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Sample records for cl andoh radicals

  1. 13C, 18O, and D Fractionation Effects in the Reactions of CH3OH Isotopologues with Cl andOH Radicals

    DEFF Research Database (Denmark)

    Feilberg, Karen; Gruber-Stadler, Margaret; Johnson, Matthew Stanley;

    2008-01-01

    ( 10 mbar. The OH source in the reaction chamber is photolysis of ozone to produce O(1D) in the presence of a large excess of molecular hydrogen: O(1D) + H2 f OH + H. Cl is produced by the photolysis of Cl2. The FTIR spectra are fitted using a nonlinear least-squares spectral fitting method...

  2. High resolution FTIR spectroscopy of the ClO radical

    Science.gov (United States)

    Lang, Valerie; Sander, Stanley P.; Friedl, Randy

    1988-01-01

    The chlorine monoxide radical, ClO, plays a significant role in the catalytic destruction of ozone in the Earth's stratosphere. Because of its atmospheric importance, ClO has been the subject of numerous observational attempts. In order to deduce ClO concentrations from stratospheric infrared measurements, the infrared spectroscopy of ClO must be well characterized. Approximately 830 individual lines were measured form ClO imfrared spectra with the ClO concentration between 1 x 10 to the 13th power and 6 x 10 to the 13th power molecules per cu cu. The lines were then averaged and fit to a function of m (where m = O, -J or J+1 for the Q,P and R branches respectively) to obtain the band strength, S sub v and the first Herman-Wallis coefficient, alpha. The total S sub v for the two main isotopmers was 13.11 plus or minus 1 cm(-2) atm(-1) while alpha was 0.00412 plus or minus .00062.

  3. Theoretical study on the reaction of CN radicals with ClO radicals by density functional theory

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The reaction mechanism of CN radicals with ClO radicals has been studied theoretically using ab initio and density functional theory(DFT).The result shows that the main reaction path is the O atom in radical ClO attacks the C atom in radical CN to compose the intermediate 1 ClOCN.Three thermodynamically accessible prodncts,P1(CO+ClN),P3(NO+CCl),and P4(ClNCO),were obtained from intermediate 1 through isomerization and decomposition reactions.P4 is the primary product,and P1 and P3 are the secondary product.Compared with the singlet potential energy surface,the contribution of the triplet potential energy surface can be ignored.

  4. Lewis Structure Representation of Free Radicals Similar to ClO

    Science.gov (United States)

    Hirsch, Warren; Kobrak, Mark

    2007-01-01

    The study describes the Lewis structure representation of various free radicals, which are quite similar to the ClO radical and its isoelectronic analogues. The analysis of the periodic trends of these radicals shows that oxygen is the most electronegative atom among them.

  5. UV spectra and kinetics of radicals produced in the gas phase reactions of Cl, F and OH with toluene

    DEFF Research Database (Denmark)

    Markert, F.; Pagsberg, P.

    1993-01-01

    The gas phase reactions of Cl, F and OH with toluene have been studied by pulse radiolysis combined with time-resolved UV spectroscopy. The formation of benzyl radicals via the abstraction reactions C6H5-CH3 + X --> C6H5-CH2 + HX was observed with X = Cl, F and OH. In the reaction with chlorine...

  6. Kinetics and mechanism of the gas-phase reaction of Cl atoms and OH radicals with fluorobenzene at 296 K

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Nielsen, Ole John; Hurley, MD;

    2002-01-01

    radical and adduct formation to give the C6H5F-Cl adduct. At 296 K the rate constant for the abstraction channel is k(5a)(Cl+C6H5F) = (1.1 +/- 0.1) x 10(-17) cm(3) molecule(-1) s(-1). The C6H5F-Cl adduct undergoes rapid (k similar to 10(8) s(-1)) decomposition to reform C6H5F and Cl atoms and reaction......Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms and OH radicals with fluorobenzene, C6H5F, in 700 Torr of N-2 or air diluent at 296 K. Reaction of Cl atoms with C6H5F proceeds via two pathways: H-atom abstraction to give HCl and the C6H4F...... with Cl atoms via a mechanism which, at least in part, leads neither to production of C6H5Cl nor to reformation of C6H5F. As the steady-state Cl atom concentration is increased, the fraction of the C6H5F-Cl adduct undergoing reaction with Cl atoms increases causing an increase in the effective rate...

  7. Kinetic of the gas-phase reactions of OH radicals and Cl atoms with Diethyl Ethylphosphonate and Triethyl Phosphate

    KAUST Repository

    Laversin, H.

    2015-11-30

    In this paper, the relative-rate technique has been used to obtain rate coefficients for the reaction of two organophosphorus compounds: Triethyl phosphate (TEP) and Diethyl ethylphosphonate (DEEP) with OH radicals and Cl atoms at atmospheric pressure and at different temperatures. The calculated rate constants were fitted to the Arrhenius expression over the temperature range 298 – 352 K. The following expressions (in cm3molecule-1s-1) were obtained for the reactions of OH and CL with DEEP and TEP: kOH+DEEP= (7.84±0.65)x10-14exp((1866±824)/T), kOH+TEP = (6.54±0.42)x10-14exp((1897±626)/T), kCl+DEEP = (5.27± 0.80)x10−11exp(765±140/T) and kCl+TEP = (5.23± 0.80)x10−11exp(736± 110/T). These results show that the reaction of the studied compounds with Cl atoms proceeds more rapidly than that with OH radicals. The related tropospheric lifetimes suggest that once emitted into the atmosphere, TEP and DEEP can be removed within a few hours in areas close to their emission sources. TEP and DEEP are principally removed by OH radicals. However, in coastal areas where the Cl atoms’ concentration is higher, TEP and DEEP removal by reaction with Cl atoms could be a competitive process.

  8. Theoretical study on the reaction of CN radicals with ClO radicals by density functional theory

    Institute of Scientific and Technical Information of China (English)

    YANG YuHong; HUANG XuRi; SUN ChiaChung

    2009-01-01

    The reaction mechanism of CN radicals with CIO radicals has been studied theoretically using ab initio and density functional theory (DFT).The result shows that the main reaction path is the O atom in radical CIO attacks the C atom in radical CN to compose the intermediate 1 CIOCN.Three thermodynamically accessible prodncts,P_1 (CO+CIN),P_3 (NO+CCI),and P_4 (CINCO),were obtained from intermediate 1 through isomerization and decomposition reactions.P_4 is the primary product,and P_1 and P_3 are the secondary product.Compared with the singlet potential energy surface,the contribution of the triplet potential energy surface can be ignored.

  9. Controlled radical polymerization of vinyl acetate in presence of mesoporous silica supported TiCl4 heterogeneous catalyst

    Indian Academy of Sciences (India)

    M A Semsarzadeh; S Amiri; M Azadeh

    2012-10-01

    The heterogeneous TiCl4 catalysts supported on mesoporous mobile composition of matter (MCM-41) and mesoporous silicone particles synthesized from block copolymer of PPG–PEG–PPG (SPB) complexed with dimethyl formamide (DMF) ligand were used in a controlled free radical reaction with benzoyl peroxide (BPO) initiator in bulk polymerization of vinyl acetate (VAc). In this polymerization process, mesoporous particle of SPB increased the reactivity of TiCl4 catalyst with DMF ligand. The active site formed on the surface and the pores of the catalyst produced specific sequences of VAc on the chain with different thermal and microstructural properties and crystallinity.

  10. Complexes trans-[RuCl(2)(nic)(4)] and trans-[RuCl(2)(i-nic)(4)] as free radical scavengers.

    Science.gov (United States)

    Creczynski-Pasa, T B; Bonetti, V R; Beirith, A; Ckless, K; Konzen, M; Seifriz, I; Paula, M S; Franco, C V; Wilhelm Filho, D; Calixto, J B

    2001-09-01

    This study evaluates the action of the new ruthenium complexes trans-RuCl(2)(nic)(4)] (I) and trans-[RuCl(2)(i-nic)(4)] (II) as free radical scavengers. In our experiments, both compounds acted as scavengers of superoxide anion (O(2)*(-)), hydroxyl radicals (HO*) and nitrogen monoxide (formally known as 'nitric oxide'; NO*). In addition, complexes I and II potentiated the release of NO* from S-nitroso-N-acetyl-DL-penicilamine (SNAP), a NO* donor. Complex II, but not I, also decreased the nitrite levels in culture media of activated macrophages. A hypsochromic shift of lambda(max) and a significant change in half-wave potential (E(1/2)) was observed when NO* was added to the Complex II. Thiobarbituric reactive substance (TBARS) levels were significantly reduced in rats treated for 1 week with Complex II plus tert-butylhydroperoxide, when compared to rats treated only with tert-butylhydroperoxide. None of the complexes showed cytotoxicity. These findings support the suggestion that the new ruthenium complexes, especially trans-[RuCl(2)(i-nic)(4)] or its derivatives, might provide potential therapeutic benefits in disorders where reactive nitrogen (RNS) or oxygen (ROS) species are involved.

  11. Atmospheric chemistry of CF3CHCH2 and C4F9CHCH2: Products of the gas-phase reactions with Cl atoms and OH radicals

    DEFF Research Database (Denmark)

    Nakayama, T.; Takahashi, K.; Matsumi, Y.;

    2007-01-01

    +/- 5% and 6.2 +/- 0.5 respectively. Reaction with Cl atoms proceeds via addition to the > CC Cl and CF3CHClCH2O radicals. Reaction with O-2 and decomposition via C-C bond scission...... presence of NOx gives CxF2x+1CHO in a yield of 88 +/- 9 Reaction with OH radicals proceeds via addition to the > CC radicals. Decomposition via C-C bond scission is the sole fate of CxF2x+1CH(O)CH2OH and CxF2x+1CH(OH)CH2O...... are competing loss mechanisms for CF3CH(O)CH2Cl radicals, k(O2)/k(diss) = (3.8 +/- 1.8) x 10(-18) cm(3) molecule(-1). The atmospheric fate of CF3CHClCH2O radicals is reaction with O-2 to give CF3CHClCHO. The OH radical initiated oxidation of CxF2x+1CHCH2 (x = 1 and 4) in 700 Torr of air in the...

  12. Fock-space multi-reference coupled-cluster response with the effect of triples on dipole moment of ClO and SF radicals

    Indian Academy of Sciences (India)

    Lalitha Ravichandran; Debarati Bhattacharya; Nayana Vaval; Sourav Pal

    2012-01-01

    Dipole moment calculations of SF and ClO radicals have been carried out using the recently developed partial triples correction to Fock-space multi-reference coupled cluster method. Theoretical calculation of the doublet SF and ClO radicals is useful due to their importance in atmospheric chemistry. The dipole moments of these radicals are extremely sensitive to correlation effects. A brief insight to the way the triples correction has been implemented is presented. We compare the results obtained from our analytic response treatment with that of restricted open Hartree-Fock (ROHF) calculations. Results are presented for both relaxed and non-relaxed approach in the ROHF method. Results suggest the importance of triples corrections. The effects of orbital relaxation are also analysed from the results.

  13. Reverse atom transfer radical polymerization (RATRP) for anti-clotting PU-LaCl3-g-P(MPC) films

    Science.gov (United States)

    Lu, Chunyan; Zhou, Ninglin; Xiao, Yinghong; Tang, Yida; Jin, Suxing; Wu, Yue; Shen, Jian

    2013-01-01

    Low grafting density is a disadvantage both in reverse atom transfer radical polymerization (RATRP) and ATRP. In this work, the surfaces of polyurethane (PU) were treated by LaCl3·6H2O to obtain modified surfaces with hydrated layers. The reaction of surface-initiated RATRP was carried out easily, which may be attributed to the enriched hydroxyl groups on the hydrated layers. An innovation found in this work is that some free lanthanum ions (La3+) reacted with the silane coupling agent (CPTM) and the product served as mixed ligand complex. The mixed ligand complex instead of conventional 2,2‧-bipyridine was adopted to serve as a ligand in the process of RATRP. As a result, PU surfaces grafted with well-defined polymer brushes (MPC) were obtained. PU substrates before and after modification were characterized by FTIR, XPS, AFM, SEM, SCA, respectively. The results showed that zwitterionic brushes were successfully fabricated on the PU surfaces (P(MPC)), and the content of the grafted layer increased gradually with polymerization time with the grafting density as high as 97.9%. The blood compatibility of the PU substrates was evaluated by plasma recalcification profiles test and platelet adhesion tests in vitro. It was found that all PU functionalized with zwitterionic brush showed improved resistance to nonspecific protein adsorption and platelet adhesion.

  14. Reverse atom transfer radical polymerization (RATRP) for anti-clotting PU-LaCl3-g-P(MPC) films

    International Nuclear Information System (INIS)

    Highlights: ► A facile and efficient approach for surface modification of PU was introduced. ► MPC was grafted onto the surface of PU film by RATRP. ► Some free La3+ ions reacted with CPTM and the product served as mixed ligand complex. ► The obtained PUs had good blood compatibility and a possible usage in biomedicine. - Abstract: Low grafting density is a disadvantage both in reverse atom transfer radical polymerization (RATRP) and ATRP. In this work, the surfaces of polyurethane (PU) were treated by LaCl3·6H2O to obtain modified surfaces with hydrated layers. The reaction of surface-initiated RATRP was carried out easily, which may be attributed to the enriched hydroxyl groups on the hydrated layers. An innovation found in this work is that some free lanthanum ions (La3+) reacted with the silane coupling agent (CPTM) and the product served as mixed ligand complex. The mixed ligand complex instead of conventional 2,2′-bipyridine was adopted to serve as a ligand in the process of RATRP. As a result, PU surfaces grafted with well-defined polymer brushes (MPC) were obtained. PU substrates before and after modification were characterized by FTIR, XPS, AFM, SEM, SCA, respectively. The results showed that zwitterionic brushes were successfully fabricated on the PU surfaces (P(MPC)), and the content of the grafted layer increased gradually with polymerization time with the grafting density as high as 97.9%. The blood compatibility of the PU substrates was evaluated by plasma recalcification profiles test and platelet adhesion tests in vitro. It was found that all PU functionalized with zwitterionic brush showed improved resistance to nonspecific protein adsorption and platelet adhesion.

  15. Applied quantum chemistry: Spectroscopic detection and characterization of the F2BS and Cl2BS free radicals in the gas phase

    International Nuclear Information System (INIS)

    In this and previous work [D. J. Clouthier, J. Chem. Phys. 141, 244309 (2014)], the spectroscopic signatures of the X2BY (X = H, halogen, Y = O, S) free radicals have been predicted using high level ab initio theory. The theoretical results have been used to calculate the electronic absorption and single vibronic level (SVL) emission spectra of the radicals under typical jet-cooled conditions. Using these diagnostic predictions, the previously unknown F2BS and Cl2BS free radicals have been identified and characterized. The radicals were prepared in a free jet expansion by subjecting precursor mixtures of BF3 or BCl3 and CS2 vapor to an electric discharge at the exit of a pulsed molecular beam valve. The B~2A1–X~ 2B2 laser-induced fluorescence spectra were found within 150 cm−1 of their theoretically predicted positions with vibronic structure consistent with our Franck-Condon simulations. The B~2A1 state emits down to the ground state and to the low-lying A~2B1 excited state and the correspondence between the observed and theoretically derived SVL emission Franck-Condon profiles was used to positively identify the radicals and make assignments. Excited state Coriolis coupling effects complicate the emission spectra of both radicals. In addition, a forbidden component of the electronically allowed B~–X~ band system of Cl2BS is evident, as signaled by the activity in the b2 modes in the spectrum. Symmetry arguments indicate that this component gains intensity due to a vibronic interaction of the B~2A1 state with a nearby electronic state of 2B2 symmetry

  16. Applied quantum chemistry: Spectroscopic detection and characterization of the F{sub 2}BS and Cl{sub 2}BS free radicals in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Bing; Clouthier, Dennis J., E-mail: dclaser@uky.edu [Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055 (United States); Sheridan, Phillip M. [Department of Chemistry and Biochemistry, Canisius College, Buffalo, New York 14208 (United States)

    2015-03-28

    In this and previous work [D. J. Clouthier, J. Chem. Phys. 141, 244309 (2014)], the spectroscopic signatures of the X{sub 2}BY (X = H, halogen, Y = O, S) free radicals have been predicted using high level ab initio theory. The theoretical results have been used to calculate the electronic absorption and single vibronic level (SVL) emission spectra of the radicals under typical jet-cooled conditions. Using these diagnostic predictions, the previously unknown F{sub 2}BS and Cl{sub 2}BS free radicals have been identified and characterized. The radicals were prepared in a free jet expansion by subjecting precursor mixtures of BF{sub 3} or BCl{sub 3} and CS{sub 2} vapor to an electric discharge at the exit of a pulsed molecular beam valve. The B{sup ~2}A{sub 1}–X{sup ~} {sup 2}B{sub 2} laser-induced fluorescence spectra were found within 150 cm{sup −1} of their theoretically predicted positions with vibronic structure consistent with our Franck-Condon simulations. The B{sup ~2}A{sub 1} state emits down to the ground state and to the low-lying A{sup ~2}B{sub 1} excited state and the correspondence between the observed and theoretically derived SVL emission Franck-Condon profiles was used to positively identify the radicals and make assignments. Excited state Coriolis coupling effects complicate the emission spectra of both radicals. In addition, a forbidden component of the electronically allowed B{sup ~}–X{sup ~} band system of Cl{sub 2}BS is evident, as signaled by the activity in the b{sub 2} modes in the spectrum. Symmetry arguments indicate that this component gains intensity due to a vibronic interaction of the B{sup ~2}A{sub 1} state with a nearby electronic state of {sup 2}B{sub 2} symmetry.

