (FT-IR) analysis of sn-1,2-stearoylglycerol (DSG) at 25 and 120 °C suggested the possible involvement of an ester carbonyl group in forming 3-MCPD diesters. On the basis of these results, a novel free radical mediated chemical mechanism was proposed for 3-MCPD diester formation. Furthermore, a quadrupole-time of flight (Q-TOF) MS/MS investigation was performed and detected the DMPO adducts with the cyclic acyloxonium free radical (CAFR) and its product MS ions, proving the presence of CAFR. Furthermore, the free radical mechanism was validated by the formation of 3-MCPD diesters through reacting DSG with a number of organic and inorganic chlorine sources including chlorine gas at 120 and 240 °C. The findings of this study might lead to the improvement of oil and food processing conditions to reduce the level of 3-MCPD diesters in foods and enhance food safety.

  8. Radical formation at the gallium nitride nanowire-electrolyte interface by photoactivated charge transfer.

    PubMed

    Philipps, J M; Müntze, G M; Hille, P; Wallys, J; Schörmann, J; Teubert, J; Hofmann, D M; Eickhoff, M

    2013-08-16

    We investigated the transfer of photogenerated charge carriers from GaN nanowires into a surrounding electrolyte by electron paramagnetic resonance (EPR) and fluorescence spectroscopy. Using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap we find that the formation of hydroxyl radicals dominates in acidic, neutral and moderately basic environments, while in an electrolyte with a pH of 13.5 the superoxide formation becomes detectable. We explain the two processes considering the redox potentials for radical formation in the electrolyte as well as the positions of the conduction and valence bands. The role of surface band bending and surface states in the semiconductor is discussed.

  9. Photoinduced formation of peroxyl radicals in aqueous solutions of nucleobase derivatives at 77 K

    NASA Astrophysics Data System (ADS)

    Lozinova, T. A.; Lander, A. V.

    2015-05-01

    It is shown that the formation of free radicals photoinduced by near-UV irradiation at 77 K in aqueous solutions of guanosine-5'-monophosphate (GMP), adenosine (Ado), adenine (A), and thymine (T) containing NaCl (0.1 M) is intensified in the presence of O2. Signals of peroxyl radicals O{2/-·} and HO{2/·} are indicated in analyzing EPR spectra, and their overall yield is 20-40% of the total amount of the formed paramagnetic products. It is found that the concentration ratio of O{2/-·} and HO{2/·} radicals depends not only on pH of the solutions before freezing but also on the duration of irradiation and method of freezing the samples. Plausible mechanisms of the processes are discussed.

  10. Energetics of Radical Formation in Eumelanin Building Blocks: Implications for Understanding Photoprotection Mechanisms in Eumelanin.

    PubMed

    Agapito, Filipe; Cabral, Benedito J Costa

    2016-12-22

    The supramolecular structure of melanin pigments is characterized by a high concentration of radical species. Therefore, the energetics of the radical formation in melanin building blocks is key for understanding the structure and the electronic properties of the pigments at the molecular level. Nevertheless, the radical energetics of even the simplest melanin building blocks are largely unknown. In order to address this fundamental issue, the bond dissociation enthalpies (BDEs) for the melanin monomers 5,6-dihydroxy-1H-indole-2-carboxylic acid (DHICA), 1H-indole-5,6-diol (DHI), and 1H-indole-5,6-dione (IQ) were determined through high-accuracy ab initio quantum chemistry methods. Our results provide strong evidence of the importance on BDEs for explaining the experimentally observed dependence of the antioxidant properties of eumelanin pigments on the DHICA/DHI ratio, and the role that these two species play on the photoprotection mechanism.

  11. Studies of radiation-produced radicals and radical ions. Progress report, September 1, 1990--October 15, 1991

    SciTech Connect

    Williams, T.F.

    1991-12-31

    The radiolytic oxidation of anti-5-methylbicyclo[2.1.0]pentane gives the 1-methylcyclopentene radical cation as the sole rearrangement product H migration whereas oxidation of its syn isomer results in the highly selective formation of the 3-methylcyclopentene radical cation by methyl group migration. Since exactly the same stereoselectivity of olefin formation was observed in corresponding PET (photosensitized electron transfer) studies in the liquid phase, it is concluded that the rearrangement in this case also occurs through the intermediacy of radical cations. Clearly, the radical cation rearrangement must occur very rapidly (10{sup {minus}8}--10{sup {minus}9}s) under liquid-phase conditions at room temperature to compete with back electron transfer, and therefore the hydrogen (or methyl) migration is a fast process under these conditions. An intramolecular cycloaddition reaction was demonstrated in the radical cation rearrangement of 4-vinylcyclohexene to bicyclo[3.2.1]oct-2-ene. ESR studies show that the radiolytic oxidation of quadricyclane in Freon matrices under conditions of high substrate dilution leads to the bicyclo[3.2.0]hepta-2,6-diene radical cation as well as the previously reported norbornadiene radical cation, the former species predominating at sufficiently low concentrations.

  12. Acid-base equilibria involved in secondary reactions following the 4-carboxybenzophenone sensitized photooxidation of methionylglycine in aqueous solution. Spectral and time resolution of the decaying (S...N){sup +} radical cation

    SciTech Connect

    Hug, G.L.; Marciniak, B. |; Bobrowski, K. ||

    1996-09-05

    A radical cation with an intramolecular sulfur-nitrogen bond was formed in the photoinitiated transfer of an electron from the sulfur atom of the dipeptide Met-Gly to 4-carboxybenzophenone in its triplet state. The sulfur-nitrogen coupling involved two-center, three-electron bonds. The kinetics of the reactions of these radical cations, which were initiated by a laser flash, were followed over time. The principal method of implementing the spectral resolutions was accomplished through a multiple linear regression technique. This spectral analysis was repeated for numerous time windows during the lifetime of the transients` decays. The resulting concentrations of the transients were consistent with an independent factor analysis. It was found that the decay of the radical cations was multiexponential and that the decay varied with pH. A simplified reaction scheme was proposed whereby the absorbing radical cations can alternatively decay by an irreversible channel or react reversibly with OH{sup -}. Rate constants for the three elementary reactions of this scheme were determined from an analysis of the decay of the concentration of the radical cations. In addition, the equilibrium constant for the reversible reaction was determined by two separate procedures. 35 refs., 7 figs., 2 tabs.

  13. Aluminium substitution in iron(II-III)-layered double hydroxides: Formation and cationic order

    SciTech Connect

    Ruby, Christian Abdelmoula, Mustapha; Aissa, Rabha; Medjahdi, Ghouti; Brunelli, Michela; Francois, Michel

    2008-09-15

    The formation and the modifications of the structural properties of an aluminium-substituted iron(II-III)-layered double hydroxide (LDH) of formula Fe{sub 4}{sup II}Fe{sub (2-6y)}{sup III}Al{sub 6y}{sup III} (OH){sub 12} SO{sub 4}, 8H{sub 2}O are followed by pH titration curves, Moessbauer spectroscopy and high-resolution X-ray powder diffraction using synchrotron radiation. Rietveld refinements allow to build a structural model for hydroxysulphate green rust, GR(SO{sub 4}{sup 2-}), i.e. y=0, in which a bilayer of sulphate anions points to the Fe{sup 3+} species. A cationic order is proposed to occur in both GR(SO{sub 4}{sup 2-}) and aluminium-substituted hydroxysulphate green rust when y<0.08. Variation of the cell parameters and a sharp decrease in average crystal size and anisotropy are detected for an aluminium content as low as y=0.01. The formation of Al-GR(SO{sub 4}{sup 2-}) is preceded by the successive precipitation of Fe{sup III} and Al{sup III} (oxy)hydroxides. Adsorption of more soluble Al{sup III} species onto the initially formed ferric oxyhydroxide may be responsible for this slowdown of crystal growth. Therefore, the insertion of low aluminium amount (y{approx}0.01) could be an interesting way for increasing the surface reactivity of iron(II-III) LDH that maintains constant the quantity of the reactive Fe{sup II} species of the material. - Graphical abstract: (a) Crystallographical structure of sulphated green rust: SO{sub 4}{sup 2-} point to the Fe{sup 3+} cations (red) that form an ordered array with the Fe{sup 2+} cations (green). (b) Width and asymmetry of the synchrotron XRD peaks increase rapidly when some Al{sup 3+} species substitute the Fe{sup 3+} cations; z is molar ratio Al{sup 3+}/Fe{sup 3+}.

  14. Some polyphenols inhibit the formation of pentyl radical and octanoic acid radical in the reaction mixture of linoleic acid hydroperoxide with ferrous ions.

    PubMed Central

    Iwahashi, H

    2000-01-01

    Effects of some polyphenols and their related compounds (chlorogenic acid, caffeic acid, quinic acid, ferulic acid, gallic acid, D-(+)-catechin, D-(-)-catechin, 4-hydroxy-3-methoxybenzoic acid, salicylic acid, L-dopa, dopamine, L-adrenaline, L-noradrenaline, o-dihydroxybenzene, m-dihydroxybenzene, and p-dihydroxybenzene) on the formation of 13-hydroperoxide octadecadienoic (13-HPODE) acid-derived radicals (pentyl radical and octanoic acid radical) were examined. The ESR spin trapping showed that chlorogenic acid, caffeic acid, gallic acid, D-(+)-catechin, D-(-)-catechin, L-dopa, dopamine, L-adrenaline, L-noradrenaline, and o-dihydroxybenzene inhibited the overall formation of 13-HPODE acid-derived radicals in the reaction mixture of 13-HPODE with ferrous ions. The ESR peak heights of alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone (4-POBN)/13-HPODE-derived radical adducts decreased to 46+/-4% (chlorogenic acid), 54+/-2% (caffeic acid), 49+/-2% (gallic acid), 55+/-1% [D-(+)-catechin], 60+/-3% [D-(-)-catechin], 42+/-1% (L-dopa), 30+/-2% (dopamine), 49+/-2% (L-adrenaline), 24+/-2% (L-noradrenaline), and 54+/-5% (o-dihydroxybenzene) of the control, respectively. The high performance liquid chromatography-electron spin resonance (HPLC-ESR) and high performance liquid chromatography-electron spin resonance-mass spectrometries (HPLC-ESR-MS) showed that caffeic acid inhibited the formation of octanoic acid radical and pentyl radical to 42+/-2% and 52+/-7% of the control, respectively. On the other hand, the polyphenols and their related compounds had few inhibitory effects on the radical formation in the presence of EDTA. Visible absorbance measurement revealed that all the polyphenols exhibiting the inhibitory effect chelate ferrous ions. Above results indicated that the chelation of ferrous ion is essential to the inhibitory effects of the polyphenols. PMID:10677343

  15. Arylperoxyl radicals. Formation, absorption spectra, and reactivity in aqueous alcohol solutions

    SciTech Connect

    Alfassi, Z.B.; Khaikin, G.I.; Neta, P. )

    1995-01-05

    Aryl radicals (phenyl, 4-biphenylyl, 2-naphthyl, 1-naphthyl, and 9-phenanthryl) were produced by the reaction of the corresponding aryl bromide with solvated electrons and reacted rapidly with oxygen to produce the arylperoxyl radicals. These radicals exhibit optical absorptions in the visible range, with [lambda][sub max] at 470, 550, 575, 650, and 700 nm, respectively. Arylperoxyl radicals react with 2,2[prime]-azinobis(3-ethylbenzothiazoiine-6-sulfonate ion) (ABTS), chlorpromazine, and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox C) by one-electron oxidation. The rate constants k for these reactions, determined from the rate of formation of the one-electron oxidation products as a function of substrate concentration, vary between 4 [times] 10[sup 6] and 2 [times] 10[sup 9] L mol[sup [minus]1] s[sup [minus]1] and increase in the order phenyl-, 4-biphenyl-, 2-naphthyl-, 1-naphthyl-, and 9-phenanthrylperoxyl, the same order as the absorption peaks of these radicals. Good correlation was found between log k and the energy of the absorption peak. 16 refs., 2 figs., 2 tabs.

  16. Effect of electrolytes and temperature on dications and radical cations of carotenoids: Electrochemical, optical absorption, and high-performance liquid chromatography studies

    SciTech Connect

    He, Z.; Kispert, L.D.

    1999-11-25

    The effect of supporting electrolytes and temperature on the behavior of dications and radical cations of carotenoids is studied. Cyclic voltammograms (CVs) of canthaxanthin (I) at 23 and {minus}25 C show that Car{sup sm{underscore}bullet+} of I has similar stability during the time of the CV scan, when using tetrabutylammonium perchlorate (TBAPC), tetrabutylammonium tetrafluoroborate (TBATFB), or tetrabutylammonium hexafluorophosphate (TBAHFP) as supporting electrolyte. However, the stability of Car{sup 2+} decreases when using TBAPC or TBATFB; {beta}-carotene (II) shows similar behavior. The CV of I at {minus}25 C shows a strong cathodic wave (wave 6) near {minus}0.15 V (vs Ag) with an intensity about half that of the neutral oxidation wave when TBAPC or TBATFB is the supporting electrolyte. When TBAHFP is used, wave 6 (ca. {minus}0.05 V vs Ag) is ca. 8 times weaker than when TBAPC or TBATFB is used. This wave results from the reduction of a species that may be a decay product of Car{sup 2+} of I. Results show that these electrolytes commonly used in electrochemical studies may affect the studied systems to different extents. In simultaneous bulk electrolysis (BE) and optical absorption spectroscopic measurements, the absorption band of Car{sup 2+} of I in the presence of 0.1 M TBAHFP can be observed by lowering the BE temperature to {minus}20 C. In the presence of 0.1 M TBAPC or TBATFB, this band is not observed, even at {minus}50 C. Isomerization of neutral I (as shown by HPLC and its blue absorption band shift) is observed only when the Car{sup 2+} absorption band is absent during BE. This observation, along with an increase of the neutral absorption band after stopping BE, suggests that the equilibrium Car + Car{sup 2+} {r{underscore}equilibrium} 2Car{sup {sm{underscore}bullet}+} is shifted to the left because Car{sup 2+} decays more quickly than Car{sup {sm{underscore}bullet}+} in the presence of electrolyte and this is a major path for formation of cis

  17. Formation of cationic [RP5Cl](+)-cages via insertion of [RPCl](+)-cations into a P-P bond of the P4 tetrahedron.

    PubMed

    Holthausen, Michael H; Feldmann, Kai-Oliver; Schulz, Stephen; Hepp, Alexander; Weigand, Jan J

    2012-03-19

    Fluorobenzene solutions of RPCl(2) and a Lewis acid such as ECl(3) (E = Al, Ga) in a 1:1 ratio are used as reactive sources of chlorophosphenium cations [RPCl](+), which insert into P-P bonds of dissolved P(4). This general protocol represents a powerful strategy for the synthesis of new cationic chloro-substituted organophosphorus [RP(5)Cl](+)-cages as illustrated by the isolation of several monocations (21a-g(+)) in good to excellent yields. For singular reaction two possible reaction mechanisms are proposed on the basis of quantum chemical calculations. The intriguing NMR spectra and structures of the obtained cationic [RP(5)Cl](+)-cages are discussed. Furthermore, the reactions of dichlorophosphanes and the Lewis acid GaCl(3) in various stoichiometries are investigated to obtain a deeper understanding of the species involved in these reactions. The formation of intermediates such as RPCl(2)·GaCl(3) (14) adducts, dichlorophosphanylchlorophosphonium cations [RPCl(2)-RPCl](+) (16(+)) and [RPCl(2)-RPCl-GaCl(3)](+) (17(+)) in reaction mixtures of RPCl(2) and GaCl(3) in fluorobenzene strongly depends on the basicity of the dichlorophosphane RPCl(2) (R = tBu, Cy, iPr, Et, Me, Ph, C(6)F(5)) and the reaction stoichiometry.

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

    PubMed

    Comandini, A; Malewicki, T; Brezinsky, K

    2012-03-15

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

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

    PubMed

    Sinha, Sourab; Raj, Abhijeet

    2016-03-21

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

  20. One-electron oxidation of 2-(4-methoxyphenyl)-2-methylpropanoic and 1-(4-methoxyphenyl)cyclopropanecarboxylic acids in aqueous solution. the involvement of radical cations and the influence of structural effects and pH on the side-chain fragmentation reactivity.

    PubMed

    Bietti, Massimo; Capone, Alberto

    2008-01-18

    A product and time-resolved kinetic study on the one-electron oxidation of 2-(4-methoxyphenyl)-2-methylpropanoic acid (2), 1-(4-methoxyphenyl)cyclopropanecarboxylic acid (3), and of the corresponding methyl esters (substrates 4 and 5, respectively) has been carried out in aqueous solution. With 2, no direct evidence for the formation of an intermediate radical cation 2*+ but only of the decarboxylated 4-methoxycumyl radical has been obtained, indicating either that 2*+ is not formed or that its decarboxylation is too fast to allow detection under the experimental conditions employed (k > 1 x 10(7) s(-1)). With 3, oxidation leads to the formation of the corresponding radical cation 3*+ or radical zwitterion -3*+ depending on pH. At pH 1.0 and 6.7, 3*+ and -3*+ have been observed to undergo decarboxylation as the exclusive side-chain fragmentation pathway with rate constants k = 4.6 x 10(3) and 2.3 x 10(4) s(-1), respectively. With methyl esters 4 and 5, direct evidence for the formation of the corresponding radical cations 4*+ and 5*+ has been obtained. Both radical cations have been observed to display a very low reactivity and an upper limit for their decay rate constants has been determined as k < 10(3) s(-1). Comparison between the one-electron oxidation reactions of 2 and 3 shows that the replacement of the C(CH3)2 moiety with a cyclopropyl group determines a decrease in decarboxylation rate constant of more than 3 orders of magnitude. This large difference in reactivity has been qualitatively explained in terms of three main contributions: substrate oxidation potential, stability of the carbon-centered radical formed after decarboxylation, and stereoelectronic effects. In basic solution, -3*+ and 5*+ have been observed to react with -OH in a process that is assigned to the -OH-induced ring-opening of the cyclopropane ring, and the corresponding second-order rate constants (k-OH) have been obtained. With -3*+, competition between decarboxylation and -OH

  1. Histidinyl radical formation in the self-peroxidation reaction of bovine copper-zinc superoxide dismutase.

    PubMed

    Gunther, Michael R; Peters, J Andrew; Sivaneri, Meena K

    2002-03-15

    In the absence of suitable oxidizable substrates, the peroxidase reaction of copper-zinc superoxide dismutase (SOD) oxidizes SOD itself, ultimately resulting in its inactivation. A SOD-centered free radical adduct of 2-methyl-2-nitrosopropane (MNP) was detected upon incubation of SOD with the spin trap and a hydroperoxide (either H(2)O(2) or peracetic acid). Proteolysis by Pronase converted the anisotropic electron paramagnetic resonance (EPR) spectrum of MNP/(center dot)SOD to a nearly isotropic spectrum with resolved hyperfine couplings to several atoms with non-zero nuclear spin. Authentic histidinyl radical (from histidine + HO(center dot)) formed a MNP adduct with a very similar EPR spectrum to that of the Pronase-treated MNP/(center dot)SOD, suggesting that the latter was centered on a histidine residue. An additional hyperfine coupling was detected when histidine specifically (13)C-labeled at C-2 of the imidazole ring was used, providing evidence for trapping at that atom. All of the experimental spectra were convincingly simulated assuming hyperfine couplings to 2 nearly equivalent nitrogen atoms and 2 different protons, also consistent with trapping at C-2 of the imidazole ring. Free histidinyl radical consumed oxygen, implying peroxyl radical formation. MNP-inhibitable oxygen consumption was also observed when cuprous SOD but not cupric SOD was added to a H(2)O(2) solution. Formation of 2-oxohistidine, the stable product of the SOD-hydroperoxide reaction, required oxygen and was inhibited by MNP. These results support formation of a transient SOD-peroxyl radical.

  2. Aqueous SOA formation from radical oligomerization of methyl vinyl ketone (MVK) and methacrolein (MACR)

    NASA Astrophysics Data System (ADS)

    Renard, P.; Siekmann, F.; Ravier, S.; Temime-Roussel, B.; Clément, J.; Ervens, B.; Monod, A.

    2013-12-01

    It is now accepted that one of the important pathways of secondary organic aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the chemical mechanisms leading to macromolecules are still not well understood. It was recently shown that oligomer production by OH radical oxidation in the aerosol aqueous phase from α-dicarbonyl precursors, such as methylglyoxal and glyoxal, is irreversible and fast. We have investigated the aqueous phase photooxidation of MACR and MVK, which are biogenic organic compounds derived from isoprene. Aqueous phase photooxidation of MVK and MACR was investigated in a photoreactor using photolysis of H2O2 as OH radical source. Electrospray high resolution mass spectrometry analysis of the solutions brought clear evidence for the formation of oligomer systems having a mass range of up to 1800 Da within less than 15 minutes of reaction. Highest oligomer formation rates were obtained under conditions of low dissolved oxygen, highest temperature (T = 298 K) and highest precursor initial concentrations ([MVK]0 = 20 mM). A radical mechanism of oligomerization is proposed to explain the formation of the high molecular weight products. Furthermore, we quantified the total amount of carbon present in oligomers. Kinetic parameters of the proposed oligomerization mechanism are constrained by means of a box model that is able to reproduce the temporal evolution of intermediates and products as observed in the laboratory experiments. Additional model simulations for atmospherically-relevant conditions will be presented that show the extent to which these radical processes contribute to SOA formation in the atmospheric multiphase system as compared to other aqueous phase as well as traditional SOA sources. MVK time profile (as measured by UV Spectroscopy) and mass spectra (obtained using UPLC-ESI-MS for the retention time range 0-5 min in the positive mode) at 5, 10 and 50 min of reaction (MVK 20 mM, 25° C, under

  3. Kinetics and product branching fractions of reactions between a cation and a radical: Ar(+) + CH3 and O2(+) + CH3.

    PubMed

    Sawyer, Jordan C; Shuman, Nicholas S; Wiens, Justin P; Viggiano, Albert A

    2015-02-12

    A novel technique is described for the measurement of rate constants and product branching fractions of thermal reactions between cation and radical species. The technique is a variant of the variable electron and neutral density attachment mass spectrometry (VENDAMS) method, employing a flowing afterglow-Langmuir probe apparatus. A radical species is produced in situ via dissociative electron attachment to a neutral precursor; this allows for a quantitative derivation of the radical concentration and, as a result, a quantitative determination of rate constants. The technique is applied to the reactions of Ar(+) and O2(+) with CH3 at 300 K. The Ar(+) + CH3 reaction proceeds near the collisional rate constant of 1.1 × 10(-9) cm(3) s(-1) and has three product channels: → CH3(+) + Ar (k = 5 ± 2 × 10(-10) cm(3) s(-1)), → CH2(+) + H + Ar (k = 7 ± 2 × 10(-10) cm(3) s(-1)), → CH(+) + H2 + Ar (k = 5 ± 3 × 10(-11) cm(3) s(-1)). The O2(+) + CH3 reaction is also efficient, with direct charge transfer yielding CH3(+) as the primary product channel. Several results needed to support these measurements are reported, including the kinetics of Ar(+) and O2(+) with CH3I, electron attachment to CH3I, and mutual neutralization of CH3(+) and CH2(+) with I(-).

  4. Microsolvated and chelated butylzinc cations: formation, relative stability, and unimolecular gas-phase chemistry.

    PubMed

    Fleckenstein, Julia E; Koszinowski, Konrad

    2009-11-23

    Solutions of butylzinc iodide in tetrahydrofuran, acetonitrile, and N,N-dimethylformamide were analyzed by electrospray ionization mass spectrometry. In all cases, microsolvated butylzinc cations [ZnBu(solvent)(n)](+), n=1-3, were detected. The parallel observation of the butylzincate anion [ZnBuI(2)](-) suggests that these ions result from disproportionation of neutral butylzinc iodide in solution. In the presence of simple bidentate ligands (1,2-dimethoxyethane, N,N-dimethyl-2-methoxyethylamine, and N,N,N',N'-tetramethylethylenediamine), chelate complexes of the type [ZnBu(ligand)](+) form quite readily. The relative stabilities of these complexes were probed by competition experiments and analysis of their unimolecular gas-phase reactivity. Fragmentation of mass-selected [ZnBu(ligand)](+) leads to the elimination of butene and formation of [ZnH(ligand)](+). In marked contrast, the microsolvated cations [ZnBu(solvent)(n)](+) lose the attached solvent molecules upon gas-phase fragmentation to produce bare [ZnBu](+), which subsequently dissociates into [C(4)H(9)](+) and Zn. This difference in reactivity resembles the situation in organozinc solution chemistry, in which chelating ligands are needed to activate dialkylzinc compounds for the nucleophilic addition to aldehydes.

  5. Immunolocalization of hypochlorite-induced, catalase-bound free radical formation in mouse hepatocytes

    PubMed Central

    Bonini, Marcelo G.; Siraki, Arno G.; Atanassov, Boyko S.; Mason., Ronald P.

    2007-01-01

    The establishment of oxidants as mediators of signal transduction has renewed the interest of investigators in oxidant production and metabolism. In particular, H2O2 has been demonstrated to play pivotal roles in mediating cell differentiation, proliferation and death. Intracellular concentrations of H2O2 are modulated by its rate of production and its rate of decomposition by catalase and peroxidases. In inflammation and infection some of the H2O2 is converted to hypochlorous acid, a key mediator of the host immune response against pathogens. In vivo HOCl production is mediated by myeloperoxidase, which uses excess H2O2 to oxidize Cl−. Mashino and Fridovich (1988) observed that a high excess of HOCl over catalase inactivated the enzyme by mechanisms that remain unclear. The potential relevance of this as an alternative mechanism for catalase activity control and its potential impact on H2O2-mediated signaling and HOCl-production compelled us to explore in depth the HOCl-mediated catalase inactivation pathways. Here, we demonstrate that HOCl induces formation of catalase protein radicals and carbonyls, which are temporally correlated with catalase aggregation. Hypochlorite-induced catalase aggregation and free radical formation that paralleled the enzyme loss of function in vitro were also detected in mouse hepatocytes treated with the oxidant. Interestingly, the novel immunospin-trapping technique was applied to image radical production in the cells. Indeed, in HOCl-treated hepatocytes, catalase and protein-DMPO nitrone adducts were colocalized in the cells’ peroxisomes. In contrast, when hepatocytes from catalase-knockout mice were treated with hypochlorous acid, there was extensive production of free radicals in the plasma membrane. Because free radicals are short-lived species with fundamental roles in biology, the possibility of their detection and localization to cell compartments is expected to open new and stimulating research venues in the interface of

  6. Photochemical formation and chemistry of long-lived adamantylidene-quinone methides and 2-adamantyl cations.

    PubMed

    Basarić, Nikola; Zabcić, Ivana; Mlinarić-Majerski, Kata; Wan, Peter

    2010-01-01

    Hydroxymethylphenols strategically substituted with the 2-hydroxy-2-adamantyl moiety, AdPh 8-10, were synthesized, and their photochemical reactivity was investigated. On excitation to the singlet excited state, AdPh 8 undergoes intramolecular proton transfer coupled with a loss of H(2)O giving quinone methide 8QM. The presence of 8QM has been detected by laser flash photolysis (CH(3)CN-H(2)O 1:1, tau = 0.55 s) and UV-vis spectroscopy. Singlet excited states of AdPh 9 and 10 in the presence of H(2)O dehydrate giving 9QM and 10QM. Photochemically formed QMs are trapped by nucleophiles giving the addition products (e.g., Phi for methanolysis of 8 is 0.55). In addition, the zwitterionic 9QM undergoes an unexpected rearrangement involving transformation of the 2-phenyl-2-adamantyl cation into the 4-phenyl-2-adamantyl cation (Phi approximately 0.03). An analogous rearrangement was observed with methoxy derivatives 9a and 10a. Zwitterionic 9QM was characterized by LFP in 2,2,2-trifluoroethanol (tau = 1 mus). In TFE, in the ground state, AdPh 10 is in equilibrium with 10QM, which allowed for recording the (1)H and (13)C NMR spectra of the QM. Introduction of the adamantyl substituent into the o-hydroxymethylphenol moiety increased the quantum yield of the associated QM formation by up to 3-fold and significantly prolonged their lifetimes. Furthermore, adamantyl substituent made the study of the alkyl-substituted quinone methides easier by LFP by prolonging their lifetimes and increasing the quantum yields of formation.

  7. Photochemical formation of hydroxyl radical in red-soil-polluted seawater - effects of dissolved organic compounds

    NASA Astrophysics Data System (ADS)

    Uehara, M.; Arakaki, T.

    2006-12-01

    Development of pineapple farmlands and construction of recreational facilities caused runoff of red soil into the coastal ocean (locally termed as red soil pollution) in the north of Okinawa Island, Japan. Red soil is acidic and contains a few percent of iron oxide. We were interested in the formation of hydroxyl radical (·OH), the most potent oxidant in the environment, from the photo-Fenton reaction (reaction between Fe(II) and HOOH) in red-soil-polluted seawater. Various artificial seawater solutions were prepared by adding red soil, HOOH, and/or humic acid to clean seawater, and were used for photochemical experiments. Commercially available humic acid was used to represent natural organic compounds. All the solutions were filtered through 0.45 micron filter before conducting photochemical experiments. Comparisons among the solutions indicated that dissolved chemicals from the red-soil only slightly increased the OH radical photoformation. Photoformation rates of OH radicals of the HOOH + red soil solutions were similar to the calculated rates from direct photolysis of HOOH. Furthermore, addition of humic acid to the HOOH + red soil solutions did not significantly enhance the photo-Fenton reaction, suggesting that Fe(II), even if it had been formed, did not react with HOOH to form OH radicals at detectable level in seawater.

  8. The mechanism of CO2- radical formation in biological and synthetic apatites.

    PubMed

    Rudko, V V; Vorona, I P; Baran, N P; Ishchenko, S S; Zatovsky, I V; Chumakova, L S

    2010-02-01

    Biological apatites (tooth enamel, bone) and their synthetic analogues were exposed to gamma rays, UV light, or thermal treatment and studied by electron paramagnetic resonance (EPR). The thermal generation of CO2- radicals in synthetic apatite was observed for the first time. It was shown that the experimental EPR spectra of all of the above-mentioned materials are caused by the contribution of two types of CO2- radicals: axial and orthorhombic. The ratio of their concentrations depends on the characteristic energy of the external influence (i.e., the energy of quantum for radiation or kT for thermal treatment) and also on the quality of the initial material (defectiveness). Based on the analysis of EPR spectra recorded immediately after gamma-irradiation, the authors conclude that the main short-lived radical in bioapatites is CO3(3)- . The unified mechanism of CO2- radical formation in hydroxyapatites at different external influences is proposed; the main stages of transformation are CO3(2)- + e --> CO3(3)- --> CO2-, where the electron (e) originates from the ionization of impurities by radiation/temperature.

  9. A manganese(V)-oxo π-cation radical complex: influence of one-electron oxidation on oxygen-atom transfer.

    PubMed

    Prokop, Katharine A; Neu, Heather M; de Visser, Sam P; Goldberg, David P

    2011-10-12

    One-electron oxidation of Mn(V)-oxo corrolazine 2 affords 2(+), the first example of a Mn(V)(O) π-cation radical porphyrinoid complex, which was characterized by UV-vis, EPR, LDI-MS, and DFT methods. Access to 2 and 2(+) allowed for a direct comparison of their reactivities in oxygen-atom transfer (OAT) reactions. Both complexes are capable of OAT to PPh(3) and RSR substrates, and 2(+) was found to be a more potent oxidant than 2. Analysis of rate constants and activation parameters, together with DFT calculations, points to a concerted OAT mechanism for 2(+) and 2 and indicates that the greater electrophilicity of 2(+) likely plays a dominant role in enhancing its reactivity. These results are relevant to comparisons between Compound I and Compound II in heme enzymes.

  10. An electron spin resonance investigation of the structure and formation of sulfinyl radicals: Reaction of peroxyl radicals with thiols

    SciTech Connect

    Swarts, S.G.; Becker, D.; DeBolt, S.; Sevilla, M.D. )

    1989-01-12

    In this work we present an electron spin resonance investigation of the irradiation of the alkyl mercaptans methyl, n-butyl, and tert-butyl mercaptan and the radioprotective thiols cysteamine and dithiothreitol in a number of aqueous and organic matrices in the present of oxygen. Matrix peroxyl radicals (ROO*) are formed after the irradiation of organic matrices in the presence of oxygen at 77 K. Upon annealing, these react with added thiols to form sulfinyl radicals (RSO*). Evidence for a thiol peroxyl radical (RSOO*) intermediate is found. Hyperfine couplings and g values are reported for the sulfinyl radicals formed from the five thiols investigated. The incorporation of {sup 17}O-labeled oxygen into the RSO* radical confirms that molecular oxygen is the source of the oxygen atom in the radical. The isotropic and parallel anisotropic {sup 17}O couplings indicate slightly less than 0.5 spin density on the oxygen. The couplings and spin densities are compared to those predicted from ab inito molecular orbital calculations for CH{sub 3}SO*. Calculations for the sulfur-peroxyl intermediate, CH{sub 3}SOO*, predict that it will have similar ESR parameters as those predicted for the carbon-centered peroxyl radical, CH{sub 3}OO*.

  11. Mitigation of 3-Monochloro-1,2-propanediol Ester Formation by Radical Scavengers.

    PubMed

    Zhang, Hai; Jin, Pengwei; Zhang, Min; Cheong, Ling-Zhi; Hu, Peng; Zhao, Yue; Yu, Liangli; Wang, Yong; Jiang, Yuanrong; Xu, Xuebing

    2016-07-27

    The present study investigated the possible mechanism of free radical scavengers on mitigation of 3-monochloro-1,2-propanediol (3-MCPD) fatty acid ester formation in vegetable oils. The electron spin resonance investigation showed that the concentration of free radicals could be clearly decreased in 1,2-distearoyl-sn-glycerol (DSG) samples by all four antioxidants (l-ascorbyl palmitate, α-tocopherol, lipophilic tea polyphenols, and rosemary extract) at 120 °C for 20 min under a N2 atmosphere. Moreover, the rosemary extract exhibited the highest inhibition efficiency. The Fourier transform infrared spectroscopy examination of DSG with α-tocopherol at 25 and 120 °C revealed that α-tocopherol could prevent the involvement of an ester carbonyl group of DSG in forming the cyclic acyloxonium free radical intermediate. Furthermore, the ultraperformance liquid chromatography-quadrupole-time-of-flight mass spectrometry analysis showed that α-tocopherol could suppress the formation of 3-MCPD di- and monoesters. Finally, the four antioxidants could decrease 3-MCPD esters in the palm oil during deodorization. Particularly, the rosemary extract also showed the highest efficiency in 3-MCPD ester mitigation.