  17. Applied quantum chemistry: Spectroscopic detection and characterization of the F2BS and Cl2BS free radicals in the gas phase.

    Science.gov (United States)

    Jin, Bing; Sheridan, Phillip M; Clouthier, Dennis J

    2015-03-28

    In this and previous work [D. J. Clouthier, J. Chem. Phys. 141, 244309 (2014)], the spectroscopic signatures of the X2BY (X = H, halogen, Y = O, S) free radicals have been predicted using high level ab initio theory. The theoretical results have been used to calculate the electronic absorption and single vibronic level (SVL) emission spectra of the radicals under typical jet-cooled conditions. Using these diagnostic predictions, the previously unknown F2BS and Cl2BS free radicals have been identified and characterized. The radicals were prepared in a free jet expansion by subjecting precursor mixtures of BF3 or BCl3 and CS2 vapor to an electric discharge at the exit of a pulsed molecular beam valve. The B̃(2)A1-X̃(2)B2 laser-induced fluorescence spectra were found within 150 cm(-1) of their theoretically predicted positions with vibronic structure consistent with our Franck-Condon simulations. The B̃(2)A1 state emits down to the ground state and to the low-lying Ã(2)B1 excited state and the correspondence between the observed and theoretically derived SVL emission Franck-Condon profiles was used to positively identify the radicals and make assignments. Excited state Coriolis coupling effects complicate the emission spectra of both radicals. In addition, a forbidden component of the electronically allowed B̃-X̃ band system of Cl2BS is evident, as signaled by the activity in the b2 modes in the spectrum. Symmetry arguments indicate that this component gains intensity due to a vibronic interaction of the B̃(2)A1 state with a nearby electronic state of (2)B2 symmetry.

  18. Kinetic study of the OH, NO3 radicals and Cl atom initiated atmospheric photo-oxidation of iso-propenyl methyl ether

    Science.gov (United States)

    Taccone, Raúl Alberto; Moreno, Alberto; Colmenar, Inmaculada; Salgado, Sagrario; Martín, María Pilar; Cabañas, Beatriz

    2016-02-01

    Rate coefficients at room temperature and atmospheric pressure for the reaction of isopropenyl methyl ether (i-PME) (CH2dbnd C(CH3)OCH3), with OH and NO3 radicals and with Cl atoms have been determined in a 50 L Pyrex glass reaction chamber in conjunction with Fourier Transform Infrared absorption spectroscopy (FTIR) as a detection technique. The chamber is equipped with a White-type multiple-reflection mirror system with a total optical path length of ≈200 m. Additional experiments were carried out using evacuable Teflon-coated bags (volume 150 L) and a gas chromatography/mass spectrometry-time of flight (GC-TOF MS) detection system. This is the first kinetic study carried out to date for these reactions. The rate coefficients k (in units of cm3 molecule-1 s-1) obtained are: (1.14 ± 0.10) × 10-10 for the OH reaction, (2.41 ± 0.50) × 10-11, for the NO3 reaction and (7.03 ± 0.67) × 10-10 for the Cl reaction. A mechanism is proposed from the observed reaction products. The atmospheric lifetimes of the studied ether is estimated considering the rate coefficients of the reactions with OH and NO3 radicals and Cl atom. Calculated atmospheric lifetimes reveal that the dominant loss process for i-PME is clearly the night-time reaction with the NO3 radical. The radiative efficiency (RE) is obtained from the infrared spectra of the ether and the global warming potential (GWP) is then estimated. Atmospheric implications of the ether emission are discussed.

  19. The Light Detection of Free Radical on HMX,CL-20 and DNTF%HMX,CL-20和DNTF自由基的光照检测

    Institute of Scientific and Technical Information of China (English)

    马海霞; 宋纪蓉; 胡荣祖; 赵凤起

    2007-01-01

    为研究含能材料热分解过程的瞬间性和安全性,运用电子自旋共振技术(ESR)检测了HMX,CL-20和DNTF的自由基,得到了它们在相同的光照强度和时间间隔中,各体系的电子自旋共振谱图.结果表明,DNTF在没有光照的情况下即会产生自由基,HMX和CL-20光照一定时间后有自由基产生.随着光照时间的延长,自由基逐渐增多,DNTF的自由基信号最强.

  20. Atmospheric chemistry of (CF3)2C=CH2: OH radicals, Cl atoms and O3 rate coefficients, oxidation end-products and IR spectra.

    Science.gov (United States)

    Papadimitriou, Vassileios C; Spitieri, Christina S; Papagiannakopoulos, Panos; Cazaunau, Mathieu; Lendar, Maria; Daële, Véronique; Mellouki, Abdelwahid

    2015-10-14

    The rate coefficients for the gas phase reactions of OH radicals, k1, Cl atoms, k2, and O3, k3, with 3,3,3-trifluoro-2(trifluoromethyl)-1-propene ((CF3)2C=CH2, hexafluoroisobutylene, HFIB) were determined at room temperature and atmospheric pressure employing the relative rate method and using two atmospheric simulation chambers and a static photochemical reactor. OH and Cl rate coefficients obtained by both techniques were indistinguishable, within experimental precision, and the average values were k1 = (7.82 ± 0.55) × 10(-13) cm(3) molecule(-1) s(-1) and k2 = (3.45 ± 0.24) × 10(-11) cm(3) molecule(-1) s(-1), respectively. The quoted uncertainties are at 95% level of confidence and include the estimated systematic uncertainties. An upper limit for the O3 rate coefficient was determined to be k3 global warming potential (GWP) calculations, radiative efficiency (RE) was determined from the measured IR absorption cross-sections and treating HFIB both as long (LLC) and short (SLC) lived compounds, including estimated lifetime dependent factors in the SLC case. The HFIB lifetime was estimated from kinetic measurements considering merely the OH reaction, τOH = 14.8 days and including both OH and Cl chemistry, τeff = 10.3 days. Therefore, GWP(HFIB,OH) and GWP(HFIB,eff) were estimated to be 4.1 (LLC) and 0.6 (SLC), as well as 2.8 (LLC) and 0.3 (SLC) for a hundred year time horizon. Moreover, the estimated photochemical ozone creation potential (ε(POCP)) of HFIB was calculated to be 4.60. Finally, HCHO and (CF3)2C(O) were identified as final oxidation products in both OH- and Cl-initiated oxidation, while HC(O)Cl was additionally observed in the Cl-initiated oxidation. PMID:26372403

  1. Halogen Bonding or Hydrogen Bonding between 2,2,6,6-Tetramethyl-piperidine-noxyl Radical and Trihalomethanes CHX3 (X=Cl, Br, I)

    Institute of Scientific and Technical Information of China (English)

    Xiao-ran Zhao; Xue Pang; Xiao-qing Yan; Wei-jun Jin

    2013-01-01

    The halogen and hydrogen bonding complexes between 2,2,6,6-tetramethylpiperidine-noxyl and trihalomethanes (CHX3,X=Cl,Br,I) are simulated by computational quantum chemistry.The molecular electrostatic potentials,geometrical parameters and interaction energy of halogen and hydrogen bonding complexes combined with natural bond orbital analysis are obtained.The results indicate that both halogen and hydrogen bonding interactions obey the order Cl<Br<I,and hydrogen bonding is stronger than the corresponding halogen bond ing.So,hydrogen bonding complexes should be dominant in trihalomethanes.However,it is possible that halogen bonding complex is competitive,even preponderant,in triiodomethane due to the similar interaction energy.This work might provide useful information on specific solvent effects as well as for understanding the mechanism of nitroxide radicals as a bioprobe to interact with the halogenated compounds in biological and biochemical fields.

  2. Analyses of the tilde{A}-tilde{X} Electronic Transitions of the CH{_2}XOO{\\cdot}(X = i, Br, Cl) Radicals

    Science.gov (United States)

    Kline, Neal; Huang, Meng; Miller, Terry A.

    2016-06-01

    Cavity ringdown, near-infrared spectra have been previously observed following the photolysis of the dihalomethanes(CH{_2}XI, X = I, Br, Cl) in the presence of O{_2} and N{_2}. In last year's Symposium, we presented evidence that all the spectra could be attributed to the tilde{A}-tilde{X} electronic transition of the appropriate CH{_2}XOO{\\cdot} radical. We now present detailed analyses of these spectra. Similar spectral features have been observed for all radicals. The first strong transitions are located around 6800 cm{-1}, and are assigned as associated with the origin. Other strong transitions are observed about 800 cm{-1} blue of the origin, and have a multiple-peak structure similar to the corresponding origin bands. These bands are assigned to be the OO stretch of the tilde{A}-tilde{X} electronic transitions, which are typically strong in the spectra of peroxy radicals, based on electronic structure calculations that provide vibrational frequencies and Franck-Condon factors. One-dimensional calculations of the internal torsion mode are applied to specifically explain the multiple-peak features in both the origin and OO stretch region as series of transitions including sequence bands and other hot bands from the vibrationally excited states of the low-frequency torsion mode in the tilde{X} state, which are significantly populated at room temperature. Additional bands can be assigned to fundamentals or combination bands of various other tilde{A} state modes. N. D. Kline, M. Huang, T. A. Miller, P. Lolur, R. Dawes, FD05, 70th International Symposium of Molecular Spectroscopy(2015)

  3. Atmospheric chemistry of CxF2x+1CH=CH2 (x=1, 2, 4, 6, and 8): Kinetics of gas-phase reactions with Cl atoms, OH radicals, and O-3

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Nielsen, OJ; Toft, A;

    2005-01-01

    Long-path length FT-IR-smog chamber techniques were used to study the title reactions in 700 Torr of N-2 or N-2/O-2, diluent at 296K. There was no discernable effect of CchiF2 chi+1-group size on the reactivity of CchiF2 chi+1CH=CH2 towards Cl atoms and OH radicals. Values of k(Cl+C(chi)Fa(2 chi+...

  4. Atmospheric Chemistry of CF3CF=CH2: Reactions With Cl Atoms, OH Radicals and Ozone

    Science.gov (United States)

    Sulbaek Andersen, M. P.; Javadi, M. S.; Nielsen, O. J.; Hurley, M. D.; Wallington, T. J.; Singh, R.

    2006-12-01

    The detrimental effects of chlorine chemistry on stratospheric ozone levels are well established. Consequently, there has been a concerted international effort to find replacements for chlorofluorocarbons (CFCs) used previously as electronic equipment cleaners, heat transfer agents, refrigerants, and carrier fluids for lubricant deposition. The replacements for CFCs, hydrofluorocarbons (HFCs) and hydrofluorochlorocarbons (HCFCs), have found widespread industrial use over the past decade. Unsaturated fluorinated hydrocarbons are a new class of compounds which have been developed to replace CFCs and HFCs in air condition units. Prior to any large-scale industrial use an assessment of the atmospheric chemistry, and hence environmental impact, of these compounds is needed. To address this need the atmospheric chemistry of CF3CF=CH2 was investigated. Smog chamber/FTIR techniques were used to determine the following properties for this compound: (i) kinetics of reactions with chlorine atoms (ii) kinetics of reactions with hydroxyl radicals (iii) kinetics of reactions with ozone, (iv) atmospheric lifetimes, (v) atmospheric degradation mechanism, and (vi) global warming potentials. The results are discussed with regard to the environmental impact of CF3CF=CH2 and the atmospheric chemistry of unsaturated fluorinated hydrocarbons.

  5. Fístula Arteriovenosa após Nefrectomia Radical: A Propósito de um Caso Clínico Arteriovenous fistula after Radical Nephrectomy:: a case report

    Directory of Open Access Journals (Sweden)

    Nádia Duarte

    2011-09-01

    Full Text Available Existem três tipos diferentes de fístulas arteriovenosas (FAV renais, as congénitas, as idiopáticas e as adquiridas, sendo as últimas as mais frequentes. Dentro destas, as resultantes da nefrectomia são uma raridade. A FAV entre a artéria renal e a veia cava inferior (VCI é uma complicação rara após nefrectomia, estando descritos cerca de 10 casos na literatura. Os autores descrevem um caso de um homem de 51 anos, insuficiente renal crónico (IRC em hemodiálise, enviado à consulta de Urologia por nódulo sólido do rim direito sugestivo de neoplasia, detectado em ressonância magnética (RMN. Foi submetido a nefrectomia radical direita, tendo sido efectuada laqueação conjunta do pedículo renal, sem intercorrências cirúrgicas. Quatro meses depois, inicia clínica de sobrecarga hídrica, de difícil controlo com a hemodiálise e surge um sopro abdominal localizado no flanco direito, contínuo. O estudo por eco-doppler abdominal e angiografia demonstrou a presença de fístula entre a artéria renal e a veia cava inferior. Foi submetido a embolização da FAV com coils, tendo-se registado migração dos mesmos para a artéria pulmonar. A sua recolha foi efectuada imediatamente com basket, sem outras intercorrências. Posteriormente, foi submetido a laparotomia com laqueação simples da artéria renal justa-aórtica, com resolução e estabilização do quadro clínico. A propósito deste caso clínico os autores discutem a abordagem diagnóstica e a hierarquia terapêutica da FAV reno-VCI nomeadamente na cirurgia directa e endovascular.There are three different types of renal arteriovenous fistula (AVF, congenital, idiopathic and acquired, being the latter the most frequent. Within these, those resulting from nephrectomy are rare. The AVF between the renal artery and the inferior vena cava (IVC is a rare complication, with about 10 cases described in literature. The authors describe the case of a 51 year old man, with chronic

  6. Free radical hydrogen atom abstraction from saturated hydrocarbons: A crossed-molecular-beams study of the reaction Cl + C{sub 3}H{sub 8} {yields} HCl + C{sub 3}H{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Blank, D.A.; Hemmi, N.; Suits, A.G.; Lee, Y.T. [Lawrence Berkeley National Lab., CA (United States)

    1997-04-01

    The abstraction of hydrogen atoms from saturated hydrocarbons are reactions of fundamental importance in combustion as well as often being the rate limiting step in free radical substitution reactions. The authors have begun studying these reactions under single collision conditions using the crossed molecular beam technique on beamline 9.0.2.1, utilizing VUV undulator radiation to selectively ionize the scattered hydrocarbon free radical products (C{sub x}H{sub 2x+1}). The crossed molecular beam technique involves two reactant molecular beams fixed at 90{degrees}. The molecular beam sources are rotatable in the plane defined by the two beams. The scattered neutral products travel 12.0 cm where they are photoionized using the VUV undulator radiation, mass selected, and counted as a function of time. In the authors initial investigations they are using halogen atoms as protypical free radicals to abstract hydrogen atoms from small alkanes. Their first study has been looking at the reaction of Cl + propane {r_arrow} HCl + propyl radical. In their preliminary efforts the authors have measured the laboratory scattering angular distribution and time of flight spectra for the propyl radical products at collision energies of 9.6 kcal/mol and 14.9 kcal/mol.

  7. Li+ Ion Attachment to Chloromethyl and Chlorofluoromethyl Peroxyl Radicals: Structures and Properties of CHnCl3-nO2-Li+ and CFnCl3-nO2-Li+ (n=0-3) Complexes

    Institute of Scientific and Technical Information of China (English)

    CHENG, Shuang; LI, Hai-Yang; LIU, Ying

    2006-01-01

    The structures and stabilities of these still experimentally unknown CHnCl3-nO2-Li+ and CFnCl3-nO2-Li+ ions have been theoretically investigated by ab initio molecular orbital theory and density functional theory (DFF) in conjunction with the 6-311G(d,p), 6-311 + G(d,p), 6-311 + G(2d,p) and 6-311 + G(2df,2p) basis sets. The optimized geometries, chemical bonding and NBO analysis indicate that these complexes of CHnCl3-nO2-Li+ and CFnCl3-nO2-Li+ exist as ion-dipole molecules. The calculated affinity energies of these species exceed 41.9 kJ/mol, which are large enough to suggest the possibility that these title complexes could be detected as stable species in gas phase by Li+ ion attachment mass spectrometry.

  8. Pseudoaneurisma de arteria renal principal asociado a fistula cecal tras nefrectomia radical: caso clínico y revisión de la literatura

    OpenAIRE

    A. Hernando Arteche; C. Alpuente Roman; R. Martin del Toro; A. Pérez-Piqueras Gómez; F. Sainz González; JA. Cabrera Cabrera

    2014-01-01

    Las complicaciones vasculares secundarias al tratamiento quirúrgico del cáncer de riñón localizado son más frecuentes cuando se realiza una cirugía conservadora de nefronas. Sin embargo, la nefrectomía radical no está exenta de ellas. Presentamos el caso de un pseudoaneurisma de la arteria renal principal con comunicación fistulosa a colon ascendente tras nefrectomía radical. El paciente debutó con un episodio de shock hipovolémico debido a hemorragia digestiva baja.

  9. Pseudoaneurisma de arteria renal principal asociado a fistula cecal tras nefrectomia radical: caso clínico y revisión de la literatura

    Directory of Open Access Journals (Sweden)

    A. Hernando Arteche

    2014-06-01

    Full Text Available Las complicaciones vasculares secundarias al tratamiento quirúrgico del cáncer de riñón localizado son más frecuentes cuando se realiza una cirugía conservadora de nefronas. Sin embargo, la nefrectomía radical no está exenta de ellas. Presentamos el caso de un pseudoaneurisma de la arteria renal principal con comunicación fistulosa a colon ascendente tras nefrectomía radical. El paciente debutó con un episodio de shock hipovolémico debido a hemorragia digestiva baja.

  10. EPR spectroscopy as a tool for investigation of differences in radical status in wheat plants of various tolerances to osmotic stress induced by NaCl and PEG-treatment.

    Science.gov (United States)

    Labanowska, Maria; Filek, Maria; Kurdziel, Magdalena; Bidzińska, Ewa; Miszalski, Zbigniew; Hartikainen, Hélina

    2013-01-15

    Two kinds of wheat genotypes with different tolerance to osmotic stress (NaCl and PEG-treatment) were investigated with biochemical analyses, including the measurements of total antioxidant capacity, 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical-scavenging activity, reducing power and starch content. The results were compared with electron paramagnetic resonance (EPR) data concerning the nature and amounts of stable long lived radicals present in the control and stressed plants. In addition, the changes in manganese content upon stress conditions were monitored. Different mechanisms of protection against PEG stress in sensitive and tolerant wheat genotypes were postulated. In sensitive genotypes, electrons were created in excess in stress conditions, and were stabilized by polysaccharide molecules, whereas in tolerant genotypes, protection by antioxidants dominated. Moreover, the quinone-semiquinone balance shifted towards semiquinone, which became the place of electron trapping. NaCl-treatment yielded significant effects mainly in sensitive genotypes and was connected with the changes of water structure, leading to inactivation of reactive oxygen species by water molecules.

  11. Atmospheric chemistry of trans-CF3CH=CHCl: Kinetics of the gas-phase reactions with Cl atoms, OH radicals, and O3

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbaek; Nilsson, Elna Johanna Kristina; Nielsen, Ole John;

    2008-01-01

    .22±0.72)×10-11 cm3 molecule-1 s-1, k(OH + t-CF3CH CHCl) = (4.40±0.38)×10-13 cm3 molecule-1 s-1 and k(O3 + t-CF3CH CHCl) = (1.46±0.12)×10-21 cm3 molecule-1 s-1, were established (quoted uncertainties are 2; see Experimental section). The IR spectrum of t-CF3CH CHCl is reported. The atmospheric lifetime of t-CF3CH...... CHCl is determined by reaction with OH radicals and is approximately 26 days. The global warming potential of t-CF3CH CHCl is approximately 7 for a 100-year time horizon....

  12. Atmospheric chemistry of trans-CF3CH = CHCl: Kinetics of the gas-phase reactions with Cl atoms, OH radicals, and O-3

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Nilsson, E. J. K.; Nielsen, O. J.;

    2008-01-01

    = CHCl) = (5.22 +/- 0.72) x 10(-11) cm(3) molecule(-1) s(-1), k(OH + t-CF3CH = CHCl) = (4.40 +/- 0.38) x 10(-13) cm(3) molecule(-1) s(-1) and k(O-3 + t-CF3CH = CHCl) = (1.46 +/- 0.12) x 10(-21) cm(3) molecule(-1) s(-1), were established (quoted uncertainties are 2 sigma: see Experimental section). The IR...... spectrum of t-CF3CH = CHCl is reported. The atmospheric lifetime of t-CF3CH = CHCl is determined by reaction with OH radicals and is approximately 26 days. The global warming potential of t-CF3CH = CHCl is approximately 7 for a 100-year time horizon. (C) 2008 Elsevier B.V. All rights reserved....

  13. Reaction dynamics and photochemistry of divalent systems. [Reaction of Ba with NO sub 2 , H sub 2 O, methanol, ClO sub 2 , O sub 3; photodissociation of NO sub 3 radical and OClO

    Energy Technology Data Exchange (ETDEWEB)

    Davis, H.F.

    1992-05-01

    Results are presented of molecular beam studies of bimolecular and unimolecular reactions of Ba. Chapter 1 discusses the reaction Ba + NO{sub 2}. Formation of the dominant BaO({sup 1}{Sigma}) + NO products resulted primarily from decay of long-lived Ba{sup +}NO{sub 2}{sup {minus}} collision complexes. Secondary mechanisms led to formation of forward scattered, internally excited BaO, and BaNO + O. D{sub o}(Ba-NO) = 65{plus minus}20 kcal/mol. Reactions of ground state and electronically excited Ba with water and alcohols are examined in Chapter 2. Reaction of Ba({sup 1}S) + H{sup 2}O led to BaO + H{sub 2}, whereas excited state Ba({sup 1}D) + H{sub 2}O reacted to form BaOH + H. Collisions between Ba and CH{sub 3}OH led to BaOCH{sub 3} + H. Radical channels involve H-atom migration and are promoted by excitation of the incident Ba atom. In Chapter 3, reactions of Ba({sup 1}S) with ClO{sub 2}2 and O{sub 3} are discussed. Again, direct and complex mechanisms were observed. Formation of BaCl + O{sub 2} from decomposition of Ba{sup +}ClO{sub 2}{sup {minus}} accounted for 10% of total reaction crass section. Although Ba + O{sub 3} {yields} BaO + 0{sub 2} occurs primarily by direct reaction mechanisms, the secondary channel Ba + 0{sub 3} {yields} BaO{sub 2} + 0 involved decay of long lived Ba{sup +}O{sub 3}{sup {minus}} intermediates. D{sub o}(Ba{minus}O{sub 2}) = 120 {plus minus}20 kcal/mol. Photodissociation dynamics of NO{sub 3} is explored in chapter 4. Visible excitation leads to formation of NO + 0{sub 2} and NO{sub 2} + O. Wavelength dependence of branching ratios is investigated. D{sub o}(O-NO{sub 2}) = 48.55 kcal/mole ;and calculate {Delta}H{sub f}(NO{sub 3}) = 17.75 kcal/mole (298K). Chapter 5 discusses the photodissociation of OClO in a molecular beam. Although ClO({sup 2}II) + O({sup 3}P) is dominant, Cl({sup 2}P) + O{sub 2} also forms, with a max yield of 3.9{plus minus}0.8% near 404nm.

  14. Kinetics of the reaction of hydroxyl radical with methane and with nine Cl- and F-substituted methanes. 1. Experimental results, comparisons, and applications

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, K.M.; Kaufman, F.

    1982-05-13

    The rates of reaction of OH with CH/sub 4/ and with all nine Cl- and F-substituted methanes that contain at least one abstractable H atom are measured over wide temperature ranges (mainly 250-480 K) by the discharge-flow method under strictly comparable experimental conditions. Curvature is found in all but one Arrhenius plot, that of CHF/sub 3/, which is slower reacting and was studied over a smaller temperature range. Optimized three-parameter expressions require a temperature exponent, n, of 2.0-2.2. They are reduced to Arrhenius A's and E's centered at 300 K. Substantial variation is found in the A's for related compounds, less so in the E's which correlate roughly with the bond energy of the abstracted C-H. The results are compared with all published data, and their use in atmospheric science and combustion is briefly discussed.

  15. A dinuclear [{(p-cym)Ru(II)Cl}2(μ-bpytz˙(-))](+) complex bridged by a radical anion: synthesis, spectroelectrochemical, EPR and theoretical investigation (bpytz = 3,6-bis(3,5-dimethylpyrazolyl)1,2,4,5-tetrazine; p-cym = p-cymene).

    Science.gov (United States)

    Tripathy, Suman Kumar; van der Meer, Margarethe; Sahoo, Anupam; Laha, Paltan; Dehury, Niranjan; Plebst, Sebastian; Sarkar, Biprajit; Samanta, Kousik; Patra, Srikanta

    2016-08-01

    The reaction of the chloro-bridged dimeric precursor [{(p-cym)Ru(II)Cl}(μ-Cl)]2 (p-cym = p-cymene) with the bridging ligand 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine (bpytz) in ethanol results in the formation of the dinuclear complex [{(p-cym)Ru(II)Cl}2(μ-bpytz˙(-))](+), [1](+). The bridging tetrazine ligand is reduced to the anion radical (bpytz˙(-)) which connects the two Ru(II) centres. Compound [1](PF6) has been characterised by an array of spectroscopic and electrochemical techniques. The radical anion character has been confirmed by magnetic moment (corresponding to one electron paramagnetism) measurement, EPR spectroscopic investigation (tetrazine radical anion based EPR spectrum) as well as density functional theory based calculations. Complex [1](+) displays two successive one electron oxidation processes at 0.66 and 1.56 V versus Ag/AgCl which can be attributed to [{(p-cym)Ru(II)C}2(μ-bpytz˙(-))](+)/[{(p-cym)Ru(II)Cl}2(μ-bpytz)](2+) and [{(p-cym)Ru(II)Cl}2(μ-bpytz)](+)/[{(p-cym)Ru(III)Cl}2(μ-bpytz)](2+) processes (couples I and II), respectively. The reduction processes (couple III-couple V), which are irreversible, likely involve the successive reduction of the bridging ligand and the metal centres together with loss of the coordinated chloride ligands. UV-Vis-NIR spectroelectrochemical investigation reveals typical tetrazine radical anion containing bands for [1](+) and a strong absorption in the visible region for the oxidized form [1](2+), which can be assigned to a Ru(II) → π* (tetrazine) MLCT transition. The assignment of spectroscopic bands was confirmed by theoretical calculations. PMID:27435992

  16. Vertical transport rates and concentrations of OH and Cl radicals in the Tropical Tropopause Layer from observations of CO2 and halocarbons: implications for distributions of long- and short-lived chemical species

    Directory of Open Access Journals (Sweden)

    T. P. Bui

    2010-07-01

    Full Text Available Rates for large-scale vertical transport of air in the Tropical Tropopause Layer (TTL were determined using high-resolution, in situ observations of CO2 concentrations in the tropical upper troposphere and lower stratosphere during the NASA Tropical Composition, Cloud and Climate Coupling (TC4 campaign in August 2007. Upward movement of trace gases in the deep tropics was notably slower in TC4 than during the Costa Rica AURA Validation Experiment (CR-AVE, in January 2006. Transport rates in the TTL were combined with in situ measurements of chlorinated and brominated organic compounds from whole air samples to determine chemical loss rates for reactive chemical species, providing empirical vertical profiles for 24-h mean concentrations of hydroxyl radicals (OH and chlorine atoms in the TTL. The analysis shows that important short-lived species such as CHCl3, CH2Cl2, and CH2Br2 have longer chemical lifetimes than the time for transit of the TTL, implying that these species, which are not included in most models, could readily reach the stratosphere and make significant contributions of chlorine and/or bromine to stratospheric loading.

  17. Vertical transport rates and concentrations of OH and Cl radicals in the Tropical Tropopause Layer from Observations of CO2 and halocarbons: implications for distributions of long- and short-lived chemical species

    Directory of Open Access Journals (Sweden)

    T. P. Bui

    2010-03-01

    Full Text Available Rates for large-scale vertical transport of air in the Tropical Tropopause Layer (TTL were determined using high-resolution, in situ observations of CO2 concentrations in the tropical upper troposphere and lower stratosphere during the NASA Tropical Composition, Cloud and Climate Coupling (TC4 campaign in August 2007. Upward movement of trace gases in the deep tropics was notably slower in TC4 than during the Costa Rica AURA Validation Experiment (CR-AVE, in January 2006. Transport rates in the TTL were combined with in situ measurements of chlorinated and brominated organic compounds from whole air samples to determine chemical loss rates for reactive chemical species, providing empirical vertical profiles for 24-h mean concentrations of hydroxyl radicals (OH and chlorine atoms in the TTL. The analysis shows that important short-lived species such as CHCl3, CH2Cl2, and CH2Br2 have longer chemical lifetimes than the time for transit of the TTL, implying that these species, which are not included in most models, could readily reach the stratosphere and make significant contributions of chlorine and/or bromine to stratospheric loading.

  18. Spectroscopic Properties of SiCl (X2Π, A2Σ+) Radical%SiCl自由基X2Π和A2Σ+态的光谱性质

    Institute of Scientific and Technical Information of China (English)

    刘慧; 邢伟; 施德恒; 孙金锋; 朱遵略

    2015-01-01

    采用内收缩多参考组态相互作用( icMRCI)方法结合Dunning等相关一致基,计算SiCl自由基X2Π和A2Σ+态的势能曲线。讨论参考能和相关能外推对X2Π和A2Σ+态光谱的影响。对势能进行相对论修正及核价修正计算。拟合势能曲线得到X2Π和A2Σ+态的光谱常数。它们与实验结果一致。利用Breit⁃Pauli算符,计算旋轨耦合效应,得到X2Π1/2和X2Π3/2的势能曲线、并计算它们的光谱常数。求解双原子分子核运动的径向Schrödinger方程,获得无转动SiCl自由基2个Λ⁃S态及X2Π态的耦合分裂态的全部振动态。得到J=0时X2Π态的自旋⁃轨道耦合常数、较高振动态的惯性转动常数以及X2Π1/2和X2Π3/2的振动能级等分子常数。%Potential energy curves (PEC) of ground X2Π and A2Σ+ states of SiCl radical are calculated with internally contracted multireference configuration interaction approach in combination with Dunning’ s correlation⁃consistent basis sets. Reference energy and correlation energy are extrapolated to complete basis set limit. Scalar relativistic and core⁃valence correlation corrections are calculated. Spectroscopic parameters of X2Π and A2Σ+ states are obtained. With Breit⁃Pauli operator, PECs of X2Π1/2 and X2Π3/2 states are computed. Spectroscopic parameters of twoΩstates are determined. Vibration manifolds are evaluated for twoΛ⁃S and twoΩstates of non⁃rotation SiCl radical by numerically solving radical Schrödinger equation of nuclear motion. For each vibrational state, vibrational levels and inertial rotation constants, spin⁃orbital coupling constants of X2Π state are determined.

  19. Urethral catheter removal 7 or 14 days after radical retropubic prostatectomy: clinical implications and complications in a randomized study Sete ou quatorze dias para a retirada da sonda vesical de demora após prostatectomia radical retropúbica: implicações clínicas e complicações em um estudo randomizado

    Directory of Open Access Journals (Sweden)

    Carlos Ary Vargas Souto

    2004-01-01

    , setenta e três pacientes submetidos à prostatectomia radical retropúbica foram prospectivamente randomizados em dois grupos: grupo 1 - 37 pacientes em que a sonda vesical foi removida 7 dias após o procedimento e, grupo 2 - 36 nos quais a sonda foi removida 14 dias após a cirurgia. Os dois grupos apresentavam características clínicas similares, os cirurgiões e técnicas foram as mesmas, e nenhuma cistografia foi realizada para avaliar a presença de vazamentos. RESULTADOS: Dois pacientes no grupo 1 apresentaram sangramento e retenção por coágulos após a retirada da sonda no sétimo dia pós-operatório, e foram manejados através da recolocação da sonda vesical por mais 7 dias. Dois pacientes do grupo 2 desenvolveram esclerose do colo vesical e foram tratados através de incisão do colo vesical com sucesso. A taxa de continência foi a mesma, com dois casos de incontinência em cada grupo. Em torno de duas fraldas por dia eram utilizadas pelos pacientes com incontinência. O seguimento médio foi de 17.5 meses (2 - 30 meses. Não houve formação de fístula urinária, urinoma ou abcesso pélvico após a retirada da sonda vesical. Dois pacientes foram excluidos da análise desta série: um faleceu devido a embolia pulmonar no terceiro dia pós-operatório, e o outro desenvolveu fístula urinária suprapúbica antes da retirada do cateter, que foi mantido por 16 dias. CONCLUSÃO: A retirada da sonda vesical 7 dias após a prostatectomia radical retropúbica, sem realização de cistografia, tem uma baixa taxa de complicações de curto prazo, equivalentes às da retirada da sonda aos 14 dias de pós-operatório.

  20. Radical Evil

    Directory of Open Access Journals (Sweden)

    Carlos Manrique

    2007-12-01

    Full Text Available There is an aporia in Kant’s analysis of evil: he defines radical evilas an invisible disposition of the will, but he also demands an inferential connection between visible evil actions and this invisible disposition. This inference,however, undermines the radical invisibility of radical evil according to Kant’s own definition of the latter. Noting how this invisibility of moral worth is a distinctive feature of Kant’s approach to the moral problem, the paper then asks why, in the Groundwork, he nonetheless forecloses a question about evil that seems to be consistent with this approach. It is argued that to account for this aporia and this foreclosure, one has to interrogate the way in which the category of religion orients Kant’s incipient philosophy of history in Die Religion.