  12. UVA-induced phenoxyl radical formation: A new cytotoxic principle in photodynamic therapy.

    PubMed

    Volkmar, Christine M; Vukadinović-Walter, Britta; Opländer, Christian; Bozkurt, Ahmet; Korth, Hans-Gert; Kirsch, Michael; Mahotka, Csaba; Pallua, Norbert; Suschek, Christoph V

    2010-09-15

    Psoralens are regularly used in therapy in combination with ultraviolet A light irradiation (PUVA) to treat skin diseases such as psoriasis, vitiligo, and mycosis fungoides. PUVA therapy is also used within the scope of extracorporeal photopheresis to treat a variety of diseases that have a suspected involvement of pathogenic T cells, including rejection of organ transplants, graft-vs-host disease, cutaneous T cell lymphoma, and autoimmune disorders. Because psoralens are the only photosensitizers used in PUVA therapies and are considered to be responsible for a number of side effects, the identification of alternative drugs is of practical interest. Here we investigated the impact of activated Trolox (6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid), a hydrophilic vitamin E analog lacking the phytyl tail, as an alternative photoactivatable agent with T cell cytotoxic properties. Despite the well-known antioxidative capacity of Trolox, we found that at low UVA doses and in the presence of supraphysiological concentration of nitrite, a natural constituent of human skin, this compound selectively enhances radical-mediated cytotoxicity toward T cells but not toward human skin fibroblasts, keratinocytes, or endothelial cells. The cytotoxic mechanism comprises a reaction of Trolox with photo-decomposition products of nitrite, which leads to increased Trolox phenoxyl radical formation, increased intracellular oxidative stress, and a consecutive induction of apoptosis and necrosis in fast proliferating T cells. Thus, the identified UVA/nitrite-induced phenoxyl radical formation provides an opportunity for a new cytotoxic photodynamic therapy.

  13. Divalent cation-induced cluster formation by polyphosphoinositides in model membranes.

    PubMed

    Wang, Yu-Hsiu; Collins, Agnieszka; Guo, Lin; Smith-Dupont, Kathryn B; Gai, Feng; Svitkina, Tatyana; Janmey, Paul A

    2012-02-22

    Polyphosphoinositides (PPIs) and in particular phosphatidylinositol-(4,5)-bisphosphate (PI4,5P2), control many cellular events and bind with variable levels of specificity to hundreds of intracellular proteins in vitro. The much more restricted targeting of proteins to PPIs in cell membranes is thought to result in part from the formation of spatially distinct PIP2 pools, but the mechanisms that cause formation and maintenance of PIP2 clusters are still under debate. The hypothesis that PIP2 forms submicrometer-sized clusters in the membrane by electrostatic interactions with intracellular divalent cations is tested here using lipid monolayer and bilayer model membranes. Competitive binding between Ca(2+) and Mg(2+) to PIP2 is quantified by surface pressure measurements and analyzed by a Langmuir competitive adsorption model. The physical chemical differences among three PIP2 isomers are also investigated. Addition of Ca(2+) but not Mg(2+), Zn(2+), or polyamines to PIP2-containing monolayers induces surface pressure drops coincident with the formation of PIP2 clusters visualized by fluorescence, atomic force, and electron microscopy. Studies of bilayer membranes using steady-state probe-partitioning fluorescence resonance energy transfer (SP-FRET) and fluorescence correlation spectroscopy (FCS) also reveal divalent metal ion (Me(2+))-induced cluster formation or diffusion retardation, which follows the trend: Ca(2+) ≫ Mg(2+) > Zn(2+), and polyamines have minimal effects. These results suggest that divalent metal ions have substantial effects on PIP2 lateral organization at physiological concentrations, and local fluxes in their cytoplasmic levels can contribute to regulating protein-PIP2 interactions.

  14. Interaction and complex formation between catalase and cationic polyelectrolytes: chitosan and Eudragit E100.

    PubMed

    Boeris, Valeria; Romanini, Diana; Farruggia, Beatriz; Picó, Guillemo

    2009-08-01

    Interactions between catalase and the cationic polyelectrolytes: chitosan and Eudragit E100 have been investigated owing to their scientific and technological importance. These interactions have been characterized by turbidimetry, circular dichroism and fluorescence spectroscopy. It was found that the catalase conformation does not change significantly during the chain entanglements between the protein and the polyelectrolytes. The effects of pH, ionic strength and anions which modify the water structure were evaluated on the polymer-protein complex formation. A net coulombic interaction force between them was found since the insoluble complex formation decreased after the NaCl addition. Both polymers were found to precipitate around 80% of the protein in solution. No modification of the tertiary and secondary protein structure or the enzymatic activity was observed when the precipitate was dissolved by changing the pH of the medium. Chitosan and Eudragit E100 proved to be a useful framework to isolate catalase or proteins with a slightly acid isoelectrical pH by means of precipitation.

  15. Aluminium substitution in iron(II III)-layered double hydroxides: Formation and cationic order

    NASA Astrophysics Data System (ADS)

    Ruby, Christian; Abdelmoula, Mustapha; Aissa, Rabha; Medjahdi, Ghouti; Brunelli, Michela; François, Michel

    2008-09-01

    The formation and the modifications of the structural properties of an aluminium-substituted iron(II-III)-layered double hydroxide (LDH) of formula Fe4IIFe(2-6y)IIIAl6yIII (OH) 12 SO 4, 8H 2O are followed by pH titration curves, Mössbauer spectroscopy and high-resolution X-ray powder diffraction using synchrotron radiation. Rietveld refinements allow to build a structural model for hydroxysulphate green rust, GR(SO 42-), i.e. y=0, in which a bilayer of sulphate anions points to the Fe 3+ species. A cationic order is proposed to occur in both GR(SO 42-) and aluminium-substituted hydroxysulphate green rust when y<0.08. Variation of the cell parameters and a sharp decrease in average crystal size and anisotropy are detected for an aluminium content as low as y=0.01. The formation of Al-GR(SO 42-) is preceded by the successive precipitation of Fe III and Al III (oxy)hydroxides. Adsorption of more soluble Al III species onto the initially formed ferric oxyhydroxide may be responsible for this slowdown of crystal growth. Therefore, the insertion of low aluminium amount ( y˜0.01) could be an interesting way for increasing the surface reactivity of iron(II-III) LDH that maintains constant the quantity of the reactive Fe II species of the material.

  16. A pro-chelator triggered by hydrogen peroxide inhibits iron-promoted hydroxyl radical formation.

    PubMed

    Charkoudian, Louise K; Pham, David M; Franz, Katherine J

    2006-09-27

    The synthesis and structural characterization of a new pro-chelating agent, isonicotinic acid [2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzylidene]-hydrazide (BSIH), are presented. BSIH only weakly interacts with iron unless hydrogen peroxide (H2O2) is present to remove the boronic ester protecting group to reveal a phenol that is a key metal-binding group of tridentate salicylaldehyde isonicotinoyl hydrazone (SIH). BSIH prevents deoxyribose degradation caused by hydroxyl radicals that are generated from H2O2 and redox-active iron by sequestering Fe3+ and preventing iron-promoted hydroxyl radical formation. The rate-determining step for iron sequestration is conversion of BSIH to SIH, followed by rapid Fe3+ complexation. The pro-chelate approach of BSIH represents a promising strategy for chelating a specific pool of detrimental metal ions without disturbing healthy metal ion distribution.

  17. Illuminating the Atmospheric Oxidation Mechanisms, SOA Formation Pathways and Radical Yields of the Monoterpene Myrcene

    NASA Astrophysics Data System (ADS)

    Wyche, Kevin; Carr, Timo; Monks, Paul; Ellis, Andrew; Alfarra, Rami; McFiggans, Gordon; Hamilton, Jacqueline; Ward, Martyn; Boss, William; Camredon, Marie

    2010-05-01

    Biogenic Volatile Organic Compounds (BVOCs) are ubiquitous in the global troposphere, being emitted primarily from terrestrial plant life in significant quantities. Indeed, it is estimated that the total annual emission rate of all (non-methane) BVOCs is roughly ten times that of all anthropogenic volatile organic compounds (Guenther et al., 1995). With the exception of methane, the most dominant species of BVOC, in terms of emission strength, reactivity and their impact upon the atmosphere, are terpenes. Terpenes are a subdivision of BVOCs, composed primarily of hemiterpenes (C5), monoterpenes (C10), sesquiterpenes (C15) and diterpenes (C20). Under troposheric conditions terpenes react via complex and extensive gas phase oxidation pathways, have strong photochemical ozone creation potentials, constitute a significant radical source and are known to generate secondary organic aerosol (SOA) in high yields. At present there exists a certain lack of understanding regarding the oxidation mechanisms of certain terpenes and their role in SOA and radical formation. Consequently, as part of the NERC funded Aerosol Coupling in the Earth's System (ACES) and Total RAdical Production from the OZonolysis of alkenes (TRAPOZ) projects, a comprehensive series of simulation chamber experiments were conducted at the University of Manchester aerosol chamber facility, and at the EUropean PHOto REactor (EUPHORE) in order to investigate the gas phase degradation mechanisms, and SOA and radical formation potentials of a number of atmospherically significant terpenes. Both simulation chambers were highly instrumented during all experiments such that detailed and concomitant gas and aerosol phase measurements were made across a range of conditions. The work presented here describes the findings obtained from both photooxidation and ozonolysis experiments involving the common, but less well studied, aliphatic monoterpene, myrcene. The data presented include NOx and ozone measurements and

  18. Cascade Dissociations of Peptide Cation-Radicals. Part 1. Scope and Effects of Amino Acid Residues in Penta-, Nona- and Decapeptides

    PubMed Central

    Chung, Thomas W.; Hui, Renjie; Ledvina, Aaron; Coon, Joshua J.

    2013-01-01

    Amino acid residue-specific backbone and side-chain dissociations of peptide z ions in MS3 spectra were elucidated for over 40 pentapeptides with arginine C-terminated sequences of the AAXAR and AAHXR type, nonapeptides of the AAHAAXYAR and AAHAXAYAR type, and AAHAAXYAAR decapeptides. Peptide zn ions containing amino acid residues with readily transferrable benzylic or tertiary β-hydrogen atoms (Phe, Tyr, His, Trp, Val) underwent facile backbone cleavages to form dominant zn-2 or zn-3 ions. These backbone cleavages are thought to be triggered by a side-chain β-hydrogen atom transfer to the z ion Cα radical site followed by homolytic dissociation of the adjacent Cα—CO bond, forming zn-2 + HNCO cation-radicals that spontaneously dissociate by loss of HNCO. Amino acid residues that do not have readily transferrable β-hydrogen atoms (Gly, Ala) do not undergo the zn → zn-2 dissociations. The backbone cleavages compete with side-chain dissociations in z ions containing Asp and Asn residues. Side-chain dissociations are thought to be triggered by α-hydrogen atom transfers that activate the Cβ—Cγ or Cβ—heteroatom bonds for dissociations that dominate the MS3 spectra of z ions from peptides containing Leu, Cys, Lys, Met, Ser, Arg, Glu and Gln residues. The Lys, Arg, Gln, and Glu residues also participate in γ-hydrogen atom transfers that trigger other side-chain dissociations. PMID:22669761

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  20. Gas phase hydration and deprotonation of the cyclic C3H3+ cation. Solvation by acetonitrile, and comparison with the benzene radical cation.

    PubMed

    Mabrouki, Ridha; Ibrahim, Yehia; Xie, Enli; Meot-Ner Mautner, Michael; El-Shall, M Samy

    2006-06-15

    The binding energies of the first 5 H2O molecules to c-C3H3+ were determined by equilibrium measurements. The measured binding energies of the hydrated clusters of 9-12 kcal/mol are typical of carbon-based CH+...X hydrogen bonds. The ion solvation with the more polar CH3CN molecules results in stronger bonds consistent with the increased ion-dipole interaction. Ab initio calculations show that the lowest energy isomer of the c-C3H3+(H2O)4 cluster consists of a cyclic water tetramer interacting with the c-C3H3+ ion, which suggests the presence of orientational restraint of the water molecules consistent with the observed large entropy loss. The c-C3H3+ ion is deprotonated by 3 or more H2O molecules, driven energetically by the association of the solvent molecules to form strongly hydrogen bonded (H2O)nH+ clusters. The kinetics of the associative proton transfer (APT) reaction C3H3+ + nH2O --> (H2O)nH+ + C3H2* exhibits an unusually steep negative temperature coefficient of k = cT(-63+/-4) (or activation energy of -37 +/- 1 kcal mol(-1)). The behavior of the C3H3+/water system is exactly analogous to the benzene+*/water system, suggesting that the mechanism, kinetics and large negative temperature coefficients may be general to multibody APT reactions. These reactions can become fast at low temperatures, allowing ionized polycyclic aromatics to initiate ice formation in cold astrochemical environments.

  1. Influence of various functional groups on the relative stability of alkylperoxy triplet cations: A theoretical study

    NASA Astrophysics Data System (ADS)

    Smith, Kenneth J.; Meloni, Giovanni

    2015-07-01

    CBS-QB3 energy calculations show that the formation of a stable triplet cation for alkylperoxy radicals is dependent on factors other than the stability of the daughter cations exclusively. We have found that in cases where the daughter ions are not capable of stabilizing the cation through hyperconjugation, it is possible for the triplet cation to be bound. In many circumstances, CBS-QB3 calculations have found bound triplet cation states with 'negative dissociation energies.' These results are attributed to the effects that electron donating/withdrawing substituents have on the spin and charge densities of the resulting cations.

  2. Formation of Polyion Complex (PIC) Micelles and Vesicles with Anionic pH-Responsive Unimer Micelles and Cationic Diblock Copolymers in Water.

    PubMed

    Ohno, Sayaka; Ishihara, Kazuhiko; Yusa, Shin-Ichi

    2016-04-26

    A random copolymer (p(A/MaU)) of sodium 2-(acrylamido)-2-methylpropanesulfonate (AMPS) and sodium 11-methacrylamidoundecanate (MaU) was prepared via conventional radical polymerization, which formed a unimer micelle under acidic conditions due to intramolecular hydrophobic interactions between the pendant undecanoic acid groups. Under basic conditions, unimer micelles were opened up to an expanded chain conformation by electrostatic repulsion between the pendant sulfonate and undecanoate anions. A cationic diblock copolymer (P163M99) consisting of poly(3-(methacrylamido)propyl)trimethylammonium chloride (PMAPTAC) and hydrophilic polybetaine, 2-(methacryloyloxy)ethylphosphorylcholine (MPC), blocks was prepared via controlled radical polymerization. Mixing of p(A/MaU) and P163M99 in 0.1 M aqueous NaCl under acidic conditions resulted in the formation of spherical polyion complex (PIC) micelles and vesicles, depending on polymer concentration before mixing. Shapes of the PIC micelles and vesicles changed under basic conditions due to collapse of the charge balance between p(A/MaU) and P163M99. The PIC vesicles can incorporate nonionic hydrophilic guest molecules, and the PIC micelles and vesicles can accept hydrophobic guest molecules in the hydrophobic core formed from p(A/MaU).

  3. Hydroxyl radical formation upon oxidation of reduced humic acids by oxygen in the dark.

    PubMed

    Page, Sarah E; Sander, Michael; Arnold, William A; McNeill, Kristopher

    2012-02-07

    Humic acids (HAs) accept and donate electrons in many biogeochemical redox reactions at oxic/anoxic interfaces. The products of oxidation of reduced HAs by O(2) are unknown but are expected to yield reactive oxygen species, potentially including hydroxyl radical (·OH). To quantify the formation of ·OH upon oxidation of reduced HAs by O(2), three HAs were reduced electrochemically to well-defined redox states and were subsequently oxidized by O(2) in the presence of the ·OH probe terephthalate. The formation of ·OH upon oxidation increased with increasing extent of HA reduction. The yield of ·OH ranged from 42 to 160 mmol per mole of electrons donated by the reduced HA. The intermediacy of hydrogen peroxide (H(2)O(2)) in the formation of ·OH was supported by enhancement of ·OH formation upon addition of exogenous H(2)O(2) sources and by the suppression of ·OH formation upon addition of catalase as a quencher of endogenous H(2)O(2). The formation of ·OH in the dark during oxidation of reduced HA represents a previously unknown source of ·OH formation at oxic/anoxic interfaces and may affect the biogeochemical and pollutant redox dynamics at these interfaces.

  4. Radical polymerization in holographic grating formation in PQ-PMMA photopolymer part I: Short exposure

    NASA Astrophysics Data System (ADS)

    Yu, Dan; Liu, Hongpeng; Geng, Yaohui; Wang, Weibo; Zhao, Yuanyuan

    2014-11-01

    Photochemical radical polymerization in phenathrenequinone doped poly(methyl methacrylate) photopolymer are investigated theoretically and experimentally at short exposure. In experiments, the dynamic evolution of diffraction efficiency in grating formation is measured. Based on the rate equations of chemical reactions, the analytical expressions of components evolution are deduced to compare the contributions of several photochemical processes to the grating formation. The percentages of these radical polymerizations, namely the polymerization of one PQ with one matrix molecule, the bimolecular combination of MMA molecules, and the disproportionation of MMA molecules, are extracted quantitatively by nonlinear fitting experimental curves. Furthermore, the kinetics parameters, quantum yield Φ and molar absorption coefficient ε of photosensitizers, are determined to demonstrate the rationality of chemical processes. The theoretical results indicate that the polymerization of PQ with matrix is primary photochemical process which dominated the grating formation at short exposure. The contribution of chain polymerization of MMA molecules on the grating can be neglected. This investigation can provide a significant foundation for improving holographic characteristics by photochemical mechanism.

  5. Catalase Expression Is Modulated by Vancomycin and Ciprofloxacin and Influences the Formation of Free Radicals in Staphylococcus aureus Cultures.

    PubMed

    Wang, Ying; Hougaard, Anni B; Paulander, Wilhelm; Skibsted, Leif H; Ingmer, Hanne; Andersen, Mogens L

    2015-09-01

    Detection of free radicals in biological systems is challenging due to their short half-lives. We have applied electron spin resonance (ESR) spectroscopy combined with spin traps using the probes PBN (N-tert-butyl-α-phenylnitrone) and DMPO (5,5-dimethyl-1-pyrroline N-oxide) to assess free radical formation in the human pathogen Staphylococcus aureus treated with a bactericidal antibiotic, vancomycin or ciprofloxacin. While we were unable to detect ESR signals in bacterial cells, hydroxyl radicals were observed in the supernatant of bacterial cell cultures. Surprisingly, the strongest signal was detected in broth medium without bacterial cells present and it was mitigated by iron chelation or by addition of catalase, which catalyzes the decomposition of hydrogen peroxide to water and oxygen. This suggests that the signal originates from hydroxyl radicals formed by the Fenton reaction, in which iron is oxidized by hydrogen peroxide. Previously, hydroxyl radicals have been proposed to be generated within bacterial cells in response to bactericidal antibiotics. We found that when S. aureus was exposed to vancomycin or ciprofloxacin, hydroxyl radical formation in the broth was indeed increased compared to the level seen with untreated bacterial cells. However, S. aureus cells express catalase, and the antibiotic-mediated increase in hydroxyl radical formation was correlated with reduced katA expression and catalase activity in the presence of either antibiotic. Therefore, our results show that in S. aureus, bactericidal antibiotics modulate catalase expression, which in turn influences the formation of free radicals in the surrounding broth medium. If similar regulation is found in other bacterial species, it might explain why bactericidal antibiotics are perceived as inducing formation of free radicals.

  6. Formation and disappearance of superoxide radicals in aqueous solutions. [79 references

    SciTech Connect

    Allen, A O; Bielski, B H.J.

    1980-01-01

    A literature review of superoxide radicals in aqueous solutions is presented covering the following: history; methods of formation of aqueous HO/sub 2//HO/sub 2//sup -/ by radiolysis and photolysis, electrolysis, mixing nonaqueous solutions into water, chemical reactions, enzymatic generation of O/sub 2//sup -/, and photosensitization; and properties of HO/sub 2//O/sub 2//sup -/ in aqueous solution, which cover spontaneous dismutation rates, pk and absorption spectra, catalyzed dismutation, thermodynamics and the so-called Haber-Weiss Reaction.

  7. A search for pure compounds suitable for use as matrix in spectroscopic studies of radiation-produced radical cations. III. A selection of compounds based on the thermochemistry of hydrogen and proton transfer reactions between neutral molecules and their cations

    NASA Astrophysics Data System (ADS)

    Van den Bosch, Ann; Ceulemans, Jan

    A systematic investigation is made of the thermochemistry of hydrogen and proton transfer between neutral molecules and their cations covering the entire organic chemistry, with the aim of selecting those compounds that are suitable for use as matrices in spectroscopic studies of radiation-produced radical cations. Compounds that are characterized by positive reaction enthalpies may be considered promising for use as matrices in such studies. Calculations are based on experimentally determined ionization energies and proton affinities and on carbon-hydrogen bond strengths that are arbitrarily taken as 418 kJ.mol -1 (100 kcal.mol -1). Effects of actual deviations from this value are considered. In the aliphatic series of compounds, reaction enthalpies depend strongly on functional groups present. Marked positive reaction enthalpies are obtained for alkenes, alkadienes, thioethers, mercaptans, iodoalkanes and tertiary amines. Non-aromatic cyclic compounds generally behave as their aliphatic counterparts. Thus, positive reaction enthalpies are generally obtained for unsaturated alicyclic hydrocarbons and cyclic thioethers. Positive reaction enthalpies are also obtained for piperidine, quinuclidine, manxine and derivatives. In the homocyclic aromatic series of compounds, reaction enthalpies are generally positive. Thus, positive reaction enthalpies are obtained for aromatic hydrocarbons, fluoro- and chlorobenzenes, aromatic amines (amino group attached directly to the ring) and halo- and methoxyanilines. In the heterocyclic aromatic series of compounds reaction enthalpies are generally negative. This is for instance the case for a large number of pyridine derivatives, di- and triazines and a number of bi- and tricyclic compounds. Positive reaction enthalpies are however obtained for furan and pyrrole.

  8. Effect of copper oxide concentration on the formation and persistency of environmentally persistent free radicals (EPFRs) in particulates.

    PubMed

    Kiruri, Lucy W; Khachatryan, Lavrent; Dellinger, Barry; Lomnicki, Slawo

    2014-02-18

    Environmentally persistent free radicals (EPFRs) are formed by the chemisorption of substituted aromatics on metal oxide surfaces in both combustion sources and superfund sites. The current study reports the dependency of EPFR yields and their persistency on metal loading in particles (0.25, 0.5, 0.75, 1, 2, and 5% CuO/silica). The EPFRs were generated through exposure of particles to three adsorbate vapors at 230 °C: phenol, 2-monochlorophenol (2-MCP), and dichlorobenzene (DCBz). Adsorption resulted in the formation of surface-bound phenoxyl- and semiquinoine-type radicals with characteristic EPR spectra displaying a g value ranging from ∼ 2.0037 to 2.006. The highest EPFR yield was observed for CuO concentrations between 1 and 3% in relation to MCP and phenol adsorption. However, radical density, which is expressed as the number of radicals per copper atom, was highest at 0.75-1% CuO loading. For 1,2-dichlorobenzene adsorption, radical concentration increased linearly with decreasing copper content. At the same time, a qualitative change in the radicals formed was observed--from semiquinone to chlorophenoxyl radicals. The two longest lifetimes, 25 and 23 h, were observed for phenoxyl-type radicals on 0.5% CuO and chlorophenoxyl-type radicals on 0.75% CuO, respectively.

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

    PubMed

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

    2015-10-15

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

  10. Cationic Si−H−Si Bridges in Polysilanes: Their Detection and Targeted Formation in Stable Ion Studies

    PubMed Central

    Albers, Lena

    2016-01-01

    Abstract The ionization of 1,1‐dihydridocyclopentasilane 7 has been found to yield the cyclic polysilanylsilyl cation 8 instead of the expected hydrogen‐substituted silylium ion 6. The silyl cation 8 is stabilized by the formation of an intramolecular Si−H−Si bridge, which also provides the thermodynamic driving force for its formation. In general, the preference for the formation of Si−H−Si bridges can be used to scavenge and identify transient intermediates in the Lewis acid induced rearrangement of polysilanes. The validity of this concept has been demonstrated for one central step in this chemistry, the ring‐contraction reaction of cyclohexasilanes to form silylcyclopentasilanes. PMID:27105609

  11. Contribution of the photo-Fenton reaction to hydroxyl radical formation rates in river and rain water samples.

    PubMed

    Nakatani, Nobutake; Ueda, Marina; Shindo, Hirotaka; Takeda, Kazuhiko; Sakugawa, Hiroshi

    2007-09-01

    The hydroxyl radical (OH radical) formation rates from the photo-Fenton reaction in river and rain water samples were determined by using deferoxamine mesylate (DFOM), which makes a stable and strong complex with Fe(III), resulting in a suppression of the photo-Fenton reaction. The difference between the OH radical formation rates with and without added DFOM denotes the rate from the photo-Fenton reaction. The photoformation rates from the photo-Fenton reaction were in the range of 0.7 - 45.8 x 10(-12) and 2.7 - 32.3 x 10(-12) M s(-1) in river and rain water samples, respectively. A strong positive correlation between the OH radical formation rate from the photo-Fenton reaction and the amount of fluorescent matter in river water suggests that fluorescent matter, such as humic substances, plays an important role in the photo-Fenton reaction. In rain water, direct photolysis of hydrogen peroxide was an important source of OH radicals as well as the photo-Fenton reaction. The contributions of the photo-Fenton reaction to the OH radical photoformation rates in river and rain water samples were in the ranges of 2 - 29 and 5 - 38%, respectively. Taking into account the photo-Fenton reaction, 33 - 110 (mean: 80) and 42 - 110 (mean: 84)% of OH radical sources in river and rain water samples, respectively, collected in Hiroshima prefecture were elucidated.

  12. Ascorbate-dependent formation of hydroxyl radicals in the presence of iron chelates.

    PubMed

    Prabhu, H R; Krishnamurthy, S

    1993-10-01

    The autoxidation of L-ascorbate on incubation in saline phosphate buffer (pH 7.4) is accompanied by hydroxyl radical (.OH) generation. The metal chelator EDTA showed significant inhibition of ascorbate autoxidation and ascorbate-dependent .OH release. On the other hand, Fe2+ (EDTA) greatly augmented both ascorbate autoxidation and ascorbate-dependent .OH production. The biological iron chelating compounds such as ATP, ADP, citrate and pyrophosphate suppressed both ascorbate autoxidation and ascorbate-mediated .OH production, thereby indicating that these compounds suppress the activating effect of iron. Ascorbate autoxidation and ascorbate-dependent .OH formation, stimulated by Fe2+ (EDTA) were significantly inhibited by .OH scavengers, namely mannitol, thiourea and sodium formate, as well as by catalase and to a lesser extent by bovine serum albumin, superoxide dismutase (native and heat denatured) and heat denatured catalase.

  13. The antimicrobial activity of gramicidin A is associated with hydroxyl radical formation.

    PubMed

    Liou, Je-Wen; Hung, Yu-Jiun; Yang, Chin-Hao; Chen, Yi-Cheng

    2015-01-01

    Gramicidin A is an antimicrobial peptide that destroys gram-positive bacteria. The bactericidal mechanism of antimicrobial peptides has been linked to membrane permeation and metabolism disruption as well as interruption of DNA and protein functions. However, the exact bacterial killing mechanism of gramicidin A is not clearly understood. In the present study, we examined the antimicrobial activity of gramicidin A on Staphylococcus aureus using biochemical and biophysical methods, including hydroxyl radical and NAD+/NADH cycling assays, atomic force microscopy, and Fourier transform infrared spectroscopy. Gramicidin A induced membrane permeabilization and changed the composition of the membrane. The morphology of Staphylococcus aureus during gramicidin A destruction was divided into four stages: pore formation, water permeability, bacterial flattening, and lysis. Changes in membrane composition included the destruction of membrane lipids, proteins, and carbohydrates. Most interestingly, we demonstrated that gramicidin A not only caused membrane permeabilization but also induced the formation of hydroxyl radicals, which are a possible end product of the transient depletion of NADH from the tricarboxylic acid cycle. The latter may be the main cause of complete Staphylococcus aureus killing. This new finding may provide insight into the underlying bactericidal mechanism of gA.

  14. Formation of hydroxyl radicals from photolysis of secondary organic aerosol material

    NASA Astrophysics Data System (ADS)

    Badali, K. M.; Zhou, S.; Aljawhary, D.; Antiñolo, M.; Chen, W. J.; Lok, A.; Mungall, E.; Wong, J. P. S.; Zhao, R.; Abbatt, J. P. D.

    2015-02-01

    This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA) material formed by terpene ozonolysis. The SOA aerosol is collected on filters, dissolved in water containing a radical trap (benzoic acid), and then exposed to ultraviolet light in a photochemical reactor. The OH formation rates, which are similar for both α-pinene and limonene SOA, are measured from the formation rate of p-hydroxybenzoic acid as measured using offline HPLC analysis. To evaluate whether the OH is formed by photolysis of H2O2 or organic hydroperoxides (ROOH), the peroxide content of the SOA was measured using the horseradish peroxidase-dichlorofluorescein (HRP-DCF) assay, which was calibrated using H2O2. The OH formation rates from SOA are five times faster than from the photolysis of H2O2 solutions whose concentrations correspond to the peroxide content of the SOA solutions assuming that the HRP-DCF signal arises from H2O2 alone. The higher rates of OH formation from SOA are likely due to ROOH photolysis. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over three times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA, the quantum yield for OH generation from α-pinene SOA is 0.8 ± 0.4. This is the first demonstration of an efficient photolytic source of OH in SOA, one that may affect both cloudwater and aerosol chemistry.

  15. Formation of hydroxyl radicals from photolysis of secondary organic aerosol material

    NASA Astrophysics Data System (ADS)

    Badali, K. M.; Zhou, S.; Aljawhary, D.; Antiñolo, M.; Chen, W. J.; Lok, A.; Mungall, E.; Wong, J. P. S.; Zhao, R.; Abbatt, J. P. D.

    2015-07-01

    This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA) material formed by terpene ozonolysis. The SOA is collected on filters, dissolved in water containing a radical trap (benzoic acid), and then exposed to ultraviolet light in a photochemical reactor. The OH formation rates, which are similar for both α-pinene and limonene SOA, are measured from the formation rate of p-hydroxybenzoic acid as measured using offline HPLC analysis. To evaluate whether the OH is formed by photolysis of H2O2 or organic hydroperoxides (ROOH), the peroxide content of the SOA was measured using the horseradish peroxidase-dichlorofluorescein (HRP-DCF) assay, which was calibrated using H2O2. The OH formation rates from SOA are 5 times faster than from the photolysis of H2O2 solutions whose concentrations correspond to the peroxide content of the SOA solutions, assuming that the HRP-DCF signal arises from H2O2 alone. The higher rates of OH formation from SOA are likely due to ROOH photolysis, but we cannot rule out a contribution from secondary processes as well. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over 3 times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA and assuming that the peroxides drive most of the ultraviolet absorption, the quantum yield for OH generation from α-pinene SOA is 0.8 ± 0.4. This is the first demonstration of an efficient photolytic source of OH in SOA, one that may affect both cloud water and aerosol chemistry.

  16. Estimating hydroxyl radical photochemical formation rates in natural waters during long-term laboratory irradiation experiments.

    PubMed

    Sun, Luni; Chen, Hongmei; Abdulla, Hussain A; Mopper, Kenneth

    2014-04-01

    In this study it was observed that, during long-term irradiations (>1 day) of natural waters, the methods for measuring hydroxyl radical (˙OH) formation rates based upon sequentially determined cumulative concentrations of photoproducts from probes significantly underestimate actual ˙OH formation rates. Performing a correction using the photodegradation rates of the probe products improves the ˙OH estimation for short term irradiations (<1 day), but not long term irradiations. Only the 'instantaneous' formation rates, which were obtained by adding probes to aliquots at each time point and irradiating these sub-samples for a short time (≤2 h), were found appropriate for accurately estimating ˙OH photochemical formation rates during long-term laboratory irradiation experiments. Our results also showed that in iron- and dissolved organic matter (DOM)-rich water samples, ˙OH appears to be mainly produced from the Fenton reaction initially, but subsequently from other sources possibly from DOM photoreactions. Pathways of ˙OH formation in long-term irradiations in relation to H2O2 and iron concentrations are discussed.

  17. Cascade dissociations of peptide cation-radicals. Part 1. Scope and effects of amino acid residues in penta-, nona-, and decapeptides.

    PubMed

    Chung, Thomas W; Hui, Renjie; Ledvina, Aaron; Coon, Joshua J; Tureček, Frantisek

    2012-08-01

    Amino acid residue-specific backbone and side-chain dissociations of peptide z ions in MS(3) spectra were elucidated for over 40 pentapeptides with arginine C-terminated sequences of the AAXAR and AAHXR type, nonapeptides of the AAHAAXX"AR and AAHAXAX"AR type, and AAHAAXX"AAR decapeptides. Peptide z(n) ions containing amino acid residues with readily transferrable benzylic or tertiary β-hydrogen atoms (Phe, Tyr, His, Trp, Val) underwent facile backbone cleavages to form dominant z(n-2) or z(n-3) ions. These backbone cleavages are thought to be triggered by a side-chain β-hydrogen atom transfer to the z ion C(α) radical site followed by homolytic dissociation of the adjacent C(α)-CO bond, forming x(n-2) cation-radicals that spontaneously dissociate by loss of HNCO. Amino acid residues that do not have readily transferrable β-hydrogen atoms (Gly, Ala) do not undergo the z(n) → z(n-2) dissociations. The backbone cleavages compete with side-chain dissociations in z ions containing Asp and Asn residues. Side-chain dissociations are thought to be triggered by α-hydrogen atom transfers that activate the C(β)-C(γ) or C(β)-heteroatom bonds for dissociations that dominate the MS(3) spectra of z ions from peptides containing Leu, Cys, Lys, Met, Ser, Arg, Glu, and Gln residues. The Lys, Arg, Gln, and Glu residues also participate in γ-hydrogen atom transfers that trigger other side-chain dissociations.

  18. Stepwise association of hydrogen cyanide and acetonitrile with the benzene radical cation: structures and binding energies of (C6H6•+)(HCN)n, n = 1-6, and (C6H6•+)(CH3CN)n, n = 1-4, clusters.

    PubMed

    Hamid, Ahmed M; Soliman, Abdel-Rahman; El-Shall, M Samy

    2013-02-14

    Equilibrium thermochemical measurements using the ion mobility drift cell technique have been utilized to investigate the binding energies and entropy changes associated with the stepwise association of HCN and CH(3)CN molecules with the benzene radical cation in the C(6)H(6)(•+)(HCN)(n) and C(6)H(6)(•+)(CH(3)CN)(n) clusters with n = 1-6 and 1-4, respectively. The binding energy of CH(3)CN to the benzene cation (14 kcal/mol) is stronger than that of HCN (9 kcal/mol) mostly due to a stronger ion-dipole interaction because of the large dipole moment of acetonitrile (3.9 D). However, HCN can form hydrogen bonds with the hydrogen atoms of the benzene cation (CH(δ+)···NCH) and linear hydrogen bonding chains involving HCN···HCN interaction. HCN molecules tend to form externally solvated structures with the benzene cation where the ion is hydrogen bonded to the exterior of HCN chains. For the C(6)H(6)(•+)(CH(3)CN)(n) clusters, internally solvated structures are formed where the acetonitrile molecules are directly interacting with the benzene cation through ion-dipole and hydrogen bonding interactions. The lack of formation of higher clusters with n > 4, in contrast to HCN, suggests the formation of a solvent shell at n = 4, which is attributed to steric interactions among the acetonitrile molecules attached to the benzene cation and to the presence of the blocking CH(3) groups, both effects make the addition of more than four acetonitrile molecules less favorable.