  1. Radical prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Sønksen, Jens; Jakobsen, Henrik

    2014-01-01

    OBJECTIVE: The aim of this study was to compare oncological and functional outcomes between robot-assisted laparoscopic radical prostatectomy (RALP) and retropubic radical prostatectomy (RRP) during the initial phase with RALP at a large university hospital. MATERIAL AND METHODS: Patient and tumour...... surgery and at follow-up and they were asked to report their use of pads/diapers. Potency was defined as an IIEF-5 score of at least 17 with or without phosphodiesterase-5 inhibitors. Patients using up to one pad daily for security reasons only were considered continent. Positive surgical margins, blood...... loss and functional outcomes were compared between groups. RESULTS: Overall, 453 patients were treated with RRP and 585 with RALP. On multivariate logistic regression analyses, the type of surgery did not affect surgical margins (p = 0.96) or potency at 12 months (p = 0.7). Patients who had undergone...

  2. Roaming Radicals

    Science.gov (United States)

    Bowman, Joel M.; Shepler, Benjamin C.

    2011-05-01

    Roaming is a recently verified unusual pathway to molecular products from unimolecular dissociation of an energized molecule. Here we present the evidence for this pathway for H2CO and CH3CHO. Theoretical analysis shows that this path visits the plateau region of the potential energy surface near dissociation to radical products. It is not clear whether roaming is a distinct isolated pathway, in addition to the conventional one via the well-known molecular saddle-point transition state. Evidence is presented to suggest that the two pathways may originate from a single, but highly complicated, dividing surface. Other examples of unusual reaction dynamics are also reviewed.

  3. Kinetics of OH- and Cl-initiated oxidation of CH2dbnd CHC(O)O(CH2)2CH3 and CH2dbnd CHCH2C(O)O(CH2)2CH3 and fate of the alkoxy radicals formed

    Science.gov (United States)

    Rivela, Cynthia; Blanco, María B.; Teruel, Mariano A.

    2016-05-01

    Rate coefficients of the reactions of OH and Cl radicals with vinyl and allyl butyrate were determined for the first time at 298 K and 1 atm using the relative method to be (in cm3 molecule-1 s-1): k1(OH + CH2dbnd CHC(O)O(CH2)2CH3) = (2.61 ± 0.31) × 10-11, k2(Cl + CH2dbnd CHC(O)O(CH2)2CH3) = (2.48 ± 0.89) × 10-10, k3(OH + CH2dbnd CHCH2C(O)O(CH2)2CH3) = (2.89 ± 0.31) × 10-11, and k4(Cl + CH2dbnd CHCH2C(O)O(CH2)2CH3) = (2.25 ± 0.96) × 10-10. Reactivity trends and atmospheric lifetimes of esters are presented. Additionally, a product study shown butyric acid and polifunctional products for the reactions of vinyl and allyl butyrate, respectively and general mechanism is proposed.

  4. Atmospheric chemistry of CF3CFHCF2OCF3 and CF3CFHCF2OCF2H: Reaction with Cl atoms and OH radicals, degradation mechanism, and global warming potentials

    DEFF Research Database (Denmark)

    Wallington, TJ; Hurley, MD; Nielsen, OJ;

    2004-01-01

    Fourier transform infrared (FTIR) smog chamber techniques were used to measure k(Cl + CF3CFHCF2OCF3) = (4.09 +/- 0.42) x 10(-17), k(OH + CF3CFHCF2OCF3) = (1.43 +/- 0.28) x 10(-15), k(Cl + CF3CFHCF2OCF2H) = (6.89 +/- 1.29) x 10(-17), and k(OH + CF3CFHCF2OCF2H) = (1.79 +/- 0.34) x 10(-15) cm(3) mol...... respectively. The 100-year time horizon global warming potentials of CF3CFHCF2OCF3 and CF3CFHCF2OCF2H relative to CO2 are 4530 and 4340. Results are discussed with respect to the atmospheric chemistry of hydrofluoroethers....

  5. Quantum chemical study of chlorine-dissociation of oxalyl chloride (ClCO)2→2Cl + 2CO

    Institute of Scientific and Technical Information of China (English)

    戴年珍; 李宗和

    2003-01-01

    The multi-bond dissociation dynamics of oxalyl chloride ((ClCO)2) is investigated by ab initio calculation. Dissociation of C-Cl bond of oxalyl chloride in the ground state is of barrierless. After the absorption of a photon, (ClCO)2 is excited to the first excited state and one of its C-Cl bonds is broken toyield Cl and ClCOCO* free radicals. In addition, ClCOCO* with high energy is prone to release energy (Q), and to turn into ClCOCO in the ground state. The energy (Q) is adequate for ClCOCO to break down into ClCO and CO, and even for ClCO into Cl and CO. The result is consistent with the experimental data that Kong reported.

  6. Ignorance Radicalized

    Directory of Open Access Journals (Sweden)

    Gergo Somodi

    2009-12-01

    Full Text Available The aim of this paper is twofold. I criticize Michael Devitt's linguistic---as opposed to Chomsky's psychological---conception of linguistics on the one hand, and I modify his related view on linguistic intuitions on the other. I argue that Devitt's argument for the linguistic conception is in conflict with one of the main theses of that very conception, according to which linguistics should be about physical sentence tokens of a given language rather than about the psychologically real competence of native speakers. The basis of this conflict is that Devitt's view on language, as I will show, inherits too much from the criticized Chomskian view. This is also the basis of Devitt's strange claim that it is the linguist, and not the ordinary speaker, whose linguistic intuition should have an evidential role in linguistics. I will argue for the opposite by sketching a view on language that is more appropriate to the linguistic conception. That is, in criticizing Devitt, I am not defending the Chomskian approach. My aim is to radicalize Devitt's claims.

  7. Atmospheric chemistry of C2F5CHO: reaction with Cl atoms and OH radicals, IR spectrum of C2F5C(O)O2NO2

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Hurley, MD; Wallington, TJ;

    2003-01-01

    Smog chamber/FTIR techniques were used to measure k(Cl + C2F5CHO) = (1. 96 +/- 0.28) X 10(-12) and k(OH + C2F5CHO) = (5.26 +/- 0.80) x 10(-13) cm(3) molecule(-1) s(-1) in 700 Torr of N-2 or air at 296 +/- 2 K. The C1 initiated oxidation Of C2F5CHO in the presence of NO in air diluent gave COF2, CF3......ONO2, and C2F5C(O)O2NO2 in molar yields of 180 +/- 19 6.1 +/- 0.6 and 1.0 +/- 0.3 respectively. The IR spectrum for C2F5C(O)O2NO2 is reported. Results are discussed with respect to the potential for the atmospheric degradation of fluorinated aldehydes, CnF2n+1CHO, to contribute to the observed...... environmental burden of fluorinated carboxylic acids, CnF2n+1C(O)OH. (C) 2003 Elsevier B.V. All rights reserved....

  8. Radical prostatectomy - discharge

    Science.gov (United States)

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

  9. Radical theory of rings

    CERN Document Server

    Gardner, JW

    2003-01-01

    Radical Theory of Rings distills the most noteworthy present-day theoretical topics, gives a unified account of the classical structure theorems for rings, and deepens understanding of key aspects of ring theory via ring and radical constructions. Assimilating radical theory's evolution in the decades since the last major work on rings and radicals was published, the authors deal with some distinctive features of the radical theory of nonassociative rings, associative rings with involution, and near-rings. Written in clear algebraic terms by globally acknowledged authorities, the presentation

  10. [Lavoisier and radicals].

    Science.gov (United States)

    Lafont, Olivier

    2007-01-01

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

  11. A chain mechanism of radiolysis and photolysis in H[AuCl4]-polyvinyl alcohol system

    International Nuclear Information System (INIS)

    A study of optical properties of H[AuCl4]-containing polyvinyl alcohol (PVA) films allows the basis of a chain mechanism of their photolysis and radiolysis to be put forward. A suggestion is made, that in these chain reactions the Cl radical functions as an active particle, initiating the formation of two interacting chains in reactions of this radical with PVA and [AuCl4]-ions correspondingly. (author)

  12. Laparoscopic Radical Trachelectomy

    OpenAIRE

    Rendón, Gabriel J.; Ramirez, Pedro T.; Frumovitz, Michael; Schmeler, Kathleen M.; Pareja, Rene

    2012-01-01

    Introduction: The standard treatment for patients with early-stage cervical cancer has been radical hysterectomy. However, for women interested in future fertility, radical trachelectomy is now considered a safe and feasible option. The use of minimally invasive surgical techniques to perform this procedure has recently been reported. Case Description: We report the first case of a laparoscopic radical trachelectomy performed in a developing country. The patient is a nulligravid, 30-y-old fem...

  13. Laparoscopic radical cystectomy

    OpenAIRE

    Fergany, Amr

    2012-01-01

    Objective Laparoscopic radical cystectomy (LRC) has emerged as a minimally invasive alternative to open radical cystectomy (ORC). This review focuses on patient selection criteria, technical aspects and postoperative outcomes of LRC. Methods Material for the review was obtained by a PubMed search over the last 10 years, using the keywords ‘laparoscopic radical cystectomy’ and ‘laparoscopic bladder cancer’ in human subjects. Results Twenty-two publications selected for relevance and content we...

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

    Science.gov (United States)

    Atkinson, Roger

    1990-01-01

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

  15. Physiology of free radicals

    Directory of Open Access Journals (Sweden)

    Stevanović Jelka

    2011-01-01

    Full Text Available Free radicals imply that every atom, molecule, ion, group of atoms, or molecules with one or several non-paired electrons in outer orbital. Among these are: nitrogenoxide (NO•, superoxide-anion-radical (O2•-, hydroxyl radical (OH•, peroxyl radical (ROO•, alcoxyl radical (RO• and hydroperoxyl radical (HO2•. However, reactive oxygen species also include components without non-paired electrons in outer orbital (so-called reactive non-radical agents, such as: singlet oxygen (1O2, peroxynitrite (ONOO-, hydrogen-peroxide (H2O2, hypochloric acid (eg. HOCl and ozone (O3. High concentrations of free radicals lead to the development of oxidative stress which is a precondition for numerous pathological effects. However, low and moderate concentrations of these matter, which occur quite normally during cell metabolic activity, play multiple significant roles in many reactions. Some of these are: regulation of signal pathways within the cell and between cells, the role of chemoattractors and leukocyte activators, the role in phagocytosis, participation in maintaining, changes in the position and shape of the cell, assisting the cell during adaption and recovery from damage (e.g.caused by physical effort, the role in normal cell growth, programmed cell death (apoptosis and cell ageing, in the synthesis of essential biological compounds and energy production, as well as the contribution to the regulation of the vascular tone, actually, tissue vascularization.

  16. Orgasm after radical prostatectomy

    NARCIS (Netherlands)

    Koeman, M; VanDriel, MF; Schultz, WCMW; Mensink, HJA

    1996-01-01

    Objective To evaluate the ability to obtain and the quality of orgasm after radical prostatectomy, Patients and methods The orgasms experienced after undergoing radical prostatectomy were evaluated in 20 men (median age 65 years, range 56-76) using a semi-structured interview and a self-administered

  17. Cd 2+ effect on free radicals in Cladosporium cladosporioides-melanin tested by EPR spectroscopy

    Science.gov (United States)

    Matuszczyk, Magdalena; Buszman, Ewa; Pilawa, Barbara; Witoszyńska, Teresa; Wilczok, Tadeusz

    2004-08-01

    Changes in free radicals system of Cladosporium cladosporioides-melanin and model DOPA-melanin caused by diamagnetic Cd 2+ ions were studied by electron paramagnetic resonance (EPR) spectroscopy. EPR line of eumelanin was mainly found in the spectrum of Cl.cl.-melanin. Cd 2+ ions increased o-semiquinone free radicals concentration in both natural and synthetic melanins. Cd 2+ broadened EPR lines of Cl.cl.-melanin in mycelium and the ions fastened spin-lattice relaxation processes. The narrower EPR lines and slower spin-lattice relaxation were obtained for DOPA-melanin-Cd 2+ complexes than for DOPA-melanin. Pheomelanin additionally existing in Cl.cl. samples was responsible for differences between the EPR data for Cl.cl. melanin and DOPA-melanin.

  18. Kinetic isotope effects in the gas phase reactions of OH and Cl with CH3Cl, CD3Cl, and 13CH3Cl

    OpenAIRE

    A. A. Gola; B. D'Anna; Feilberg, K. L.; Sellevåg, S. R.; L. Bache-Andreassen; Nielsen, C. J.

    2005-01-01

    The kinetic isotope effects in the reactions of CH3Cl, 13CH3Cl and CD3Cl with OH radicals and Cl atoms were studied in relative rate experiments at 298±2 K and 1013±10 mbar. The reactions were carried out in a smog chamber using long path FTIR detection and the spectroscopic data analyzed employing a non-linear least squares spectral fitting method using measured high-resolution infrared spectra as well as absorption cross sections from the HITRAN database. The reaction rates of...

  19. Interaction of quadruple bonding rhenium unit with free radicals

    International Nuclear Information System (INIS)

    The interaction of cis-Re2(RCOO)2Cl4, trans-Re2(RCOO)2Cl4, Re2(RCOO)3Cl3 and Re2(RCOO)4Cl2 (where R - alkyl group) with 1,3,5-triphenylverdazyle radical in 1,2-dichlorethane was investigated. It is discovered, that gradual substitution of halogenide ligands by carboxylates in dirhenium(III) clusters led to slowing down of reaction with a radical due to different influence of these ligands on parameters of rhenium - rhenium bond. Presented data showed perspective of Re26+-substances applications as therapeutic agents due to their low toxicity and antiradical properties that occurred by δ-component of quadruple Re-Re bond electron transition. (authors)

  20. Roaming dynamics in radical addition-elimination reactions

    Science.gov (United States)

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

    2014-06-01

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

  1. Radical chemistry of artemisinin

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2010-12-29

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

  2. Radical cystectomy in eldery

    OpenAIRE

    Bančević Vladimir; Aleksić Predrag; Milović Novak; Spasić Aleksandar; Kovačević Božidar; Toševski Perica; Čampara Zoran; Milošević Radovan; Cerović Snežana

    2015-01-01

    Background/Aim. Radical cystectomy is the method of choice for the treatment of muscle invasive bladder cancer. This major surgery is associated with many complications, especially in older patients. The aim of this study was to analyze preoperative comorbidity, and intraoperative and postoperative complicatons in patients older than 75 years. Methods. This clinical, retrospective study included 46 patients over 75 years, who underwent radical cystectomy. I...

  3. Abdominal Radical Trachelectomy

    OpenAIRE

    Căpîlna, Mihai Emil; Ioanid, Nicolae; Scripcariu, Viorel; Gavrilescu, Madalina Mihaela; Szabo, Bela

    2014-01-01

    Objective Abdominal radical trachelectomy (ART) is one of the fertility-sparing procedures in women with early-stage cervical cancer. The published results of ART, in comparison with vaginal radical trachelectomy, so far are limited. Materials and Methods This retrospective study comprises all cases of female patients referred to ART with early-stage cervical cancer from 2 gynecologic oncology centers in Romania. Results A total of 29 women were referred for ART, but subsequently, fertility c...

  4. Reactivities of tetracycline and oxytetracycline with OH radicals

    International Nuclear Information System (INIS)

    Decomposition yields of tetracycline sulphate and oxytetracycline sulphate were determined in argon saturated 0.1N H2SO4 solutions. The decomposition yields of teracyclines decrease in the presence of the Cl- ions. The reaction rate constants of the OH radicals with tetracyclines were also determined. (author)

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

    International Nuclear Information System (INIS)

    Fourier transform infrared emission experiments were used to study photofragmentation processes, single collision reactions, energy transfer events, and laser-initiated radical-radical reactions: CH3 + O, Cl + C2H5, CF3CH2 + D, H + H2O, H + HF, and H + NH2

  6. Free Radical Reactions in Food.

    Science.gov (United States)

    Taub, Irwin A.

    1984-01-01

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

  7. Sexuality Following Radical Prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Serefoglu, Ege C; Albersen, Maarten;

    2016-01-01

    INTRODUCTION: Radical prostatectomies can result in urinary incontinence and sexual dysfunction. Traditionally, these issues have been studied separately, and the sexual problem that has received the most focus has been erectile dysfunction. AIM: To summarize the literature on sexually related side...... effects and their consequences after radical prostatectomy and focus on the occurrence and management of problems beyond erectile dysfunction. METHODS: The literature on sexuality after radical prostatectomy was reviewed through a Medline search. Original research using quantitative and qualitative...... methodologies was considered. Priority was given to studies exploring aspects of sexuality other than erectile function. MAIN OUTCOME MEASURES: The prevalence, predictive factors, and management of post-prostatectomy sexual problems beyond erectile dysfunction. RESULTS: Most patients will develop urinary...