  19. Peroxynitrite-mediated formation of free radicals in human plasma: EPR detection of ascorbyl, albumin-thiyl and uric acid-derived free radicals.

    PubMed Central

    Vásquez-Vivar, J; Santos, A M; Junqueira, V B; Augusto, O

    1996-01-01

    Formation of peroxynitrite by the fast reaction between nitric oxide and superoxide anion may represent a critical control point in cells producing both species, leading to either down-regulation of the physiological effects of superoxide anion and nitric oxide by forming an inert product, nitrate, or to potentiation of their toxic effects by oxidation of nearby molecules by peroxynitrite. (The term peroxynitrite is used to refer to the sum of all possible forms of peroxynitrite anion and peroxynitrous acid unless otherwise specified.) In this report we demonstrate that, in spite of all the antioxidant defences present in human plasma, its interaction with peroxynitrite leads to generation of free radical intermediates such as (i) the ascorbyl radical, detected by direct EPR, (ii) the albumin-thiyl radical, detected by spin-trapping experiments with both N-tert-butyl-alpha-phenylnitrone and 5,5-dimethyl-1-pyrroline N-oxide (DMPO), and (iii) a uric acid-derived free radical, detected as the DMPO radical adduct in plasma whose thiol groups were previously blocked with 5,5-dithiobis-(2-nitrobenzoic acid). The identity of the latter adduct was confirmed by parallel experiments demonstrating that it is not detectable in plasma pretreated with uricase, whereas it is formed in incubations of peroxynitrite with uric acid. Peroxynitrite-mediated oxidations were also followed by oxygen consumption and ascorbate and plasma-thiol depletion. Our results support the view that peroxynitrite-mediated one-electron oxidation of biomolecules may be an important event in its cytotoxic mechanism. In addition, the data have methodological implications by providing support for the use of EPR methodologies for monitoring both free radical reactions and ascorbate concentrations in biological fluids. PMID:8615782

  20. Heterogeneous photochemistry of imidazole-2-carboxaldehyde: HO2 radical formation and aerosol growth

    NASA Astrophysics Data System (ADS)

    González Palacios, Laura; Corral Arroyo, Pablo; Aregahegn, Kifle Z.; Steimer, Sarah S.; Bartels-Rausch, Thorsten; Nozière, Barbara; George, Christian; Ammann, Markus; Volkamer, Rainer

    2016-09-01

    The multiphase chemistry of glyoxal is a source of secondary organic aerosol (SOA), including its light-absorbing product imidazole-2-carboxaldehyde (IC). IC is a photosensitizer that can contribute to additional aerosol ageing and growth when its excited triplet state oxidizes hydrocarbons (reactive uptake) via H-transfer chemistry. We have conducted a series of photochemical coated-wall flow tube (CWFT) experiments using films of IC and citric acid (CA), an organic proxy and H donor in the condensed phase. The formation rate of gas-phase HO2 radicals (PHO2) was measured indirectly by converting gas-phase NO into NO2. We report on experiments that relied on measurements of NO2 formation, NO loss and HONO formation. PHO2 was found to be a linear function of (1) the [IC] × [CA] concentration product and (2) the photon actinic flux. Additionally, (3) a more complex function of relative humidity (25 % < RH < 63 %) and of (4) the O2 / N2 ratio (15 % < O2 / N2 < 56 %) was observed, most likely indicating competing effects of dilution, HO2 mobility and losses in the film. The maximum PHO2 was observed at 25-55 % RH and at ambient O2 / N2. The HO2 radicals form in the condensed phase when excited IC triplet states are reduced by H transfer from a donor, CA in our system, and subsequently react with O2 to regenerate IC, leading to a catalytic cycle. OH does not appear to be formed as a primary product but is produced from the reaction of NO with HO2 in the gas phase. Further, seed aerosols containing IC and ammonium sulfate were exposed to gas-phase limonene and NOx in aerosol flow tube experiments, confirming significant PHO2 from aerosol surfaces. Our results indicate a potentially relevant contribution of triplet state photochemistry for gas-phase HO2 production, aerosol growth and ageing in the atmosphere.

  1. Bactericidal effect of colistin on planktonic Pseudomonas aeruginosa is independent of hydroxyl radical formation.

    PubMed

    Brochmann, Rikke Prejh; Toft, Anders; Ciofu, Oana; Briales, Alejandra; Kolpen, Mette; Hempel, Casper; Bjarnsholt, Thomas; Høiby, Niels; Jensen, Peter Østrup

    2014-02-01

    The bactericidal effect of several major types of antibiotics has recently been demonstrated to be dependent on the formation of toxic amounts of hydroxyl radicals (OH·) resulting from oxidative stress in metabolically active cells. Since killing by the antimicrobial peptide colistin does not require bacterial metabolic activity, we tested whether the bactericidal effect of colistin depends on the formation of OH·. In Pseudomonas aeruginosa cultures, OH-mediated killing by ciprofloxacin was demonstrated by decreased bacterial survival and induction of 3'-(p-hydroxyphenyl) fluorescein (HPF) fluorescence. OH·-mediated killing by ciprofloxacin was further confirmed by rescue of cells and reduction of HPF fluorescence due to prevention of OH· accumulation by scavenging with thiourea, by chelating with dipyridyl, by decreasing metabolism as well as by anoxic growth. In contrast, no formation of OH· was seen in P. aeruginosa during killing by colistin, and prevention of OH· accumulation could not rescue P. aeruginosa from killing by colistin. These results therefore demonstrate that the bactericidal activity of colistin on P. aeruginosa is not dependent on oxidative stress. In conclusion, antimicrobial peptides that do not rely on OH· formation should be considered for treatment of Gram-negative bacteria growing at low oxygen tension such as in endobronchial mucus and paranasal sinuses in cystic fibrosis patients, in abscesses and in infectious biofilm.

  2. Dark formation of hydroxyl radical in Arctic soil and surface waters.

    PubMed

    Page, Sarah E; Kling, George W; Sander, Michael; Harrold, Katherine H; Logan, J Robert; McNeill, Kristopher; Cory, Rose M

    2013-11-19

    Hydroxyl radical (•OH) is a highly reactive and unselective oxidant in atmospheric and aquatic systems. Current understanding limits the role of DOM-produced •OH as an oxidant in carbon cycling mainly to sunlit environments where •OH is produced photochemically, but a recent laboratory study proposed a sunlight-independent pathway in which •OH forms during oxidation of reduced aquatic dissolved organic matter (DOM) and iron. Here we demonstrate this non-photochemical pathway for •OH formation in natural aquatic environments. Across a gradient from dry upland to wet lowland habitats, •OH formation rates increase with increasing concentrations of DOM and reduced iron, with highest •OH formation predicted at oxic-anoxic boundaries in soil and surface waters. Comparison of measured vs expected electron release from reduced moieties suggests that both DOM and iron contribute to •OH formation. At landscape scales, abiotic DOM oxidation by this dark •OH pathway may be as important to carbon cycling as bacterial oxidation of DOM in arctic surface waters.

  3. Hydrogen peroxide release and hydroxyl radical formation in mixtures containing mineral fibres and human neutrophils.

    PubMed

    Leanderson, P; Tagesson, C

    1992-11-01

    The ability of different mineral fibres (rock wool, glass wool, ceramic fibres, chrysotile A, chrysotile B, amosite, crocidolite, antophyllite, erionite, and wollastonite) to stimulate hydrogen peroxide (H2O2) and hydroxyl radical (OH.) formation in mixtures containing human polymorphonuclear leucocytes (PMNLs) was investigated. In the presence of azide, all the fibres caused considerable H2O2 formation, and about twice as much H2O2 was found in mixtures with the natural fibres (asbestos, erionite, and wollastonite) than in mixtures with the manmade fibres (rock wool, glass wool, and ceramic fibres). In the presence of externally added iron, all the fibres were found to generate OH. and the natural fibres caused about three times more OH. formation than the manmade fibres. In the absence of external iron, there was less OH. formation; however, amosite, crocidolite, antophyllite, erionite, and wollastonite still generated considerable amounts of OH., also under circumstances in which only small amounts of OH. were produced in mixtures with the manmade fibres. These findings indicate that natural fibres generate more H2O2 and OH. than manmade fibres when incubated with PMNLs in the presence of external iron. They also suggest that the natural fibres, amosite, crocidolite, antophyllite, erionite, and wollastonite may act catalytically in the dissociation of H2O2 to OH. in the absence of external iron, whereas manmade fibres such as rock wool, glass wool, and ceramic fibres, do not seem to be able to generate OH. in the absence of external iron.

  4. Hydrogen peroxide release and hydroxyl radical formation in mixtures containing mineral fibres and human neutrophils.

    PubMed Central

    Leanderson, P; Tagesson, C

    1992-01-01

    The ability of different mineral fibres (rock wool, glass wool, ceramic fibres, chrysotile A, chrysotile B, amosite, crocidolite, antophyllite, erionite, and wollastonite) to stimulate hydrogen peroxide (H2O2) and hydroxyl radical (OH.) formation in mixtures containing human polymorphonuclear leucocytes (PMNLs) was investigated. In the presence of azide, all the fibres caused considerable H2O2 formation, and about twice as much H2O2 was found in mixtures with the natural fibres (asbestos, erionite, and wollastonite) than in mixtures with the manmade fibres (rock wool, glass wool, and ceramic fibres). In the presence of externally added iron, all the fibres were found to generate OH. and the natural fibres caused about three times more OH. formation than the manmade fibres. In the absence of external iron, there was less OH. formation; however, amosite, crocidolite, antophyllite, erionite, and wollastonite still generated considerable amounts of OH., also under circumstances in which only small amounts of OH. were produced in mixtures with the manmade fibres. These findings indicate that natural fibres generate more H2O2 and OH. than manmade fibres when incubated with PMNLs in the presence of external iron. They also suggest that the natural fibres, amosite, crocidolite, antophyllite, erionite, and wollastonite may act catalytically in the dissociation of H2O2 to OH. in the absence of external iron, whereas manmade fibres such as rock wool, glass wool, and ceramic fibres, do not seem to be able to generate OH. in the absence of external iron. Images PMID:1334424

  5. Radical-induced purine lesion formation is dependent on DNA helical topology.

    PubMed

    Terzidis, Michael A; Prisecaru, Andreea; Molphy, Zara; Barron, Niall; Randazzo, Antonio; Dumont, Elise; Krokidis, Marios G; Kellett, Andrew; Chatgilialoglu, Chryssostomos

    2016-11-01

    Herein we report the quantification of purine lesions arising from gamma-radiation sourced hydroxyl radicals (HO(•)) on tertiary dsDNA helical forms of supercoiled (SC), open circular (OC), and linear (L) conformation, along with single-stranded folded and non-folded sequences of guanine-rich DNA in selected G-quadruplex structures. We identify that DNA helical topology and folding plays major, and unexpected, roles in the formation of 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxo-dG) and 8-oxo-7,8-dihydro-2'-deoxyadenosine (8-oxo-dA), along with tandem-type purine lesions 5',8-cyclo-2'-deoxyguanosine (5',8-cdG) and 5',8-cyclo-2'-deoxyadenosine (5',8-cdA). SC, OC, and L dsDNA conformers together with folded and non-folded G-quadruplexes d[TGGGGT]4 (TG4T), d[AGGG(TTAGGG)3] (Tel22), and the mutated tel24 d[TTGGG(TTAGGG)3A] (mutTel24) were exposed to HO(•) radicals and purine lesions were then quantified via stable isotope dilution LC-MS/MS analysis. Purine oxidation in dsDNA follows L > OC ≫ SC indicating greater damage towards the extended B-DNA topology. Conversely, G-quadruplex sequences were significantly more resistant toward purine oxidation in their unfolded states as compared with G-tetrad folded topologies; this effect is confirmed upon comparative analysis of Tel22 (∼50% solution folded) and mutTel24 (∼90% solution folded). In an effort to identify the accessibly of hydroxyl radicals to quadruplex purine nucleobases, G-quadruplex solvent cavities were then modeled at 1.33 Å with evidence suggesting that folded G-tetrads may act as potential oxidant traps to protect against chromosomal DNA damage.

  6. The hydrogen-bridged radical cation [NH 2C dbnd O⋯H⋯O dbnd CHCH 3] rad + and its dissociation by proton-transport catalysis

    NASA Astrophysics Data System (ADS)

    Jobst, Karl J.; Terlouw, Johan K.

    2012-01-01

    The title ion (HBRC-1) is an easily accessible hydrogen-bridged radical cation when generated by the decarbonylation of ionized ethyl oxamate, NH2COCOOC2H5. Tandem mass spectrometry experiments and CBS-QB3 model chemistry calculations agree that HBRC-1 dissociates into HC(OH)NH2+ + CH3COrad by proton-transport catalysis. Its CH3CHO component catalyzes the isomerization NH2-C-OHrad + → NH2C(O)Hrad + and the ensuing intermediate [NH2C(O)H⋯OCHCH3]rad + loses CH3COrad by a facile proton transfer. In support of this, lactamide ions ND2C(O)CH(OD)CH3rad + dissociate into DC(OH)ND2+ + CH3COrad via the HBRC-1 isotopologue [ND2CO⋯D⋯OCHCH3]rad +. HBRC-1 also plays a key role in the decarbonylation of its isomer ionized urethan, NH2COOC2H5.

  7. Structural and magnetic effects of meso-substitution in alkyl-substituted metalloporphyrinate pi-cation radicals: characterization of [Fe(TalkylP*)(Cl)]SbCl6 (alkyl = ethyl and n-propyl).

    PubMed

    Li, Ming; Neal, Teresa J; Wyllie, Graeme R A; Schulz, Charles E; Scheidt, W Robert

    2010-09-06

    We report the preparation and characterization of two meso-alkyl substituted porphyrin pi-cation radical derivatives, [Fe(TalkylP(*))(Cl)]SbCl(6) (alkyl = ethyl or propyl). Both complexes have been characterized by UV/vis/near-IR, IR, and Mossbauer spectroscopy, temperature-dependent solid-state magnetic susceptibility measurements, and X-ray structure determinations. All data for both oxidized species are consistent with the formulation of the complexes as ring-oxidized iron(III) porphyrin species. The molecular structures of the two five-coordinate species have the typical square-pyramidal coordination group of high-spin iron(III) derivatives. The crystal structures also reveal that the species form cofacial pi-pi dimers with lateral shifts of 1.44 A and 3.22 A, respectively, for the propyl and ethyl radical derivatives. Both radicals exhibit porphyrin cores with alternating bond distance patterns in the inner 16-membered ring. In addition, [Fe(TEtP(*))(Cl)]SbCl(6) and [Fe(TPrP(*))(Cl)]SbCl(6) have been characterized by temperature-dependent (6-300 K) magnetic susceptibility studies, the best fitting of the temperature-dependent moments reveal strong coupling between iron spins and porphyrin radical, and a smaller magnitude of antiferromagnetic coupling between ring radicals, which are opposite to those found in the five-coordinate iron(III) OEP radicals. The differences in structure and properties of the cation radical meso-alkyl and beta-alkyl derivatives possibly reflect differences in properties of a(1u)- and a(2u)-forming radicals.

  8. Geminate recombination kinetics of solute radical ions. Singlet excited state formation in cyclohexane solutions of biphenyl

    NASA Astrophysics Data System (ADS)

    Tagawa, S.; Washio, M.; Tabata, Y.; Kobayashi, H.

    Transient absorption spectra of the solute anion, cation and triplet state and the solute fluorescence in the pulse radiolysis of 0.1 mole 1 -1 biphenyl in cyclohexane were observed on a nanosecond timescale longer than 1 ns after a 20 ps pulse. The formation of the solute excited singlet state is mainly due to the geminate ion recombination reaction even in the high concentrated solutions. The decay of the solute ions obeys the reciprocal square root dependence on time longer than 10 ns from the end of a 10 ps pulse. The slope of this reciprocal square root plots agrees with the literature value on a longer timescale obtained by microwave absorption. The yield of free ions obtained from the intercept of the slope agrees also with the literature values obtained by the field clearing method. Ratio of the formation rate of the solute excited triplet state to the decay rate of the solute anion changes in a time range between 5 and 20 ns. It is very well correlated with a theoretical calculation of spin correlation decay of the germinate ion pairs by Brocklehurst, although the formation of the solute triplet state was observed even on a timescale shorter than 5 ns from the end of a 20 ps pulse, where loss of spin correlation is negligibly small.

  9. A CROSSED MOLECULAR BEAMS STUDY ON THE FORMATION OF THE EXOTIC CYANOETHYNYL RADICAL IN TITAN'S ATMOSPHERE

    SciTech Connect

    Gu, X.; Kaiser, R. I.; Mebel, A. M.; Kislov, V. V.; Klippenstein, S. J.; Harding, L. B.; Liang, M. C.; Yung, Y. L.

    2009-08-20

    The reaction of the dicarbon molecule (C{sub 2}) in its {sup 1}{sigma}{sub g} {sup +} electronic ground state with hydrogen cyanide HCN(X{sup 1}{sigma}{sup +}) is investigated in a crossed molecular beam setup to untangle the formation of the cyanoethynyl radical CCCN(X{sup 2}{sigma}{sup +}) in hydrocarbon-rich atmospheres of planets and their moons such as Titan. Combined with electronic structure and rate theory calculations, we show that this elementary reaction is rapid, has no entrance barriers, and yields CCCN via successive rearrangements of the initial HC{sub 3}N collision complex to the cyanoacetylene intermediate (HCCCN) followed by unimolecular decomposition of the latter without exit barrier. New photochemical models imply that this radical could serve as a key building block to form more complex molecules as observed in situ by the Cassini spacecraft, ultimately leading to organic aerosol particles, which make up the orange-brownish haze layers in Titan's atmosphere.

  10. A crossed molecular beams study on the formation of the exotic cyanoethynyl radical in Titan's atmosphere.

    SciTech Connect

    Gu, X.; Kaiser, R. I.; Mebel, A. M.; Kislov, V. V.; Klippenstein, S. J.; Harding, L. B.; Liang, M. C.; Yung, Y. L.

    2009-08-01

    The reaction of the dicarbon molecule (C{sub 2}) in its {sup 1}{Sigma}{sub g}{sup +} electronic ground state with hydrogen cyanide HCN(X{sup 1}{Sigma}{sup +}) is investigated in a crossed molecular beam setup to untangle the formation of the cyanoethynyl radical CCCN(X{sup 2}{Sigma}{sup +}) in hydrocarbon-rich atmospheres of planets and their moons such as Titan. Combined with electronic structure and rate theory calculations, we show that this elementary reaction is rapid, has no entrance barriers, and yields CCCN via successive rearrangements of the initial HC{sub 3}N collision complex to the cyanoacetylene intermediate (HCCCN) followed by unimolecular decomposition of the latter without exit barrier. New photochemical models imply that this radical could serve as a key building block to form more complex molecules as observed in situ by the Cassini spacecraft, ultimately leading to organic aerosol particles, which make up the orange-brownish haze layers in Titan's atmosphere.

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

    NASA Astrophysics Data System (ADS)

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

    2008-03-01

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

  12. Formation and decay of the peroxy radicals in the oxidation process of Glyoxal, Methylglyoxal and Hydroxyacetone in aqueous solution

    NASA Astrophysics Data System (ADS)

    Schaefer, Thomas; Weller, Christian; Herrmann, Hartmut

    2013-04-01

    Volatile organic compounds (VOCs) are emitted into the atmosphere in large amounts from biogenic and anthropogenic sources. For example, the semivolatile carbonyl compounds glyoxal and methylglyoxal will be produced in the oxidation process of isoprene, while hydroxyacetone can be formed by the combustion of biomass. Additionally, these semivolatile carbonyl compounds might be important for the formation of secondary organic aerosol (SOA) by partitioning between gas- and liquid phase of pre-existing particles. In the gas phase as well as in the aqueous phase (cloud droplets, fog, rain and deliquescent particles) these compounds can be further oxidized, e.g., by radicals (OH and NO3) leading to peroxy radical and then to substitued organics. There are still uncertainties concerning the oxidation pathways of glyoxal, after H-atom abstraction by, e.g., OH radicals, via alkyl radical to the peroxy radical under addition of molecular oxygen. One concept[1] claims that for dilute solutions ( 1 mM the formation of the peroxy radicals is a minor reaction pathway because of a lower rate constant of k = 1 × 106 M-1 s-1 estimated after Guzman et al., 2006[3]. The difference in the rate constants of the oxygen addition is of about three orders of magnitude and thus leads to different oxidation products and yields in the aqueous solution. Laboratory studies of glyoxal oxidation under varying oxygen concentrations have been performed in order to investigate the importance of the peroxy radical formation and alkyl radical recombination in more detail. The formation and the decay of the formed glyoxyl radicals and glyoxyl peroxy radicals were studied in low and high concentrated oxygen solutions using a laser photolysis long path absorption setup (LP-LPA). Additionally, the Tdependent decay of the peroxy radicals formed in the oxidation of methyglyoxal and hydroxyacetone was also studied using the same experiment. 1 Buxton, G. V., Malone, T. N. und Salmon, G. A., J. Chem. Soc

  13. Microgel formation in the free radical crosslinking copolymerization of methyl methacrylate (MMA) and ethylene glycol dimethcrylate (EGDMA)

    SciTech Connect

    Xiudong Sung; Yuen-Yuen Chiu; Lee, L.J.

    1996-12-31

    The formation of heterogeneous structure through intramolecular reaction is an important feature in the free radical crosslinking copolymerization of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA). Such structure formation affects not only the curing behavior but also the rheological changes of the resin. In this work, the effect of co-monomer composition on the reaction kinetics, rheological changes and microgel formation of MMA-EGDMA copolymerization was studied. A percolation model was adopted to simulate such monovinyl-divinyl reactions.

  14. Orientation dependence for Br formation in the reaction of oriented OH radical with HBr molecule.

    PubMed

    Tsai, Po-Yu; Che, Dock-Chil; Nakamura, Masaaki; Lin, King-Chuen; Kasai, Toshio

    2011-01-28

    The orientation dependence of Br-atom formation in the reaction of the oriented OH radical with the HBr molecule using the hexapole electrostatic field was studied. Experimental results for the orientation dependence in the reaction were analyzed using a Legendre polynomial fit. The results show two reactive sites. It was found that O-end attack is most favored for this reaction, and that H-end attack also shows a pronounced reactivity. The reactivity of the side-ways attack was found to be small. By comparing the results of the orientation dependence in the reaction with studies of inelastic collisions and theoretical calculations, two reaction pathways are proposed. Reaction by O-end attack is followed by a direct abstraction of the H-atom from the HBr molecule. The mechanism for H-end attack may have H-atom migration from HBr to form the water molecule.

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

    NASA Astrophysics Data System (ADS)

    Mezyk, Stephen P.

    1995-03-01

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

  16. Hydroxyl radical mediates N epsilon-(carboxymethyl)lysine formation from Amadori product.

    PubMed

    Nagai, R; Ikeda, K; Higashi, T; Sano, H; Jinnouchi, Y; Araki, T; Horiuchi, S

    1997-05-08

    Recent studies demonstrated N epsilon-(carboxymethyl)lysine (CML) in several tissue proteins. Incubation of proteins with glucose leads through a Schiff base to Amadori products. Oxidative cleavage of Amadori products is considered as a major route to CML formation in vivo, whereas it is not known which reactive oxygen species (ROS) is involved. The present study is undertaken to identify such a ROS. We prepared heavily glycated human serum albumin (HSA) which contained a high level of Amadori products, but an undetectable level of CML. Incubation of glycated HSA with FeCl2, but not with H2O2, led to CML formation which was enhanced by H2O2, but inhibited by catalase or mannitol, whereas superoxide dismutase had no effect. Similar data were obtained by experiments using Boc-fructose-lysine as a model Amadori compound. These data indicate that hydroxyl radical generated by the reaction of Fe2+ with H2O2 mediates CML formation from Amadori compounds.

  17. Formation and characteristics of aqueous two-phase systems formed by a cationic surfactant and a series of ionic liquids.

    PubMed

    Wei, Xi-Lian; Wang, Xiu-Hong; Ping, A-Li; Du, Pan-Pan; Sun, De-Zhi; Zhang, Qing-Fu; Liu, Jie

    2013-11-15

    Aqueous two-phase systems (ATPS) were obtained in the aqueous mixtures of a cationic surfactant and a series of ionic liquids (ILs). The effects of IL structure, temperature and additives on the phase separation were systematically investigated. The microstructures of some ATPS were observed by freeze-fracture replication technique. Lyotropic liquid crystal was found in the bottom phase besides micelles under different conditions. Remarkably, both IL structure and additives profoundly affected the formation and properties of the ATPSs. The phase separation can be attributed to the existence of different aggregates and the cation-π interactions of the cationic surfactant with the ILs, which has a significant role in the formation of ATPS. The extraction capacity of the studied ATPS was also evaluated through their application in the extraction of two biosubstances. The results indicate that the ILs with BF4(-) as anion show much better extraction efficiencies than the corresponding ILs with Br(-) as anion do under the same conditions. l-Tryptophan was mainly distributed into the NPTAB-rich phase, while methylene blue and capsochrome were mainly in the IL-rich phase.

  18. Secondary Organic Aerosol (SOA) Formation from Hydroxyl Radical Oxidation and Ozonolysis of Monoterpenes

    NASA Astrophysics Data System (ADS)

    Zhao, Defeng; Kaminski, Martin; Schlag, Patrick; Fuchs, Hendrik; Acir, Ismail-Hakki; Bohn, Birger; Haeseler, Rolf; Kiendler-Scharr, Astrid; Rohrer, Franz; Tillmann, Ralf; Wang, Mingjin; Wegner, Robert; Wahner, Andreas; Mentel, Thomas

    2014-05-01

    Hydroxyl radical (OH) oxidation and ozonolysis are the two major pathways of daytime biogenic volatile organic compounds (VOCs) oxidation and secondary organic aerosol (SOA) formation. The pure OH oxidation of monoterpenes, an important biogenic VOC class, has seldom been investigated. In order to elucidate the importance of the reaction pathyways of the OH oxidation and ozonolysis and their roles in particle formation and growth, we investigated the particle formation of several common monoterpenes (alpha-pinene, beta-pinene, and limonene) in the large atmosphere simulation chamber SAPHIR in Juelich, Germany. The experiments were conducted for both OH dominant and pure ozonolysis case (in the presence of CO as OH scavenger) at ambient relevant conditions (low OA, low VOC and low NOx concentration). OH and ozone (O3) concentrations were measured so that the oxidation rates of OH and O3 with precursors were quantified. The particle formation and growth, aerosol yield, multi-generation reaction process and aerosol composition were analyzed. Pure ozonolysis generated a large amount of particles indicating ozonolysis plays an important role in particle formation as well as OH oxidation. In individual experiments, particle growth rates did not necessarily correlate with OH or O3 oxidation rates. However, comparing the growth rates at similar OH or O3 oxidation rates shows that generally, OH oxidation and ozonolysis have similar efficiency in particle growth. Multi-generation products are shown to be important in the OH oxidation experiment based on aerosol yield "growth curve" (Ng et al., 2006). The reaction process of OH oxidation experiments was analyzed as a function of OH dose to elucidate the role of functionalization and fragmentation. A novel analysis was developed to link the particle formation with the reaction with OH, which was also used to examine the role of functionalization and fragmentation in the particle formation by OH oxidation. These analyses show

  19. Full dimensional quantum-mechanical simulations for the vibronic dynamics of difluorobenzene radical cation isomers using the multilayer multiconfiguration time-dependent Hartree method

    NASA Astrophysics Data System (ADS)

    Meng, Qingyong; Faraji, Shirin; Vendrell, Oriol; Meyer, Hans-Dieter

    2012-10-01

    Full dimensional multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) calculations of the dynamics of the three difluorobenzene cationic isomers in five lowest-lying doublet electronic states using the ab initio multistate multimode vibronic coupling Hamiltonian (MMVCH) model are carried out using the Heidelberg MCTDH package. The same dynamical problems, but treated with the MCTDH scheme and using a reduced dimensional ab initio MMVCH model, have been previously reported [S. Faraji, H.-D. Meyer, and H. Köppel, "Multistate vibronic interactions in difluorobenzene radical cations. II Quantum dynamical simulations," J. Chem. Phys. 129, 074311 (2008), 10.1063/1.2958918]. For easy comparison with the reduced dimensional results, 11D or 10D ML-MCTDH calculations are also performed. Extensive ML-MCTDH test calculations are performed to find appropriate ML-MCTDH wavefunction structures (ML-trees), and the convergence of the ML-MCTDH calculations are carefully checked to ensure accurate results. Based on the appropriate ML-trees, the photoelectron (PE) spectrum and the mass analyzed threshold ionization (MATI) spectrum are simulated, analyzed, and compared with corresponding experimental spectra. Because of its efficient simulation capability for large systems, ML-MCTDH calculations save a considerable amount of central processing unit (CPU)-time, even when a reduced dimensional MMVCH is used, i.e., the same reduced model as in the corresponding MCTDH calculations. Simulations of the experimental PE spectra by full dimensional ML-MCTDH calculations reproduced main peaks, which originate from different electronic states. The agreement is improved as compared to the reduced dimensionality calculations. Unfortunately, the experimental PE spectra are not very well resolved. Therefore, we compare our calculations additionally with highly resolved MATI spectra, which, however, are only available for the tilde{X} state. Based on a series of ML-MCTDH simulations with

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

    PubMed

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

    2015-01-20

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

  1. THE ROLE OF SELECTED CATIONS IN THE FORMATION OF PSEUDOMICELLES IN AQUEOUS HUMIC ACID (R822832)

    EPA Science Inventory

    The fluorescence intensity enhancement of a pyrene probe in aqueous humic acid solutions was assessed in terms of added lanthanide and thorium cations. Among the trivalent ions it was found that size played a role, with the small Lu3+ ion producing the greatest increase in pyrene...

  2. Conformational Distortions of π-Cation Radical (β-Oxoporphyrin)copper(II) Derivatives: [Cu(2,7,12-TrioxoOEHP)][SbCl(6)] and [Cu(2,7-DioxoOEiBC)][SbCl(6)].

    PubMed

    Turowska-Tyrk, Ilona; Kang, Seong-Joo; Scheidt, W Robert

    2011-03-01

    The preparation and characterization of two π-cation radical derivatives of copper β-oxo porphyrins is described. [3,3,8,8,13,13,17,18-Octaethyl-(3H,8H,13H)-porphine-2,7,12-trionato (2-)] copper π-cation radical, [Cu(2,7,12-trioxoOEHP(.))](+), and [3,3,8,8,12,13,17,18-octaethyl-(3H,8H)-porphine-2,7-dionato(2-)] copper π-cation radical, [Cu(2,7-dioxoOEiBC(.))](+), have been prepared and characterized by single-crystal X-ray determinations, UV/vis/NIR, and IR spectroscopies. Both molecules have modest distortion from the planarity and show monomeric units in the solid state. [Cu(2,7-dioxoOEiBC(.))](+) shows a concentration dependent near-IR band at 1410 nm. Crystal data for [Cu(2,7,12-trioxoOEHP(.))][SbCl(6)]: tetragonal, space group P4(2)/n, a = 31.085 (14) Å, c = 9.410 (4) Å, V = 9093 Å(3), Z = 8, T = 127 K. Crystal data for [Cu(2,7-dioxoOEiBC(.))][SbCl(6)]: monoclinic, space group P2(1)/n, a = 9.655 (4) Å, b = 20.592 (8) Å, c = 43.347 (17) Åβ = 89.97(1)(°), V = 8618. Å(3), Z = 8, T = 100 K.

  3. Secondary Organic Aerosol (SOA) formation from hydroxyl radical oxidation and ozonolysis of monoterpenes

    NASA Astrophysics Data System (ADS)

    Zhao, D. F.; Kaminski, M.; Schlag, P.; Fuchs, H.; Acir, I.-H.; Bohn, B.; Häseler, R.; Kiendler-Scharr, A.; Rohrer, F.; Tillmann, R.; Wang, M. J.; Wegener, R.; Wildt, J.; Wahner, A.; Mentel, T. F.

    2014-05-01

    Oxidation by hydroxyl radical (OH) and ozonolysis are the two major pathways of daytime biogenic volatile organic compounds (VOCs) oxidation and secondary organic aerosol (SOA) formation. In this study, we investigated the particle formation of several common monoterpenes (α-pinene, β-pinene, and limonene) by OH dominated oxidation, which has seldom been investigated. OH oxidation experiments were carried out in the SAPHIR chamber in Jülich, Germany, at low NOx (0.01-1 ppbV) and low ozone (O3) concentration. OH concentration and OH reactivity were measured directly so that the overall reaction rates of organic compounds with OH were quantified. Multi-generation reaction process, particle growth, new particle formation, particle yield, and chemical composition were analyzed and compared with that of monoterpene ozonolysis. Multi-generation products were found to be important in OH dominated SOA formation. The relative role of functionalization and fragmentation in the reaction process of OH oxidation was analyzed by examining the particle mass and the particle size as a function of OH dose. We developed a novel method which quantitatively links particle growth to the reaction of OH with organics in a reaction system. This method was also used to analyze the evolution of functionalization and fragmentation of organics in the particle formation by OH oxidation. It shows that functionalization of organics was dominant in the beginning of the reaction (within two lifetimes of the monoterpene) and fragmentation started to be dominant after that. We compared particle formation from OH oxidation with that from pure ozonolysis. In individual experiments, growth rates of the particle size did not necessarily correlate with the reaction rate of monoterpene with OH and O3. Comparing the size growth rates at the similar reaction rates of monoterpene with OH or O3 indicates that generally, OH oxidation and ozonolysis had similar efficiency in particle growth. The SOA yield of

  4. Secondary organic aerosol formation from hydroxyl radical oxidation and ozonolysis of monoterpenes

    NASA Astrophysics Data System (ADS)

    Zhao, D. F.; Kaminski, M.; Schlag, P.; Fuchs, H.; Acir, I.-H.; Bohn, B.; Häseler, R.; Kiendler-Scharr, A.; Rohrer, F.; Tillmann, R.; Wang, M. J.; Wegener, R.; Wildt, J.; Wahner, A.; Mentel, Th. F.