  8. Gangs, Terrorism, and Radicalization

    Directory of Open Access Journals (Sweden)

    Scott Decker

    2011-01-01

    Full Text Available What can street gangs tell us about radicalization and extremist groups? At first glance, these two groups seem to push the boundaries of comparison. In this article, we examine the important similarities and differences across criminal, deviant, and extremist groups. Drawing from research on street gangs, this article explores issues such as levels of explanation,organizational structure, group process, and the increasingly important role of technology and the Internet in the context of radicalization. There are points of convergence across these groups, but it is important to understand the differences between these groups. This review finds little evidence to support the contention that American street gangs are becoming increasingly radicalized. This conclusion is based largely on organizational differences between gangs and terror groups.

  9. Mixed-valence, layered, cation radical salts of the ethane-bridged dimeric tetrathiafulvalene [(EDT-TTF-CH2-)2#centre dot#+] [X-][THF]0.5, X-=FeCl4-, GaCl4-

    DEFF Research Database (Denmark)

    Mézière, C.; Fourmigué, M.; Canadell, E.;

    2000-01-01

    other give rise to both 1D- and 2D-type HOMO ... HOMO interactions whose origin is correlated with the details of the peculiar overlap patterns obtained with those dimeric tetrathiafulvalenes. The weak paramagnetism observed in the GaCl4- salt due to the organic spins of the conducting slabs is hidden...

  10. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali

    2009-12-17

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication. © 2010 Macmillan Publishers Limited. All rights reserved.

  11. Violent Radicalization in Europe

    DEFF Research Database (Denmark)

    Dalgaard-Nielsen, Anja

    2010-01-01

    When, why, and how do people living in a democracy become radicalized to the point of being willing to use or directly support the use of terrorist violence against fellow citizens? This question has been at the center of academic and public debate over the past years as terrorist attacks...

  12. Homegrown religious radicalization

    DEFF Research Database (Denmark)

    Khawaja, Iram

    and their families. Existing literature and ways of thinking about the social psychological process of radicalization will be reviewed, such as social identity theory and transformative learning theory, and a theoretical framework based on a focus on belonging, recognition and the sense of community will be proposed...

  13. Radical School Reform.

    Science.gov (United States)

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

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

  14. Radical Financial Innovation

    OpenAIRE

    Robert J. Shiller

    2004-01-01

    Radical financial innovation is the development of new institutions and methods that permit risk management to be extended far beyond its former realm, covering important new classes of risks. This paper compares past such innovation with potential future innovation, looking at the process that produced past success and the possibilities for future financial innovation.

  15. On Radical Feminism

    Institute of Scientific and Technical Information of China (English)

    翟良锴

    2015-01-01

    <正>All men are created equal.For centuries,human have been struggling for their rights.Women,as a special social force,are fighting vigorously for their equal rights with men.According to an introduction to feminism,there are three main types of feminism:socialist,reformist and radical(Feminism 101).In order

  16. Controlled Radical Polymerization of Methyl Methacrylate Catalyzed by Hybrid Supported Iron Catalyst

    Institute of Scientific and Technical Information of China (English)

    LI Zhong-hui; ZHANG Yong-ming; XUE Min-zhao; ZHOU Lei; LIU Yan-gang

    2005-01-01

    A supported iron catalyst, which was prepared by anchoring FeCl2/FeCl3 on the cross-linking macroporous polyacrylate ion exchange resin, was evaluated via the controlled radical polymerization. When a small amount of CuCl2/Me6TREN was added, the controllability of the polymerization over the iron-mediated catalyst was significantly improved(Mw/Mn=1.23-1.73), affording a polymer with a low residual metal via a simple catalyst separation procedure. After suitable regeneration, the supported iron catalyst could also be recycled. UV-Vis analysis showed that the additional copper catalyst could facilitate the radical deactivation process.

  17. Free radical transfer in polymers

    International Nuclear Information System (INIS)

    For the present study of free-radical transfer in polymers pulse radiolysis and product studies have been carried out in aqueous solutions using thus far only the water-soluble polymers polyacrylic acid, polymethacrylic acid and polyvinyl alcohol. When OH radicals, generated in the radiolysis of N2O-saturated aqueous solutions, react with polymers the lifetime of the polymer radical thus created very much depends on the number of radicals per polymer chain. When there are a large number of radicals per chain their bimolecular decay may be faster than the corresponding (diffusion controlled) decay of monomeric radicals, but when the macromolecule contains only few or even just one radical their lifetime is considerably prolonged. Highly charged polymers such as polyacrylic acid at high pH attain a rod-like conformation which again favors a long lifetime of the radicals. Under such conditions, radical transfer reactions can occur. For example, in polyacrylic acid OH radicals generate two kinds of radicals side by side. The radical in β-position to the carboxylate group converts into the thermodynamically more stable α-radicals by an H-transfer reaction as can be followed by spectrophotometry. Besides radical transfer reactions β-fragmentation reactions occur causing chain scission. Such reactions can be followed in a pulse radiolysis experiment by conductometry, because counter ions are released upon chain scission. Such a process is especially effective in the case of polymethacrylic acid, where it results in a chain depolymerization. An intramolecular H-abstraction is also observed in the γ-radiolysis of polyacrylic acid with the corresponding peroxyl radicals. This causes a chain reaction to occur. The resulting hydroperoxides are unstable and decarboxylate given rise to acetylacetone-like products. In polyvinyl alcohol the peroxyl radicals in α-position to the alcohol function undergo HO2-elimination. This prevents a scission of the polymer chain in the

  18. 75 FR 6862 - Airworthiness Directives; Bombardier, Inc. Model CL-600-1A11 (CL-600), CL-600-2A12 (CL-601), CL...

    Science.gov (United States)

    2010-02-12

    ... Policies and Procedures (44 FR 11034, February 26, 1979); and 3. Will not have a significant economic.... Model CL-600-1A11 (CL- 600), CL-600-2A12 (CL-601), CL-600-2B16 (CL-601-3A, CL-601-3R, and CL- 604 Variants (Including CL-605 Marketing Variant)) Airplanes AGENCY: Federal Aviation Administration (FAA),...

  19. Effect of Trapping Agent and Polystyrene Chain End Functionality on Radical Trap-Assisted Atom Transfer Radical Coupling

    Directory of Open Access Journals (Sweden)

    Elizabeth M. Carnicom

    2014-10-01

    Full Text Available Coupling reactions were performed to gauge the effect of the inclusion of a radical trap on the success of coupling reactions of monohalogenated polystyrene (PSX chains in atom transfer radical coupling (ATRC type reactions. The effect of both the specific radical trap chosen and the structure of the polymer chain end were evaluated by the extent of dimerization observed in a series of analogous coupling reactions. The commonly used radical trap 2-methyl-2-nitrosopropane (MNP showed the highest amounts of dimerization for PSX (X = Br, Cl compared to coupling reactions performed in its absence or with a different radical trap. A dinitroxide coupling agent was also studied with the extent of coupling nearly matching the effectiveness of MNP in RTA (Radical trap-assisted-ATRC reactions, while N-nitroso and electron rich nitroso coupling agents were the least effective. (2,2,6,6-Tetramethyl-piperin-l-yloxyl-capped PS (PS-TEMPO, prepared by NMP, was subjected to a coupling sequence conceptually similar to RTA-ATRC, but dimerization was not observed regardless of the choice of radical trap. Kinetic experiments were performed to observe rate changes on the coupling reaction of PSBr as a result of the inclusion of MNP, with substantial rate enhancements found in the RTA-ATRC coupling sequence compared to traditional ATRC.

  20. Oxalyl chloride, ClC(O)C(O)Cl: UV/vis spectrum and Cl atom photolysis quantum yields at 193, 248, and 351 nm

    Science.gov (United States)

    Ghosh, Buddhadeb; Papanastasiou, Dimitrios K.; Burkholder, James B.

    2012-10-01

    Oxalyl chloride, (ClCO)2, has been used as a Cl atom photolytic precursor in numerous laboratory kinetic and photochemical studies. In this study, the UV/vis absorption spectrum of (ClCO)2 and the Cl atom quantum yields in its photolysis at 193, 248, and 351 nm are reported. The UV/vis spectrum was measured between 200 and 450 nm at 296 K using diode array spectroscopy in conjunction with an absolute cross section obtained at 213.9 nm. Our results are in agreement with the spectrum reported by Baklanov and Krasnoperov [J. Phys. Chem. A 105, 97-103 (2001), 10.1021/jp0019456], which was obtained at 11 discrete wavelengths between 193.3 and 390 nm. Cl atom quantum yields, Φ(λ), were measured using pulsed laser photolysis coupled with time resolved atomic resonance fluorescence detection of Cl. The UV photolysis of (ClCO)2 has been shown in previous studies to occur via an impulsive three-body dissociation mechanism, (COCl)2 + hv → ClCO* + Cl + CO (2), where the excited ClCO radical, ClCO*, either dissociates or stabilizes ClCO* → Cl + CO (3a), → ClCO (3b). ClCO is thermally unstable at the temperatures (253-298 K) and total pressures (13-128 Torr) used in our experiments ClCO + M → Cl + CO + M (4) leading to the formation of a secondary Cl atom that was resolvable in the Cl atom temporal profiles obtained in the 248 and 351 nm photolysis of (ClCO)2. Φ(193 nm) was found to be 2.07 ± 0.37 independent of bath gas pressure (25.8-105.7 Torr, N2), i.e., the branching ratio for channel 2a or the direct formation of 2Cl + 2CO in the photolysis of (ClCO)2 is >0.95. At 248 nm, the branching ratio for channel 2a was determined to be 0.79 ± 0.15, while the total Cl atom yield, i.e., following the completion of reaction (4), was found to be 1.98 ± 0.26 independent of bath gas pressure (15-70 Torr, N2). Φ(351 nm) was found to be pressure dependent between 7.8 and 122.4 Torr (He, N2). The low-pressure limit of the total Cl atom quantum yield, Φ0(351 nm), was 2.05

  1. Radical substitution with azide

    DEFF Research Database (Denmark)

    Pedersen, Christian Marcus; Marinescu, Lavinia Georgeta; Bols, Mikael

    2005-01-01

    and the substrate. A primary deuterium kinetic isotope effect was found for the azidonation of benzyl ethers both with TMSN3-PhI(OAc)2 and with IN3. Also a Hammett free energy relationship study of this reaction showed good correlation with sigma+ constants giving with rho-values of -0.47 for TMSN3-PhI(OAc)2 and -0.......39 for IN3. On this basis a radical mechanism of the reaction was proposed....

  2. Activation of C-Cl by ground-state aluminum atoms: an EPR and DFT investigation.

    Science.gov (United States)

    Joly, Helen A; Newton, Trevor; Myre, Maxine

    2012-01-01

    The reaction of ground-state Al atoms with dichloromethane (CH(2)Cl(2)) in an adamantane matrix at 77 K yielded two mononuclear Al species. The magnetic parameters, extracted from the axial EPR spectrum of Species A/A' (g(1) = 2.0037, g(2) = g(3) = 2.0030, a(Al,1) = 1307 MHz, a(Al,2) = a(Al,3) = 1273 MHz, a(35Cl) = 34 MHz and a(37Cl) = 28 MHz) were assigned to the Al-atom insertion product, ClCH(2)AlCl. Density functional theory (DFT) calculations of the values of the Al and Cl hyperfine interaction (hfi) of the Cl(1)-Cl(2)gauche conformer were in close agreement with the experimental values of ClCH(2)AlCl. The second species, B/B', had identical magnetic parameters to those of ClCH(2)AlCl with the exception that the Al hfi was 15% smaller. Coordination of a ligand, possessing a lone pair of electrons, to the Al atom of the insertion product, [ClCH(2)AlCl]:X, could cause the a(Al) to decrease by 15%. Alternatively, it is possible that the Cl(1)-Cl(2) anti conformer of ClCH(2)AlCl is also isolated in the matrix. Support for the spectral assignments is given by calculation of the nuclear hfi of [ClCH(2)AlCl]:H(2)O and the Cl(1)-Cl(2) anti conformer of ClCH(2)AlCl using a DFT method. The potential energy hypersurface for an Al atom approaching CH(2)Cl(2), calculated at the B3LYP level, suggests that Al atom abstraction of Cl forming AlCl and CH(2)Cl is favoured in the gas phase. When produced in a matrix, the close proximity of AlCl and CH(2)Cl could account for the formation of ClCH(2)AlCl. EPR evidence was also found for the formation of the CHCl(2) radical. PMID:22086441

  3. THERMOCHEMISTRY OF HYDROCARBON RADICALS

    Energy Technology Data Exchange (ETDEWEB)

    Kent M. Ervin, Principal Investigator

    2004-08-17

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

  4. [Radical prostatectomy - pro robotic].

    Science.gov (United States)

    Gillitzer, R

    2012-05-01

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

  5. Effect of Cl substituent in the aromatic tetracycline ring on its reactivity with solvated electrons

    International Nuclear Information System (INIS)

    Decomposition yields of tetracycline hydrochloride (TC.HCl) and chlorotetracycline hydrochloride (ClTC.HCl) in methanol solution saturated with Ar or N2O were determined. Rate constants of the reaction esub(s)- with some antibiotics were obtained. It was demonstrated by 1H NMR that the radical formed by degradation of 7-C-Cl group is recombined with the H atoms leading to ClTC.HCl being converted into tetracycline hydrochloride (TC.HCl). (author)

  6. Nitroreductase catalyzed biotransformation of CL-20.

    Science.gov (United States)

    Bhushan, Bharat; Halasz, Annamaria; Hawari, Jalal

    2004-09-10

    Previously, we reported that a salicylate 1-monooxygenase from Pseudomonas sp. ATCC 29352 biotransformed CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-isowurtzitane) (C(6)H(6)N(12)O(12)) and produced a key metabolite with mol. wt. 346 Da corresponding to an empirical formula of C(6)H(6)N(10)O(8) which spontaneously decomposed in aqueous medium to produce N(2)O, NH(4)(+), and HCOOH [Appl. Environ. Microbiol. (2004)]. In the present study, we found that nitroreductase from Escherichia coli catalyzed a one-electron transfer to CL-20 to form a radical anion (CL-20(-)) which upon initial N-denitration also produced metabolite C(6)H(6)N(10)O(8). The latter was tentatively identified as 1,4,5,8-tetranitro-1,3a,4,4a,5,7a,8,8a-octahydro-diimidazo[4,5-b:4',5'-e]pyrazine [IUPAC] which decomposed spontaneously in water to produce glyoxal (OHCCHO) and formic acid (HCOOH). The rates of CL-20 biotransformation under anaerobic and aerobic conditions were 3.4+/-0.2 and 0.25+/-0.01 nmol min(-1)mg of protein(-1), respectively. The product stoichiometry showed that each reacted CL-20 molecule produced about 1.8 nitrite ions, 3.3 molecules of nitrous oxide, 1.6 molecules of formic acid, 1.0 molecule of glyoxal, and 1.3 ammonium ions. Carbon and nitrogen products gave mass-balances of 60% and 81%, respectively. A comparative study between native-, deflavo-, and reconstituted-nitroreductase showed that FMN-site was possibly involved in the biotransformation of CL-20. PMID:15313201

  7. 75 FR 37994 - Airworthiness Directives; Bombardier, Inc. Model CL-600-1A11 (CL-600), CL-600-2A12 (CL-601), CL...

    Science.gov (United States)

    2010-07-01

    ... FR 6862). That NPRM proposed to correct an unsafe condition for the specified products. The MCAI... ``significant rule'' under the DOT Regulatory Policies and Procedures (44 FR 11034, February 26, 1979); and 3..., Inc. Model CL-600-1A11 (CL- 600), CL-600-2A12 (CL-601), CL-600-2B16 (CL-601-3A, CL-601-3R, and CL-...

  8. Radical production from photosensitization of imidazoles

    Science.gov (United States)

    Corral Arroyo, P.; Gonzalez, L.; Steimer, S.; Aellig, R.; Volkamer, R. M.; George, C.; Bartels-Rausch, T.; Ammann, M.

    2015-12-01

    Reactions promoted by light are key in atmospheric chemistry. Some of them occur in the condensed phase of aerosols containing light absorbing organic compounds (George et al., 2015). This work explores the radical reactions initiated by near-UV light in mixtures of citric acid (CA) and imidazole-2-carboxaldehyde (IC) using NO as a probe molecule for HO2, by means of coated wall flow tube experiments. Citric acid may act as H atom or electron donor in condensed phase radical cycles. IC may act as a photosensitizer. The loss of NO was measured by a chemiluminescence detector. The dependence of the NO loss on the NO concentration, the IC/CA ratio in the film, relative humidity, light intensity, oxygen molar fraction were investigated as well as the HONO and NO2 yields. We also added halide salts to investigate the effect of a competing electron donor in the system and the output of halogens to the gas phase. We found a correlation between the loss of NO above the film and the molar ratio of IC/CA and the light intensity. The variation of the NO loss with oxygen corroborates a mechanism, in which the triplet excited state of IC is reduced by citric acid, to a reduced ketyl radical that transfers an electron to molecular oxygen, which in turn leads to production of HO2 radicals. Therefore, the NO loss in the gas phase is related to the production of HO2 radicals. Relative humidity had a strong impact on the HO2 output, which shows a maximum production rate at around 30%. The addition of halide ions (X- = Cl-, Br-, I-) increases the HO2 output at low concentration and decrease it at higher concentration when X2- radical ions likely scavenge HO2. We could preliminarily quantify for the first time the contribution of these processes to the oxidative capacity in the atmosphere and conclude that their role is significant for aerosol aging and potentially a significant source of halogen compounds to the gas phase.

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

    Science.gov (United States)

    Studer, Armido; Curran, Dennis P

    2016-01-01

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

  10. Bursectomy at radical gastrectomy

    Institute of Scientific and Technical Information of China (English)

    Cuneyt; Kayaalp

    2015-01-01

    Radical gastrectomy with extended lymph node dissec tion and prophylactic resection of the omentum, peri toneum over the posterior lesser sac, pancreas and/o spleen was advocated at the beginning of the 1960 s in Japan. In time, prophylactic routine resections of the pancreas and/or spleen were abandoned because of the high incidence of postoperative complications. However omentectomy and bursectomy continued to be standard parts of traditional radical gastrectomy. The bursaomentalis was thought to be a natural barrier against invasion of cancer cells into the posterior part of the stomach. The theoretical rationale for bursectomy was to reduce the risk of peritoneal recurrences by eliminating the peritoneum over the lesser sac, which might include free cancer cells or micrometastases. Over time, the indication for bursectomy was gradually reduced to only patients with posterior gastric wall tumors penetrating the serosa. Despite its theoretical advantages, its benefit for recurrence or survival has not been proven yet. The possible reasons for this inconsistency are discussed in this review. In conclusion, the value of bursectomy in the treatment of gastric cancer is still under debate and large-scale randomized studies are necessary. Until clear evidence of patient benefit is obtained, its routine use cannot be recommended.

  11. Asymmetrical ClO3 - Its possible formation from ClO and O2 and its possible reactions

    Science.gov (United States)

    Prasad, S. S.; Adams, W. M.

    1980-01-01

    An analysis of recent accurate experimental studies of Cl2-photosensitized O3 decomposition, in which O3 disappearance and OClO formation were directly monitored, suggests the possibility that the suppression of the quantum yield in the presence of O2 may be due to the formation of asymmetrical chlorine trioxide (ClO.O2). Other intermediaries, such as Cl2O2, which may also form in the system are not thought to explain the observations. In addition to its capacity to oxidize, which it shares with other peroxo compounds, asymmetrical ClO3 appears to undergo an interesting class of reactions in which the loosely bound O2 adduct is relatively easily displaced by reactive atoms and radicals such as chlorine.

  12. Theoretical Study on Reaction Mechanism of H2S with Hydroxide Radical and Cl in the Absence and Presence of Water Molecule%理论研究H2S与羟基和Cl在没有水分子和有水分子条件下的反应机理

    Institute of Scientific and Technical Information of China (English)

    毛文雪; 隆正文

    2011-01-01

    The quantum chemical calculations were applied to study the two reactions of Cl + H2S and OH + H2S without water and with a single water molecule. The computed results predict that the activated barriers for two reactions of Cl + H2S and OH + H2S are reduced by 4.3 kal/mol and 3.6 kal/mol respectively. In addition, the calculated results show that the rate constant are increased by 2.5 × 10-9cm3 molecule-1 s-1 and increased 5.18× 10-12cm3 molecule-1 s-1, respectively. The calculation results agree well with theoretical value of literature.Thus, the calculations show that the single water would play a catalytic role in the reaction of Cl + H2S , but pro duce negative influence to the reaction of OH + H2S.%本文用量子化学计算方法研究没有水分子和有水分子条件下对Cl+H2S和OH+H2S这两个反应产生的影响.在wb97xd/aug-cc-pvtz水平下的计算结果表明,单个水分子加到反应中会使Cl+H2S和OH+H2S这两个反应的能垒分别减小3.0kal/mol和2.2kal/mol.同时两个反应的速率常数在水分子影响下也分别增加了2.5×10-9cm3 molecule-1s-1和减小了5.18×10-12cm3 molecule-1s-1,计算结果和文献理论值符合得很好.说明水分子对Cl+H2S反应体系有催化的效果,对OH+H2S反应体系没有催化的效果,反而具有减缓反应.

  13. A radical publishing collective: the Journal of Radical Librarianship

    Directory of Open Access Journals (Sweden)

    Simon Barron

    2015-03-01

    Full Text Available In Brief: the Journal of Radical Librarianship is a new open-access journal publishing scholarly work in the field of radical librarianship. The focus on critical approaches to librarianship and anti-marketisation of information is reflected not only in our subject matter but in our publishing model, our licensing model, and our organisational practices. We hope to […

  14. Radical cystectomy in eldery

    Directory of Open Access Journals (Sweden)

    Bančević Vladimir

    2015-01-01

    Full Text Available Background/Aim. Radical cystectomy is the method of choice for the treatment of muscle invasive bladder cancer. This major surgery is associated with many complications, especially in older patients. The aim of this study was to analyze preoperative comorbidity, and intraoperative and postoperative complicatons in patients older than 75 years. Methods. This clinical, retrospective study included 46 patients over 75 years, who underwent radical cystectomy. Indications for surgery, and complications during and after the surgery were followed up. Results. Preoperatively, anemia caused by hematuria was registered in 76% of the patients. In 52% of the patients urine derivation was performed by ileal conduit, in 35% by ureterocutaneostomy and in 13% orthotopic ileal neobladder was created. The average duration of surgery was 190 (120-300 min. A total of 76% of the patients were treated by blood supstitution intraoperatively, average 630 (310-1230 mL. Concerning pathological stage of transitional cell carcinoma of urinary bladder, 26% of the patients had T2, 4% T3a, 52% T3b, and 14% T4a stage. In one case, planocellular carcinoma was diagnosed by patohistological examination, and in 2 cases prostate carcinoma was incidentally found. The average duration of hospitalization was 16 (8-35 days. Conclusion. The main reason for cystectomy in patients over 70 and 80 years was gross hematuria caused by bladder cancer, with consecutive anemia which could not be solved using endoscopic treatment or blood supstitution. As expected, a prolonged stay in hospital after cystectomy, and a higher rate of complications were recorded in this population.

  15. Muoniated acyl and thioacyl radicals

    Energy Technology Data Exchange (ETDEWEB)

    McKenzie, Iain [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Brodovitch, Jean-Claude [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Ghandi, Khashayar [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Percival, Paul W. [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada)]. E-mail: percival@sfu.ca

    2006-03-31

    The product of the reaction of muonium with tert-butylisocyanate was previously assigned as the muoniated tert-butylaminyl radical (I. McKenzie, J.-C. Brodovitch, K. Ghandi, S. Kecman, P. W. Percival, Physica B 326 (2003) 76). This assignment is incorrect since the muon and {sup 14}N hyperfine-coupling constants (hfcc) of this radical would have the opposite sign, which is in conflict with the experimental results. The radical is now reassigned as the muoniated N-tert-butylcarbamoyl radical, based on the similarities between the experimental muon and {sup 14}N hfcc and hfcc calculated at the UB3LYP/6-311G(d,p)//UB3LYP/EPR-III level. The large zero-point energy in the N-Mu bond results in the dissociation barrier of the muoniated N-tert-butylcarbamoyl radical being above the combined energy of the reactants, in contrast to the N-tert-butylcarbamoyl radical where the dissociation barrier lies below the combined energy of the reactants. The reaction of muonium with tert-butylisothiocyanate produced both conformers of the muoniated N-tert-butylthiocarbamoyl radical and their assignment was based on the similarities between the experimental and calculated muon hfcc. These are the first acyl and thioacyl radicals to be directly detected by muon spin spectroscopy.

  16. Site reactivity in the free radicals induced damage to leucine residues: a theoretical study.

    Science.gov (United States)

    Medina, M E; Galano, A; Alvarez-Idaboy, J R

    2015-02-21

    Several recent computational studies have tried to explain the observed selectivity in radical damage to proteins. In this work we use Density Functional Theory and Transition State Theory including tunnelling corrections, reaction path degeneracy, the effect of diffusion, and the role of free radicals to get further insights into this important topic. The reaction between a leucine derivative and free radicals of biological significance, in aqueous and lipid media, has been investigated. Both thermochemical and kinetic analyses, in both hydrophilic and hydrophobic environments, have been carried out. DPPH, ˙OOH, ˙OOCH3, ˙OOCH2Cl, ˙OOCHCl2 and ˙OOCHCH2 radicals do not react with the target molecule. The reactions are proposed to be kinetically controlled. The leucine gamma site was the most reactive for the reactions with ˙N3, ˙OOCCl3, ˙OCH3, ˙OCH2Cl, and ˙OCHCl2 radicals, with rate constants equal to 1.97 × 10(5), 3.24 × 10(4), 6.68 × 10(5), 5.98 × 10(6) and 8.87 × 10(8) M(-1) s(-1), respectively, in aqueous solution. The ˙Cl, ˙OH and ˙OCCl3 radicals react with leucine at the beta, gamma, and delta positions at rates close to the diffusion limit with the alpha position which is the slowest path and the most thermodynamically favored. The presented results confirm that the Bell-Evans-Polanyi principle does not apply for the reactions between amino acid residues and free radicals. Regarding the influence of the environment on the reactivity of the studied series of free radicals towards leucine residues, it is concluded that hydrophilic media slightly lower the reactivity of the studied radicals, compared to hydrophobic ones, albeit the trends in reactivity are very similar.

  17. Site reactivity in the free radicals induced damage to leucine residues: a theoretical study.

    Science.gov (United States)

    Medina, M E; Galano, A; Alvarez-Idaboy, J R

    2015-02-21

    Several recent computational studies have tried to explain the observed selectivity in radical damage to proteins. In this work we use Density Functional Theory and Transition State Theory including tunnelling corrections, reaction path degeneracy, the effect of diffusion, and the role of free radicals to get further insights into this important topic. The reaction between a leucine derivative and free radicals of biological significance, in aqueous and lipid media, has been investigated. Both thermochemical and kinetic analyses, in both hydrophilic and hydrophobic environments, have been carried out. DPPH, ˙OOH, ˙OOCH3, ˙OOCH2Cl, ˙OOCHCl2 and ˙OOCHCH2 radicals do not react with the target molecule. The reactions are proposed to be kinetically controlled. The leucine gamma site was the most reactive for the reactions with ˙N3, ˙OOCCl3, ˙OCH3, ˙OCH2Cl, and ˙OCHCl2 radicals, with rate constants equal to 1.97 × 10(5), 3.24 × 10(4), 6.68 × 10(5), 5.98 × 10(6) and 8.87 × 10(8) M(-1) s(-1), respectively, in aqueous solution. The ˙Cl, ˙OH and ˙OCCl3 radicals react with leucine at the beta, gamma, and delta positions at rates close to the diffusion limit with the alpha position which is the slowest path and the most thermodynamically favored. The presented results confirm that the Bell-Evans-Polanyi principle does not apply for the reactions between amino acid residues and free radicals. Regarding the influence of the environment on the reactivity of the studied series of free radicals towards leucine residues, it is concluded that hydrophilic media slightly lower the reactivity of the studied radicals, compared to hydrophobic ones, albeit the trends in reactivity are very similar. PMID:25592549

  18. Halogen radicals contribute to photooxidation in coastal and estuarine waters

    Science.gov (United States)

    Parker, Kimberly M.; Mitch, William A.

    2016-05-01

    Although halogen radicals are recognized to form as products of hydroxyl radical (•OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM (3DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater •OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark •OH generation by gamma radiolysis demonstrates that halogen radical production via •OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl- and Br- by 3DOM*, an •OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters.

  19. Halogen radicals contribute to photooxidation in coastal and estuarine waters.

    Science.gov (United States)

    Parker, Kimberly M; Mitch, William A

    2016-05-24

    Although halogen radicals are recognized to form as products of hydroxyl radical ((•)OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM ((3)DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater (•)OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark (•)OH generation by gamma radiolysis demonstrates that halogen radical production via (•)OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl(-) and Br(-) by (3)DOM*, an (•)OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters. PMID:27162335

  20. Synthesis of polystyrene with high melting temperature through BDE/CuCl catalyzed polymerization

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    No matter what the polymerization manner was, polystyrene withunique high Tm (Tm = 170-285℃) was obtained through polymerization of styrene if the amount of BDE/CuCl catalyst was highly increased (mol ratio: St:CuCl = 25:1-2.5:1). Partial crystallinity of the PSt was observed by characterizations of X-ray diffraction and DSC. Spectra of 1H-NMR and 13C-NMR showed that syndiotactic structure contained in the obtained PSt was 5% more than that in aPSt (atactic polystyrene). According to the proposed "coordinated radical cage" mechanism, the coordinated state between radical and catalyst center metal Cu should be more closely packed with increasing the BDE/CuCl catalyst amount, which was induced to partial stereospecific polymerization in the coordinated radical polymerization of St.

  1. Reactions between the (SO·4-) radical and some common anions in atmospheric aqueous droplets

    Institute of Scientific and Technical Information of China (English)

    OUYANG Bin; FANG Hao-jie; ZHU Cheng-zhu; DONG Wen-bo; HOU Hui-qi

    2005-01-01

    The rate constants of reactions between the SO4·- radical and some common anions in atmospheric aqueous droplets e.g. Cl-,NO3-, HSO3- and HCO3- were determined using the laser flash photolysis technique. Absorption spectra of SO4·- and the product radicals were also reported. The chloride ion was evaluated among all the anions to be the most efficient scavenger of SO4·- . The results may supply useful information for a better understanding of the vigorous radical-initiated reactions in atmospheric aqueous droplets such as clouds, rains or fogs.

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

    Energy Technology Data Exchange (ETDEWEB)

    Leone, S.R. [Univ. of Colorado, Boulder (United States)

    1993-12-01

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

  3. Cl atom initiated oxidation of 1-alkenes under atmospheric conditions

    Science.gov (United States)

    Walavalkar, M.; Sharma, A.; Alwe, H. D.; Pushpa, K. K.; Dhanya, S.; Naik, P. D.; Bajaj, P. N.

    2013-03-01

    In view of the importance of the oxidation pathways of alkenes in the troposphere, and the significance of Cl atom as an oxidant in marine boundary layer (MBL) and polluted industrial atmosphere, the reactions of four 1-alkenes (C6-C9) with Cl atoms are investigated. The rate coefficients at 298 K are measured to be (4.0 ± 0.5), (4.4 ± 0.7), (5.5 ± 0.9) and (5.9 ± 1.7) × 10-10 cm3 molecule-1 s-1 for 1-hexene, 1-heptene, 1-octene and 1-nonene, respectively. The quoted errors include the experimental 2σ, along with the error in the reference rate coefficients. From the systematic increase in the rate coefficients with the number of carbon atoms, an approximate value for the average rate coefficient for hydrogen abstraction per CH2 group in alkenes is estimated to be (4.9 ± 0.3) × 10-11 cm3 molecule-1 s-1. Based on these rate coefficients, the contribution of Cl atom reactions towards the degradation of these molecules is found to be comparable to that of OH radical reactions, under MBL conditions. The products identified in gas phase indicate that Cl atom addition occurs mainly at the terminal carbon, leading to the formation of 1-chloro-2-ketones and 1-chloro-2-ols. The major gas phase products from the alkenyl radicals (formed by H atom abstraction) are different positional isomers of long chain enols and enones. A preference for dissociation leading to an allyl radical, resulting in aldehydes, lower by three carbon atoms, is indicated. The observed relative yields suggest that in general, the increased contribution of the reactions of Cl atoms towards degradation of 1-alkenes in NOx free air does not result in an increase in the generation of small aldehydes (carbon number < 4), including chloroethanal, as compared to that in the reaction of 1-butene.

  4. Radical-scavenging Activity of Natural Methoxyphenols vs. Synthetic Ones using the Induction Period Method

    Directory of Open Access Journals (Sweden)

    Ichiro Yokoe

    2007-02-01

    Full Text Available The radical-scavenging activities of the synthetic antioxidants 2-allyl-4-X-phenol (X=NO2, Cl, Br, OCH3, COCH3, CH3, t-(CH33, C6H5 and 2,4-dimethoxyphenol, and the natural antioxidants eugenol and isoeugenol, were investigated using differential scanning calorimetry (DSC by measuring their anti-1,1-diphenyl-2-picrylhydrazyl (DPPH radical activity and the induction period for polymerization of methyl methacrylate (MMA initiated by thermal decomposition of 2,2'-azobisisobutyronitrile (AIBN and benzoyl peroxide (BPO. 2-Allyl-4-methoxyphenol and 2,4-dimethoxy-phenol scavenged not only oxygen-centered radicals (PhCOO. derived from BPO, but also carbon-centered radicals (R. derived from the AIBN and DPPH radical much more efficiently, in comparison with eugenol and isoeugenol. 2-Allyl-4-methoxyphenol may be useful for its lower prooxidative activity.