    2015-01-01

    Oxidation by hydroxyl radical (OH) and ozonolysis are the two major pathways of daytime biogenic volatile organic compound (BVOC) oxidation and secondary organic aerosol (SOA) formation. In this study, we investigated the particle formation of several common monoterpenes (α-pinene, β-pinene and limonene) by OH-dominated oxidation, which has seldom been investigated. OH oxidation experiments were carried out in the SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction) chamber in Jülich, Germany, at low NOx (0.01 ~ 1 ppbV) and low ozone (O3) concentration (< 20 ppbV). OH concentration and total OH reactivity (kOH) were measured directly, and through this the overall reaction rate of total organics with OH in each reaction system was quantified. Multi-generation reaction process, particle growth, new particle formation (NPF), particle yield and chemical composition were analyzed and compared with that of monoterpene ozonolysis. Multi-generation products were found to be important in OH-dominated SOA formation. The relative role of functionalization and fragmentation in the reaction process of OH oxidation was analyzed by examining the particle mass and the particle size as a function of OH dose. We developed a novel method which quantitatively links particle growth to the reaction rate of OH with total organics in a reaction system. This method was also used to analyze the evolution of functionalization and fragmentation of organics in the particle formation by OH oxidation. It shows that functionalization of organics was dominant in the beginning of the reaction (within two lifetimes of the monoterpene) and fragmentation started to play an important role after that. We compared particle formation from OH oxidation with that from pure ozonolysis. In individual experiments, growth rates of the particle size did not necessarily correlate with the reaction rate of monoterpene with OH and O3. Comparing the size growth rates at the similar reaction rates

  5. Solvent driving force ensures fast formation of a persistent and well-separated radical pair in plant cryptochrome.

    PubMed

    Lüdemann, Gesa; Solov'yov, Ilia A; Kubař, Tomáš; Elstner, Marcus

    2015-01-28

    The photoreceptor protein cryptochrome is thought to host, upon light absorption, a radical pair that is sensitive to very weak magnetic fields, endowing migratory birds with a magnetic compass sense. The molecular mechanism that leads to formation of a stabilized, magnetic field sensitive radical pair has despite various theoretical and experimental efforts not been unambiguously identified yet. We challenge this unambiguity through a unique quantum mechanical molecular dynamics approach where we perform electron transfer dynamics simulations taking into account the motion of the protein upon the electron transfer. This approach allows us to follow the time evolution of the electron transfer in an unbiased fashion and to reveal the molecular driving force that ensures fast electron transfer in cryptochrome guaranteeing formation of a persistent radical pair suitable for magnetoreception. We argue that this unraveled molecular mechanism is a general principle inherent to all proteins of the cryptochrome/photolyase family and that cryptochromes are, therefore, tailored to potentially function as efficient chemical magnetoreceptors.

  6. Formation of hydroxyl radicals contributes to the bactericidal activity of ciprofloxacin against Pseudomonas aeruginosa biofilms.

    PubMed

    Jensen, Peter Ø; Briales, Alejandra; Brochmann, Rikke P; Wang, Hengzhuang; Kragh, Kasper N; Kolpen, Mette; Hempel, Casper; Bjarnsholt, Thomas; Høiby, Niels; Ciofu, Oana

    2014-04-01

    Antibiotic-tolerant, biofilm-forming Pseudomonas aeruginosa has long been recognized as a major cause of chronic lung infections of cystic fibrosis patients. The mechanisms involved in the activity of antibiotics on biofilm are not completely clear. We have investigated whether the proposed induction of cytotoxic hydroxyl radicals (OH˙) during antibiotic treatment of planktonically grown cells may contribute to action of the commonly used antibiotic ciprofloxacin on P. aeruginosa biofilms. For this purpose, WT PAO1, a catalase deficient ΔkatA and a ciprofloxacin resistant mutant of PAO1 (gyrA), were grown as biofilms in microtiter plates and treated with ciprofloxacin. Formation of OH˙ and total amount of reactive oxygen species (ROS) was measured and viability was estimated. Formation of OH˙ and total ROS in PAO1 biofilms treated with ciprofloxacin was shown but higher levels were measured in ΔkatA biofilms, and no ROS production was seen in the gyrA biofilms. Treatment with ciprofloxacin decreased the viability of PAO1 and ΔkatA biofilms but not of gyrA biofilms. Addition of thiourea, a OH˙ scavenger, decreased the OH˙ levels and killing of PAO1 biofilm. Our study shows that OH˙ is produced by P. aeruginosa biofilms treated with ciprofloxacin, which may contribute to the killing of biofilm subpopulations.

  7. Temperature dependence of the photochemical formation of hydroxyl radical from dissolved organic matter.

    PubMed

    McKay, Garrett; Rosario-Ortiz, Fernando L

    2015-04-07

    The temperature dependence of the photochemical production of the hydroxyl radical (•OH) from dissolved organic matter (DOM) was investigated by measuring the apparent temperature dependence of the quantum yield (Φa) for this process. Temperature dependent Φa values were analyzed using the Arrhenius equation. Apparent activation energies obtained for DOM isolates purchased from the International Humic Substances Society ranged from 16 to 34 kJ mol(-1). Addition of 40 units mL(-1) catalase, used to hinder the hydrogen peroxide (H2O2)-dependent pathway to •OH, did not impact the observed activation energy. However, an increase in activation energy was observed in lower molecular weight DOM obtained by size fractionation. We also measured the temperature dependence of p-benzoquionone photolysis as a model compound for DOM and observed no temperature dependence (slope p = 0.41) for the formation of phenol from oxidation of benzene (the •OH probe used), but a value of about 10 kJ mol(-1) for p-benzoquinone loss, which is consistent with formation of a quinone-water exciplex. These data provide insight into DOM photochemistry as well as provide parameters useful for modeling steady state •OH concentrations in natural systems.

  8. Comparison of free radicals formation induced by cold atmospheric plasma, ultrasound, and ionizing radiation.

    PubMed

    Rehman, Mati Ur; Jawaid, Paras; Uchiyama, Hidefumi; Kondo, Takashi

    2016-09-01

    Plasma medicine is increasingly recognized interdisciplinary field combining engineering, physics, biochemistry and life sciences. Plasma is classified into two categories based on the temperature applied, namely "thermal" and "non-thermal" (i.e., cold atmospheric plasma). Non-thermal or cold atmospheric plasma (CAP) is produced by applying high voltage electric field at low pressures and power. The chemical effects of cold atmospheric plasma in aqueous solution are attributed to high voltage discharge and gas flow, which is transported rapidly on the liquid surface. The argon-cold atmospheric plasma (Ar-CAP) induces efficient reactive oxygen species (ROS) in aqueous solutions without thermal decomposition. Their formation has been confirmed by electron paramagnetic resonance (EPR) spin trapping, which is reviewed here. The similarities and differences between the plasma chemistry, sonochemistry, and radiation chemistry are explained. Further, the evidence for free radical formation in the liquid phase and their role in the biological effects induced by cold atmospheric plasma, ultrasound and ionizing radiation are discussed.

  9. 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.

  10. Hydroxyl radical in/on illuminated polar snow: formation rates, lifetimes, and steady-state concentrations

    NASA Astrophysics Data System (ADS)

    Chen, Zeyuan; Chu, Liang; Galbavy, Edward S.; Ram, Keren; Anastasio, Cort

    2016-08-01

    While the hydroxyl radical (OH) in the snowpack is likely a dominant oxidant for organic species and bromide, little is known about the kinetics or steady-state concentrations of OH on/in snow and ice. Here we measure the formation rate, lifetime, and concentration of OH for illuminated polar snow samples studied in the laboratory and in the field. Laboratory studies show that OH kinetics and steady-state concentrations are essentially the same for a given sample studied as ice and liquid; this is in contrast to other photooxidants, which show a concentration enhancement in ice relative to solution as a result of kinetic differences in the two phases. The average production rate of OH in samples studied at Summit, Greenland, is 5 times lower than the average measured in the laboratory, while the average OH lifetime determined in the field is 5 times higher than in the laboratory. These differences indicate that the polar snows we studied in the laboratory are affected by contamination, despite significant efforts to prevent this; our results suggest similar contamination may be a widespread problem in laboratory studies of ice chemistry. Steady-state concentrations of OH in clean snow studied in the field at Summit, Greenland, range from (0.8 to 3) × 10-15 M, comparable to values reported for midlatitude cloud and fog drops, rain, and deliquesced marine particles, even though impurity concentrations in the snow samples are much lower. Partitioning of firn air OH to the snow grains will approximately double the steady-state concentration of snow-grain hydroxyl radical, leading to an average [OH] in near-surface, summer Summit snow of approximately 4 × 10-15 M. At this concentration, the OH-mediated lifetimes of organics and bromide in Summit snow grains are approximately 3 days and 7 h, respectively, suggesting that hydroxyl radical is a major

  11. Theoretical study of the formation of naphthalene from the radical/π-bond addition between single-ring aromatic hydrocarbons.

    PubMed

    Comandini, Andrea; Brezinsky, Kenneth

    2011-06-09

    The experimental investigations performed in the 1960s on the o-benzyne + benzene reaction as well as the more recent studies on reactions involving π-electrons highlight the importance of π-bonding for different combustion processes related to PAH's and soot formation. In the present investigation radical/π-bond addition reactions between single-ring aromatic compounds have been proposed and computationally investigated as possible pathways for the formation of two-ring fused compounds, such as naphthalene, which serve as precursors to soot formation. The computationally generated optimized structures for the stationary points were obtained with uB3LYP/6-311+G(d,p) calculations, while the energies of the optimized complexes were refined using the uCCSD(T) method and the cc-pVDZ basis set. The computations have addressed the relevance of a number of radical/π-bond addition reactions including the singlet benzene + o-benzyne reaction, which leads to formation of naphthalene and acetylene through fragmentation of the benzobicyclo[2,2,2]octatriene intermediate. For this reaction, the high-pressure limit rate constants for the individual elementary reactions involved in the overall process were evaluated using transition state theory analysis. Other radical/π-bond addition reactions studied were between benzene and triplet o-benzyne, between benzene and phenyl radical, and between phenyl radicals, for all of which potential energy surfaces were produced. On the basis of the results of these reaction studies, it was found necessary to propose and subsequently confirm additional, alternative pathways for the formation of the types of PAH compounds found in combustion systems. The potential energy surface for one reaction in particular, the phenyl + phenyl addition, is shown to contain a low-energy channel leading to formation of naphthalene that is energetically comparable to the other examined conventional pathways leading to formation of biphenyl compounds. This

  12. Type-II nanorod heterostructure formation through one-step cation exchange.

    PubMed

    Chen, Meng-Yu; Hsu, Yung-Jung

    2013-01-07

    A novel one-step cation exchange approach has been developed to prepare ZnO-decorated ZnSe nanorods (ZnSe-ZnO NRs), a prototype type-II semiconductor nanoheterostructure. Because of the staggered band offset which promoted effective charge separation, the as-synthesized ZnSe-ZnO NRs exhibited remarkable photocatalytic activities under visible light illumination, demonstrating their promising potentials in relevant photoconversion applications.

  13. From Molecules to Surfaces: Radical-Based Mechanisms of Si-S and Si-Se Bond Formation on Silicon.

    PubMed

    Buriak, Jillian M; Sikder, Md Delwar H

    2015-08-05

    The derivatization of silicon surfaces can have profound effects on the underlying electronic properties of the semiconductor. In this work, we investigate the radical surface chemistry of silicon with a range of organochalcogenide reagents (comprising S and Se) on a hydride-terminated silicon surface, to cleanly and efficiently produce surface Si-S and Si-Se bonds, at ambient temperature. Using a diazonium-based radical initiator, which induces formation of surface silicon radicals, a group of organochalcogenides were screened for reactivity at room temperature, including di-n-butyl disulfide, diphenyl disulfide, diphenyl diselenide, di-n-butyl sulfide, diphenyl selenide, diphenyl sulfide, 1-octadecanethiol, t-butyl disulfide, and t-butylthiol, which comprises the disulfide, diselenide, thiol, and thioether functionalities. The surface reactions were monitored by transmission mode Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ionization mass spectrometry. Calculation of Si-Hx consumption, a semiquantitative measure of yield of production of surface-bound Si-E bonds (E = S, Se), was carried out via FTIR spectroscopy. Control experiments, sans the BBD diazonium radical initiator, were all negative for any evident incorporation, as determined by FTIR spectroscopy. The functional groups that did react with surface silicon radicals included the dialkyl/diphenyl disulfides, diphenyl diselenide, and 1-octadecanethiol, but not t-butylthiol, diphenyl sulfide/selenide, and di-n-butyl sulfide. Through a comparison with the rich body of literature regarding molecular radicals, and in particular, silyl radicals, reaction mechanisms were proposed for each. Armed with an understanding of the reaction mechanisms, much of the known chemistry within the extensive body of radical-based reactivity has the potential to be harnessed on silicon and could be extended to a range of technologically relevant semiconductor

  14. Hypochlorite-induced damage to DNA, RNA, and polynucleotides: formation of chloramines and nitrogen-centered radicals.

    PubMed

    Hawkins, Clare L; Davies, Michael J

    2002-01-01

    Stimulated monocytes and neutrophils generate hypochlorite (HOCl) via the release of the enzyme myeloperoxidase and hydrogen peroxide. HOCl is a key bactericidal agent, but can also damage host tissue. As there is a strong link between chronic inflammation and some cancers, we have investigated HOCl damage to DNA, RNA, and polynucleotides. Reaction of HOCl with these materials is shown to yield multiple semistable chloramines (RNHCl/RR'NCl), which are the major initial products, and account for 50-95% of the added HOCl. These chloramines decay by thermal and metal-ion catalyzed processes, to give nucleoside-derived, nitrogen-centered, radicals. The latter have been characterized by EPR spin trapping. The propensity for radical formation with polynucleotides is cytidine > adenosine = guanosine > uridine = thymidine. The rates of decay, and yield of radicals formed, are dependent on the nature of the nucleobase on which they are formed, with chloramines formed from ring heterocyclic amine groups being less stable than those formed on exocyclic amines (RNH2 groups). Evidence is presented for chlorine transfer from the former, kinetically favored, sites to the more thermodynamically favored exocyclic amines. EPR experiments have also provided evidence for the rapid addition of pyrimidine-derived nitrogen-centered radicals to other nucleobases to give dimers and the oxidation of DNA by radicals derived from preformed nucleoside chloramines. Direct reaction of HOCl with plasmid DNA gives rise to single- and double-strand breaks via chloramine-mediated reactions. Preformed nucleoside chloramines also induce plasmid cleavage, though this only occurs to a significant extent with unstable thymidine- and uridine-derived chloramines, where radical formation is rapid. Overall the data rationalize the preferential formation of chlorinated 2'-deoxycytidine and 2'-deoxyadenosine in DNA and suggest that DNA damage induced by HOCl, and preformed chloramines, occurs at sequence

  15. Quantum chemical studies of a model for peptide bond formation. 3. Role of magnesium cation in formation of amide and water from ammonia and glycine

    NASA Technical Reports Server (NTRS)

    Oie, T.; Loew, G. H.; Burt, S. K.; MacElroy, R. D.

    1984-01-01

    The SN2 reaction between glycine and ammonia molecules with magnesium cation Mg2+ as a catalyst has been studied as a model reaction for Mg(2+)-catalyzed peptide bond formation using the ab initio Hartree-Fock molecular orbital method. As in previous studies of the uncatalyzed and amine-catalyzed reactions between glycine and ammonia, two reaction mechanisms have been examined, i.e., a two-step and a concerted reaction. The stationary points of each reaction including intermediate and transition states have been identified and free energies calculated for all geometry-optimized reaction species to determine the thermodynamics and kinetics of each reaction. Substantial decreases in free energies of activation were found for both reaction mechanisms in the Mg(2+)-catalyzed amide bond formation compared with those in the uncatalyzed and amine-catalyzed amide bond formation. The catalytic effect of the Mg2+ cation is to stabilize both the transition states and intermediate, and it is attributed to the neutralization of the developing negative charge on the electrophile and formation of a conformationally flexible nonplanar five-membered chelate ring structure.

  16. Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

    NASA Technical Reports Server (NTRS)

    Huang, C. J.; Yeager, E.; Ogrady, W. E.

    1975-01-01

    The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

  17. Role of nitrite in the photochemical formation of radicals in the snow.

    PubMed

    Jacobi, Hans-Werner; Kleffmann, Jörg; Villena, Guillermo; Wiesen, Peter; King, Martin; France, James; Anastasio, Cort; Staebler, Ralf

    2014-01-01

    Photochemical reactions in snow can have an important impact on the composition of the atmosphere over snow-covered areas as well as on the composition of the snow itself. One of the major photochemical processes is the photolysis of nitrate leading to the formation of volatile nitrogen compounds. We report nitrite concentrations determined together with nitrate and hydrogen peroxide in surface snow collected at the coastal site of Barrow, Alaska. The results demonstrate that nitrite likely plays a significant role as a precursor for reactive hydroxyl radicals as well as volatile nitrogen oxides in the snow. Pollution events leading to high concentrations of nitrous acid in the atmosphere contributed to an observed increase in nitrite in the surface snow layer during nighttime. Observed daytime nitrite concentrations are much higher than values predicted from steady-state concentrations based on photolysis of nitrate and nitrite indicating that we do not fully understand the production of nitrite and nitrous acid in snow. The discrepancy between observed and expected nitrite concentrations is probably due to a combination of factors, including an incomplete understanding of the reactive environment and chemical processes in snow, and a lack of consideration of the vertical structure of snow.

  18. Photochemical formation of hydroxyl radical from effluent organic matter: role of composition.

    PubMed

    Lee, Eunkyung; Glover, Caitlin M; Rosario-Ortiz, Fernando L

    2013-01-01

    The photochemical formation of hydroxyl radical (HO(•)) from effluent organic matter (EfOM) depends upon the chemical properties of this heterogeneous mixture. In this study, two EfOM samples collected from wastewater treatment plants (WWTP A and B) were fractionated by both hydrophobicity (bulk and non-humic) and apparent molecular weight (AMW). The apparent quantum yield for HO(•) formation (ΦHO(•)) and the maximum fluorescence quantum yield (ΦF) were subsequently measured for each subfraction. The formation rates of HO(•) (considering only the hydrogen-peroxide-independent pathways) for the bulk waters were 4.8 × 10(-10) and 9.6 × 10(-11) M s(-1) for WWTP A and B, respectively. For the AMW fractions, the values of ΦHO(•) increased as the AMW of the material decreased. For the WWTP A sample, the ΦHO(•) increased from 2.54 × 10(-4) (bulk water) to 6.29 × 10(-4) for the <1 kDa fraction, and for the WWTP B sample, the value of ΦHO(•) increased from 6.50 × 10(-5) for bulk water to 3.45 × 10(-4) for the <1 kDa fraction. In the case of fluorescence, the values of ΦF ranged from 2.37 × 10(-4) (bulk water) to 3.48 × 10(-4) (<1 kDa fraction) for WWTP A and 3.19 × 10(-4) (bulk water) to 5.75 × 10(-4) (<1 kDa fraction) for WWTP B. There was a linear correlation between ΦHO(•) and ΦF, suggesting that different photophysical processes occur in the chemical components of the fractions. Understanding the formation of HO(•) from EfOM is essential for understanding wastewater-impacted aquatic systems because these results influence the photochemical degradation and mineralization of trace organic contaminants.

  19. Crystalline bipyridinium radical complexes and uses thereof

    DOEpatents

    Fahrenbach, Albert C.; Barnes, Jonathan C.; Li, Hao; Stoddart, J. Fraser; Basuray, Ashish Neil; Sampath, Srinivasan

    2015-09-01

    Described herein are methods of generating 4,4'-bipyridinium radical cations (BIPY.sup..cndot.+), and methods for utilizing the radical-radical interactions between two or more BIPY.sup..cndot.+ radical cations that ensue for the creation of novel materials for applications in nanotechnology. Synthetic methodologies, crystallographic engineering techniques, methods of physical characterization, and end uses are described.

  20. Nitro radical anion formation from nitrofuryl substituted 1,4-dihydropyridine derivatives in mixed and non-aqueous media.

    PubMed

    Argüello, J; Núñez-Vergara, L J; Bollo, S; Squella, J A

    2006-09-01

    Three new nitrofuryl substituted 1,4-dihydropyridine derivatives were electrochemically tested in the scope of newly found compounds useful as chemotherapeutic alternative to the Chagas' disease. All the compounds were capable to produce nitro radical anions sufficiently stabilized in the time window of the cyclic voltammetric experiment. In order to quantify the stability of the nitro radical anion we have calculated the decay constant, k2. Furthermore, from the voltammetric results, some parameters of biological significance as E7(1) (indicative of in vivo nitro radical anion formation) and KO2 (thermodynamic indicator of oxygen redox cycling) have been calculated. From the comparison of E7(1), KO2 and k2 values between the studied nitrofuryl 1,4-DHP derivatives and well-known current drugs an auspicious activity for one of the studied compounds i.e. FDHP2, can be expected.

  1. IN VIVO EVIDENCE OF FREE RADICAL FORMATION AFTER ASBESTOS INSTILLATION: AN ESR SPIN TRAPPING INVESTIGATION

    EPA Science Inventory


    It has been postulated that the in vivo toxicity of asbestos results from its catalysis of free radical generation. We examined in vivo radical production using electron spin resonance (ESR) coupled with the spin trap alpha-(4-pyridyl-1-oxide)-N-t-butylnitrone (4-POBN); 180 d...

  2. 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.

  3. Reverse-micelle formation in the partitioning of trivalent F-element cations by biphasic systems containing a tetraalkyldiglycolamide.

    PubMed

    Jensen, Mark P; Yaita, Tsuyoshi; Chiarizia, Renato

    2007-04-24

    The conditions for reverse-micelle formation were studied for solutions of tetra-n-octyldiglycolamide (TODGA) in alkane diluents equilibrated with aqueous solutions of nitric or hydrochloric acids in the presence and absence of Nd3+. Small-angle neutron scattering, vapor-pressure osmometry, and tensiometry are all consistent with the partial formation of TODGA dimers at the lowest acidities, transitioning to a polydisperse mixture containing TODGA monomers, dimers, and small reverse-micelles of TODGA tetramers at aqueous nitric acid acidities of 0.7 M or higher in the absence of Nd. Application of the Baxter model to the samples containing 0.005-0.015 M Nd reveals the persistence of tetrameric TODGA reverse-micelles with significant interparticle attraction between the polar cores of the micelles that increases with increasing organic phase concentrations of acid or Nd. Our experimental findings suggest that the peculiar behavior of TODGA with respect to the extraction of trivalent lanthanide and actinide cations arises from the affinity of these metal cations for the preformed TODGA reverse-micelle tetramers.

  4. Formation of long-lived hydroxyl free radical adducts of proline and hydroxyproline in a Fenton reaction.

    PubMed

    Floyd, R A; Nagy, I

    1984-10-09

    Proline and hydroxyproline when exposed to the hydroxyl free radical generating system of ADP-Fe(II)-H2O2 yielded long-lived free radicals. An analysis of the electron paramagnetic resonance spectra of the long-lived hydroxyl free radical adducts of proline and hydroxyproline is consistent with a free electron on a nitroxyl group interacting with the nitrogen atom as well as with three separate protons. In the case of proline, nitroxide formation was observed under the influence of tert-butyl-hydroperoxide, giving a similar EPR spectrum (Lin, J.S., Tom, T.C. and Olcott, H.S. (1974) J. Agr. Food Chem. 22, 526-528); however, the hydroxyl free radical adduct of hydroxyproline has not been described yet. In the case of the proline nitroxide radical, two of the three protons involved interact with the free electron equivalently. The coupling constants for the hydroxyl free radical adduct of proline are AN = 1.58 mT, AH1 beta = AH2 beta = 2.13 mT, AH3 beta = 1.77 mT and for hydroxyproline are AN = 1.54 mT, AH1 beta = 2.56 mT, AH2 beta = 2.03 and AH3 beta = 1.51. The data are consistent with the amine nitrogen of proline and hydroxyproline being oxidized to a nitroxyl group and the free electron of the nitroxyl interacting with the beta-protons of these amino acid hydroxyl free radical adducts.

  5. A high performance liquid chromatography system for quantification of hydroxyl radical formation by determination of dihydroxy benzoic acids.

    PubMed

    Owen, R W; Wimonwatwatee, T; Spiegelhalder, B; Bartsch, H

    1996-08-01

    The hypoxanthine/xanthine oxidase enzyme system is known to produce the superoxide ion and hydrogen peroxide during the hydroxylation of hypoxanthine via xanthine to uric acid. When chelated iron is included in this system, superoxide reduces iron (III) to iron(II) and the iron(II)-chelate further reacts with hydrogen peroxide to form the highly reactive hydroxyl radical. Because of the limitations of colourimetric and spectrophotometric techniques by which, to date, the mechanisms of hydroxyl radical formation in the hypoxanthine/xanthine oxidase system have been monitored, a high performance liquid chromatography method utilizing the ion-pair reagent tetrabutylammonium hydroxide and salicylic acid as an aromatic probe for quantification of hydroxyl radical formation was set up. In the hypoxanthine/xanthine oxidase system the major products of hydroxyl radical attack on salicylic acid were 2,5-dihydroxy benzoic acid and 2,3-dihydroxy benzoic acid in the approximate ratio of 5:1. That the hydroxyl radical is involved in the hydroxylation of salicylic acid in this system was demonstrated by the potency especially of dimethyl sulphoxide, butanol and ethanol as scavengers. Phytic acid, which is considered to be an important protective dietary constituent against colorectal cancer, inhibited hydroxylation of salicylic acid at a concentration one order of magnitude lower than the classical scavengers, but was only effective in the absence of EDTA. The method has been applied to the study of free radical generation in faeces, and preliminary results indicate that the faecal flora are able to produce reactive oxygen species in abundance.

  6. Strong Inhibition of O-Atom Transfer Reactivity for Mn(IV)(O)(π-Radical-Cation)(Lewis Acid) versus Mn(V)(O) Porphyrinoid Complexes.

    PubMed

    Zaragoza, Jan Paulo T; Baglia, Regina A; Siegler, Maxime A; Goldberg, David P

    2015-05-27

    The oxygen atom transfer (OAT) reactivity of two valence tautomers of a Mn(V)(O) porphyrinoid complex was compared. The OAT kinetics of Mn(V)(O)(TBP8Cz) (TBP8Cz = octakis(p-tert-butylphenyl)corrolazinato(3-)) reacting with a series of triarylphosphine (PAr3) substrates were monitored by stopped-flow UV-vis spectroscopy, and revealed second-order rate constants ranging from 16(1) to 1.43(6) × 10(4) M(-1) s(-1). Characterization of the OAT transition state analogues Mn(III)(OPPh3)(TBP8Cz) and Mn(III)(OP(o-tolyl)3)(TBP8Cz) was carried out by single-crystal X-ray diffraction (XRD). A valence tautomer of the closed-shell Mn(V)(O)(TBP8Cz) can be stabilized by the addition of Lewis and Brønsted acids, resulting in the open-shell Mn(IV)(O)(TBP8Cz(•+)):LA (LA = Zn(II), B(C6F5)3, H(+)) complexes. These Mn(IV)(O)(π-radical-cation) derivatives exhibit dramatically inhibited rates of OAT with the PAr3 substrates (k = 8.5(2) × 10(-3) - 8.7 M(-1) s(-1)), contrasting the previously observed rate increase of H-atom transfer (HAT) for Mn(IV)(O)(TBP8Cz(•+)):LA with phenols. A Hammett analysis showed that the OAT reactivity for Mn(IV)(O)(TBP8Cz(•+)):LA is influenced by the Lewis acid strength. Spectral redox titration of Mn(IV)(O)(TBP8Cz(•+)):Zn(II) gives Ered = 0.69 V vs SCE, which is nearly +700 mV above its valence tautomer Mn(V)(O)(TBP8Cz) (Ered = -0.05 V). These data suggest that the two-electron electrophilicity of the Mn(O) valence tautomers dominate OAT reactivity and do not follow the trend in one-electron redox potentials, which appear to dominate HAT reactivity. This study provides new fundamental insights regarding the relative OAT and HAT reactivity of valence tautomers such as M(V)(O)(porph) versus M(IV)(O)(porph(•+)) (M = Mn or Fe) found in heme enzymes.

  7. Formation of cation channels in planar lipid bilayers by brefeldin A.

    PubMed

    Zizi, M; Fisher, R S; Grillo, F G

    1991-10-05

    Brefeldin A (BFA) is a novel agent with the unique property of effecting a rapid increase of Golgi cisternae volume and subsequent loss of a recognizable Golgi apparatus in treated cells. Although a receptor-mediated mechanism has been proposed, the molecular basis of BFA action remains unknown (Lippincott-Schwartz, J., Glickman, J., Donaldson, J. G., Robbins, J., Kreis, T. E., Seamon, K. B., Sheetz, M. P., and Klausner, R. D. (1991) J. Cell Biol. 112, 567-577). Since a variety of ionophores distort Golgi architecture by initially causing osmotic swelling of the cisternae (Mollenhauer, H. H., Morre, D. J., and Rowe, L. D. (1990) Biochim. Biophys. Acta 1031, 225-246), Golgi membrane permeabilization by BFA seemed possible. We examined the effects of BFA on the conductance of planar lipid bilayers bathed in several aqueous salt solutions. Addition of BFA (1 microgram/ml) quickly augmented alkali cation conductance (K+ greater than Na+ much greater than Li+) but not anion conductance of the bilayer. Lower concentrations (1 ng/ml) indicated that BFA formed discrete, cation-selective channels in these bilayers. Given that Golgi cisternae volume increases immediately upon treatment with BFA, these findings suggest that alteration of ion gradients or Golgi membrane potential followed by an influx of water may be the mechanism by which BFA initiates disruption of Golgi structural integrity. Subsequent functional perturbations may then ensue either as a consequence of these initial structural changes or by a combination of several distinct mechanisms.

  8. Electron Paramagnetic Resonance Characterization of Tetrahydrobiopterin Radical Formation in Bacterial Nitric Oxide Synthase Compared to Mammalian Nitric Oxide Synthase

    PubMed Central

    Brunel, Albane; Santolini, Jérôme; Dorlet, Pierre

    2012-01-01

    H4B is an essential catalytic cofactor of the mNOSs. It acts as an electron donor and activates the ferrous heme-oxygen complex intermediate during Arg oxidation (first step) and NOHA oxidation (second step) leading to nitric oxide and citrulline as final products. However, its role as a proton donor is still debated. Furthermore, its exact involvement has never been explored for other NOSs such as NOS-like proteins from bacteria. This article proposes a comparative study of the role of H4B between iNOS and bsNOS. In this work, we have used freeze-quench to stop the arginine and NOHA oxidation reactions and trap reaction intermediates. We have characterized these intermediates using multifrequency electron paramagnetic resonance. For the first time, to our knowledge, we report a radical formation for a nonmammalian NOS. The results indicate that bsNOS, like iNOS, has the capacity to generate a pterin radical during Arg oxidation. Our current electron paramagnetic resonance data suggest that this radical is protonated indicating that H4B may not transfer any proton. In the 2nd step, the radical trapped for iNOS is also suggested to be protonated as in the 1st step, whereas it was not possible to trap a radical for the bsNOS 2nd step. Our data highlight potential differences for the catalytic mechanism of NOHA oxidation between mammalian and bacterial NOSs. PMID:22828337

  9. Vitamin C (ascorbic acid) induced hydroxyl radical formation in copper contaminated household drinking water: role of bicarbonate concentration.

    PubMed

    Jansson, Patric J; Asplund, Klara U M; Mäkelä, Johanna C; Lindqvist, Christer; Nordström, Tommy

    2003-08-01

    We have previously shown that Vitamin C (ascorbic acid) can trigger hydroxyl radical formation in copper contaminated household drinking water. We report here that the capacity of ascorbic acid to catalyze hydroxyl radical generation in the drinking water samples is strongly dependent on the bicarbonate concentration (buffer capacity and pH) of the samples. We found that at least 50 mg/l bicarbonate was required in the water samples to maintain the pH over 5.0 after ascorbic acid addition. At this pH, that is higher than the pKa1 4.25 of ascorbic acid, a hydroxyl radical generating redox cycling reaction involving the mono-anion of vitamin C and copper could take place. The ascorbic acid induced hydroxyl radical generating reaction could easily be mimicked in Milli-Q water by supplementing the water with copper and bicarbonate. Our results demonstrate that ascorbic acid can induce a pH dependent hydroxyl radical generating reaction in copper contaminated household tap water that is buffered with bicarbonate. The impact of consuming ascorbic acid together with copper and bicarbonate containing drinking water on human health is discussed.

  10. Formation of hydroxyl radical from San Joaquin Valley particles extracted in a cell-free solution

    NASA Astrophysics Data System (ADS)

    Shen, H.; Anastasio, C.

    2011-06-01

    Previous studies have suggested that the adverse health effects from ambient particulate matter (PM) are linked to the formation of reactive oxygen species (ROS) by PM. While hydroxyl radical (•OH) is the most reactive of the ROS species, there are few quantitative studies of •OH generation from PM. Here we report on •OH formation from PM collected at an urban (Fresno) and rural (Westside) site in the San Joaquin Valley (SJV) of California. We quantified •OH in PM extracts using a cell-free, phosphate-buffered saline (PBS) solution with or without 50 μM ascorbate (Asc). The results show that generally the urban Fresno PM generates much more •OH than the rural Westside PM. The presence of Asc at a physiologically relevant concentration in the extraction solution greatly enhances •OH formation from all the samples. Fine PM (PM2.5) generally makes more •OH than the corresponding coarse PM (PMcf, i.e., 2.5 to 10 μm) normalized by air volume collected, while the coarse PM typically generates more •OH normalized by PM mass. •OH production by SJV PM is reduced on average by (97 ± 6) % when the transition metal chelator desferoxamine (DSF) is added to the extraction solution, indicating a dominant role of transition metals. By measuring calibration curves of •OH generation from copper and iron, and quantifying copper and iron concentrations in our particle extracts, we find that PBS-soluble copper is primarily responsible for •OH production by the SJV PM, while iron often makes a significant contribution. Extrapolating our results to expected burdens of PM-derived •OH in human lung lining fluid suggests that typical daily PM exposures in the San Joaquin Valley are unlikely to result in a high amount of pulmonary •OH, although high PM events could produce much higher levels of •OH, which might lead to cytotoxicity.

  11. Investigation of Model Sunscreen Formulations Comparing the Sun Protection Factor, the Universal Sun Protection Factor and the Radical Formation Ratio.

    PubMed

    Syring, Felicia; Weigmann, Hans-Jürgen; Schanzer, Sabine; Meinke, Martina C; Knorr, Fanny; Lademann, Jürgen

    2016-01-01

    In view of globally rising skin cancer rates and harmful effects exerted by sunlight throughout the ultraviolet, visible and infrared ranges, an objective, safe and comprehensive method for determining sunscreen efficacy is required in order to warrant safe sun exposure. In this study, the influence of characteristic active ingredients (chemical filters, physical filters and antioxidants) on different sunscreen indicators, including the universal sun protection factor and the radical formation ratio, was determined and compared to their influence on sun protection factor values. Spectroscopic universal sun protection factor measurements were conducted ex vivo by analyzing tape strips taken from human skin, and radical formation ratio determination was performed via electron paramagnetic resonance spectroscopy using porcine ear skin ex vivo. The sun protection factor determination was conducted according to ISO standards (ISO 24444:2010). It was shown that chemical filters provide a protective effect which was measurable by all methods examined (spectroscopy, electron paramagnetic resonance spectroscopy and erythema formation). Physical filters, when used as single active ingredients, increased protective values in universal sun protection factor and sun protection factor measurements but exhibited no significant effect on universal sun protection factor measurements when used in combination with chemical filters or antioxidants. Antioxidants were shown to increase sun protection factor values. Radical formation ratio values were shown to be influenced merely by chemical filters, leading to the conclusion that the universal sun protection factor is the most suitable efficacy indicator for the ultraviolet range.

  12. Fourier transform infrared study of the cation radical of P680 in the photosystem II reaction center: evidence for charge delocalization on the chlorophyll dimer.