  5. Kinetics and mechanism of protection of thymine from sulphate radical anion under anoxic conditions

    Indian Academy of Sciences (India)

    M Sudha Swaraga; M Adinarayana

    2003-04-01

    The rates of photooxidation of thymine in presence of peroxydisulphate (PDS) have been determined by measuring the absorbance of thymine at 264 nm spectrophotometrically. The rates and the quantum yields () of oxidation of thymine by sulphate radical anion have been determined in the presence of different concentrations of caffeic acid. Increase in [caffeic acid] is found to decrease the rate of oxidation of thymine suggesting that caffeic acid acts as an efficient scavenger of SO$^{\\bullet -}_{4}$ and protects thymine from it. Sulphate radical anion competes for thymine as well as for caffeic acid. The rate constant of sulphate radical anion with caffeic acid has been calculated to be 1.24 × 1010 dm3 mol-1 s-1. The quantum yields of photooxidation of thymine have been calculated from the rates of oxidation of thymine and the light intensity absorbed by PDS at 254 nm, the wavelength at which PDS is activated to sulphate radical anion. From the results of experimentally determined quantum yields (exptl) and the quantum yields calculated (cl) assuming caffeic acid acting only as a scavenger of SO$^{\\bullet -}_{4}$ radicals show that exptl values are lower than cl values. The ' values, which are experimentally found quantum yield values at each caffeic acid concentration and corrected for SO$^{\\bullet-}_{4}$ scavenging by caffeic acid, are also found to be greater than exptl values. These observations suggest that the thymine radicals are repaired by caffeic acid in addition to scavenging of sulphate radical anions.

  6. 76 FR 46597 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2A12 (CL-601) and CL-600-2B16 (CL-601-3A...

    Science.gov (United States)

    2011-08-03

    .... Model CL-600-2A12 (CL- 601) and CL-600-2B16 (CL-601-3A, CL-601-3R, and CL-604 Variants) Airplanes... Bombardier, Inc. model-- Task(s)-- Initial compliance time (whichever occurs later)-- CL-600-2A12 (CL-601... icing. accumulation of 4,800 after the effective inclusive; and CL-600-2B16 (CL- total flight hours;...

  7. A hydrochemical investigation using 36Cl/Cl in groundwaters

    OpenAIRE

    Metcalfe, R.

    2003-01-01

    This report describes 36Cl studies which were undertaken during the H14 financial year. 6 groundwater samples were collected for 36Cl analysis. The results of this study suggest that 36Cl data could potentially be useful for interpreting groundwater origins and flow paths.

  8. Guest Editorial: Processes of Radicalization and De-Radicalization

    Directory of Open Access Journals (Sweden)

    Donatella Della Porta

    2012-05-01

    Full Text Available The study of radicalization and de-radicalization, understood as processes leading towards the increased or decreased use of political violence, is central to the question of how political violence emerges, how it can be prevented, and how it can be contained. The focus section of this issue of the International Journal of Conflict and Violence addresses radicalization and de-radicalization, seeking to develop a more comprehensive understanding of the processes, dynamics, and mechanisms involved and taking an interdisciplinary approach to overcome the fragmentation into separate disciplines and focus areas. Contributions by Pénélope Larzillière, Felix Heiduk, Bill Kissane, Hank Johnston, Christian Davenport and Cyanne Loyle, Veronique Dudouet, and Lasse Lindekilde address repressive settings, legitimacy, institutional aspects, organizational outcomes, and dynamics in Europe, Asia, Africa, and North and South America.

  9. Free radical reactions of monochloramine and hydroxylamine in aqueous solution

    International Nuclear Information System (INIS)

    The use of Advanced Oxidation Technologies to destroy organic contaminants in drinking water may be impacted by the presence of disinfection chemicals such as monochloramine (NH2Cl). To allow a quantitative evaluation of the effect of NH2Cl on the destruction of organics in water rate constants for its reaction with the hydrated electron, the hydroxyl radical and the hydrogen atom were determined in this study. The corresponding values of (2.2±0.2)x1010, (2.8±0.2)x109, and (1.2±0.1)x109 M-1 s-1, respectively, were incorporated into a kinetic computer model whose predictions were in good agreement with experimental chloramine removal under large scale, steady-state electron-beam irradiation conditions. Rate constants were also determined for the reaction of the hydroxyl radical and hydrogen atom with the chloramine hydration product hydroxylamine to supplement established literature data. Hydroxyl radical rate constants for the basic (NH2OH) and acidic (NH3OH+) forms were determined as (8.5±0.4)x109 and ≤5x107 M-1 s-1, respectively, while for hydrogen atom reaction, corresponding rate constants of (4.5±0.1)x107 and (3.6±1.5)x105 M-1 s-1 were found

  10. Redox Properties of Free Radicals.

    Science.gov (United States)

    Neta, P.

    1981-01-01

    Describes pulse radiolysis as a useful means in studing one-electron redox potentials. This method allows the production of radicals and the determination of their concentration and rates of reaction. (CS)

  11. Ecoporn, Irrationalities and Radical Environmentalism

    OpenAIRE

    Măntescu, Liviu

    2016-01-01

    This study explores the ‘irrationalities’ of deep ecology activism in the context of radical environmentalism by using the empirical example of ecoporn. Fuck For Forest is an environmental Non-Governmental Organisation which undertakes fund-raising for re-forestation and forest protection by means of pornography. Following twelve months of ethnographic fieldwork, this study presents first research results on a radical environmental project which does not promote democratic and established pro...

  12. Constitutional Isomerism of BiW6Cl15: (BiCl)[W6Cl14] and (BiCl2)[W6Cl13

    OpenAIRE

    Meyer, Hans-Juergen

    2009-01-01

    Abstract The compound (BiCl)[W6Cl14] was previously characterized as a product of the reduction of tungsten hexachloride with elemental bismuth. Another modification of BiW6Cl15 is now presented as (BiCl2)[W6Cl13], based on the results of an X-ray single crystal structure determination (space group P21/c, a = 1354.3(2) pm, b = 1234.4(2) pm, c = 1538.9(2) pm, and ? = 118.76(1) ?). The structure of (BiCl2)[W6Cl13] contains chains of [(W6Cl8i)Cl4aCl2/2a-a]- clusters bridged by chlorin...

  13. Acrylamide Homopolymers and Acrylamide-N-Isopropylacrylamide Block Copolymers by Atomic Transfer Radical Polymerization in Water

    NARCIS (Netherlands)

    Wever, D. A. Z.; Raffa, P.; Picchioni, F.; Broekhuis, A. A.

    2012-01-01

    Atomic transfer radical polymerization (ATRP) of acrylamide has been accomplished in aqueous media at room temperature. By using methyl 2-chloropropionate (MeClPr) as the initiator and tris[2-(dimethylamino)ethyl]-amine (Me6TREN)/copper halogenide (CuX) as the catalyst system, different linear polya

  14. Dimethylzinc-Initiated Radical Coupling of β-Bromostyrenes with Ethers and Amines

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte; Ahlburg, Andreas; Madsen, Robert

    2015-01-01

    A new coupling reaction has been developed in which β-bromostyrenes react with ethers and tertiary amines to introduce the styryl group in the α-position. The transformation is mediated by Me2Zn/O2 with 10 % MnCl2 and is believed to proceed by a radical addition-elimination mechanism. The ether...

  15. The games radicals play : special issue on free radicals and radical ions

    OpenAIRE

    Walton, John C; Ffrancon Williams

    2015-01-01

    Chemistry and Physics have aptly been described as “most excellent children of Intellect and Art” [1]. Both these “children” engage with many playthings, and molecules rank as one of their first favorites, especially radicals, which are amongst the most lively and exciting. Checking out radicals dancing to the music of entropy round their potential energy ballrooms is surely both entertaining and enlightening. Radicals’ old favorite convolutions are noteworthy, but the new styles, modes and a...

  16. Crystalline bipyridinium radical complexes and uses thereof

    Science.gov (United States)

    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.

  17. Probing the radical chemistry in UV/persulfate-based saline wastewater treatment: kinetics modeling and byproducts identification.

    Science.gov (United States)

    Yuan, Ruixia; Wang, Zhaohui; Hu, Yin; Wang, Baohui; Gao, Simeng

    2014-08-01

    The effect of Cl(-) on the oxidative degradation of Acid Orange 7 (AO7) was investigated in UV/S2O8(2-) system to elucidate the chlorination pathways in saline wastewaters. Lower amount of Cl(-) as well as Br(-) enhanced the decoloration of AO7, but such promotion effect reduced gradually with the increasing halide ion dosage. The dye mineralization was found to be inhibited by Cl(-), especially under acidic conditions. Results of kinetics modeling demonstrated that the fraction of different oxidizing radicals largely depended on the content of Cl(-). At the initial pH of 6.5, Cl2(-) was much more abundant than SO4(-). The significance of Cl2(-) for AO7 degradation increased with the increasing Cl(-) concentration and overwhelmed that of SO4(-) at [Cl(-)]>1mM. Without Cl(-), SO4(-) was the predominant radical for AO7 degradation under acidic conditions, while OH prevailed gradually at higher pH. Under high salinity conditions, more OH can be formed and contributed to the dye degradation especially in alkaline medium, leading to higher destruction efficiency of AO7. Several chlorinated byproducts were detected in the presence of chloride ions, and SO4(-)/Cl2(-)-based degradation pathways of AO7 were proposed. This work provides further understanding of the complex reaction mechanisms for SO4(-)-based advanced oxidation processes in chloride-rich environments.

  18. High 36Cl/Cl ratios in Chernobyl groundwater

    International Nuclear Information System (INIS)

    After the explosion of the Chernobyl Nuclear Power Plant in April 1986, contaminated material was buried in shallow trenches within the exclusion zone. A 90Sr plume was evidenced downgradient of one of these trenches, trench T22. Due to its conservative properties, 36Cl is investigated here as a potential tracer to determine the maximal extent of the contamination plume from the trench in groundwater. 36Cl/Cl ratios measured in groundwater, trench soil water and leaf leachates are 1–5 orders of magnitude higher than the theoretical natural 36Cl/Cl ratio. This contamination occurred after the Chernobyl explosion and currently persists. Trench T22 acts as an obvious modern point source of 36Cl, however other sources have to be involved to explain such contamination. 36Cl contamination of groundwater can be explained by dilution of trench soil water by uncontaminated water (rainwater or deep groundwater). With a plume extending further than that of 90Sr, radionuclide which is impacted by retention and decay processes, 36Cl can be considered as a suitable tracer of contamination from the trench in groundwater provided that modern release processes of 36Cl from trench soil are better characterized. - Highlights: • High 36Cl/Cl ratios measured in the Chernobyl Pilot Site groundwater. • Trench T22 acts as a modern source of groundwater contamination by 36Cl but other sources are involved. • Contamination results from dilution of a contaminated “T22” soil water with rainwater. • Processes involved in the modern release need to be investigated

  19. Peroxy radical partitioning during the AMMA radical intercomparison exercise

    Directory of Open Access Journals (Sweden)

    M. D. Andrés-Hernández

    2010-04-01

    Full Text Available Peroxy radicals were measured onboard two scientific aircrafts during the AMMA (African Monsoon Multidisciplinary Analysis campaign in summer 2006. This paper reports results from the flight on 16 August 2006 during which measurements of HO2 by laser induced fluorescence spectroscopy at low pressure (LIF-FAGE and total peroxy radicals (RO2*=HO2+ΣRO2, R= organic chain by two similar instruments based on the peroxy radical chemical amplification (PerCA technique were subject of a blind intercomparison. The German DLR-Falcon and the British FAAM-BAe-146 flew wing tip to wing tip for about 30 min making concurrent measurements on 2 horizontal level runs at 697 and 485 hPa over the same geographical area in Burkina Faso. A full set of supporting measurements comprising photolysis frequencies, and relevant trace gases like CO, NO, NO2, NOy, O3 and a wider range of VOCs were collected simultaneously.

    Results are discussed on the basis of the characteristics and limitations of the different instruments used. Generally, no data bias are identified and the RO2* data available agree quite reasonably within the instrumental errors. The [RO2*]/[HO2] ratios, which vary between 1:1 and 3:1, as well as the peroxy radical variability, concur with variations in photolysis rates and in other potential radical precursors. Model results provide additional information about dominant radical formation and loss processes.

  20. NaCl islands decorated with 2D or 3D 3,4,9,10-perylene-tetracarboxylic-dianhydride nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Sun Xiaonan [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, NL-9747 AG Groningen (Netherlands); Silly, Fabien, E-mail: Fabien.silly@cea.fr [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, NL-9747 AG Groningen (Netherlands); CEA, IRAMIS, SPCSI, Nanostructures and Organic Semiconductors Laboratory, F-91191 Gif-sur-Yvette (France); UPMC, IPCM, UMR CNRS 7201, 4 place Jussieu, F-75005 Paris (France)

    2010-01-15

    The formation of PTCDA (3,4,9,10-perylene-tetracarboxylic-dianhydride) nanostrutures on Au(1 1 1)-(22x{radical}(3)) covered with NaCl islands has been studied using scanning tunneling microscopy (STM). Atomically resolved STM images show that NaCl grows as (1 0 0)-terminated layers on Au(1 1 1)-(22x{radical}(3)). Local atomic hexagonal packing has also been observed in the NaCl(1 0 0) layer. At submonolayer NaCl coverage, PTCDA forms two-dimensional islands on the Au(1 1 1) surface and nucleate preferentially at the NaCl island step edges. When the Au surface is fully covered with NaCl layers, PTCDA molecules form three-dimensional molecular clusters decorating the step edges of NaCl layers.

  1. Standard Electrode Potentials Involving Radicals in Aqueous Solution: Inorganic Radicals

    Energy Technology Data Exchange (ETDEWEB)

    Armstrong, David A.; Huie, Robert E.; Koppenol, Willem H.; Lymar, Sergei V.; Merenyi, Gabor; Neta, Pedatsur; Ruscic, Branko; Stanbury, David M.; Steenken, Steen; Wardman, Peter

    2015-12-01

    Recommendations are made for standard potentials involving select inorganic radicals in aqueous solution at 25 °C. These recommendations are based on a critical and thorough literature review and also by performing derivations from various literature reports. The recommended data are summarized in tables of standard potentials, Gibbs energies of formation, radical pKa’s, and hemicolligation equilibrium constants. In all cases, current best estimates of the uncertainties are provided. An extensive set of Data Sheets is appended that provide original literature references, summarize the experimental results, and describe the decisions and procedures leading to each of the recommendations

  2. Radical formation by heavy metals

    Energy Technology Data Exchange (ETDEWEB)

    Beuter, W.

    1982-09-01

    Certain reduced heavy metal ions can convert oxygen to a ''reactive oxygen species'' by donation of an electron. The reactive oxygen then attacks structures susceptible to oxidation, in particular unsaturated fatty acids, and peroxidizes them in a radical reaction. This process is inhibited by the presence of vitamin E and by other means. Peroxidized lipids decay forming free radicals in the process which themselves can peroxidise neighbouring lipids in a radical chain reaction. This decay is, moreover, catalysed by reduced heavy metal ions but on the other hand retarded by selenium-containing glutathione peroxidase. Radical formation by heavy metals is considerably involved in (i) the production of parenteral iron poisoning of the piglet (ii) haemolytic crisis occurring in ruminants through chronic copper poisoning (iii) the production of lead poisoning in ruminants and other animals. These types of poisonings are made worse by a deficiency of vitamin E and/or selenium. Factors which increase the bio-availability of the free heavy metal ion or reduce the redox potential thereof can aid radical formation as well as factors which lead to a reduction of the heavy metal ion e.g. cysteine, ascorbic acid or glucose.

  3. 75 FR 30740 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2B16 (CL-604 Variants (Including CL-605...

    Science.gov (United States)

    2010-06-02

    ... Procedures (44 FR 11034, February 26, 1979); and 3. Will not have a significant economic impact, positive or... Directives; Bombardier, Inc. Model CL-600-2B16 (CL- 604 Variants (Including CL-605 Marketing Variant... addition to Bombardier Inc. Models CL-600-2B19, CL-600-2C10 and CL-600-2D24. The latter three models...

  4. 76 FR 477 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2A12 (CL-601) and CL-600-2B16 (CL-601-3A...

    Science.gov (United States)

    2011-01-05

    ... Policies and Procedures (44 FR 11034, February 26, 1979); and 3. Will not have a significant economic.... Model CL-600-2A12 (CL- 601) and CL-600-2B16 (CL-601-3A, CL-601-3R, and CL-604 Variants) Airplanes AGENCY... applicability of the directive for CL-600-2A12 aircraft, serial numbers 3001 through 3066, and for CL-...

  5. 76 FR 66203 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2B16 (CL-601-3A, CL-601-3R, and CL-604...

    Science.gov (United States)

    2011-10-26

    ... Policies and Procedures (44 FR 11034, February 26, 1979); and 3. Will not have a significant economic.... Model CL-600-2B16 (CL- 601-3A, CL-601-3R, and CL-604 Variants) Airplanes AGENCY: Federal Aviation... Bombardier, Inc. Model CL-600-2B16 (CL- 601-3A, CL-601-3R, and CL-604 Variants) airplanes, certificated...