    PubMed

    Noguchi, T; Tomo, T; Inoue, Y

    1998-09-29

    A Fourier transform infrared (FTIR) difference spectrum of the primary electron donor (P680) of photosystem II upon its photooxidation (P680+/P680) was obtained in the frequency region of 1000-3000 cm-1. The reaction center (RC) complex (D1-D2-Cytb559) was used for the measurements in the presence of ferricyanide as an exogenous electron acceptor. Control measurements of electronic absorption (300-1200 nm) showed that illumination of the RC complex at 150 K induced major oxidation of P680 concomitant with oxidation of a carotenoid and an accessory chlorophyll (Chl). Illumination at 250 K also specifically bleached one of the two beta-carotene molecules bound to the RC complex, and the sample thus treated exhibited little formation of a carotenoid cation on subsequent illumination at 150 K. The P680+/P680 FTIR difference spectrum (with minor contamination of Chl+/Chl) was measured at 150 K using this partially carotenoid-deficient RC complex. The spectrum showed a broad positive band centered at approximately 1940 cm-1, which could be ascribed to an infrared electronic transition of P680+ analogous to that previously observed in various bacterial P+. This finding indicates that a positive charge is delocalized over (or hopping between) the two Chl molecules in P680+. The low intensity of this electronic band compared with that of the bacterial band could have three possible explanations: weak resonance interaction between the constituent Chl molecules, an asymmetric structure of P680+, and the difference in Chl species. Bands in the C=O stretching region (1600-1750 cm-1) were interpreted in comparison with resonance Raman spectra of the RC complex. The negative peaks at 1704 and 1679 cm-1 were proposed as candidates for the keto C9=O bands of P680. The observation that neither of these bands agreed with the main keto C9=O band at 1669 cm-1 in the previous 3P680/P680 FTIR spectrum [Noguchi et al. (1993) Biochemistry 32, 7186-7195] led to the idea that the triplet

  13. Toward the Oxidation of the Phenyl Radical and Prevention of PAH Formation in Combustion Systems.

    PubMed

    Parker, Dorian S N; Kaiser, Ralf I; Troy, Tyler P; Kostko, Oleg; Ahmed, Musahid; Mebel, Alexander M

    2015-07-16

    The reaction of the phenyl radical (C6H5) with molecular oxygen (O2) plays a central role in the degradation of poly- and monocyclic aromatic radicals in combustion systems which would otherwise react with fuel components to form polycyclic aromatic hydrocarbons (PAHs) and eventually soot. Despite intense theoretical and experimental scrutiny over half a century, the overall reaction channels have not all been experimentally identified. Tunable vacuum ultraviolet photoionization in conjunction with a combustion simulating chemical reactor uniquely provides the complete isomer specific product spectrum and branching ratios of this prototype reaction. In the reaction of phenyl radicals and molecular oxygen at 873 K and 1003 K, ortho-benzoquinone (o-C6H4O2), the phenoxy radical (C6H5O), and cyclopentadienyl radical (C5H5) were identified as primary products formed through emission of atomic hydrogen, atomic oxygen and carbon dioxide. Furan (C4H4O), acrolein (C3H4O), and ketene (C2H2O) were also identified as primary products formed through ring opening and fragmentation of the 7-membered ring 2-oxepinoxy radical. Secondary reaction products para-benzoquinone (p-C6H4O2), phenol (C6H5OH), cyclopentadiene (C5H6), 2,4-cyclopentadienone (C5H4O), vinylacetylene (C4H4), and acetylene (C2H2) were also identified. The pyranyl radical (C5H5O) was not detected; however, electronic structure calculations show that it is formed and isomerizes to 2,4-cyclopentadienone through atomic hydrogen emission. In combustion systems, barrierless phenyl-type radical oxidation reactions could even degrade more complex aromatic radicals. An understanding of these elementary processes is expected to lead to a better understanding toward the elimination of carcinogenic, mutagenic, and environmentally hazardous byproducts of combustion systems such as PAHs.

  14. Surface functionalized SiO2 nanoparticles with cationic polymers via the combination of mussel inspired chemistry and surface initiated atom transfer radical polymerization: Characterization and enhanced removal of organic dye.

    PubMed

    Huang, Qiang; Liu, Meiying; Mao, Liucheng; Xu, Dazhuang; Zeng, Guangjian; Huang, Hongye; Jiang, Ruming; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-03-28

    Monodispersed SiO2 particles functionalized with cationic polymers poly-((3-acrylamidopropyl)trimethylammonium chloride) (PAPTCl) were prepared using mussel inspired surface modification strategy and surface initiated atom transfer radical polymerization (SI-ATRP). Fourier transform infrared spectroscopy, transmission electron microscope, thermogravimetric analysis, X-ray photoelectron spectroscopy, and zeta potential were employed to characterize these SiO2 samples. The adsorption performance of the functionalized SiO2 (donated as SiO2-PDA-PAPTCl) towards anionic organic dye Congo red (CR) was investigated to evaluate their potential environmental applications. We demonstrated that the surface of SiO2 particles can be successfully functionalized with cationic PAPTCl. The adsorption capability of as-prepared SiO2 was found to increases from 28.70 and 106.65mg/g after surface grafted with cationic polymers. The significant enhancement in the adsorption capability of SiO2-PDA-PAPTCl is mainly attributed to the introduction of cationic polymers. More importantly, this strategy is expected to be promising for fabrication of many other functional polymer nanocomposites for environmental applications due to the universality of mussel inspired chemistry and well designability and good monomer adaptability of SI-ATRP.

  15. Determination of melamine and cyromazine in milk by high performance liquid chromatography coupled with online solid-phase extraction using a novel cation-exchange restricted access material synthesized by surface initiated atom transfer radical polymerization.

    PubMed

    Zhang, Yingying; Lin, Shen; Jiang, Ping; Zhu, Xudong; Ling, Jing; Zhang, Wen; Dong, Xiangchao

    2014-04-11

    A novel strong-cation-exchange restricted access material has been synthesized by atom transfer radical polymerization (ATRP). In the synthesis, poly(3-sulfopropyl methacrylate-co-ethylene dimethacrylate), [p(SPM/EDMA)] was grafted on the silica by surface-initiated ATRP first. The poly(glycerol mono-methacrylate) [pGMMA] was then immobilized on the external surface, which created a chemical diffusion barrier for protein exclusion. The resulting Sil-g-p(SPM/EDMA)-g-pGMMA has both functions of protein exclusion and cation exchange, exhibiting the property of cation-exchange restricted access material. The application of Sil-g-p(SPM/EDMA)-g-pGMMA has been studied by the determination of melamine and cyromazine in bovine milk using the online solid-phase extraction/HPLC method. In the process, the Sil-g-p(SPM/EDMA)-g-pGMMA was used for the sample pre-treatment and a HILIC column was employed as the analytical column. The method has shown good accuracy, precision and low limits of detections. The result demonstrated that the Sil-g-p(SPM/EDMA)-g-pGMMA can be used for the cation extraction from biological samples by direct HPLC injection.

  16. Theoretical studies on atmospheric chemistry of HFE-245mc and perfluoro-ethyl formate: Reaction with OH radicals, atmospheric fate of alkoxy radical and global warming potential

    NASA Astrophysics Data System (ADS)

    Lily, Makroni; Baidya, Bidisha; Chandra, Asit K.

    2017-02-01

    Theoretical studies have been performed on the kinetics, mechanism and thermochemistry of the hydrogen abstraction reactions of CF3CF2OCH3 (HFE-245mc) and CF3CF2OCHO with OH radical using DFT based M06-2X method. IRC calculation shows that both hydrogen abstraction reactions proceed via weakly bound hydrogen-bonded complex preceding to the formation of transition state. The rate coefficients calculated by canonical transition state theory along with Eckart's tunnelling correction at 298 K: k1(CF3CF2OCH3 + OH) = 1.09 × 10-14 and k2(CF3CF2OCHO + OH) = 1.03 × 10-14 cm3 molecule-1 s-1 are in very good agreement with the experimental values. The atmospheric implications of CF3CF2OCH3 and CF3CF2OCHO are also discussed.

  17. Radical polymerization in holographic grating formation in PQ-PMMA photopolymer part II: Consecutive exposure and dark decay

    NASA Astrophysics Data System (ADS)

    Yu, Dan; Liu, Hongpeng; Geng, Yaohui; Wang, Weibo; Zhao, Yuanyuan

    2014-11-01

    Photochemical radical polymerization in phenathrenequinone doped poly(methyl methacrylate) photopolymer are investigated theoretically and experimentally under consecutive exposure. The detailed photochemical mechanisms are analyzed. Based on the rate equations of photochemical reactions, the diffusion models with nonlocal response are proposed to describe the kinetic process of radical polymerization and the significance of photochemical processes for the grating formation. In experiments, the temporal evolution of diffraction efficiency in grating formation is measured under consecutive exposure and after exposure. The percentages of these radical polymerizations, namely the polymerization of PQ with matrix, the bimolecular combination of MMA molecules, and the disproportionation of MMA molecules, are extracted quantitatively by comparing theory with experiments. It is indicated that the polymerization of PQ with matrix is primary photochemical process which dominated the grating formation under consecutive exposure. In this period, the contribution of chain polymerization of MMA radicals is weak for the grating formation. After reaching the peak values of grating strength, the influence of the free MMA molecules and photoproduct macromolecules on the grating decay is discussed in a long-term period. The diffusion coefficients of MMA and photoproduct are extracted by fitting the curves using double exponential function. MMA’s diffusion contributed to the fast decay process of grating after exposure and photoproduct’s diffusion contributed to the slow and long decay of grating. The results break previous understanding about the diffusion of single photoproduct macromolecules lead to the dark decay of grating. This investigation can provide a significant foundation for improving modulation depth and long-term stability by photochemical mechanism.

  18. Radical formation and accumulation in vivo, in desiccation tolerant and intolerant mosses.

    PubMed

    Seel, W; Hendry, G; Atherton, N; Lee, J

    1991-01-01

    Water loss in a desiccation-sensitive moss resulted in destruction of chlorophyll, loss of carotenoids and increased lipid peroxidation, indicating the presence of damaging forms of activated oxygen. These effects were exaggerated when the plants were desiccated at high light intensities. During water-deprivation there was a build up of a free radical, detected in vivo, with a close correlation between molecular damage and radical accumulation. In contrast, in a desiccation-tolerant moss there was almost no indication of molecular (oxidative) damage. However a stable radical similar in type and concentration to that found in the desiccation-sensitive species accumulated, particularly under high irradiances. The stable radical appears to be one of the end-products of a process initiated by environmental stress, desiccation and high irradiance: its association with molecular damage depending on the degree to which the species is tolerant of desiccation. Identification of the radical in intact tissue from EPR and ENDOR studies, suggests that this is not a short-lived peroxy-radical but instead is relatively stable and carbon-centred.

  19. Screening of free radical formation in crystals of guanosine by ESR study

    NASA Astrophysics Data System (ADS)

    Usta, Ayhan; Vural, Hasibe Cingilli; Asik, Biray; Usta, Keziban

    2011-10-01

    In this study, to obtain guanosine polycrystalline, novel crystallization method was performed on powder guanosine material. Effective crystallization conditions were achieved by adjustment of the concentration of the metal ions, chemical solutions, NaCl, KCl, glacial acetic acid, nitric oxide, perchloric acid, glutamic acid, and pH of buffer. Behaviors of the guanosine polycrystal samples exposed to high-energy values were investigated using ESR method. The polycrystal samples were exposed to gamma-rays for 48 and 72 h. ESR signals were not recorded from the non-irradiated sample and the sample irradiated for 48 h, but the polycrystalline sample irradiated for 72 h exhibited complex ESR spectra. ESR measurements were taken on the irradiated sample in temperature range from 300 to 450 K. On the basis of all these measurements dependence temperature, it can be said that the shape of the spectrum was to be dependent on temperature slightly. Hence, we assume that the radical structure occurred was resistance to high temperature. Two radicals were determined in the structure irradiated and these were called radical I and radical II. The g, hyperfine constants, and spin density were found to be ρ = 0.96, a=2.7 mT, a=1.155 mT, aN = 0.35 mT and g1 = 2.0093 for the radical I; aN = 4.7 mT and g2 = 2.0094 for the radical II.

  20. Cyclic voltammetry, spectroelectrochemical and photochemical studies of 7,7{prime}-diphenyl-7,7{prime}-diapocarotene cation radicals and dications adsorbed on the surface of electrodes

    SciTech Connect

    Gao, G.; Kispert, L.D.

    1996-10-01

    7,7{prime}-diphenyl-7,7{prime}-diapocarotene in dichloromethane can adsorb on glassy carbon, platinum and gold electrode surfaces upon electrochemical oxidation, resulting in an intense cyclic voltammogram(CV) cathodic peak. Spectroelectrochemical studies of the adsorbed material on ITO electrode surfaces showed that cation radicals, dications and possibly dimers were formed. Irradiation of the surface with visible light resulting in changes in the optical absorption bands. Similar adsorption behavior was also observed by using various supporting electrolytes and solvents. However CV and simultaneous bulk electrolysis-optical spectra obtained in anhydrous acetonitrile show no adsorption. A mechanism involving electrode reactions and adsorption equilibria will be presented.

  1. H and D attachment to naphthalene: spectra and thermochemistry of cold gas-phase 1-C10H9 and 1-C10H8D radicals and cations.

    PubMed

    Krechkivska, Olha; Wilcox, Callan M; Chan, Bun; Jacob, Rebecca; Liu, Yu; Nauta, Klaas; Kable, Scott H; Radom, Leo; Schmidt, Timothy W

    2015-04-02

    Excitation spectra of the 1H-naphthalene (1-C10H9) and 1D-naphthalene (1-C10H8D) radicals, and their cations, are obtained by laser spectroscopy and mass spectrometry of a skimmed free-jet expansion following an electrical discharge. The spectra are assigned on the basis of density functional theory calculations. Isotopic shifts in origin transitions, vibrational frequencies and ionization energies were found to be well reproduced by (time-dependent) density functional theory. Absolute bond dissociation energies, ionization energies and proton affinities were calculated using high-level quantum chemical methods.

  2. Linear Four-Chalcogen Interactions in Radical Cationic and Dicationic Dimers of 1,5-(Dichalcogena)canes: Nature of the Interactions Elucidated by QTAIM Dual Functional Analysis with QC Calculations.

    PubMed

    Hayashi, Satoko; Nagata, Kengo; Otsuki, Shota; Nakanishi, Waro

    2017-03-15

    The dynamic and static nature of extended hypervalent interactions of the (B)E···(A)E···(A)E···(B)E type are elucidated for four center-seven electron interactions (4c-7e) in the radical cationic dimers (1·(+)) and 4c-6e in the dicationic dimers (1(2+)) of 1,5-(dichalcogena)canes (2: (A)E(CH2CH2CH2)2(B)E: (A)E, (B)E = S, Se, Te, and O). The quantum theory of atoms-in-molecules dual functional analysis (QTAIM-DFA) is applied for the analysis. Total electron energy densities Hb(rc) are plotted versus Hb(rc) - Vb(rc)/2 [= (ℏ(2)/8m)∇(2)ρb(rc)] at bond critical points (BCPs) of the interactions, where Vb(rc) values show potential energy densities at BCPs. Data from the fully optimized structures correspond to the static nature of the interactions. Those from the perturbed structures around the fully optimized ones are also plotted, in addition to those of the fully optimized ones, which represent the dynamic nature of interactions. The (B)E···(A)E-(A)E···(B)E interactions in 1(2+) are stronger than the corresponding ones in 1·(+), respectively. On the one hand, for 1(2+) with (A)E, (B)E = S, Se, and Te, (A)E···(A)E are all classified by the shared shell interactions and predicted to have the weak covalent nature, except for those in 1a(2+) ((A)E = (B)E = S) and 1d(2+) ((A)E = (B)E = Se), which have the nature of regular closed shell (r-CS)/trigonal bipyramidal adduct formation through charge transfer (CT-TBP). On the other hand, (A)E···(B)E are predicted to have the nature of r-CS/molecular complex formation through charge transfer for 1a(2+), 1b(2+) ((A)E = Se; (B)E = S), and 1d(2+) or r-CS/CT-TBP for 1c(2+) ((A)E = Te; (B)E = S), 1e(2+) ((A)E = Te; (B)E = Se), and 1f(2+) ((A)E = (B)E = Te). The (B)E···(A)E-(A)E···(B)E interactions in 1·(+) and 1(2+) are well-analyzed by applying QTAIM-DFA.

  3. Selective Generation of the Radical Cation Isomers [CH3CN](•+) and [CH2CNH](•+) via VUV Photoionization of Different Neutral Precursors and Their Reactivity with C2H4.

    PubMed

    Polášek, Miroslav; Zins, Emilie-Laure; Alcaraz, Christian; Žabka, Ján; Křížová, Věra; Giacomozzi, Linda; Tosi, Paolo; Ascenzi, Daniela

    2016-07-14

    Experimental and theoretical studies have been carried out to demonstrate the selective generation of two different C2H3N(+) isomers, namely, the acetonitrile [CH3CN](•+) and the ketenimine [CH2CNH](•+) radical cations. Photoionization and dissociative photoionization experiments from different neutral precursors (acetonitrile and butanenitrile) have been performed using vacuum ultraviolet (VUV) synchrotron radiation in the 10-15 eV energy range, delivered by the DESIRS beamline at the SOLEIL storage ring. For butanenitrile (CH3CH2CH2CN) an experimental ionization threshold of 11.29 ± 0.05 eV is obtained, whereas the appearance energy for the formation of [CH2CNH](•+) fragments is 11.52 ± 0.05 eV. Experimental findings are fully supported by theoretical calculations at the G4 level of theory (ZPVE corrected energies at 0 K), giving a value of 11.33 eV for the adiabatic ionization energy of butanenitrile and an exothermicity of 0.49 for fragmentation into [CH2CNH](•+) plus C2H4, hampered by an energy barrier of 0.29 eV. The energy difference between [CH3CN](•+) and [CH2CNH](•+) is 2.28 eV (with the latter being the lowest energy isomer), and the isomerization barrier is 0.84 eV. Reactive monitoring experiments of the [CH3CN](•+) and [CH2CNH](•+) isomers with C2H4 have been performed using the CERISES guided ion beam tandem mass spectrometer and exploiting the selectivity of ethylene that gives exothermic charge exchange and proton transfer reactions with [CH3CN](•+) but not with [CH2CNH](•+) isomers. In addition, minor reactive channels are observed leading to the formation of new C-C bonds upon reaction of [CH3CN](•+) with C2H4, and their astrochemical implications are briefly discussed.

  4. Formation of Zirconium Hydrophosphate Nanoparticles and Their Effect on Sorption of Uranyl Cations

    NASA Astrophysics Data System (ADS)

    Perlova, Nataliya; Dzyazko, Yuliya; Perlova, Olga; Palchik, Alexey; Sazonova, Valentina

    2017-03-01

    Organic-inorganic ion-exchangers were obtained by incorporation of zirconium hydrophosphate into gel-like strongly acidic polymer matrix by means of precipitation from the solution of zirconium oxychloride with phosphoric acid. The approach for purposeful control of a size of the incorporated particles has been developed based on Ostwald-Freundich equation. This equation has been adapted for precipitation in ion exchange materials. Both single nanoparticles (2-20 nm) and their aggregates were found in the polymer. Regulation of salt or acid concentration allows us to decrease size of the aggregates approximately in 10 times. Smaller particles are formed in the resin, which possess lower exchange capacity. Sorption of U(VI) cations from the solution containing also hydrochloride acid was studied. Exchange capacity of the composites is ≈2 times higher in comparison with the pristine resin. The organic-inorganic sorbents show higher sorption rate despite chemical interaction of sorbed ions with functional groups of the inorganic constituent: the models of reaction of pseudo-first or pseudo-second order can be applied. In general, decreasing in size of incorporated particles provides acceleration of ion exchange. The composites can be regenerated completely, this gives a possibility of their multiple use.

  5. The formation of stain on acrylic surfaces by the interaction of cationic antiseptic mouthwashes and tea.

    PubMed

    Addy, M; Moran, J

    1984-01-01

    Clinical and in vitro studies have implicated dietary components as major aetiological factors in staining of teeth and acrylic materials associated with chlorhexidine use, a local side effect not unique to this antiseptic. These experiments studied the precipitation and surface staining reactions of the cationic antiseptics alexidine, cetyl pyridinium chloride (CPC), chlorhexidine, and hexetidine, with the beverage tea. All of the antiseptics precipitated a standard tea solution and for alexidine and chlorhexidine acetate and gluconate, this was at concentrations greater than 100 mumol/L, for hexetidine greater than 200 mumol/L, and for CPC greater than 400 mumol/L. With the exception of CPC precipitation was reduced with decreasing pH and for chlorhexidine was inhibited below pH 3. The addition of polymethylmethacrylate (PMMA) to the antiseptic solutions increased the precipitation concentrations by an amount calculated to be adsorbed by polymer. Acrylic blocks treated with equimolar solutions of the antiseptics became progressively and significantly more stained by tea than control specimens over a 5-day period. Alexidine induced significantly greater staining and hexetidine significantly less than the other antiseptics. Staining was pH dependent and significantly reduced as the pH decreased. Both stain and precipitates were insoluble in strong acids and alkalis. It is concluded that staining observed clinically may represent a precipitation reaction with the complexing of antiseptics with dietary chromogenic material.

  6. Formation of Zirconium Hydrophosphate Nanoparticles and Their Effect on Sorption of Uranyl Cations.

    PubMed

    Perlova, Nataliya; Dzyazko, Yuliya; Perlova, Olga; Palchik, Alexey; Sazonova, Valentina

    2017-12-01

    Organic-inorganic ion-exchangers were obtained by incorporation of zirconium hydrophosphate into gel-like strongly acidic polymer matrix by means of precipitation from the solution of zirconium oxychloride with phosphoric acid. The approach for purposeful control of a size of the incorporated particles has been developed based on Ostwald-Freundich equation. This equation has been adapted for precipitation in ion exchange materials. Both single nanoparticles (2-20 nm) and their aggregates were found in the polymer. Regulation of salt or acid concentration allows us to decrease size of the aggregates approximately in 10 times. Smaller particles are formed in the resin, which possess lower exchange capacity. Sorption of U(VI) cations from the solution containing also hydrochloride acid was studied. Exchange capacity of the composites is ≈2 times higher in comparison with the pristine resin. The organic-inorganic sorbents show higher sorption rate despite chemical interaction of sorbed ions with functional groups of the inorganic constituent: the models of reaction of pseudo-first or pseudo-second order can be applied. In general, decreasing in size of incorporated particles provides acceleration of ion exchange. The composites can be regenerated completely, this gives a possibility of their multiple use.

  7. Exploring Atmospheric Aqueous Chemistry (and Secondary Organic Aerosol Formation) through OH Radical Oxidation Experiments, Droplet Evaporation and Chemical Modeling

    NASA Astrophysics Data System (ADS)

    Turpin, B. J.; Kirkland, J. R.; Lim, Y. B.; Ortiz-Montalvo, D. L.; Sullivan, A.; Häkkinen, S.; Schwier, A. N.; Tan, Y.; McNeill, V. F.; Collett, J. L.; Skog, K.; Keutsch, F. N.; Sareen, N.; Carlton, A. G.; Decesari, S.; Facchini, C.

    2013-12-01

    Gas phase photochemistry fragments and oxidizes organic emissions, making water-soluble organics ubiquitous in the atmosphere. My group and others have found that several water-soluble compounds react further in the aqueous phase forming low volatility products under atmospherically-relevant conditions (i.e., in clouds, fogs and wet aerosols). Thus, secondary organic aerosol can form as a result of gas followed by aqueous chemistry (aqSOA). We have used aqueous OH radical oxidation experiments coupled with product analysis and chemical modeling to validate and refine the aqueous chemistry of glyoxal, methylglyoxal, glycolaldehyde, and acetic acid. The resulting chemical model has provided insights into the differences between oxidation chemistry in clouds and in wet aerosols. Further, we conducted droplet evaporation experiments to characterize the volatility of the products. Most recently, we have conducted aqueous OH radical oxidation experiments with ambient mixtures of water-soluble gases to identify additional atmospherically-important precursors and products. Specifically, we scrubbed water-soluble gases from the ambient air in the Po Valley, Italy using four mist chambers in parallel, operating at 25-30 L min-1. Aqueous OH radical oxidation experiments and control experiments were conducted with these mixtures (total organic carbon ≈ 100 μM-C). OH radicals (3.5E-2 μM [OH] s-1) were generated by photolyzing H2O2. Precursors and products were characterized using electrospray ionization mass spectrometry (ESI-MS), ion chromatography (IC), IC-ESI-MS, and ultra high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chemical modeling suggests that organic acids (e.g., oxalate, pyruvate, glycolate) are major products of OH radical oxidation at cloud-relevant concentrations, whereas organic radical - radical reactions result in the formation of oligomers in wet aerosols. Products of cloud chemistry and droplet evaporation have

  8. Effect of adenosine A(2A) receptor antagonists on L-DOPA-induced hydroxyl radical formation in rat striatum.

    PubMed

    Gołembiowska, Krystyna; Dziubina, Anna; Kowalska, Magdalena; Kamińska, Katarzyna

    2009-02-01

    A(2A) adenosine receptor antagonists have been proposed as a new therapy for Parkinson's disease (PD). Since oxidative stress plays an important role in the pathogenesis of PD, we studied the effect of the selective A(2A) adenosine receptor antagonists 8-(3-chlorostyryl)caffeine (CSC) and 4-(2-[7-amino-2-(2-furyl)[1,2,4]triazolo[2,3-a][1,3,5]triazin-5-ylamino]ethyl)phenol (ZM 241385) on L: -3,4-dihydroxyphenylalanine (L: -DOPA)-induced hydroxyl radical generation using in vivo microdialysis in the striatum of freely moving rats. L: -DOPA (100 mg/kg; in the presence of benserazide, 50 mg/kg) given acutely or repeatedly for 14 days generated a high level of hydroxyl radicals, measured by HPLC with electrochemical detection, as the product of their reaction with p-hydroxybenzoic acid (PBA). CSC (1 mg/kg) and ZM 241385 (3 mg/kg) decreased haloperidol (0.5 mg/kg)-induced catalepsy, while at low doses of 0.1 and 0.3 mg/kg, respectively, they did not display an effect. CSC (1 and 5 mg/kg) and ZM 241385 (3 and 9 mg/kg) given acutely, or CSC (1 mg/kg) and ZM 241385 (3 mg/kg) given repeatedly, increased the production of hydroxyl radicals in dialysates from rat striatum. Both acute and repeated administration of CSC (0.1 and 1 mg/kg) and ZM 241385 (3 mg/kg) decreased L: -DOPA-induced generation of hydroxyl radicals. However, a high single dose of either CSC (5 mg/kg) and ZM 241385 (9 mg/kg) markedly potentiated the effect of L: -DOPA on hydroxyl radical production. The increase in hydroxyl radical production by acute and chronic injection of CSC and ZM 241385 may be related to the increased release of dopamine (DA) and its metabolism in striatal dialysates. Similarly, increased DA release following a single high dose of CSC or ZM 241385 appears to be responsible for augmentation of L: -DOPA-induced hydroxyl radical formation. Conversely, the inhibition of L: -DOPA-induced production of hydroxyl radical by single and repeated low doses of CSC or repeated low doses of ZM

  9. Aqueous-Phase Reactions of Isoprene with Sulfoxy Radical Anions as a way of Wet Aerosol Formation in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Kuznietsova, I.; Rudzinski, K. J.; Szmigielski, R.; Laboratory of the Environmental Chemistry

    2011-12-01

    Atmospheric aerosols exhibit an important role in the environment. They have implications on human health and life, and - in the larger scale - on climate, the Earth's radiative balance and the cloud's formation. Organic matter makes up a significant fraction of atmospheric aerosols (~35% to ~90%) and may originate from direct emissions (primary organic aerosol, POA) or result from complex physico-chemical processes of volatile organic compounds (secondary organic aerosol, SOA). Isoprene (2-methyl-buta-1,3-diene) is one of the relevant volatile precursor of ambient SOA in the atmosphere. It is the most abundant non-methane hydrocarbon emitted to the atmosphere as a result of living vegetation. According to the recent data, the isoprene emission rate is estimated to be at the level of 500 TgC per year. While heterogeneous transformations of isoprene have been well documented, aqueous-phase reactions of this hydrocarbon with radical species that lead to the production of new class of wet SOA components such as polyols and their sulfate esters (organosulfates), are still poorly recognized. The chain reactions of isoprene with sulfoxy radical-anions (SRA) are one of the recently researched route leading to the formation of organosulfates in the aqueous phase. The letter radical species originate from the auto-oxidation of sulfur dioxide in the aqueous phase and are behind the phenomenon of atmospheric acid rain formation. This is a complicated chain reaction that is catalyzed by transition metal ions, such as manganese(II), iron(III) and propagated by sulfoxy radical anions . The presented work addresses the chemical interaction of isoprene with sulfoxy radical-anions in the water solution in the presence of nitrite ions and nitrous acid, which are important trace components of the atmosphere. We showed that nitrite ions and nitrous acid significantly altered the kinetics of the auto-oxidation of SO2 in the presence of isoprene at different solution acidity from 2 to 8

  10. ESR evidence for in vivo formation of free radicals in tissue of mice exposed to single-walled carbon nanotubes.

    PubMed

    Shvedova, A A; Kisin, E R; Murray, A R; Mouithys-Mickalad, A; Stadler, K; Mason, R P; Kadiiska, M

    2014-08-01

    Nanomaterials are being utilized in an increasing variety of manufactured goods. Because of their unique physicochemical, electrical, mechanical, and thermal properties, single-walled carbon nanotubes (SWCNTs) have found numerous applications in the electronics, aerospace, chemical, polymer, and pharmaceutical industries. Previously, we have reported that pharyngeal exposure of C57BL/6 mice to SWCNTs caused dose-dependent formation of granulomatous bronchial interstitial pneumonia, fibrosis, oxidative stress, acute inflammatory/cytokine responses, and a decrease in pulmonary function. In the current study, we used electron spin resonance (ESR) to directly assess whether exposure to respirable SWCNTs caused formation of free radicals in the lungs and in two distant organs, the heart and liver. Here we report that exposure to partially purified SWCNTs (HiPco technique, Carbon Nanotechnologies, Inc., Houston, TX, USA) resulted in the augmentation of oxidative stress as evidenced by ESR detection of α-(4-pyridyl-1-oxide)-N-tert-butylnitrone spin-trapped carbon-centered lipid-derived radicals recorded shortly after the treatment. This was accompanied by a significant depletion of antioxidants and elevated biomarkers of inflammation presented by recruitment of inflammatory cells and an increase in proinflammatory cytokines in the lungs, as well as development of multifocal granulomatous pneumonia, interstitial fibrosis, and suppressed pulmonary function. Moreover, pulmonary exposure to SWCNTs also caused the formation of carbon-centered lipid-derived radicals in the heart and liver at later time points (day 7 postexposure). Additionally, SWCNTs induced a significant accumulation of oxidatively modified proteins, increase in lipid peroxidation products, depletion of antioxidants, and inflammatory response in both the heart and the liver. Furthermore, the iron chelator deferoxamine noticeably reduced lung inflammation and oxidative stress, indicating an important role for

  11. Effect of pH and oxalate on hydroquinone-derived hydroxyl radical formation during brown rot wood degradation.

    PubMed

    Varela, Elisa; Tien, Ming

    2003-10-01

    The redox cycle of 2,5-dimethoxybenzoquinone (2,5-DMBQ) is proposed as a source of reducing equivalent for the regeneration of Fe2+ and H2O2 in brown rot fungal decay of wood. Oxalate has also been proposed to be the physiological iron reductant. We characterized the effect of pH and oxalate on the 2,5-DMBQ-driven Fenton chemistry and on Fe3+ reduction and oxidation. Hydroxyl radical formation was assessed by lipid peroxidation. We found that hydroquinone (2,5-DMHQ) is very stable in the absence of iron at pH 2 to 4, the pH of degraded wood. 2,5-DMHQ readily reduces Fe3+ at a rate constant of 4.5 x 10(3) M(-1)s(-1) at pH 4.0. Fe2+ is also very stable at a low pH. H2O2 generation results from the autoxidation of the semiquinone radical and was observed only when 2,5-DMHQ was incubated with Fe3+. Consistent with this conclusion, lipid peroxidation occurred only in incubation mixtures containing both 2,5-DMHQ and Fe3+. Catalase and hydroxyl radical scavengers were effective inhibitors of lipid peroxidation, whereas superoxide dismutase caused no inhibition. At a low concentration of oxalate (50 micro M), ferric ion reduction and lipid peroxidation are enhanced. Thus, the enhancement of both ferric ion reduction and lipid peroxidation may be due to oxalate increasing the solubility of the ferric ion. Increasing the oxalate concentration such that the oxalate/ferric ion ratio favored formation of the 2:1 and 3:1 complexes resulted in inhibition of iron reduction and lipid peroxidation. Our results confirm that hydroxyl radical formation occurs via the 2,5-DMBQ redox cycle.

  12. Photolysis of hydrogen peroxide, an effective disinfection system via hydroxyl radical formation.

    PubMed

    Ikai, Hiroyo; Nakamura, Keisuke; Shirato, Midori; Kanno, Taro; Iwasawa, Atsuo; Sasaki, Keiichi; Niwano, Yoshimi; Kohno, Masahiro

    2010-12-01

    The relationship between the amount of hydroxyl radicals generated by photolysis of H(2)O(2) and bactericidal activity was examined. H(2)O(2) (1 M) was irradiated with laser light at a wavelength of 405 nm to generate hydroxyl radicals. Electron spin resonance spin trapping analysis showed that the amount of hydroxyl radicals produced increased with the irradiation time. Four species of pathogenic oral bacteria, Staphylococcus aureus, Aggregatibacter actinomycetemcomitans, Streptococcus mutans, and Enterococcus faecalis, were used in the bactericidal assay. S. mutans in a model biofilm was also examined. Laser irradiation of suspensions in 1 M H(2)O(2) resulted in a >99.99% reduction of the viable counts of each of the test species within 3 min of treatment. Treatment of S. mutans in a biofilm resulted in a >99.999% reduction of viable counts within 3 min. Other results demonstrated that the bactericidal activity was dependent on the amount of hydroxyl radicals generated. Treatment of bacteria with 200 to 300 μM hydroxyl radicals would result in reductions of viable counts of >99.99%.

  13. Synthesis and characterization of two novel chiral-type formate frameworks templated by protonated diethylamine and ammonium cations

    NASA Astrophysics Data System (ADS)

    Mączka, Mirosław; Gągor, Anna; Hanuza, Jerzy; Pikul, Adam; Drozd, Marek

    2017-01-01

    Two novel formate frameworks templated by ammonium and diethylammonium (DEtA+) cations have been synthesized. Chemical analysis as well as optical, Raman and IR studies showed partial substitution of nickel ions by Cr(III) or Fe(III). X-ray diffraction revealed that these compounds crystallize in the chiral-type structure of P6322 symmetry. The oxygen atoms from formate ligands form octahedral coordination around the metal centers and the octahedra are bridged by the formate groups in the anti-anti mode configuration forming the hexagonal structure with large channels expanding along the c direction. The channels are filled with disordered DEtA+ and NH4+ ions and they show unusual compression with the c/a ratio of only 0.862 and 0.852 for the iron- and chromium-containing compound, respectively. Magnetic studies revealed that the both compounds order magnetically at low temperatures but the ordering temperature is significantly higher for the iron compound (37 K) compared to the chromium analogue (26 K).

  14. Formation of OH radicals in the gas-phase reaction of propene, isobutene, and isoprene with O{sub 3}: Yields and mechanistic implications

    SciTech Connect

    Neeb, P.; Moortgat, G.K.

    1999-11-11

    The gas-phase reaction of ozone with alkenes is one of the very few reactions of atmospheric interest that are initiated without free radicals. This tropospheric oxidation pathway for unsaturated compounds has received considerable attention because of the reported formation of OH radicals. OH radicals originating from the alkene-ozone reaction have been proposed as a relevant source of OH radicals in the lower troposphere. Since the reported yields of OH radicals differ considerably, the authors redetermined the OH radical yield for three terminal alkenes by performing a series of pseudo-first-order experiments. Ozonolysis studies were carried out under excess ozone conditions in the presence of different cyclohexane concentrations. The decay rate of the alkene ({kappa}{sub obs}) was followed by long-path FTIR spectroscopy. From the decrease of the effective rate constant ({kappa}{sub obs} = {kappa}{sub eff}[O{sub 3}]) upon addition of cyclohexane, the OH radical yield was determined. The OH radical yields were found to be independent of the concentration of reactants for the Criegee intermediates, which are formed in ozonolysis systems. From these results the authors conclude that OH radicals are formed in a unimolecular process, presumably from the decomposition of the excited Criegee intermediate. Determined yields of OH radical formation in the ozonolysis of propene, isobutene, and isoprene were 0.34, 0.60, and 0.26, respectively. Detailed product studies were performed to verify if the observed stable products can be explained by the assumption that OH radicals are formed via the hydroperoxide channel as proposed by Niki et al. For the isobutene-ozone system, experimental product yields were found to agree well with predictions from a chemical mechanism based on the chemistry of the acetonylperoxy radical CH{sub 3}C(O)CH{sub 2}O{sub 2}, which is formed as an important radical product from the decomposition of the (CH{sub 3}){sub 2}COO Criegee intermediate.

  15. Diabetes and elevated urea level predict for uretero-ileal stricture after radical cystectomy and ileal conduit formation

    PubMed Central

    Hoag, Nathan; Papa, Nathan; Beharry, Bhawanie Koonj; Lawrentschuk, Nathan; Chiu, Danny; Sengupta, Shomik; Bolton, Damien

    2017-01-01

    Introduction Benign uretero-ileal anastomotic stricture is a significant complication following radical cystectomy and ileal conduit urinary diversion after radical cystectomy. We examined risk factors for stricture formation to predict those at greatest stricture risk. Methods A retrospective chart review was conducted for patients undergoing radical cystectomy and ileal conduit diversion between 2002 and 2012. Demographic data and patient variables were analyzed to determine risk factors for uretero-ileal stricture using multivariate logistic regression. Results Over the study period, 133 patients underwent cystectomy and ileal conduit formation, with 14 (10.5%) developing uretero-ileal anastomotic stricture. Diabetes and elevated serum urea level (defined as >7.1 mmol/L) were associated with increased risk for development of uretero-ileal stricture (odds ratio 4.31 and 4.28, respectively; p<0.05 for each). Conclusions In this patient cohort, diabetes and elevated serum urea level were predictive for the development of uretero-ileal anastomotic stricture. Further prospective study with larger patient samples is required. PMID:28360953

  16. CIDEP studies of the formation of benzyl-type radicals in the photoreduction of flavones

    SciTech Connect

    Sakaguchi, Y.; Hayashi, H.; Murai, H.; I'Haya, Y.J.

    1986-11-20

    The photochemical hydrogen abstraction reactions of flavone and its derivatives with some hydrogen donors in 2-propanol solutions were investigated at room temperature with the aid of a chemically induced dynamic electron polarization technique. When xanthene and N,N-diethylaniline were used as hydrogen donors, the ketyl radical of flavone was obtained through the n..pi..* character and charge-transfer interaction of the triplet state, respectively. When tri-n-butyltin hydride and sodium borodeuteride were used as hydrogen donors, the benzyl-type radicals of flavones were obtained through the ..pi pi..* character of the triplet states.

  17. OH-radical induced degradation of hydroxybenzoic- and hydroxycinnamic acids and formation of aromatic products—A gamma radiolysis study

    NASA Astrophysics Data System (ADS)

    Krimmel, Birgit; Swoboda, Friederike; Solar, Sonja; Reznicek, Gottfried

    2010-12-01

    The OH-radical induced degradation of hydroxybenzoic acids (HBA), hydroxycinnamic acids (HCiA) and methoxylated derivatives, as well as of chlorogenic acid and rosmarinic acid was studied by gamma radiolysis in aerated aqueous solutions. Primary aromatic products resulting from an OH-radical attachment to the ring (hydroxylation), to the position occupied by the methoxyl group (replacement -OCH 3 by -OH) as well as to the propenoic acid side chain of the cinnamic acids (benzaldehyde formations) were analysed by HPLC-UV and LC-ESI-MS. A comparison of the extent of these processes is given for 3,4-dihydroxybenzoic acid, vanillic acid, isovanillic acid, syringic acid, cinnamic acid, 4-hydroxycinnamic acid, caffeic acid, ferulic acid, isoferulic acid, chlorogenic acid, and rosmarinic acid. For all cinnamic acids and derivatives benzaldehydes were significant oxidation products. With the release of caffeic acid from chlorogenic acid the cleavage of a phenolic glycoside could be demonstrated. Reaction mechanisms are discussed.

  18. The enthalpy of formation of the pentane-2,4-dionate radical: A complete basis set approach

    NASA Astrophysics Data System (ADS)

    Cabral do Couto, P.; Costa Cabral, Benedito J.; Martinho Simões, José A.

    2006-02-01

    Thermochemical properties of pentane-2,4-dione (acetylacetone, Hacac) and its radical (acac) were investigated by DFT and ab initio calculations based on complete basis set (CBS) extrapolation procedures, including CBS-QB3 and a modified CBS procedure that we named CBS-QB3-tz. We provide evidence that the most stable acac radical conformer is generated by C-H bond homolysis. The enthalpy of formation of gaseous acac, Δ fH∘(acac,g), was estimated as -228.3 kJ/mol (CBS-QB3) and -226.7 kJ/mol (CBS-QB3-tz). Based on these results, our recommended value for Δ fH∘(acac,g) is -227 ± 8 kJ/mol, implying that many literature values reported for metal-acac bond dissociation enthalpies in coordination complexes should be revised.

  19. Free-radical formation in cellulose-acetate-based dosimetric materials

    SciTech Connect

    Bazhenov, A.N.; Karasev, A.L.; Bolduzev, Yu.A.; Zheleztsov, E.E.; Vannikov, A.V.

    1987-05-01

    Free radicals are formed in the radiolysis of cellulose acetates at room temperature, which are products of deacetylation and the separation of hydrogen atoms in positions 1 and 2. The energy absorbed by the polymer matrix is effectively transferred to the solvent and dye molecules.

  20. Formation and fragmentation of radical peptide anions: insights from vacuum ultra violet spectroscopy.

    PubMed

    Brunet, Claire; Antoine, Rodolphe; Dugourd, Philippe; Canon, Francis; Giuliani, Alexandre; Nahon, Laurent

    2012-02-01

    We have studied the photodissociation of gas-phase deprotonated caerulein anions by vacuum ultraviolet (VUV) photons in the 4.5 to 20 eV range, as provided by the DESIRS beamline at the synchrotron radiation facility SOLEIL (France). Caerulein is a sulphated peptide with three aromatic residues and nine amide bonds. Electron loss is found to be the major relaxation channel at every photon energy. However, an increase in the fragmentation efficiency (neutral losses and peptide backbone cleavages) as a function of the energy is also observed. The oxidized ions, generated by electron photodetachment were further isolated and activated by collision (CID) in a MS(3) scheme. The branching ratios of the different fragments observed by CID as a function of the initial VUV photon energy are found to be independent of the initial photon energy. Thus, there is no memory effect of the initial excitation energy on the fragmentation channels of the oxidized species on the time scale of our tandem MS experiment. We also report photofragment yields as a function of photon energy for doubly deprotonated caerulein ions, for both closed-shell ([M-2H](2-)) non-radical ions and open-shell ([M-3H](2-•)) radical ions. These latter ions are generated by electron photodetachment from [M-3H](3-) precursor ions. The detachment yield increases monotonically with the energy with the appearance of several absorption bands. Spectra for radical and non-radical ions are quite similar in terms of observed bands; however, the VUV fragmentation yield is enhanced by the presence of a radical in caerulein peptides.

  1. Formation and Fragmentation of Radical Peptide Anions: Insights from Vacuum Ultra Violet Spectroscopy

    NASA Astrophysics Data System (ADS)

    Brunet, Claire; Antoine, Rodolphe; Dugourd, Philippe; Canon, Francis; Giuliani, Alexandre; Nahon, Laurent

    2012-02-01

    We have studied the photodissociation of gas-phase deprotonated caerulein anions by vacuum ultraviolet (VUV) photons in the 4.5 to 20 eV range, as provided by the DESIRS beamline at the synchrotron radiation facility SOLEIL (France). Caerulein is a sulphated peptide with three aromatic residues and nine amide bonds. Electron loss is found to be the major relaxation channel at every photon energy. However, an increase in the fragmentation efficiency (neutral losses and peptide backbone cleavages) as a function of the energy is also observed. The oxidized ions, generated by electron photodetachment were further isolated and activated by collision (CID) in a MS3 scheme. The branching ratios of the different fragments observed by CID as a function of the initial VUV photon energy are found to be independent of the initial photon energy. Thus, there is no memory effect of the initial excitation energy on the fragmentation channels of the oxidized species on the time scale of our tandem MS experiment. We also report photofragment yields as a function of photon energy for doubly deprotonated caerulein ions, for both closed-shell ([M-2H]2-) non-radical ions and open-shell ([M-3H]2-•) radical ions. These latter ions are generated by electron photodetachment from [M-3H]3- precursor ions. The detachment yield increases monotonically with the energy with the appearance of several absorption bands. Spectra for radical and non-radical ions are quite similar in terms of observed bands; however, the VUV fragmentation yield is enhanced by the presence of a radical in caerulein peptides.

  2. Modelling the bacterial photosynthetic reaction center. V. Assignment of the electronic transition observed at 2200 cm-1 in the special-pair radical-cation as a second-highest occupied molecular orbital to highest occupied molecular orbital transition

    NASA Astrophysics Data System (ADS)

    Reimers, Jeffrey R.; Shapley, Warwick A.; Hush, Noel S.

    2003-08-01

    Primary charge separation in photoexcited photosynthetic reaction centers produces the radical cation P+ of a bacteriochlorophyll dimer known as the special-pair P. P+ has an intense electronic transition in the vicinity of 1800-5000 cm-1 which is usually assigned to the interchromophore hole-transfer excitation of the dimer radical cation; in principle, this spectrum can give much insight into key steps of the solar-to-electrical energy-conversion process. The extent to which this transition is localized on one-half of the dimer or delocalized over both is of utmost importance; an authoritative deduction of this quantity from purely spectroscopic arguments requires the detailed assignment of the observed high to medium resolution spectra. For reaction centers containing bacteriochlorophylls a or b, a shoulder is observed at 2200 cm-1 on the low-energy side of the main hole-transfer absorption band, a band whose maximum is near 2700 cm-1. Before quantitative analysis of the hole-transfer absorption in these well-studied systems can be attempted, the nature of the processes leading to this shoulder must be determined. We interpret it as arising from an intrachromophore SHOMO to HOMO transition whose intensity arises wholly through vibronic coupling with the hole-transfer band. A range of ab initio and density-functional calculations are performed to estimate the energy of this transition both for monomeric cations and for P+ of Blastochloris viridis, Rhodobacter sphaeroides, Chlorobium limicola, Chlorobium tepidum, Chlamydomonas reinhardtii, Synochocystis S.6803, spinach photosystems I and II, Heliobacillus mobilis, and finally Heliobacterium modesticaldum, with the results found to qualitatively describe the available experimental data. Subsequent papers in this series provide quantitative analyses of the vibronic coupling and complete spectral simulations based on the model developed herein.

  3. Cationic lanthanide complexes of neutral tripodal N,O ligands: enthalpy versus entropy-driven podate formation in water.

    PubMed

    Bravard, Florence; Rosset, Caroline; Delangle, Pascale

    2004-07-07

    The cationic lanthanide complexes of two neutral tripodal N,O ligands, tpa (tris[(2-pyridyl)methyl]amine) and tpaam (tris[6-((2-N,N-diethylcarbamoyl)pyridyl)methyl]amine) are studied in water. The analysis of the proton lanthanide induced NMR shifts indicate that there is no abrupt structural change in the middle of the rare-earth series. Unexpectedly, the formation constant values of the lanthanide podates of tpaam and tpa in D2O at 298 K are similar, suggesting that the addition of the three amide groups to the ligand tpa does not lead to any increase in stability of the lanthanide complexes of tpaam in respect to tpa, even though the amide groups are coordinated to the metal in aqueous solution. The measurement of the enthalpy and entropy changes of the complexation reactions shows that the two similar ligands tpa and tpaam have different driving forces for lanthanide complexation. Indeed, the formation of tpa podates benefits from an exothermic enthalpy change associated with a small entropy change, whereas the complexation reaction with tpaam is clearly entropy-driven though opposed by a positive enthalpy change. The hydration states of the europium complexes were measured by luminescence and show the coordination of 4-5 water ligands in [Eu(tpa)]3+ whereas there are only 2 in [Eu(tpaam)]3+. Therefore the heptadentate ligand tpaam releases the translational entropy of more water molecules than does the tetradentate ligand tpa.

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

    PubMed

    El-Agamey, Ali; McGarvey, David J

    2016-01-01

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

  5. Redox- and non-redox-metal-induced formation of free radicals and their role in human disease.

    PubMed

    Valko, Marian; Jomova, Klaudia; Rhodes, Christopher J; Kuča, Kamil; Musílek, Kamil

    2016-01-01

    Transition metal ions are key elements of various biological processes ranging from oxygen formation to hypoxia sensing, and therefore, their homeostasis is maintained within strict limits through tightly regulated mechanisms of uptake, storage and secretion. The breakdown of metal ion homeostasis can lead to an uncontrolled formation of reactive oxygen species, ROS (via the Fenton reaction, which produces hydroxyl radicals), and reactive nitrogen species, RNS, which may cause oxidative damage to biological macromolecules such as DNA, proteins and lipids. An imbalance between the formation of free radicals and their elimination by antioxidant defense systems is termed oxidative stress. Most vulnerable to free radical attack is the cell membrane which may undergo enhanced lipid peroxidation, finally producing mutagenic and carcinogenic malondialdehyde and 4-hydroxynonenal and other exocyclic DNA adducts. While redox-active iron (Fe) and copper (Cu) undergo redox-cycling reactions, for a second group of redox-inactive metals such as arsenic (As) and cadmium (Cd), the primary route for their toxicity is depletion of glutathione and bonding to sulfhydryl groups of proteins. While arsenic is known to bind directly to critical thiols, other mechanisms, involving formation of hydrogen peroxide under physiological conditions, have been proposed. Redox-inert zinc (Zn) is the most abundant metal in the brain and an essential component of numerous proteins involved in biological defense mechanisms against oxidative stress. The depletion of zinc may enhance DNA damage by impairing DNA repair mechanisms. Intoxication of an organism by arsenic and cadmium may lead to metabolic disturbances of redox-active copper and iron, with the occurrence of oxidative stress induced by the enhanced formation of ROS/RNS. Oxidative stress occurs when excessive formation of ROS overwhelms the antioxidant defense system, as is maintained by antioxidants such as ascorbic acid, alpha

  6. Free-radical-induced formation of an 8,5'-cyclo-2'-deoxyguanosine moiety in deoxyribonucleic acid.

    PubMed Central

    Dizdaroglu, M

    1986-01-01

    Isolation and identification of a novel .OH-induced product, namely an 8,5'-cyclo-2'-deoxyguanosine moiety, in DNA and 2'-deoxyguanosine are described. .OH radicals were generated in dilute aqueous solutions by gamma-irradiation. Analyses of 2'-deoxyguanosine and enzymic hydrolysates of DNA by gas chromatography-mass spectrometry (g.c.-m.s.) after trimethylsilylation showed the presence of 8,5-cyclo-2'-deoxyguanosine on the basis of its fragment ions. This product was isolated by h.p.l.c. Its u.v. and n.m.r. spectra taken were in agreement with the structure suggested by its mass spectrum. Exact masses of the typical ions from the mass spectrum of the trimethylsilyl derivative of this product were measured by high-resolution m.s. The values found were in excellent agreement with the theoretical mass derived from the suggested fragmentation patterns. Both (5'R)- and (5'S)-epimers of 8,5'-cyclo-2'-deoxyguanosine were observed. These two diastereomers were separated from each other by g.c. as well as by h.p.l.c. The assignment of the epimers was accomplished on the basis of the n.m.r. data. The formation of 8,5'-cyclo-2'-deoxyguanosine was suppressed by the presence of O2 in the solutions. The use of g.c.-m.s. with the selected-ion monitoring technique facilitated the detection of 8,5'-cyclo-2'-deoxyguanosine in DNA at radiation doses as low as 1 Gy. Its mechanism of formation probably involves hydrogen atom abstraction by .OH radicals from the C-5' of the 2'-deoxyguanosine moiety followed by intramolecular cyclization with the formation of a covalent bond between the C-5' and C-8 and subsequent oxidation of the resulting N-7-centred radical. PMID:3800936

  7. Formation of AAB-Type Collagen Heterotrimers from Designed Cationic and Aromatic Collagen-Mimetic Peptides: Evaluation of the C-Terminal Cation-π Interactions.

    PubMed

    Chiang, Chu-Harn; Fu, Yi-Hsuan; Horng, Jia-Cherng

    2017-03-13

    Most of natural collagens are heterotrimers composed of two (AAB) or three (ABC) different peptide chains, and thus heterotrimeric constructs are preferable to mimic natural collagens. Exploring the forces to assemble synthetic collagen-mimetic peptides (CMPs) into heterotrimers has been an attractive topic in preparing collagen-related biomaterials. Here we designed and synthesized two cationic CMPs (CR and CK) in which multiple Arg or Lys residues are installed in their C-terminal region, and one aromatic CMP (CF) whose C-terminal end contains multiple Phe residues. Circular dichroism and NMR spectroscopy showed that AAB-type heterotrimers could form in both CR-CF and CK-CF mixtures, suggesting that the C-terminal cation-π interactions between cationic and aromatic residues could serve as a nucleation force and substantially promote the folding of heterotrimers. In particular, only one major heterotrimeric fold was found in each mixture. For CR-CF mixtures, either the heterotrimer with two CR chains and one CF chain or that with one CR chain and two CF chains could form, depending on the molar ratios of CR to CF in solution. By contrast, in CK-CF mixtures only the heterotrimer consisting of two CK chains and one CF chain was found in solution even increasing the ratio of CF, implying that the heterotrimer composed of one CK chain and two CF chains is highly unstable. Additionally, differential scanning calorimetry analysis showed that the folding of these heterotrimers is governed by entropic effects. Together, our results provide a new design to prepare AAB-type collagen heterotrimers and reveal new insights into their folding thermodynamics.

  8. Light-stimulated formation of hydrogen peroxide and hydroxyl radical in the presence of uroporphyrin and ascorbate

    SciTech Connect

    Bachowski, G.J.; Girotti, A.W. )

    1988-01-01

    Blue light irradiation of 2-deoxyribose (DOR) in the presence of uroporphyrin I (UP), ascorbate (AH-), trace iron, and phosphate buffer resulted in a strong stimulation of hydroxyl radical (OH.)-dependent oxidation of DOR. Photostimulated generation of H{sub 2}O{sub 2} was monitored after removal of residual AH- (i) by ascorbate oxidase treatment, or (ii) by anion exchange on mini-columns of DEAE-Sephadex. Irradiation of the above mixture produced a strong burst of H{sub 2}O{sub 2} which was intensified by desferrioxamine and suppressed by catalase or EDTA. The mechanism suggested by these observations is one in which photoreduction of UP to the radical anion initiates the formation of H{sub 2}O{sub 2}, which gives rise to OH. via Fenton chemistry. This is the first known investigation of H{sub 2}O{sub 2} fluxes in a Type I (free radical) photoreaction involving AH- as the electron donor.

  9. Efficiency of hydroxyl radical formation and phenol decomposition using UV light emitting diodes and H2O2.

    PubMed

    Vilhunen, Sari; Puton, Jarosław; Virkutyte, Jurate; Sillanpää, Mika

    2011-01-01

    A novel process combining hydrogen peroxide (H2O2) and radiation emitted by ultraviolet light emitting diodes (UV LEDs) has been investigated. The UV LEDs were used as UV-C light sources emitting radiation in the range 257-277 nm for decomposition of the model substance phenol in water. In addition, the effect of H2O2 to phenol molar ratio and initial phenol concentration was examined. Two parameters, the decomposition efficiency of phenol and characterization of hydroxyl radical (HO*) production from H2O2 when illuminated with UV radiation, were selected to provide detailed information regarding the performance of the UV LEDs in the treatment process. A new concept was introduced to characterize and describe the production of HO* radicals produced when photons were absorbed by H2O2 molecules. The phenol decomposition efficiency at the initial concentration of 100 mg/L was the most pronounced at the lowest emitted wavelength. A significant correlation was found between the phenol decomposition efficiency and the photons absorbed by H2O2 (i.e. formation of radicals).

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

    DOE PAGES

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

    2015-10-19

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

  11. Temporal variation of hydroxyl radical generation and 8-hydroxy-2'-deoxyguanosine formation by coarse and fine particulate matter

    PubMed Central

    Shi, T; Knaapen, A; Begerow, J; Birmili, W; Borm, P; Schins, R

    2003-01-01

    Aims: To determine the induction of 8-hydroxy-2'-deoxyguanosine (8-OHdG) by fine (<2.5 µm) and coarse (10–2.5 µm) particulate matter (PM) sampled over time at one sampling location, and to relate the observed effects to the hydroxyl radical (•OH) generating activities and transition metal content of these samples, and to meteorological parameters. Methods: Weekly samples of coarse and fine PM were analysed for H2O2 dependent •OH formation using electron spin resonance (ESR) and formation of 8-OHdG in calf thymus DNA using an immuno-dotblot assay. Immunocytochemistry was used to determine 8-OHdG formation in A549 human epithelial lung cells. To determine temporal effects, samples from six weeks in summer and six weeks in autumn/winter were compared using ESR and the dotblot assay. Concentrations of leachable V, Cr, Fe, Ni, and Cu were determined by inductively coupled plasma mass spectrometry. Results: Both PM fractions elicited •OH generation as well as 8-OHdG formation in calf thymus DNA and in A549 cells. 8-OHdG formation in the naked DNA was significantly related to •OH generation, but not to metal concentrations except for copper. A significantly higher •OH generation was observed for coarse PM, but not fine PM collected during the autumn/winter season; this was not due to differences in sampled mass or metal content. Specific weather conditions under which increased •OH formation in the coarse mode was observed suggest that other, as yet unknown, anthropogenic components might affect the radical generating capacity of PM. Conclusions: Both coarse and fine PM are able to generate •OH, and induce formation of 8-OHdG. When considered at equal mass, •OH formation shows considerable variability with regard to the fraction of PM, as well as the sampling season. The toxicological implications of this heterogeneity in •OH formation by PM, as can be easily determined by ESR, need further investigation. PMID:12709515

  12. Mystery of 1-Vinylpropargyl Formation from Acetylene Addition to the Propargyl Radical: An Open-and-Shut Case.

    PubMed

    da Silva, Gabriel

    2017-03-16

    The addition of acetylene (C2H2) to the propargyl radical (C3H3) initiates a cascade of molecular weight growth reactions that result in the production of polycyclic aromatic hydrocarbons (PAHs) in flames. Although it is well-established that the first reaction step produces the cyclic C5H5 radical cyclopentadienyl (c-C5H5), recent studies have also detected significant quantities of the open-chain form, 1-vinylpropargyl (l-C5H5). This work presents a mechanism for the C3H3 + C2H2 reaction from ab initio calculations, which includes pathways for the formation of both the open and shut isomers as well as for their interconversion. Formation of both isomers proceeds from the initial HCCCH2CHCH(•) reaction adduct with similar barriers, both well below the entrance channel energy. Subsequent isomerization of l-C5H5 with c-C5H5 also transpires at below the energy of the reactants, although this process connects two deep wells (being resonance stabilized radicals), and must compete with collisional energy transfer. An RRKM theory/master equation model is developed for the reported C5H5 reaction mechanism. Master equation simulations suggest that both cyclic and open-chain isomers are expected to form from the C3H3 + C2H2 reaction across a range of temperatures, although the lifetime of l-C5H5 is relatively short for rearrangement to c-C5H5.

  13. Cationic micelle based vaccine induced potent humoral immune response through enhancing antigen uptake and formation of germinal center.

    PubMed

    Luo, Zichao; Shi, Shuai; Jin, Ling; Xu, Lu; Yu, Jing; Chen, Hao; Li, Xingyi

    2015-11-01

    Nanoparticles have been proven to be an effective vaccine delivery system that can boost immune responses to subunit vaccines. Herein, we developed and characterized a cationic polymeric polyethylene glycol2000-poly ϵ-caprolactone2000-polyethylenimine2000 (mPEG2000-PCL2000-g-PEI2000) micelle as a potent vaccine delivery system to boost the immune response in vivo. The micelles that we developed exhibited great antigen-loading capability and minimal cytotoxicity in vitro. Meanwhile, micelles facilitated OVA antigen uptake by dendritic cells both in vitro and in vivo. More importantly, a micelle-formulated OVA vaccine could significantly promote anti-OVA antibody production by 190-fold and potently enhance T cell proliferation and the secretion of IL-5 and IFN-γ. We attributed these effects to its ability to promote antigen uptake, antigen deposition, and germinal center formation. In conclusion, the mPEG2000-PCL2000-PEI2000 micelle that we developed has potential as potent vaccine delivery system to induce Th2 immune response.

  14. Comparison of hydroxyl radical formation in aqueous solutions at different ultrasound frequencies and powers using the salicylic acid dosimeter.

    PubMed

    Milne, Louise; Stewart, Isobel; Bremner, David H

    2013-05-01

    Ultrasonic frequencies of 20kHz, 382kHz, 584kHz, 862kHz (and 998kHz) have been compared with regard to energy output and hydroxyl radical formation utilising the salicylic acid dosimeter. The 862kHz frequency inputs 6 times the number of Watts into water, as measured by calorimetry, with the other frequencies having roughly the same value under very similar conditions. A plausible explanation involving acoustic fountain formation is proposed although enhanced coupling between this frequency and water cannot be discounted. Using the salicylic acid dosimeter and inputting virtually the same Wattages it is established that 862kHz is around 10% more efficient at generating hydroxyl radicals than the 382kHz but both of these are far more effective than the other frequencies. Also, it is found that as temperature increases to 42°C then the total dihydroxybenzoic acid (Total DHBA) produced is virtually identical for 382kHz and 862kHz, though 582kHz is substantially lower, when the power levels are set at approximately 9W for all systems. An equivalent power level of 9W could not be obtained for the 998kHz transducer so a direct comparison could not be made in this instance. These results have implications for the optimum frequencies chosen for both Advanced Oxidation Processes (AOPs) and organic synthesis augmented by ultrasound.

  15. Reduction potential of the sulfhydryl radical: Pulse radiolysis and laser flash photolysis studies of the formation and reactions of {sm_bullet}SH and HSSH{sm_bullet}{sup {minus}} in aqueous solutions

    SciTech Connect

    Das, T.N.; Huie, R.E.; Neta, P.; Padmaja, S.

    1999-07-08

    H{sub 2}S, which is a very toxic gas, has a large number of natural and anthropogenic sources, and the safe removal of this substance has been a matter of ongoing industrial concern. Formation and reactions of the {sm_bullet}SH/{sm_bullet}S{sup {minus}} and HSSH{sm_bullet}{sup {minus}}/HSS{sm_bullet}{sup 2{minus}} radicals in aqueous solutions have been studied by excimer laser flash photolysis and by pulse radiolysis. Acidic H{sub 2}S solutions can be photolyzed with 193 nm laser pulses and produce a transient species with {lambda}{sub max} at 240 nm, ascribed to the {sm_bullet}SH/{sm_bullet}S{sup {minus}} radical. Solutions of SH{sup {minus}} can be photolyzed also with 248 nm laser pulses to produce the {sm_bullet}SH/{sm_bullet}S{sup {minus}} reacts with SH{sup {minus}} ({kappa}{sub f} = 4 {times} 10{sup 9} L/mol s, {kappa}{sub r} = 5 {times} 10{sup 5} s{sup {minus}1}) to form HSSH{sm_bullet}{sup {minus}}/HSS{sm_bullet}{sup 2{minus}}, with {lambda}{sub max} at 380 nm. Both {sm_bullet}SH/{sm_bullet}S{sup {minus}} and HSSH{sm_bullet}{sup {minus}}/HSS{sm_bullet}{sup 2{minus}} react rapidly with O{sub 2}; the former produces SO{sub 2}{sm_bullet}{sup {minus}} ({kappa} = 5 {times} 10{sup 9} L/mol s), and the latter produces O{sub 2}{sm_bullet} ({kappa} = 4 {times} 10{sup 8} L/mol s). Both radicals react with olefinic compounds. The monomeric radical oxidizes Fe(CN){sub 6}{sup 4{minus}}, SO{sub 3}{sup 2{minus}}, ClO{sub 2}{sup {minus}}, and chlorpromazine. The dimeric radical is a weaker oxidant toward ferrocyanide but reduces N-methylpyridinium compounds. The reduction potential for the dimeric radical at pH 7 was determined from one-electron transfer equilibria with Mo(CN){sub 8}{sup 3{minus}} and with the 4-methoxyaniline radical cation and found to be 0.69 V vs NHE. From the equilibrium constant K = [HSS{sm_bullet}{sup 2{minus}}]/[SH{sup {minus}}][{sm_bullet}S{sup {minus}}] = 8 {times} 10{sup 3} L/mol, the reduction potential for ({sm_bullet}S{sup {minus

  16. Electrochemistry and spectroelectrochemistry of nitroxyl free radicals

    SciTech Connect

    Fish, J.R.; Swarts, S.G.; Sevilla, M.D.; Malinski, T.

    1988-06-30

    This work reports electrochemical and spectroelectrochemical studies of the two nitroxyl radicals 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-yloxy (3-carbamoyl-PROXYL). Oxidation and reduction reactions have been observed in aqueous media over the pH range 2-12 in the potential range -0.8 to +0.8 V by differential pulse voltammetry, cyclic voltammetry, and thin-layer UV-visible spectroelectrochemistry, and the reaction products have been characterized by IR, NMR, and ESR spectrometry. At pH values less than 10, characteristic electrochemical behavior is observed to be analogous for both radicals, and the products from electron transfer compare quite favorably with those found by pulse radiolysis of aqueous solutions of nitroxyl radicals. At pH 2-9, a stable cation from a reversible oxidation and hydroxylamine following an irreversible reduction, as well as hydroxylated cation at pH higher than 9, are the same as those obtained in pulse radiolysis experiments. Spectroscopic evidence indicates that behavior following reduction at high pH differs for the two radicals. At pH 12, reduced TEMPO may undergo structural changes leading to the formation of a new radical consisting of a seven-membered ring.

  17. Hydroxyl radical induced by lipid in Maillard reaction model system promotes diet-derived N(ε)-carboxymethyllysine formation.

    PubMed

    Han, Lipeng; Li, Lin; Li, Bing; Zhao, Di; Li, Yuting; Xu, Zhenbo; Liu, Guoqin

    2013-10-01

    N(ε)-carboxymethyllysine (CML) is commonly found in food, and is considered as a potential hazard to human health. However, the effect of lipids on CML formation in Maillard reaction is still not clarified. In this study, the content of diet-derived CML and its key intermediates, epsilon-fructoselysine (FL) and glyoxal (GO), is determined with high performance liquid chromatography mass spectrum (HPLC-MS) in model system containing lipid compounds. According to the results, hydroxyl radical (OH) induced by Fenton reagent can promote the three pathways of CML formation. Moreover, in the Maillard reaction system, linoleic acid (Lin), oleic acid (Ole) and glycerol trioleate (Tri) can induce more OH·, which promotes CML formation. Their level of promoting CML formation is in the order of Ole>Lin>Tri. On the contrary, glycerol (Gly) can scavenge OH·, which inhibit the CML formation. Finally, it is proved that FL content and GO content decreases with heating time in model system, while CML content increases with heating time. Thus, it is concluded that in the Maillard reaction system lipids can induce more OH·, which promotes the conversion from FL and GO to CML. Our research may contribute to the development of inhibitory methods for diet-derived CML by scavenging OH·.

  18. Cascade dissociations of peptide cation-radicals. Part 2. Infrared multiphoton dissociation and mechanistic studies of z-ions from pentapeptides.

    PubMed

    Ledvina, Aaron R; Chung, Thomas W; Hui, Renjie; Coon, Joshua J; Tureček, Frantisek

    2012-08-01

    Dissociations of z(4) ions from pentapeptides AAXAR where X=H, Y, F, W, and V produce dominant z(2) ions that account for >50 % of the fragment ion intensity. The dissociation has been studied in detail by experiment and theory and found to involve several isomerization and bond-breaking steps. Isomerizations in z(4) ions proceed by amide trans→cis rotations followed by radical-induced transfer of a β-hydrogen atom from the side chain, forming stable C(β) radical intermediates. These undergo rate-determining cleavage of the C(α)-CO bond at the X residue followed by loss of the neutral AX fragment, forming x(2) intermediates. The latter were detected by energy-resolved resonant excitation collision-induced dissociation (CID) and infrared multiphoton dissociation (IRMPD) experiments. The x(2) intermediates undergo facile loss of HNCO to form z(2) fragment ions, as also confirmed by energy-resolved CID and IRMPD MS(4) experiments. The loss of HNCO from the x(2) ion from AAHWR is kinetically hampered by the Trp residue that traps the OCNH radical group in a cyclic intermediate.

  19. Cascade Dissociations of Peptide Cation-Radicals. Part2. Infrared Multiphoton Dissociation and Mechanistic Studies of z-Ions from Pentapeptides

    PubMed Central

    Ledvina, Aaron R.; Chung, Thomas W.; Hui, Renjie; Coon, Joshua J.

    2013-01-01

    Dissociations of z4 ions from pentapeptides AAXAR, where X = H, Y, F, W, and V, produce dominant z2 ions that account for >50% of the fragment ion intensity. The dissociation has been studied in detail by experiment and theory and found to involve several isomerization and bond-breaking steps. Isomerizations in z4 ions proceed by amide transcis rotations followed by radical-induced transfer of a β-hydrogen atom from the side chain, forming stable Cβ radical intermediates. These undergo rate-determining cleavage of the Cα—CO bond at the X residue followed by loss of the neutral AX fragment, forming x2 intermediates. The latter were detected by energy-resolved resonant excitation collision-activated dissociation (CAD) and infrared multiphoton dissociation (IRMPD) experiments. The x2 intermediates undergo facile loss of HNCO to form z2 fragment ions, as also confirmed by energy-resolved CAD and IRMPD MS4 experiments. The loss of HNCO from the x2 ion from AAHWR is kinetically hampered by the Trp residue that traps the OCNH radical group in a cyclic intermediate. PMID:22669762

  20. Modelling the bacterial photosynthetic reaction center. VI. Use of density-functional theory to determine the nature of the vibronic coupling between the four lowest-energy electronic states of the special-pair radical cation

    NASA Astrophysics Data System (ADS)

    Reimers, Jeffrey R.; Shapley, Warwick A.; Rendell, Alistair P.; Hush, Noel S.

    2003-08-01

    It is now over ten years since the first FTIR spectra were recorded of the radical cation of the special-pair, a dimer of bacteriochlorophyll molecules that forms the primary electron donor responsible for primary charge separation in bacterial photosynthesis. While spectra of this type promise to reveal much concerning the role of the special pair electron donor in photosynthesis, attempts to model and interpret them have been limited by poor knowledge of the vibrationally specific aspects of the electron-phonon coupling and have thus been restricted to crude model calculations only. We develop techniques through which density-functional theory can be employed to evaluate most of the unknown properties. This includes symmetric-mode displacements, antisymmetric-mode vibronic coupling constants, and interstate electronic couplings evaluated for interactions between the four lowest-energy states of the special-pair cation radical: the ground state, the primary hole-transfer state, and states involving these two combined with SHOMO to HOMO transitions. Geometry optimizations are performed for all four states of the dimer while vibrational analyses are obtained for the first two; vibronic coupling constants are extracted from analysis of stolen infrared transition moments using Herzberg-Teller theory. Quantitatively, these results are employed in the subsequent paper in this series to simulate the observed spectra. Qualitatively, these results indicate that: (1) vibronic coupling occurs through a large number of antisymmetric modes of the dimer rather than through a small number of strongly active modes, (2) the role of symmetric vibrational motions of the dimer is only minor, (3) that the active symmetric modes are significant in number and low in frequency, (4) that vibronic coupling between the hole-transfer state and the SHOMO to HOMO state is relatively weak and influences spectra only near resonance, and (5) that the calculated electronic couplings are

  1. Formation of a cobalt(III)-phenoxyl radical complex by acetic acid promoted aerobic oxidation of a Co(II)salen complex.

    PubMed

    Vinck, Evi; Murphy, Damien M; Fallis, Ian A; Strevens, Robert R; Van Doorslaer, Sabine

    2010-03-01

    The activation of N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino Co(II), [Co(II)(1)], by the addition of acetic acid under aerobic conditions has been investigated by a range of spectroscopic techniques including continuous-wave EPR, HYSCORE, pulsed ENDOR, and resonance Raman. These measurements have revealed for the first time the formation of a coordinated cobalt(III)-bound phenoxyl radical labeled [Co(III)(1(*))(OAc)(n)](OAc)(m) (n = m = 1 or n = 2, m = 0). This cobalt(III)-bound phenoxyl radical is characterized by the following spin Hamiltonian parameters: g(x) = 2.0060, g(y) = 2.0031, g(z) = 1.9943, A(x) = 17 MHz, A(y) = 55 MHz, and A(z) = 14 MHz. Although the radical contains coordinated acetate(s), the experiments unambiguously proved that the phenoxyl radical is situated on ligand (1) as opposed to a phenoxyl radical ligated to cobalt in the axial position. Density functional theory computations on different models corroborate the stability of such a phenoxyl radical species and suggest the ligation of one or two acetate molecules to the complex. A mechanism is proposed, which accounts for the formation of this unusual and extremely robust phenoxyl radical, never previously observed for [Co(1)].

  2. Investigation of the formation of benzoyl peroxide, benzoic anhydride, and other potential aerosol products from gas-phase reactions of benzoylperoxy radicals

    NASA Astrophysics Data System (ADS)

    Strollo, Christen M.; Ziemann, Paul J.

    2016-04-01

    The secondary organic aerosol (SOA) products of the reaction of benzaldehyde with Cl atoms and with OH radicals in air in the absence of NOx were investigated in an environmental chamber in order to better understand the possible role of organic peroxy radical self-reactions in SOA formation. SOA products and authentic standards were analyzed using mass spectrometry and liquid chromatography, and results show that the yields of benzoyl peroxide (C6H5C(O)OO(O)CC6H5) and benzoic anhydride (C6H5C(O)O(O)CC6H5), two potential products from the gas-phase self-reaction of benzoylperoxy radicals (C6H5C(O)OO·), were less than 0.1%. This is in contrast to results of recent studies that have shown that the gas-phase self-reactions of β-nitrooxyperoxy radicals formed from reactions of isoprene with NO3 radicals form dialkyl peroxides that contribute significantly to gas-phase and SOA products. Such reactions have also been proposed to explain the gas-phase formation of extremely low volatility dimers from autooxidation of terpenes. The results obtained here indicate that, at least for benzoylperoxy radicals, the self-reactions form only benzoyloxy radicals. Analyses of SOA composition and volatility were inconclusive, but it appears that the SOA may consist primarily of oligomers formed through heterogeneous/multiphase reactions possibly involving some combination of phenol, benzaldehyde, benzoic acid, and peroxybenzoic acid.

  3. Insights in understanding aggregate formation and dissociation in cation exchange chromatography for a structurally unstable Fc-fusion protein.

    PubMed

    Chen, Zhiqiang; Huang, Chao; Chennamsetty, Naresh; Xu, Xuankuo; Li, Zheng Jian

    2016-08-19

    Cation-exchange chromatography (CEX) of a structurally unstable Fc-fusion protein exhibited multi-peak elution profile upon a salt-step elution due to protein aggregation during intra-column buffer transition where low pH and high salt coexisted. The protein exhibited a single-peak elution behavior during a pH-step elution; nevertheless, the levels of soluble aggregates (i.e. high molecular weight species, HMW) in the CEX eluate were still found up to 12-fold higher than that for the load material. The amount of the aggregates formed upon the pH-step elution was dependent on column loading with maximum HMW achieved at intermediate loading levels, supporting the hypothesis that the aggregation was the result of both the conformational changes of the bound protein and the solution concentration of the aggregation-susceptible proteins during elution. Factors such as high load pH, short protein/resin contact time, hydrophilic resin surface, and weak ionizable ligand were effective, to some extent, to reduce aggregate formation by improving the structural integrity of the bound protein. An orthogonal technique, differential scanning fluorimetry (DSF) using Sypro Orange dye confirmed that the bound protein exposed more hydrophobic area than the native molecule in free solution, especially in the pH 4-5 range. The Sypro Orange dye study of resin surface property also demonstrated that the poly[styrene-divinylbenzene]-based Poros XS with polyhydroxyl surface coating is more hydrophobic compared to the agarose-based CM Sepharose FF and SP Sepharose FF. The hydrophobic property of Poros XS contributed to stronger interactions with the partially unfolded bound protein and consequently to the higher aggregate levels seen in Poros XS eluate. This work also investigates the aggregation reversibility in CEX eluate where up to 66% of the aggregates were observed to dissociate into native monomers over a period of 120h, and links the aggregate stability to such conditions as resin

  4. Hydroxyl radical formation during ozonation of multiwalled carbon nanotubes: performance optimization and demonstration of a reactive CNT filter.

    PubMed

    Oulton, Rebekah; Haase, Jason P; Kaalberg, Sara; Redmond, Connor T; Nalbandian, Michael J; Cwiertny, David M

    2015-03-17

    We explored factors influencing hydroxyl radical (•OH) formation during ozonation of multiwalled carbon nanotubes (MWCNTs) and assessed this system's viability as a next-generation advanced oxidation process (AOP). Using standard reactivity metrics for ozone-based AOPs (RCT values), MWCNTs promoted •OH formation during ozonation to levels exceeding ozone (both alone and with activated carbon) and equivalent to ozone with hydrogen peroxide. MWCNTs oxidized with nitric acid exhibited vastly greater rates of ozone consumption and •OH formation relative to as-received MWCNTs. While some of this enhancement reflects their greater suspension stability, a strong correlation between RCT values and surface oxygen concentrations from X-ray photoelectron spectroscopy suggests that surface sites generated during MWCNT oxidation promote •OH exposure. Removal of several ozone-recalcitrant species [para-chlorobenzoic acid (p-CBA), atrazine, DEET, and ibuprofen] was not significantly inhibited in the presence of radical scavengers (humic acid, carbonate), in complex aquatic matrices (Iowa River water) and after 12 h of continuous exposure of MWCNTs to concentrated ozone solutions. As a proof-of-concept, oxidized MWCNTs deposited on a ceramic membrane chemically oxidized p-CBA in a flow through system, with removal increasing with influent ozone concentration and mass of deposited MWCNTs (in mg/cm2). This hybrid membrane platform, which integrates adsorption, oxidation, and filtration via an immobilized MWCNT layer, may serve as the basis for future novel nanomaterial-enabled technologies, although long-term performance trials under representative treatment scenarios remain necessary.

  5. Sonochemiluminescence of lucigenin: Evidence of superoxide radical anion formation by ultrasonic irradiation

    NASA Astrophysics Data System (ADS)

    Matsuoka, Masanori; Takahashi, Fumiki; Asakura, Yoshiyuki; Jin, Jiye

    2016-07-01

    The sonochemiluminescence (SCL) behavior of lucigenin (Luc2+) has been studied in aqueous solutions irradiated with 500 kHz ultrasound. Compared with the SCL of a luminol system, a tremendously increased SCL intensity is observed from 50 µM Luc2+ aqueous solution (pH =11) when small amounts of coreactants such as 2-propanol coexist. It is shown that SCL intensity strongly depends on the presence of dissolved gases such as air, O2, N2, and Ar. The highest SCL intensity is obtained in an O2-saturated solution, indicating that molecular oxygen is required to generate SCL. Since SCL intensity is quenched completely in the presence of superoxide dismutase (SOD), an enzyme that can catalyze the disproportionation of O2 •-, the generation of O2 •- in the ultrasonic reaction field is important in the SCL of Luc2+. In this work, the evidence of O2 •- production is examined by a spectrofluorometric method using 2-(2-pyridyl)benzothiazoline as the fluorescent probe. The results indicate that the yield of O2 •- is markedly increased in the O2-saturated solutions when a small amount of 2-propanol coexists, which is consistent with the results of SCL measurements. 2-Propanol in the interfacial region of a cavitation bubble reacts with a hydroxyl radical (•OH) to form a 2-propanol radical, CH3C•(OH)CH3, which can subsequently react with dissolved oxygen to generate O2 •-. The most likely pathways for SCL as well as the spatial distribution of SCL in a microreactor are discussed in this study.

  6. The cubyl cation rearrangements.

    PubMed

    Jalife, Said; Mondal, Sukanta; Cabellos, Jose Luis; Martinez-Guajardo, Gerardo; Fernandez-Herrera, Maria A; Merino, Gabriel

    2016-02-25

    Born-Oppenheimer molecular dynamics simulations and high-level ab initio computations predict that the cage-opening rearrangement of the cubyl cation to the 7H(+)-pentalenyl cation is feasible in the gas phase. The rate-determining step is the formation of the cuneyl cation with an activation barrier of 25.3 kcal mol(-1) at the CCSD(T)/def2-TZVP//MP2/def2-TZVP level. Thus, the cubyl cation is kinetically stable enough to be formed and trapped at moderate temperatures, but it may be rearranged at higher temperatures.

  7. Liquid Crystalline Polymers by Cationic Polymerization,

    DTIC Science & Technology

    1986-01-01

    cation mechanism of Scholl reaction the Lewis acid and by the benzylic carbocations . Hydride transfer to benzylic carbenium ions leads to methyl groups...reviewed. Examples from ring-opening, carbocationic , and radical-cation poly- merizations and oligomerizations are discussed. Accesion For DrIC TAB3...Examples from ring- opening, carbocationic , and radical-cation polymeri- zations and oligomerizations are discussed. INTRODUCTION This paper will

  8. Key Residues of Outer Membrane Protein OprI Involved in Hexamer Formation and Bacterial Susceptibility to Cationic Antimicrobial Peptides

    PubMed Central

    Chang, Ting-Wei; Wang, Chiu-Feng; Huang, Hsin-Jye; Wang, Iren; Hsu, Shang-Te Danny

    2015-01-01

    Antimicrobial peptides (AMPs) are important components of the host innate defense mechanism against invading pathogens. Our previous studies have shown that the outer membrane protein, OprI from Pseudomonas aeruginosa or its homologue, plays a vital role in the susceptibility of Gram-negative bacteria to cationic α-helical AMPs (Y. M. Lin, S. J. Wu, T. W. Chang, C. F. Wang, C. S. Suen, M. J. Hwang, M. D. Chang, Y. T. Chen, Y. D. Liao, J Biol Chem 285:8985–8994, 2010, http://dx.doi.org/10.1074/jbc.M109.078725; T. W. Chang, Y. M. Lin, C. F. Wang, Y. D. Liao, J Biol Chem 287:418–428, 2012, http://dx.doi.org/10.1074/jbc.M111.290361). Here, we obtained two forms of recombinant OprI: rOprI-F, a hexamer composed of three disulfide-bridged dimers, was active in AMP binding, while rOprI-R, a trimer, was not. All the subunits predominantly consisted of α-helices and exhibited rigid structures with a melting point centered around 76°C. Interestingly, OprI tagged with Escherichia coli signal peptide was expressed in a hexamer, which was anchored on the surface of E. coli, possibly through lipid acids added at the N terminus of OprI and involved in the binding and susceptibility to AMP as native P. aeruginosa OprI. Deletion and mutation studies showed that Cys1 and Asp27 played a key role in hexamer formation and AMP binding, respectively. The increase of OprI hydrophobicity upon AMP binding revealed that it undergoes conformational changes for membrane fusion. Our results showed that OprI on bacterial surfaces is responsible for the recruitment and susceptibility to amphipathic α-helical AMPs and may be used to screen antimicrobials. PMID:26248382

  9. Key Residues of Outer Membrane Protein OprI Involved in Hexamer Formation and Bacterial Susceptibility to Cationic Antimicrobial Peptides.

    PubMed

    Chang, Ting-Wei; Wang, Chiu-Feng; Huang, Hsin-Jye; Wang, Iren; Hsu, Shang-Te Danny; Liao, You-Di

    2015-10-01

    Antimicrobial peptides (AMPs) are important components of the host innate defense mechanism against invading pathogens. Our previous studies have shown that the outer membrane protein, OprI from Pseudomonas aeruginosa or its homologue, plays a vital role in the susceptibility of Gram-negative bacteria to cationic α-helical AMPs (Y. M. Lin, S. J. Wu, T. W. Chang, C. F. Wang, C. S. Suen, M. J. Hwang, M. D. Chang, Y. T. Chen, Y. D. Liao, J Biol Chem 285:8985-8994, 2010, http://dx.doi.org/10.1074/jbc.M109.078725; T. W. Chang, Y. M. Lin, C. F. Wang, Y. D. Liao, J Biol Chem 287:418-428, 2012, http://dx.doi.org/10.1074/jbc.M111.290361). Here, we obtained two forms of recombinant OprI: rOprI-F, a hexamer composed of three disulfide-bridged dimers, was active in AMP binding, while rOprI-R, a trimer, was not. All the subunits predominantly consisted of α-helices and exhibited rigid structures with a melting point centered around 76°C. Interestingly, OprI tagged with Escherichia coli signal peptide was expressed in a hexamer, which was anchored on the surface of E. coli, possibly through lipid acids added at the N terminus of OprI and involved in the binding and susceptibility to AMP as native P. aeruginosa OprI. Deletion and mutation studies showed that Cys1 and Asp27 played a key role in hexamer formation and AMP binding, respectively. The increase of OprI hydrophobicity upon AMP binding revealed that it undergoes conformational changes for membrane fusion. Our results showed that OprI on bacterial surfaces is responsible for the recruitment and susceptibility to amphipathic α-helical AMPs and may be used to screen antimicrobials.

  10. Radiation induced redox reactions and fragmentation of constituent ions in ionic liquids II. Imidazolium cations.

    SciTech Connect

    Shkrob, I. A.; Marin, T. W.; Chemerisov, S. D.; Hatcher, J.; Wishart, J.

    2011-04-14

    In part 1 of this study, radiolytic degradation of constituent anions in ionic liquids (ILs) was examined. The present study continues the themes addressed in part 1 and examines the radiation chemistry of 1,3-dialkyl substituted imidazolium cations, which currently comprise the most practically important and versatile class of ionic liquid cations. For comparison, we also examined 1,3-dimethoxy- and 2-methyl-substituted imidazolium and 1-butyl-4-methylpyridinium cations. In addition to identification of radicals using electron paramagnetic resonance spectroscopy (EPR) and selective deuterium substitution, we analyzed stable radiolytic products using {sup 1}H and {sup 13}C nuclear magnetic resonance (NMR) and tandem electrospray ionization mass spectrometry (ESMS). Our EPR studies reveal rich chemistry initiated through 'ionization of the ions': oxidation and the formation of radical dications in the aliphatic arms of the parent cations (leading to deprotonation and the formation of alkyl radicals in these arms) and reduction of the parent cation, yielding 2-imidazolyl radicals. The subsequent reactions of these radicals depend on the nature of the IL. If the cation is 2-substituted, the resulting 2-imidazolyl radical is relatively stable. If there is no substitution at C(2), the radical then either is protonated or reacts with the parent cation forming a C(2)-C(2) {sigma}{sigma}*-bound dimer radical cation. In addition to these reactions, when methoxy or C{sub {alpha}}-substituted alkyl groups occupy the N(1,3) positions, their elimination is observed. The elimination of methyl groups from N(1,3) was not observed. Product analyses of imidazolium liquids irradiated in the very-high-dose regime (6.7 MGy) reveal several detrimental processes, including volatilization, acidification, and oligomerization. The latter yields a polymer with m/z of 650 {+-} 300 whose radiolytic yield increases with dose (0.23 monomer units per 100 eV for 1-methyl-3-butylimidazolium

  11. Radiation induced redox reactions and fragmentation of constituent ions in ionic liquids. 2. Imidazolium cations.

    PubMed

    Shkrob, Ilya A; Marin, Timothy W; Chemerisov, Sergey D; Hatcher, Jasmine L; Wishart, James F

    2011-04-14

    In part 1 of this study, radiolytic degradation of constituent anions in ionic liquids (ILs) was examined. The present study continues the themes addressed in part 1 and examines the radiation chemistry of 1,3-dialkyl substituted imidazolium cations, which currently comprise the most practically important and versatile class of ionic liquid cations. For comparison, we also examined 1,3-dimethoxy- and 2-methyl-substituted imidazolium and 1-butyl-4-methylpyridinium cations. In addition to identification of radicals using electron paramagnetic resonance spectroscopy (EPR) and selective deuterium substitution, we analyzed stable radiolytic products using (1)H and (13)C nuclear magnetic resonance (NMR) and tandem electrospray ionization mass spectrometry (ESMS). Our EPR studies reveal rich chemistry initiated through "ionization of the ions": oxidation and the formation of radical dications in the aliphatic arms of the parent cations (leading to deprotonation and the formation of alkyl radicals in these arms) and reduction of the parent cation, yielding 2-imidazolyl radicals. The subsequent reactions of these radicals depend on the nature of the IL. If the cation is 2-substituted, the resulting 2-imidazolyl radical is relatively stable. If there is no substitution at C(2), the radical then either is protonated or reacts with the parent cation forming a C(2)-C(2) σσ*-bound dimer radical cation. In addition to these reactions, when methoxy or C(α)-substituted alkyl groups occupy the N(1,3) positions, their elimination is observed. The elimination of methyl groups from N(1,3) was not observed. Product analyses of imidazolium liquids irradiated in the very-high-dose regime (6.7 MGy) reveal several detrimental processes, including volatilization, acidification, and oligomerization. The latter yields a polymer with m/z of 650 ± 300 whose radiolytic yield increases with dose (~0.23 monomer units per 100 eV for 1-methyl-3-butylimidazolium trifluorosulfonate). Gradual

  12. Electrochemical oxidation of pyrogallol: formation and characterization of long-lived oxygen radicals and application to assess the radical scavenging abilities of antioxidants.

    PubMed

    Mu, Shaolin; Chen, Chong

    2012-10-18

    Electrochemical oxidation of pyrogallol in a pH 5.0 phosphate buffer was carried out on a reduced graphene oxide/glassy carbon (RGO/GC) electrode. Reduced graphene oxide plays an important role in catalyzing the electrochemical oxidation of pyrogallol. A deep yellow film deposited on the electrode exhibits electroactivity in a wide pH range. On the basis of the experimental results from measurements of (1)H NMR, (13)C NMR, and IR spectra, there are hydroxyl, carbonyl, and aldehyde groups in the product. No visible absorption peak occurs in the UV-vis spectrum of the product, and its molecular weight is lower than that of the dipolymer but higher than that of the monomer. Therefore, the film is neither a polymer nor a dipolymer and is only a product of pyrogallol oxidation with oxygen radicals. No tendency toward the decay of the ESR signal intensity of the electrogenerated film deposited on the RGO/graphite electrode was observed after 210 days. Electrogenerated film was used as a radical source to test the radical scavenging abilities of ascorbic acid, catechin, and catechol in aqueous solutions based on the ESR signal intensity. The result indicates that ascorbic acid and catechin can scavenge the free radicals, but catechol can hardly scavenge the free radicals.

  13. Comparative study on DBPs formation profiles of intermediate organics from hydroxyl radicals oxidation of microbial cells.

    PubMed

    Ou, Tai-You; Wang, Gen-Shuh

    2016-05-01

    This study assessed the characteristics of disinfection byproducts (DBPs) formation from intermediate organics during UV/H2O2 treatment of activated sludge and algae cells under various reaction conditions. The DBPs including trihalomethanes (THMs), haloacetic acids (HAAs), haloketones (HKs) and haloacetonitriles (HANs) in UV/H2O2-treated and chlorinated water were measured. The results showed that both dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) increased during the initial stage of UV/H2O2 treatment due to the lysis of sludge and algae cells, which enhanced the formation of both C- and N-DBPs; however, both DOC and DON decreased after longer reaction times. During the UV/H2O2 treatments, THMs formation potential (THMFP) peaked earlier than did HAAs formation potential (HAAFP). This shows that the dissolved organics released from lysis of microbial cells in the early stages of oxidation favor the production of THMs over HAAs; however, HAAs precursors increased with the oxidation time. Chlorination with bromide increased the formation of THMs and HAAs but less HKs and HANs were produced. Comparisons of normalized DBP formation potential (DBPFP) of samples collected during UV/H2O2 treatments of four different types of organic matter showed that the highest DBPFP occurred in filtered treated wastewater effluent, followed by samples of activated sludge, filtered eutrophicated pond water, and samples of algae cells. With increasing oxidation time, the dominant DBP species shifted from THMs to HAAs in the samples of activated sludge and algae cells. The DBPFP tests also showed that more HAAs were formed in biologically treated wastewater effluent, while the eutrophicated source water produced more THMs.

  14. Formation of fluorescent polydopamine dots from hydroxyl radical-induced degradation of polydopamine nanoparticles.

    PubMed

    Lin, Jia-Hui; Yu, Cheng-Ju; Yang, Ya-Chun; Tseng, Wei-Lung

    2015-06-21

    This study describes the synthesis of fluorescent polydopamine dots (PDs) through hydroxyl radical-induced degradation of polydopamine nanoparticles. The decomposition of polydopamine nanoparticles to fluorescent PDs was confirmed using transmission electron microscopy and dark-field microscopy. The analysis of PDs by using laser desorption/ionization time-of-flight mass spectrometry revealed that the PDs consisted of dopamine, 5,6-dihydroxyindole, and trihydroxyindole units. Oligomerization and self-assembly of these units produced a broad adsorption band, resulting in an excitation-wavelength-dependent emission behavior. The maximal fluorescence of PDs appeared at 440 nm with a quantum yield of 1.2%. The coordination between the catechol groups of PDs and ferric ions (Fe(3+)) quenched the fluorescence of PDs; the limit of detection at a signal-to-noise ratio of 3 for Fe(3+) was determined to be 0.3 μM. The presence of pyrophosphate switched on the fluorescence of the PD-Fe(3+) complexes. Compared to the other reported methods for sensing Fe(3+), PDs provided simple, low-cost, and reusable detection of Fe(3+).

  15. Ultrasonic application to boost hydroxyl radical formation during Fenton oxidation and release organic matter from sludge.

    PubMed

    Gong, Changxiu; Jiang, Jianguo; Li, De'an; Tian, Sicong

    2015-06-12

    We examined the effects of ultrasound and Fenton reagent on ultrasonic coupling Fenton oxidation (U+F) pre-treatment processes for the disintegration of wastewater treatment plant sludge. The results demonstrated that U+F treatment could significantly increase soluble chemical oxygen demand (SCOD), total organic carbon (TOC), and extracellular polymeric substances (EPS) concentrations in sludge supernatant. This method was more effective than ultrasonic (U) or Fenton oxidation (F) treatment alone. U+F treatment increased the release of SCOD by 2.1- and 1.4-fold compared with U and F alone, respectively. U+F treatment increased the release of EPS by 1.2-fold compared with U alone. After U+F treatment, sludge showed a considerably finer particle size and looser microstructure based on fluorescence microscopy, and the concentration of hydroxyl radicals (OH•) increased from 0.26 mM by F treatment to 0.43 mM by U+F treatment based on fluorescence spectrophotometer. This demonstrated that U+F treatment improves the release of organic matter from sludge.

  16. Ultrasonic application to boost hydroxyl radical formation during Fenton oxidation and release organic matter from sludge

    NASA Astrophysics Data System (ADS)

    Gong, Changxiu; Jiang, Jianguo; Li, De'An; Tian, Sicong

    2015-06-01

    We examined the effects of ultrasound and Fenton reagent on ultrasonic coupling Fenton oxidation (U+F) pre-treatment processes for the disintegration of wastewater treatment plant sludge. The results demonstrated that U+F treatment could significantly increase soluble chemical oxygen demand (SCOD), total organic carbon (TOC), and extracellular polymeric substances (EPS) concentrations in sludge supernatant. This method was more effective than ultrasonic (U) or Fenton oxidation (F) treatment alone. U+F treatment increased the release of SCOD by 2.1- and 1.4-fold compared with U and F alone, respectively. U+F treatment increased the release of EPS by 1.2-fold compared with U alone. After U+F treatment, sludge showed a considerably finer particle size and looser microstructure based on fluorescence microscopy, and the concentration of hydroxyl radicals (OH•) increased from 0.26 mM by F treatment to 0.43 mM by U+F treatment based on fluorescence spectrophotometer. This demonstrated that U+F treatment improves the release of organic matter from sludge.

  17. Ultrasonic application to boost hydroxyl radical formation during Fenton oxidation and release organic matter from sludge

    PubMed Central

    Gong, Changxiu; Jiang, Jianguo; Li, De’an; Tian, Sicong

    2015-01-01

    We examined the effects of ultrasound and Fenton reagent on ultrasonic coupling Fenton oxidation (U+F) pre-treatment processes for the disintegration of wastewater treatment plant sludge. The results demonstrated that U+F treatment could significantly increase soluble chemical oxygen demand (SCOD), total organic carbon (TOC), and extracellular polymeric substances (EPS) concentrations in sludge supernatant. This method was more effective than ultrasonic (U) or Fenton oxidation (F) treatment alone. U+F treatment increased the release of SCOD by 2.1- and 1.4-fold compared with U and F alone, respectively. U+F treatment increased the release of EPS by 1.2-fold compared with U alone. After U+F treatment, sludge showed a considerably finer particle size and looser microstructure based on fluorescence microscopy, and the concentration of hydroxyl radicals (OH•) increased from 0.26 mM by F treatment to 0.43 mM by U+F treatment based on fluorescence spectrophotometer. This demonstrated that U+F treatment improves the release of organic matter from sludge. PMID:26066562

  18. Handling of radical prostatectomy specimens: total embedding with large-format histology.

    PubMed

    Montironi, Rodolfo; Lopez Beltran, Antonio; Mazzucchelli, Roberta; Cheng, Liang; Scarpelli, Marina

    2012-01-01

    A problem when handling radical prostatectomy specimens (RPS) is that cancer is often not visible at gross examination, and the tumor extent is always underestimated by the naked eye. The challenge is increased further by the fact that prostate cancer is a notoriously multifocal and heterogeneous tumor. For the pathologist, the safest method to avoid undersampling of cancer is evidently that the entire prostate is submitted. Even though whole mounts of sections from RPS appear not to be superior to sections from standard blocks in detecting adverse pathological features, their use has the great advantage of displaying the architecture of the prostate and the identification and location of tumour nodules more clearly, with particular reference to the index tumour; further, it is easier to compare the pathological findings with those obtained from digital rectal examination (DRE), transrectal ultrasound (TRUS), and prostate biopsies. We are in favour of complete sampling of the RPS examined with the whole mount technique. There are reasons in favour and a few drawbacks. Its implementation does not require an additional amount of work from the technicians' side. It gives further clinical significance to our work of uropathologists.

  19. A better understanding of hydroxyl radical photochemical sources in cloud waters collected at the puy de Dôme station - experimental versus modelled formation rates

    NASA Astrophysics Data System (ADS)

    Bianco, A.; Passananti, M.; Perroux, H.; Voyard, G.; Mouchel-Vallon, C.; Chaumerliac, N.; Mailhot, G.; Deguillaume, L.; Brigante, M.

    2015-08-01

    The oxidative capacity of the cloud aqueous phase is investigated during three field campaigns from 2013 to 2014 at the top of the puy de Dôme station (PUY) in France. A total of 41 cloud samples are collected and the corresponding air masses are classified as highly marine, marine and continental. Hydroxyl radical (HO•) formation rates (RHO•f) are determined using a photochemical setup (xenon lamp that can reproduce the solar spectrum) and a chemical probe coupled with spectroscopic analysis that can trap all of the generated radicals for each sample. Using this method, the obtained values correspond to the total formation of HO• without its chemical sinks. These formation rates are correlated with the concentrations of the naturally occurring sources of HO•, including hydrogen peroxide, nitrite, nitrate and iron. The total hydroxyl radical formation rates are measured as ranging from approximately 2 × 10-11 to 4 × 10-10 M s-1, and the hydroxyl radical quantum yield formation (ΦHO•) is estimated between 10-4 and 10-2. Experimental values are compared with modelled formation rates calculated by the model of multiphase cloud chemistry (M2C2), considering only the chemical sources of the hydroxyl radicals. The comparison between the experimental and the modelled results suggests that the photoreactivity of the iron species as a source of HO• is overestimated by the model, and H2O2 photolysis represents the most important source of this radical (between 70 and 99 %) for the cloud water sampled at the PUY station (primarily marine and continental).

  20. Validation of a robust and sensitive method for detecting hydroxyl radical formation together with evoked neurotransmitter release in brain microdialysis.

    PubMed

    Freinbichler, Wolfhardt; Colivicchi, Maria A; Fattori, Manuela; Ballini, Chiara; Tipton, Keith F; Linert, Wolfgang; Della Corte, Laura

    2008-05-01

    Sodium terephthalate was shown to be a new robust and sensitive chemical trap for highly reactive oxygen species (hROS), which lacks the drawbacks of the salicylic acid method. Reaction of the almost non-fluorescent terephthalate (TA2-) with hydroxyl radicals or ferryl-oxo species resulted in the stoichiometric formation of the brilliant fluorophor, 2-hydroxyterephthalate (OH-TA). Neither hydrogen peroxide nor superoxide reacts in this system. This procedure was validated for determining hROS formation during microdialysis under in vivo conditions as well as by in vitro studies. The detection limit of OH-TA in microdialysis samples was 0.5 fmol/muL. Derivatization of samples with o-phthalaldehyde, for amino acid detection, had no effect on OH-TA fluorescence, which could easily be resolved from the amino acid derivatives by HPLC, allowing determination in a single chromatogram. Use of terephthalate in microdialysis experiments showed the neurotoxin kainate to evoke hROS formation in a dose-dependent manner. The presence of TA2- in the perfusion fluid did not affect basal or evoked release of aspartate, glutamate, taurine and GABA. Assessment of cell death 'ex vivo' showed TA2- to be non-toxic at concentrations up to 1 mM. The in vitro results in the Fenton system (Fe2+ + H2O2) indicate a mechanism whereby TA2- forms a primary complex with Fe2+ followed by an intramolecular hydroxylation accompanied by intramolecular electron transfer.

  1. Theoretical study of the nitroalkane thermolysis. 1. Computation of the formation enthalpy of the nitroalkanes, their isomers and radical products.

    PubMed

    Kiselev, Vitaly G; Gritsan, Nina P

    2008-05-15

    The gas phase enthalpies of formation of mono-, di-, tri-, tetranitromethane and nitroethane, as well as of their nitrite and aci-form isomers were calculated using different multilevel (G2, G3, G2M(CC5)) and density functional theory (DFT)-based (B3LYP, MPW1B95 and MPWB1K) techniques. The enthalpies of the C-N bond dissociation and isomerization of these nitroalkanes were also calculated. The calculated values of the formation and reaction enthalpies were compared with the experimental data when these data were available. It was found that only the G3 procedure gave accurate (within 1 kcal/mol) results for the formation enthalpy of nitroalkanes, their isomers, and radical products. The G3 procedure and two new hybrid meta DFT methods proposed by Truhlar's group (Zhao, Y.; Truhlar, D. J. Phys. Chem. A 2004, 108, 6908) showed good results for the reaction enthalpies of the nitromethane isomerization and the C-N bond dissociation. Our calculation results were used to analyze thermodynamics of the dissociation and isomerization reactions of the poly nitro-substituted methanes.

  2. Oligorotaxane Radicals under Orders.

    PubMed

    Wang, Yuping; Frasconi, Marco; Liu, Wei-Guang; Sun, Junling; Wu, Yilei; Nassar, Majed S; Botros, Youssry Y; Goddard, William A; Wasielewski, Michael R; Stoddart, J Fraser

    2016-02-24

    A strategy for creating foldameric oligorotaxanes composed of only positively charged components is reported. Threadlike components-namely oligoviologens-in which different numbers of 4,4'-bipyridinium (BIPY(2+)) subunits are linked by p-xylylene bridges, are shown to be capable of being threaded by cyclobis(paraquat-p-phenylene) (CBPQT(4+)) rings following the introduction of radical-pairing interactions under reducing conditions. UV/vis/NIR spectroscopic and electrochemical investigations suggest that the reduced oligopseudorotaxanes fold into highly ordered secondary structures as a result of the formation of BIPY(•+) radical cation pairs. Furthermore, by installing bulky stoppers at each end of the oligopseudorotaxanes by means of Cu-free alkyne-azide cycloadditions, their analogous oligorotaxanes, which retain the same stoichiometries as their progenitors, can be prepared. Solution-state studies of the oligorotaxanes indicate that their mechanically interlocked structures lead to the enforced interactions between the dumbbell and ring components, allowing them to fold (contract) in their reduced states and unfold (expand) in their fully oxidized states as a result of Coulombic repulsions. This electrochemically controlled reversible folding and unfolding process, during which the oligorotaxanes experience length contractions and expansions, is reminiscent of the mechanisms of actuation associated with muscle fibers.

  3. Oligorotaxane Radicals under Orders

    PubMed Central

    2016-01-01

    A strategy for creating foldameric oligorotaxanes composed of only positively charged components is reported. Threadlike components—namely oligoviologens—in which different numbers of 4,4′-bipyridinium (BIPY2+) subunits are linked by p-xylylene bridges, are shown to be capable of being threaded by cyclobis(paraquat-p-phenylene) (CBPQT4+) rings following the introduction of radical-pairing interactions under reducing conditions. UV/vis/NIR spectroscopic and electrochemical investigations suggest that the reduced oligopseudorotaxanes fold into highly ordered secondary structures as a result of the formation of BIPY•+ radical cation pairs. Furthermore, by installing bulky stoppers at each end of the oligopseudorotaxanes by means of Cu-free alkyne–azide cycloadditions, their analogous oligorotaxanes, which retain the same stoichiometries as their progenitors, can be prepared. Solution-state studies of the oligorotaxanes indicate that their mechanically interlocked structures lead to the enforced interactions between the dumbbell and ring components, allowing them to fold (contract) in their reduced states and unfold (expand) in their fully oxidized states as a result of Coulombic repulsions. This electrochemically controlled reversible folding and unfolding process, during which the oligorotaxanes experience length contractions and expansions, is reminiscent of the mechanisms of actuation associated with muscle fibers. PMID:27163033

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

    PubMed

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

    2015-12-15

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

  5. Formation and decomposition of N,N,N-trimethylanilinium cations on zeolite H-Y investigated by in situ stopped-flow MAS NMR spectroscopy.

    PubMed

    Wang, Wei; Seiler, Michael; Ivanova, Irina I; Sternberg, Ulrich; Weitkamp, Jens; Hunger, Michael

    2002-06-26

    Methylation of aniline by methanol on zeolite H-Y has been investigated by in situ (13)C MAS NMR spectroscopy under flow conditions. The in situ (13)C continuous-flow (CF) MAS NMR experiments were performed at reaction temperatures between 473 and 523 K, molar methanol-to-aniline ratios of 1:1 to 4:1, and modified residence times of (13)CH(3)OH between 20 and 100 (g x h)/mol. The methylation reaction was shown to start at 473 K. N,N,N-Trimethylanilinium cations causing a (13)C NMR signal at 58 ppm constitute the major product on the catalyst surface. Small amounts of protonated N-methylaniline ([PhNH(2)CH(3)](+)) and N,N-dimethylaniline ([PhNH(CH(3))(2)](+)) were also observed at ca. 39 and 48 ppm, respectively. After increase of the temperature to 523 K, the contents of N,N-dimethylanilinium cations and ring-alkylated reaction products strongly increased, accompanied by a decrease of the amount of N,N,N-trimethylanilinium cations. With application of the in situ stopped-flow (SF) MAS NMR technique, the decomposition of N,N,N-trimethylanilinium cations on zeolite H-Y to N,N-dimethylanilinium and N-methylanilinium cations was investigated to gain a deeper insight into the reaction mechanism. The results obtained allow the proposal of a mechanism consisting of three steps: (i) the conversion of methanol to surface methoxy groups and dimethyl ether (DME); (ii) the alkylation of aniline with methanol, methoxy groups, or DME leading to an equilibrium mixture of N,N,N-trimethylanilinium, N,N-dimethylanilinium, and N-methylanilinium cations attached to the zeolite surface; (iii) the deprotonation of N,N-dimethylanilinium and N-methylanilinium cations causing the formation of N,N-dimethylaniline (NNDMA) and N-methylaniline (NMA) in the gas phase, respectively. The chemical equilibrium between the anilinium cations carrying different numbers of methyl groups is suggested to play a key role for the products distribution in the gas phase.

  6. Tar balls from Deep Water Horizon oil spill: environmentally persistent free radicals (EPFR) formation during crude weathering.

    PubMed

    Kiruri, Lucy W; Dellinger, Barry; Lomnicki, Slawo

    2013-05-07

    Tar balls collected from the Gulf of Mexico shores of Louisiana and Florida after the BP oil spill have shown the presence of electron paramagnetic resonance (EPR) spectra characteristic of organic free radicals as well as transition metal ions, predominantly iron(III) and manganese(II). Two types of organic radicals were distinguished: an asphaltene radical species typically found in crude oil (g = 2.0035) and a new type of radical resulting from the environmental transformations of crude (g = 2.0041-47). Pure asphaltene radicals are resonance stabilized over a polyaromatic structure and are stable in air and unreactive. The new radicals were identified as products of partial oxidation of crude components and result from the interaction of the oxidized aromatics with metal ion centers. These radicals are similar to semiquinone-type, environmentally persistent free radicals (EPFRs) previously observed in combustion-generated particulate and contaminated soils.

  7. Tar Balls from Deep Water Horizon Oil Spill: Environmentally Persistent Free Radicals (EPFR) Formation During Crude Weathering

    PubMed Central

    Kiruri, Lucy W.; Dellinger, Barry; Lomnicki, Slawo

    2014-01-01

    Tar balls collected from the Gulf of Mexico shores of Louisiana and Florida after the BP oil spill have shown the presence of electron paramagnetic resonance (EPR) spectra characteristic of organic free radicals as well as transition metal ions, predominantly iron(III) and manganese(II). Two types of organic radicals were distinguished: an asphaltene radical species typically found in crude oil (g = 2.0035) and a new type of radical resulting from the environmental transformations of crude (g = 2.0041−47). Pure asphaltene radicals are resonance stabilized over a polyaromatic structure and are stable in air and unreactive. The new radicals were identified as products of partial oxidation of crude components and result from the interaction of the oxidized aromatics with metal ion centers. These radicals are similar to semiquinone-type, environmentally persistent free radicals (EPFRs) previously observed in combustion-generated particulate and contaminated soils. PMID:23510127

  8. SOA Formation form the NO3 radicals Chemistry of Isoprene, Monoterpenes, Sesquiterpenes, Biogenic Oxygenated Compounds, and Aromatics

    NASA Astrophysics Data System (ADS)

    Kleindienst, T. E.; Jaoui, M.; Docherty, K.; Corse, E.; Offenberg, J. H.; Lewandowski, M.

    2011-12-01

    Volatile organic compounds (VOCs) are oxidized in the atmosphere primarily by hydroxyl radicals (OH) during daylight hours but also by nitrate radicals (NO3) during overnight, photochemically inactive periods. While reactions with OH have received considerable attention with regard to gas-phase reaction products and secondary organic aerosol (SOA) formation, less is known about the mechanisms and products resulting from nighttime NO3 reactions despite their potential for SOA formation. To date, there have been limited studies on the chemical characteristics of aerosol reaction products formed from VOCs oxidation with NO3, and few SOA reaction products have been identified. Nighttime reactions have nevertheless been incorporated into some air quality models despite the limited information available and substantial uncertainties which still exist. The National Exposure Research Laboratory of the U.S. Environmental Protection Agency recently undertook an integrated laboratory research effort to better understand the contribution of NO3 reactions to nighttime SOA formation. Isoprene, methacrolein, a-pinene, b-pinene, d-limonene, b-caryophyllene, farnesene, a-humulene, 2-methyl-3-buten-2-ol, toluene, m-xylene, and naphthalene were reacted with NO3 under a wide range of conditions in a series of separate photochemical reaction chamber experiments. These hydrocarbons are thought to contribute to ambient SOA formation. NO3 was formed through thermal decomposition of N2O5. The yield, physical characteristics, and composition of SOA formed in each experiment was analyzed by a suite of instruments including a scanning mobility particle sizer, a Sunset Labs semi continuous EC-OC monitor, a volatility differential mobility analyzer, a direct insertion probe-mass spectrometer, a high resolution time-of-flight aerosol mass spectrometer, and a gas-chromatography-mass spectrometer. To understand the relative contributions of nighttime versus daytime VOCs reactions, a similar

  9. Role of low-energy ion irradiation in the formation of an aluminum germanate layer on a germanium substrate by radical-enhanced atomic layer deposition

    SciTech Connect

    Fukuda, Yukio Yamada, Daichi; Yokohira, Tomoya; Yanachi, Kosei; Yamamoto, Chiaya; Yoo, Byeonghak; Sato, Tetsuya; Yamanaka, Junji; Takamatsu, Toshiyuki; Okamoto, Hiroshi

    2016-03-15

    Radical-enhanced atomic layer deposition uses oxygen radicals generated by a remote microwave-induced plasma as an oxidant to change the surface reactions of the alternately supplied trimethylaluminum precursor and oxygen radicals on a Ge substrate, which leads to the spontaneous formation of an aluminum germanate layer. In this paper, the effects that low-energy ions, supplied from a remote microwave plasma to the substrate along with the oxygen radicals, have on the surface reactions were studied. From a comparative study of aluminum oxide deposition under controlled ion flux irradiation on the deposition surface, it was found that the ions enhance the formation of the aluminum germanate layer. The plasma potential measured at the substrate position by the Langmuir probe method was 5.4 V. Assuming that the kinetic energy of ions arriving at the substrate surface is comparable to that gained by this plasma potential, such ions have sufficient energy to induce exchange reactions of surface-adsorbed Al atoms with the underlying Ge atoms without causing significant damage to the substrate. This ion-induced exchange reaction between Al and Ge atoms is inferred to be the background kinetics of the aluminum germanate formation by radical-enhanced atomic layer deposition.

  10. Formation of [b3 - 1 + cat]+ ions from metal-cationized tetrapeptides containing beta-alanine, gamma-aminobutyric acid or epsilon-aminocaproic acid residues.

    PubMed

    Osburn, Sandra M; Ochola, Sila O; Talaty, Erach R; Van Stipdonk, Michael J

    2008-11-01

    The presence and position of a single beta-alanine (betaA), gamma-aminobutyric acid (gammaABu) or epsilon-aminocaproic acid (Cap) residue has been shown to have a significant influence on the formation of b(n)+ and y(n)+ product ions from a series of model, protonated peptides. In this study, we examined the effect of the same residues on the formation of analogous [b3 - 1 + cat]+ products from metal (Li+, Na+ and Ag+)-cationized peptides. The larger amino acids suppress formation of b3+ from protonated peptides with general sequence AAXG (where X = beta-alanine, gamma-aminobutyric acid or epsilon-aminocaproic acid), presumably because of the prohibitive effect of larger cyclic intermediates in the 'oxazolone' pathway. However, abundant [b3 - 1 + cat]+ products are generated from metal-cationized versions of AAXG. Using a group of deuterium-labeled and exchanged peptides, we found that formation of [b3 - 1 + cat]+ involves transfer of either amide or alpha-carbon position H atoms, and the tendency to transfer the atom from the alpha-carbon position increases with the size of the amino acid in position X. To account for the transfer of the H atom, a mechanism involving formation of a ketene product as [b3 - 1 + cat]+ is proposed.

  11. Communication: Oscillating charge migration between lone pairs persists without significant interaction with nuclear motion in the glycine and Gly-Gly-NH-CH{sub 3} radical cations

    SciTech Connect

    Vacher, Morgane; Bearpark, Michael J.; Robb, Michael A.

    2014-05-28

    Coupled electron-nuclear dynamics has been studied, using the Ehrenfest method, for four conformations of the glycine molecule and a single conformation of Gly-Gly-NH-CH{sub 3}. The initial electronic wavepacket was a superposition of eigenstates corresponding to ionization from the σ lone pairs associated with the carbonyl oxygens and the amine nitrogen. For glycine, oscillating charge migration (when the nuclei were frozen) was observed for the 4 conformers studied with periods ranging from 2 to 5 fs, depending on the energy gap between the lone pair cationic states. When coupled nuclear motion was allowed (which was mainly NH{sub 2} partial inversion), the oscillations hardly changed. For Gly-Gly-NH-CH{sub 3}, charge migration between the carbonyl oxygens and the NH{sub 2} lone pair can be observed with a period similar to glycine itself, also without interaction with nuclear motion. These simulations suggest that charge migration between lone pairs can occur independently of the nuclear motion.

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

    PubMed

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

    2014-01-06

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

  13. Formation of environmentally persistent free radicals as the mechanism for reduced catechol degradation on hematite-silica surface under UV irradiation.

    PubMed

    Li, Hao; Pan, Bo; Liao, Shaohua; Zhang, Di; Xing, Baoshan

    2014-05-01

    Iron is rich in soils, and is recently reported to form stable complexes with organic free radicals, generating environmentally persistent free radicals (EPFRs). The observation may challenge the common viewpoint that iron is an effective catalyst to facilitate the degradation of various organic chemicals. But no study was specifically designed to investigate the possible inhibited degradation of organic chemicals because of the formation of EPFRs in dry environment. We observed that catechol degradation under UV irradiation was decreased over 20% in silica particles coated with 1% hematite in comparison to uncoated silica particles. Stabilized semiquinone or quinine and phenol radicals were involved in HMT-silica system. EPFR formation was thus the reason for the reduced catechol degradation on HMT-silica surface under UV irradiation at ambient temperature. EPFRs should be incorporated in the studies of organic contaminants geochemical behavior, and will be a new input in their environmental fate modeling.

  14. Oxidative damage of U937 human leukemic cells caused by hydroxyl radical results in singlet oxygen formation.

    PubMed

    Rác, Marek; Křupka, Michal; Binder, Svatopluk; Sedlářová, Michaela; Matušková, Zuzana; Raška, Milan; Pospíšil, Pavel

    2015-01-01

    The exposure of human cells to oxidative stress leads to the oxidation of biomolecules such as lipids, proteins and nuclei acids. In this study, the oxidation of lipids, proteins and DNA was studied after the addition of hydrogen peroxide and Fenton reagent to cell suspension containing human leukemic monocyte lymphoma cell line U937. EPR spin-trapping data showed that the addition of hydrogen peroxide to the cell suspension formed hydroxyl radical via Fenton reaction mediated by endogenous metals. The malondialdehyde HPLC analysis showed no lipid peroxidation after the addition of hydrogen peroxide, whereas the Fenton reagent caused significant lipid peroxidation. The formation of protein carbonyls monitored by dot blot immunoassay and the DNA fragmentation measured by comet assay occurred after the addition of both hydrogen peroxide and Fenton reagent. Oxidative damage of biomolecules leads to the formation of singlet oxygen as conformed by EPR spin-trapping spectroscopy and the green fluorescence of singlet oxygen sensor green detected by confocal laser scanning microscopy. It is proposed here that singlet oxygen is formed by the decomposition of high-energy intermediates such as dioxetane or tetroxide formed by oxidative damage of biomolecules.

  15. Oxidative Damage of U937 Human Leukemic Cells Caused by Hydroxyl Radical Results in Singlet Oxygen Formation

    PubMed Central

    Rác, Marek; Křupka, Michal; Binder, Svatopluk; Sedlářová, Michaela; Matušková, Zuzana; Raška, Milan; Pospíšil, Pavel

    2015-01-01

    The exposure of human cells to oxidative stress leads to the oxidation of biomolecules such as lipids, proteins and nuclei acids. In this study, the oxidation of lipids, proteins and DNA was studied after the addition of hydrogen peroxide and Fenton reagent to cell suspension containing human leukemic monocyte lymphoma cell line U937. EPR spin-trapping data showed that the addition of hydrogen peroxide to the cell suspension formed hydroxyl radical via Fenton reaction mediated by endogenous metals. The malondialdehyde HPLC analysis showed no lipid peroxidation after the addition of hydrogen peroxide, whereas the Fenton reagent caused significant lipid peroxidation. The formation of protein carbonyls monitored by dot blot immunoassay and the DNA fragmentation measured by comet assay occurred after the addition of both hydrogen peroxide and Fenton reagent. Oxidative damage of biomolecules leads to the formation of singlet oxygen as conformed by EPR spin-trapping spectroscopy and the green fluorescence of singlet oxygen sensor green detected by confocal laser scanning microscopy. It is proposed here that singlet oxygen is formed by the decomposition of high-energy intermediates such as dioxetane or tetroxide formed by oxidative damage of biomolecules. PMID:25730422

  16. Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

    NASA Astrophysics Data System (ADS)

    Malloy, Q. G. J.; Qi, Li; Warren, B.; Cocker, D. R., III; Erupe, M. E.; Silva, P. J.

    2008-07-01

    Primary aliphatic amines are an important class of nitrogen containing compounds found to be emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with NO3 has been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large yields of aerosol mass loadings (~44% for butylamine) are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (<17% for all amines tested) as detected by an aerosol mass spectrometer (AMS). We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities and lead to elevated nighttime PM loadings, when significant levels on NO3 exist.

  17. Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

    NASA Astrophysics Data System (ADS)

    Malloy, Q. G. J.; Qi, Li; Warren, B.; Cocker, D. R., III; Erupe, M. E.; Silva, P. J.

    2009-03-01

    Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine) are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (<1% for all amines tested) as detected by an aerosol mass spectrometer (AMS). We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.

  18. Simvastatin Reduces Endotoxin-Induced Acute Lung Injury by Decreasing Neutrophil Recruitment and Radical Formation

    PubMed Central

    Grommes, Jochen; Vijayan, Santosh; Drechsler, Maik; Hartwig, Helene; Mörgelin, Matthias; Dembinski, Rolf; Jacobs, Michael; Koeppel, Thomas Andreas; Binnebösel, Marcel; Weber, Christian; Soehnlein, Oliver

    2012-01-01

    Introduction Treatment of acute lung injury (ALI) remains an unsolved problem in intensive care medicine. As simvastatin exerts protective effects in inflammatory diseases we explored its effects on development of ALI and due to the importance of neutrophils in ALI also on neutrophil effector functions. Methods C57Bl/6 mice were exposed to aerosolized LPS (500 µg/ml) for 30 min. The count of alveolar, interstitial, and intravasal neutrophils were assessed 4 h later by flow cytometry. Lung permeability changes were assessed by FITC-dextran clearance and albumin content in the BAL fluid. In vitro, we analyzed the effect of simvastatin on neutrophil adhesion, degranulation, apoptosis, and formation of reactive oxygen species. To monitor effects of simvastatin on bacterial clearance we performed phagocytosis and bacterial killing studies in vitro as well as sepsis experiments in mice. Results Simvastatin treatment before and after onset of ALI reduces neutrophil influx into the lung as well as lung permeability indicating the protective role of simvastatin in ALI. Moreover, simvastatin reduces the formation of ROS species and adhesion of neutrophils without affecting apoptosis, bacterial phagocytosis and bacterial clearance. Conclusion Simvastatin reduces recruitment and activation of neutrophils hereby protecting from LPS-induced ALI. Our results imply a potential role for statins in the management of ALI. PMID:22701728

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

    SciTech Connect

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

    2015-10-19

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

  20. Excitation of water molecules by electron impact with formation of OH-radicals in the A2Σ+ state

    NASA Astrophysics Data System (ADS)

    Khodorkovskii, M. A.; Murashov, S. V.; Artamonova, T. O.; Rakcheeva, L. P.; Beliaeva, A. A.; Shakhmin, A. L.; Michael, D.; Timofeev, N. A.; Mel'nikov, A. S.; Shevkunov, I. A.; Zissis, G.

    2009-11-01

    The excitation cross-sections of the OH-radical band A2Σ+ → X2 (v' = 0 → v'' = 0, v' = 1 → v'' = 1) were measured. OH-radicals were formed during dissociation of water molecules by electron impact in the conditions of crossing of supersonic molecular and electron beams in the energy range 10-120 eV. Measurements were conducted at temperatures of 50, 80 and 200 K. It was shown that the excitation function had a sharp maximum in the region of low energies (at 16 eV) and an extended plateau up to 120 eV. It is proved that there are two channels of molecule dissociation with formation OH (A2Σ+) through excitation of either the triplet b3A1 or the singlet B1A1 states of H2O molecules. The form of the excitation function essentially depends on the temperature of water vapours in the beam. With the decrease of the water molecule temperature the height of the plateau in the region 30-120 eV decreases in comparison with that of the peak at 16 eV. The absolute value of the excitation cross-section of the OH band at the temperature 50 K has been measured. It is equal to (1.6 ± 0.5) × 10-18 cm2 in the maximum at 16 eV. The ratio of cross-sections of bands 1-1 and 0-0 weakly depends on the energy of the exciting electron in the range 12-120 eV and is equal to 0.28 ± 0.05. The appearance threshold is equal to (9.1 ± 0.5) eV.

  1. Reaction of dimethyl ether with hydroxyl radicals: kinetic isotope effect and prereactive complex formation.

    PubMed

    Bänsch, Cornelie; Kiecherer, Johannes; Szöri, Milan; Olzmann, Matthias

    2013-09-05

    The kinetic isotope effect of the reactions OH + CH3OCH3 (DME) and OH + CD3OCD3 (DME-d6) was experimentally and theoretically studied. Experiments were carried out in a slow-flow reactor at pressures between 5 and 21 bar (helium as bath gas) with production of OH by laser flash photolysis of HNO3 and time-resolved detection of OH by laser-induced fluorescence. The temperature dependences of the rate coefficients obtained can be described by the following modified Arrhenius expressions: k(OH+DME) = (4.5 ± 1.3) × 10(-16) (T/K)(1.48) exp(66.6 K/T) cm(3) s(-1) (T = 292-650 K, P = 5.9-20.9 bar) and k(OH+DME-d6) = (7.3 ± 2.2) × 10(-23) (T/K)(3.57) exp(759.8 K/T) cm(3) s(-1) (T = 387-554 K, P = 13.0-20.4 bar). A pressure dependence of the rate coefficients was not observed. The agreement of our experimental results for k(OH+DME) with values from other authors is very good, and from a fit to all available literature data, we derived the following modified Arrhenius expression, which reproduces the values obtained in the temperature range T = 230-1500 K at pressures between 30 mbar and 21 bar to better than within ±20%: k(OH+DME) = 8.45 × 10(-18) (T/K)(2.07) exp(262.2 K/T) cm(3) s(-1). For k(OH+DME-d6), to the best of our knowledge, this is the first experimental study. For the analysis of the reaction pathway and the kinetic isotope effect, potential energy diagrams were calculated by using three different quantum chemical methods: (I) CCSD(T)/cc-pV(T,Q)Z//MP2/6-311G(d,p), (II) CCSD(T)/cc-pV(T,Q)Z//CCSD/cc-pVDZ, and (III) CBS-QB3. In all three cases, the reaction is predicted to proceed via a prereaction OH-ether complex with subsequent intramolecular hydrogen abstraction and dissociation to give the methoxymethyl radical and water. Overall rate coefficients were calculated by assuming a thermal equilibrium between the reactants and the prereaction complex and by calculating the rate coefficients of the hydrogen abstraction step from canonical transition state theory

  2. Impacts of aqueous phase radical mechanism of oligomerization of methyl vinyl ketone (MVK) on SOA formation: on the prevailing role of dissolved oxygen

    NASA Astrophysics Data System (ADS)

    Renard, P.; Ervens, B.; Siekmann, F.; Vassalo, L.; Ravier, S.; Clement, J.; Monod, A.

    2012-12-01

    It is now recognized that the aqueous phase photochemistry of organic compounds in cloud droplets and deliquescent aerosol particles lead to the formation of oligomers and thus it might produce a substantial amount of atmospheric Secondary Organic Aerosol (SOA) with unique properties. However, the chemical mechanisms leading to these oligomers are still poorly understood, and consequently, their atmospheric impacts are difficult to assess. The goal of this study was to investigate the atmospheric impact of an aqueous phase radical mechanism of oligomerization of methyl vinyl ketone (MVK: one of the main reaction products of isoprene) on SOA formation. Aqueous phase photooxidation of MVK was investigated in a photoreactor using photolysis of H2O2 as OH radical generator. Electrospray high resolution mass spectrometry analysis of the solutions brought clear evidence for the formation of oligomer systems having a mass range of up to 1800 Da within less than 15 minutes of reaction. Highest oligomer formation rates were obtained under conditions of low dissolved oxygen, highest temperature and highest MVK initial concentrations. A radical mechanism of polymerization is proposed to explain this oligomer formation. Furthermore, we quantified the total amount of carbon present in oligomers, and the initial radical branching ratios. Kinetic parameters of the proposed oligomerization mechanism are constrained by means of a box model that is able to reproduce the temporal evolution of intermediates and products as observed in the laboratory experiments. Additional model simulations for atmospherically-relevant conditions will be presented that show the extent to which these radical processes contribute to SOA formation in the multiphase system as compared to other aqueous phase as well as traditional SOA sources.

  3. Is the formation of cationic lipid-DNA complexes a thermodynamically driven phenomenon? Structure and phase behavior of DC-Chol/DNA complexes say not

    NASA Astrophysics Data System (ADS)

    Caracciolo, Giulio; Pozzi, Daniela; Caminiti, Ruggero

    2006-07-01

    The currently accepted mechanism of formation of cationic lipid-DNA complexes (lipoplexes) relies on the basic assumption that equilibrium structure of lipoplexes is regulated by thermodynamics. The main consequence is that neutral lipoplexes are one phase whereas positively (or negatively) charged ones coexist with excess lipid (or excess DNA). The authors report a small angle x-ray diffraction study on the structure of lipoplexes made of the cationic lipid 3β-[N-(N ,N-dimethylaminoethane)-carbamoyl]cholesterol and calf thymus Na-DNA. Here the authors show that positively charged lipoplexes can coexist with unbound DNA and they claim that steric size effects are definitely important to determine the equilibrium structure of lipoplexes.

  4. When Like Charged Ions Attract in Ionic Liquids: Controlling the Formation of Cationic Clusters by the Interaction Strength of the Counterions.

    PubMed

    Strate, Anne; Niemann, Thomas; Michalik, Dirk; Ludwig, Ralf

    2017-01-09

    The properties of ionic liquids are described by a subtle balance between Coulomb interaction, hydrogen bonding, and dispersion forces. We show that lowering the attractive Coulomb interaction by choosing weakly coordinating anions leads to the formation of cationic clusters. These clusters of like-charged ions are stabilized by cooperative hydrogen bonding and controlled by the interaction potential of the anion. IR and NMR spectroscopy combined with computational methods are used to detect and characterize these unusual, counter-intuitively formed clusters. They can be only observed for weakly coordinating anions. When cationic clusters are formed, cyclic tetramers are particularly stable. Therein, cooperative hydrogen-bond attraction can compete with like-charge repulsion. We present a simple but effective spectroscopic scale for the possibility of like-charge attraction in ionic liquids, based on IR and NMR signatures.

  5. Kinetics and mechanism for formation of enols in reaction of hydroxide radical with propene.

    PubMed

    Zhou, Chong-Wen; Li, Ze-Rong; Li, Xiang-Yuan

    2009-03-19

    Recently, enols have been found to be the common intermediates in hydrocarbon combustion flames (Taatjes et al. Science 2005, 308, 1887), but the knowledge of kinetic properties for such species in combustion flames is rare. Therefore in this work, particular attention is paid to the formation of enols in combustion flames. Starting with HO and propene (CH(3)CH=CH(2)), the reaction mechanism involving eight product channels has been investigated systematically. It is revealed that the electrophilic addition of OH to the double bond of CH(3)CH=CH(2) is unselective and the chemically activated adducts, CH(3)CHOH=CH(2) and CH(3)CH=CH(2)OH, may undergo dissociation in competition with H-abstractions. The kinetics and product branching ratios of the HO and propene reaction have been evaluated in the temperature range of 200-3000 K by Variflex code, based on the weak collision master equation/microcanonical variational RRKM theory. Available experimental kinetic data can be quantitatively reproduced by this study, with a minor adjustment (1.0 kcal/mol) of the OH central addition barrier. From the theoretical calculations with multiple reflection correction included, the total rate constant is fitted to k(t) = 6.07 x 10(-5)T(-2.54) exp(108/T) cm(3) x molecule(-1) x s(-1) in the range of 200-800 K and k(t) = 7.11 x 10(-23)T(3.38) exp(-1097/T) cm(3) x molecule(-1) x s(-1) in the range of 800-3000 K, which are in close agreement with experimental data. The branching ratios of enol channels are consistent with the observation in low-pressure flames and hence the reaction mechanisms presented here provide valuable descriptions of enol formations in hydrocarbon combustion chemistry.

  6. Up to 100% Formation Ratio of Doublet Exciton in Deep-Red Organic Light-Emitting Diodes Based on Neutral π-Radical.

    PubMed

    Obolda, Ablikim; Ai, Xin; Zhang, Ming; Li, Feng

    2016-12-28

    In a neutral π-radical-based organic light-emitting diode (OLED), although the emission comes from the doublet excitons and their transition to the ground state is spin-allowed, the upper limit of internal quantum efficiency (IQE) is not clear, 50% or 100%? In this work, the deep-red OLEDs based on a neutral π-radical were fabricated. Up to 100% doublet exciton formation ratio was obtained through rational designing device structure and host-guest doping system. This indicates the IQE of neutral π-radical-based OLEDs will reach 100% if the nonradiative pathways of radicals can be suppressed. The maximum external quantum efficiency of the optimized device is as high as 4.3%, which is among the highest values of deep-red/near-infrared OLEDs with nonphosphorescent materials as emitters. Our results also indicate that using partially reduced radical mixture as emitter may be a way to solve aggregation-caused quenching in radical-based OLEDs.

  7. Generation of long-lived methylviologen radical cation in the triplet-state mediated electron transfer in a β-cyclodextrin based supramolecular triad

    NASA Astrophysics Data System (ADS)

    Rakhi, Arikkottira M.; Gopidas, Karical R.

    2015-01-01

    A novel tris(bipyridyl)ruthenium-pyrene-methylviologen supramolecular triad was assembled through inclusion complexation of adamantane-linked Ru(II)-Py dyad in MV2+-linked β-cyclodextrin. Excitation of the Ru(II) chromophore populated its 3MLCT which upon energy transfer gave 3Py, which donates an electron to MV2+ to give Ru(II)-Pyrad +-MVrad +. A second electron transfer then occurs from Ru(II) to Pyrad + to give the supramolecular Ru(III)-Py-MVrad + charge separated state. Laser flash photolysis experiments confirmed formation of MVrad + which exhibited 100 μs lifetime. Steady state irradiation of the self-assembled system in the presence of sacrificial donor also led to formation of long-lived MVrad +.

  8. Catechol degradation on hematite/silica–gas interface as affected by gas composition and the formation of environmentally persistent free radicals

    PubMed Central

    Li, Hao; Guo, Huiying; Pan, Bo; Liao, Shaohua; Zhang, Di; Yang, Xikun; Min, Chungang; Xing, Baoshan

    2016-01-01

    Environmentally persistent free radicals (EPFRs) formed on a solid particle surface have received increasing attention because of their toxic effects. However, organic chemical fate regulated by EPFRs has rarely been investigated, and this information may provide the missing link in understanding their environmental behavior. Previous studies have suggested that the reduction of transition metals is involved in EPFRs formation. We thus hypothesize that an oxidative environment may inhibit EPFRs formation in particle-gas interface, which will consequently release free radicals and accelerate organic chemical degradation. Our result indicates that a 1% hematite coating on a silica surface inhibited catechol degradation in N2, especially at low catechol loadings on solid particles (SCT). However, under an O2 environment, catechol degradation decreased when SCT was <1 μg/mg but increased when SCT was >1 μg/mg. Stable organic free radicals were observed in the N2 system with g factors in the 2.0035–2.0050 range, suggesting the dominance of oxygen-centered free radicals. The introduction of O2 into the catechol degradation system substantially decreased the free radical signals and decreased the Fe(II) content. These results were observed in both dark and light irradiation systems, indicating the ubiquitous presence of EPFRs in regulating the fate of organic chemicals. PMID:27079263

  9. Cytokine toxicity in insulin-producing cells is mediated by nitro-oxidative stress-induced hydroxyl radical formation in mitochondria.

    PubMed

    Gurgul-Convey, Ewa; Mehmeti, Ilir; Lortz, Stephan; Lenzen, Sigurd

    2011-08-01

    Although nitric oxide (NO) and oxidative stress both contribute to proinflammatory cytokine toxicity in pancreatic β-cells during type 1 diabetes mellitus (T1DM) development, the interactions between NO and reactive oxygen species (ROS) in cytokine-mediated β-cell death have not been clarified. Exposure of insulin-producing RINm5F cells to IL-1β generated NO, while exposure to a combination of IL-1β, TNF-α, and IFN-γ, which simulates T1DM conditions, generated both NO and ROS. In theory, two reactions between NO and ROS are possible, one with the superoxide radical yielding peroxynitrite, and the other with hydrogen peroxide (H(2)O(2)) yielding hydroxyl radicals. Results of the present work exclude peroxynitrite involvement in cytokine toxicity to β-cells because its generation did not correlate with the toxic action of cytokines. On the other hand, we show that H(2)O(2), produced upon exposure of insulin-producing cell clones and primary rat islet cells to cytokines almost exclusively in the mitochondria, reacted in the presence of trace metal (Fe(++)) with NO forming highly toxic hydroxyl radicals, thus explaining the severe toxicity that causes apoptotic β-cell death. Expression of the H(2)O(2)-inactivating enzyme catalase in mitochondria protected against cytokine toxicity by preventing hydroxyl radical formation. We therefore conclude that proinflammatory cytokine-mediated β-cell death is due to nitro-oxidative stress-mediated hydroxyl radical formation in the mitochondria.

  10. Catechol degradation on hematite/silica–gas interface as affected by gas composition and the formation of environmentally persistent free radicals

    NASA Astrophysics Data System (ADS)

    Li, Hao; Guo, Huiying; Pan, Bo; Liao, Shaohua; Zhang, Di; Yang, Xikun; Min, Chungang; Xing, Baoshan

    2016-04-01

    Environmentally persistent free radicals (EPFRs) formed on a solid particle surface have received increasing attention because of their toxic effects. However, organic chemical fate regulated by EPFRs has rarely been investigated, and this information may provide the missing link in understanding their environmental behavior. Previous studies have suggested that the reduction of transition metals is involved in EPFRs formation. We thus hypothesize that an oxidative environment may inhibit EPFRs formation in particle-gas interface, which will consequently release free radicals and accelerate organic chemical degradation. Our result indicates that a 1% hematite coating on a silica surface inhibited catechol degradation in N2, especially at low catechol loadings on solid particles (SCT). However, under an O2 environment, catechol degradation decreased when SCT was <1 μg/mg but increased when SCT was >1 μg/mg. Stable organic free radicals were observed in the N2 system with g factors in the 2.0035–2.0050 range, suggesting the dominance of oxygen-centered free radicals. The introduction of O2 into the catechol degradation system substantially decreased the free radical signals and decreased the Fe(II) content. These results were observed in both dark and light irradiation systems, indicating the ubiquitous presence of EPFRs in regulating the fate of organic chemicals.

  11. Catechol degradation on hematite/silica-gas interface as affected by gas composition and the formation of environmentally persistent free radicals.

    PubMed

    Li, Hao; Guo, Huiying; Pan, Bo; Liao, Shaohua; Zhang, Di; Yang, Xikun; Min, Chungang; Xing, Baoshan

    2016-04-15

    Environmentally persistent free radicals (EPFRs) formed on a solid particle surface have received increasing attention because of their toxic effects. However, organic chemical fate regulated by EPFRs has rarely been investigated, and this information may provide the missing link in understanding their environmental behavior. Previous studies have suggested that the reduction of transition metals is involved in EPFRs formation. We thus hypothesize that an oxidative environment may inhibit EPFRs formation in particle-gas interface, which will consequently release free radicals and accelerate organic chemical degradation. Our result indicates that a 1% hematite coating on a silica surface inhibited catechol degradation in N2, especially at low catechol loadings on solid particles (SCT). However, under an O2 environment, catechol degradation decreased when SCT was <1 μg/mg but increased when SCT was >1 μg/mg. Stable organic free radicals were observed in the N2 system with g factors in the 2.0035-2.0050 range, suggesting the dominance of oxygen-centered free