  6. Epistemological barriers to radical behaviorism

    Science.gov (United States)

    O'Donohue, William T.; Callaghan, Glenn M.; Ruckstuhl, L. E.

    1998-01-01

    The historian and philosopher of science Gaston Bachelard proposed the concept of epistemological barriers to describe the intellectual challenges encountered by scientists in their work. In order to embrace novel ways of approaching a problem in science, scientists must overcome barriers or obstacles posed by their prior views. For example, Einsteinian physics presents scientists with claims that space is curved and that time and space are on the same continuum. We utilize Bachelard's concept of epistemological barriers to describe the differences between the intellectual journeys students pursuing advanced studies face when attempting to accept cognitive psychology or radical behaviorism. We contend that the folk psychological beliefs that students typically hold when entering these studies pose less challenge to cognitive psychology than to radical behaviorism. We also suggest that these barriers may also partly be involved in the problematic exegesis that has plagued radical behaviorism. In close, we offer some suggestions for dealing with these epistemological barriers. PMID:22478314

  7. Measurement of free radical kinetics in pulsed plasmas by UV and VUV absorption spectroscopy and by modulated beam mass spectrometry

    International Nuclear Information System (INIS)

    This paper reviews recent progress in the development of time-resolved diagnostics to probe high-density pulsed plasma sources. We focus on time-resolved measurements of radicals' densities in the afterglow of pulsed discharges to provide useful information on production and loss mechanisms of free radicals. We show that broad-band absorption spectroscopy in the ultraviolet and vacuum ultraviolet spectral domain and threshold ionization modulated beam mass spectrometry are powerful techniques for the determination of the time variation of the radicals' densities in pulsed plasmas. The combination of these complementary techniques allows detection of most of the reactive species present in industrial etching plasmas, giving insights into the physico-chemistry reactions involving these species. As an example, we discuss briefly the radicals' kinetics in the afterglow of a SiCl4/Cl2/Ar discharge. (paper)

  8. 76 FR 6536 - Airworthiness Directives; Bombardier, Inc. Model CL-215-1A10 (CL-215), CL-215-6B11 (CL-215T...

    Science.gov (United States)

    2011-02-07

    ... products. That NPRM was published in the Federal Register on November 9, 2010 (75 FR 68728). That NPRM... Regulatory Policies and Procedures (44 FR 11034, February 26, 1979); and 3. Will not have a significant.... Model CL-215-1A10 (CL- 215), CL-215-6B11 (CL-215T Variant), and CL-215-6B11 (CL-415 Variant)...

  9. Vaginal radical trachelectomy: an update.

    Science.gov (United States)

    Plante, Marie

    2008-11-01

    The vaginal radical trachelectomy has emerged as a valuable fertility-preserving treatment option for young women with early-stage disease. Cancer-related infertility is associated with feelings of depression, grief, stress, and sexual dysfunction. Data have shown that the overall oncological outcome is safe and that the obstetrical outcome is promising. In this article, we analyze the data on the vaginal radical trachelectomy published over the last 10 years in the context of what we have learned, what issues remain unclear, and what the future holds.

  10. Radical democratic politics and feminism

    Directory of Open Access Journals (Sweden)

    Martínez Labrin, Soledad

    2006-05-01

    Full Text Available In the article I present a reflection around the radical democratic project proposed by Chantal Mouffe and Ernesto Laclau. Specifically, I examine the application of the project in the context of the “new social movements” and especially, of feminist movement. I state the need of drawing attention to universalism and essentialism as the main obstacles to generate a collective proposal without margins. Nevertheless, doubts remind about the possibility of building up a feminism tailored by the radical democratic project, in a stage in which the political action of such a movement is characterized by categories that are closed and crystallized

  11. Correlation of the EPR properties of perchlorotriphenylmethyl radicals and their efficiency as DNP polarizers.

    Science.gov (United States)

    Banerjee, Debamalya; Paniagua, Juan Carlos; Mugnaini, Veronica; Veciana, Jaume; Feintuch, Akiva; Pons, Miquel; Goldfarb, Daniella

    2011-11-01

    Water soluble perchlorinated trityl (PTM) radicals were found to be effective 95 GHz DNP (dynamic nuclear polarization) polarizers in ex situ (dissolution) (13)C DNP (Gabellieri et al., Angew Chem., Int. Ed. 2010, 49, 3360). The degree of the nuclear polarization obtained was reported to be dependent on the position of the chlorine substituents on the trityl skeleton. In addition, on the basis of the DNP frequency sweeps it was suggested that the (13)C NMR signal enhancement is mediated by the Cl nuclei. To understand the DNP mechanism of the PTM radicals we have explored the 95 GHz EPR characteristics of these radicals that are relevant to their performance as DNP polarizers. The EPR spectra of the radicals revealed axially symmetric g-tensors. A comparison of the spectra with the (13)C DNP frequency sweeps showed that although the solid effect mechanism is operational the DNP frequency sweeps reveal some extra width suggesting that contributions from EPR forbidden transitions involving (35,37)Cl nuclear flips are likely. This was substantiated experimentally by ELDOR (electron-electron double resonance) detected NMR measurements, which map the EPR forbidden transitions, and ELDOR experiments that follow the depolarization of the electron spin upon irradiation of the forbidden EPR transitions. DFT (density functional theory) calculations helped to assign the observed transitions and provided the relevant spin Hamiltonian parameters. These results show that the (35,37)Cl hyperfine and nuclear quadrupolar interactions cause a considerable nuclear state mixing at 95 GHz thus facilitating the polarization of the Cl nuclei upon microwave irradiation. Overlap of Cl nuclear frequencies and the (13)C Larmor frequency further facilitates the polarization of the (13)C nuclei by spin diffusion. Calculation of the (13)C DNP frequency sweep based on the Cl nuclear polarization showed that it does lead to an increase in the width of the spectra, improving the agreement with the

  12. Optical properties of the radical anion derived from {alpha}-alanine by deamination

    Energy Technology Data Exchange (ETDEWEB)

    Zagorski, Z.P.; Przybytniak, G.K. [Institute of Nuclear Chemistry and Technology, Warsaw (Poland)

    1997-12-31

    The free radical anion CH{sub 3}CHCOO derived during high energy irradiation from {alpha}-alanine by deamination has been investigated until now by EPR, in irradiated single crystals, for basic research or in completely randomized polycrystalline material for {gamma}-dosimetric purposes. It has been found by spectrophotometry of irradiated single crystals that the free radical absorbs light at {lambda}{sub max}=350 nm. The same radical anion is observed by pulse radiolysis of {alpha}-chloropropionic or propionic anion in aqueous solutions by Cl resp. {alpha}-H abstraction.Basic and applied aspects of the identity of the radical anion obtained in different ways are discussed, as well as consequences for dosimetric techniques. (author). 11 refs, 4 figs.

  13. Pulse radiolysis studies on reactions of hydroxyl radicals with selenocystine derivatives.

    Science.gov (United States)

    Mishra, B; Kumbhare, L B; Jain, V K; Priyadarsini, K I

    2008-04-10

    Reactions of hydroxyl radicals (*OH) with selenocystine (SeCys) and two of its analogues, diselenodipropionic acid (SeP) and selenocystamine (SeA), have been studied in aqueous solutions at pHs of 1, 7, and 10 using the pulse radiolysis technique coupled with absorption detection. All of these diselenides react with *OH radicals with rate constants of approximately 10(10) M(-1) s(-1), producing diselenide radical cations ( approximately 1-5 micros after the pulse), with an absorption maximum at 560 nm, by elimination of H(2)O or OH(-) from hydroxyl radical adducts. Assignment of the 560 nm band to the diselenide radical cation was made by comparing the transient spectra with those produced upon reaction of diselenides with specific one-electron oxidants, Cl(2)(*-) (pH 1) and Br(2)(*-) radicals (pHs of 7 and 10). SeP having a carboxylic acid functionality showed quantitative conversion of hydroxyl radical adducts to radical cations. The compounds SeCys and SeA, having an amino functional group, in addition to the radical cations, produced a new transient with lambda(max) at 460 nm, at later time scales ( approximately 20-40 micros after the pulse). The rate and yield of formation of the 460 nm band increased with increasing concentrations of either SeCys or SeA. In analogy with similar studies reported for analogous disulfides, the 460 nm transient absorption band has been assigned to a triselenide radical adduct. The one-electron reduction potentials of the compounds were estimated to be 0.96, 1.3, and 1.6 V versus NHE, respectively, for SeP, SeCys, and SeA at pH 7. From these studies, it has been concluded that the electron-donating carboxylic acid group decreases the reduction potential and facilitates quantitative conversion of hydroxyl radical adducts to radical cations, while the electron-withdrawing NH(3)(+) group not only increases the reduction potential but also leads to fragmentation of the hydroxyl radical adduct to selenyl radicals, which are converted

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

    Science.gov (United States)

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

    1997-01-01

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

  15. ClEST cluster :Cl_singleton0355 [ClEST

    Lifescience Database Archive (English)

    Full Text Available Cl_singleton0355 acyl- synthetase long- isoform b Cimex lectularius nuclear gene 19...GGAAGGTGCATTGGGAGCAATAAAAGCGATCGCATTTGTCTGTGATATCATCACTTATCCAGTGTACCTTATTCTACAACGGCCATGGG fb18010 1 acyl-CoA synthetase [Gl

  16. ClEST cluster :Cl_singleton0763 [ClEST

    Lifescience Database Archive (English)

    Full Text Available Cl_singleton0763 aldo-keto reductase Cimex lectularius nuclear gene 591 CACCGGGTAGG...GTGAATAAAGGCTTAGTTAGGTCAATCGGACTATCCAATTTCAACAAAAGACAGATCGAAGATGTTT fs09012 1 aldo-keto reductase [Gl

  17. Detecting Social Polarization and Radicalization

    DEFF Research Database (Denmark)

    Qureshi, Pir Abdul Rasool; Memon, Nasrullah; Wiil, Uffe Kock;

    2011-01-01

    This paper proposes a novel system to detect social polarization and to estimate the chances of violent radicalization associated with it. The required processes for such a system are indicated; it is also analyzed how existing technologies can be integrated into the proposed system to fulfill the...

  18. Kinetics of nitroxyl radical reactions

    International Nuclear Information System (INIS)

    Absolute rate-constants for the reaction of the nitroxyl free radicals TAN and TMPN with radiation-chemically-formed radicals and ions have been determined. k(TAN + X) (in M-1 sec-1) = 4.0 x 109 (for X =OH), 2.9 x 1010(esub(aq)-), 8.0 x 109 (H), 7.2 x 108 (CH2OH), 4.0 x 108 (CH3CHOH), 4.3 x 108 ((CH3)2COH), 2.8 x 108 (CH2(CH3)2COH), 5.9 x 107 (glucose radical), 4.0 x 108 (c-C5H9), and k(TMPN + X) = 3.4 x 109 (OH), 7.8 x 109 (esub(aq)-), 4.9 x 109 (H), 4.4 x 108 (CH2OH), 4.9 x 108 (CH3CHOH), 3.6 x 108 ((CH3)2COH), 1.5 x 108 (CH2(CH3)2COH), 4.9 x 107 (glucose radical), 4.3 x 108 (c-C5H9). Direct measurements by means of a pulse-radiolysis conductivity technique were based on the formation and destruction of charged species in these reactions within certain pH ranges. It is indicated that the radiosensitizing nitroxyles undergo both redox and addition reactions. (author)

  19. Remembering Dutch-Moluccan radicalism

    DEFF Research Database (Denmark)

    Marselis, Randi Lorenz

    2016-01-01

    This article examines memory politics in relation to radical actions of young Dutch-Moluccans, more specifically a train hijacking in 1977 at the village of De Punt in the Netherlands. The article examines how these historical events were remembered in the drama-documentary television film, De Punt...

  20. Wild radical square zero algebras

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    It is shown that a radical square zero algebra is wild, if and only if it is of Corner's type, and it is strictly wild if and only if it is Endo-wild. This gives a negative answer to a problem posed by Simson.

  1. Exploring the Theories of Radicalization

    Directory of Open Access Journals (Sweden)

    Maskaliūnaitė Asta

    2015-12-01

    Full Text Available After the London bombings in July 2005, the concern of terrorism scholars and policy makers has turned to “home-grown” terrorism and potential for political violence from within the states. “Radicalization” became a new buzz word. This article follows a number of reviews of the literature on radicalization and offers another angle for looking at this research. First, it discusses the term “radicalization” and suggests the use of the following definition of radicalization as a process by which a person adopts belief systems which justify the use of violence to effect social change and comes to actively support as well as employ violent means for political purposes. Next, it proposes to see the theories of radicalization focusing on the individual and the two dimensions of his/her motivation: whether that motivation is internal or external and whether it is due to personal choice or either internal (due to some psychological traits or external compulsion. Though not all theories fall neatly within these categories, they make it possible to make comparisons of contributions from a variety of different areas thus reflecting on the interdisciplinary nature of the study of terrorism in general and radicalization as a part of it.

  2. Laser flash photolysis studies of atmospheric free radical chemistry using optical diagnostic techniques

    Science.gov (United States)

    Wine, Paul H.; Nicovich, J. M.; Hynes, Anthony J.; Stickel, Robert E.; Thorn, R. P.; Chin, Mian; Cronkhite, Jeffrey A.; Shackelford, Christie J.; Zhao, Zhizhong; Daykin, Edward P.

    1993-01-01

    Some recent studies carried out in our laboratory are described where laser flash photolytic production of reactant free radicals has been combined with reactant and/or product detection using time-resolved optical techniques to investigate the kinetics and mechanisms of important atmospheric chemical reactions. Discussed are (1) a study of the radical-radical reaction O + BrO yields Br + O2 where two photolysis lasers are employed to prepare the reaction mixture and where the reactants O and BrO are monitored simultaneously using atomic resonance fluorescence to detect O and multipass UV absorption to detect BrO; (2) a study of the reaction of atomic chlorine with dimethylsulfide (CH3SCH3) where atomic resonance fluorescence detection of Cl is employed to elucidate the kinetics and tunable diode laser absorption spectroscopy is employed to investigate the HCl product yield; and (3) a study of the aqueous phase chemistry of Cl2(-) radicals where longpath UV absorption spectroscopy is employed to investigate the kinetics of the Cl2(-) + H2O reaction.

  3. From Radical Translation to Radical Interpretation and Back

    Directory of Open Access Journals (Sweden)

    António Zilhão

    2003-12-01

    Full Text Available Both Quine and Davidson put forth programs of empirical semantics satisfying the conditions that characterize the so-called “standpoint of interpretation.” Quine’s less ambitious program of radical translation rests upon two buttresses: causality and empathy. Davidson’s more ambitious program of radical interpretation replaces causality with truth and empathy with rationality. Although the replacement of causality with intersubjective truth seems to me to be a fully justified move, I nevertheless contend that it is more realistic to develop the work of interpretation drawing upon Quine’s less ambitious requirement of empathy than upon Davidson’s view of human agency as rational agency. In order to substantiate this contention, I present an argument to the effect that Davidson’s characterization of human agency as rational is not compatible with his other requirement that truth should pro-vide the essential link connecting speech with environment and action.

  4. Pickering emulsion templated interfacial atom transfer radical polymerization for microencapsulation.

    Science.gov (United States)

    Li, Jian; Hitchcock, Adam P; Stöver, Harald D H

    2010-12-01

    This Article describes a new microencapsulation method based on a Pickering emulsion templated interfacial atom transfer radical polymerization (PETI-ATRP). Cationic LUDOX CL nanoparticles were coated electrostatically with an anionic polymeric ATRP initiator, poly(sodium styrene sulfonate-co-2-(2-bromoisobutyryloxy)ethyl methacrylate) (PSB), prepared by radical copolymerization of sodium styrene sulfonate and 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM). The resulting PSB-modified CL particles were surface active and could be used to stabilize oil-in-water Pickering emulsions. ATRP of water-soluble cross-linking monomers, confined to the oil-water interface by the surface-bound PSB, then led to nanoparticle/polymer composite shells. This method allowed encapsulation of core solvents (xylene, hexadecane, perfluoroheptane) with different solubility parameters. The microcapsule (MC) wall chemistry could accommodate different monomers, demonstrating the versatility of this method. Double-walled MCs were formed by sequentially carrying out PETI-ATRP and in situ polymerization of encapsulated monomers. The double-walled structure was verified by both transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM).

  5. Reaction between protein radicals and other biomolecules

    DEFF Research Database (Denmark)

    Østdal, Henrik; Davies, Michael Jonathan; Andersen, Henrik J

    2002-01-01

    The present study investigates the reactivity of bovine serum albumin (BSA) radicals towards different biomolecules (urate, linoleic acid, and a polypeptide, poly(Glu-Ala-Tyr)). The BSA radical was formed at room temperature through a direct protein-to-protein radical transfer from H(2)O(2......)-activated immobilized horseradish peroxidase (im-HRP). Subsequently, each of the three different biomolecules was separately added to the BSA radicals, after removal of im-HRP by centrifugation. Electron spin resonance (ESR) spectroscopy showed that all three biomolecules quenched the BSA radicals....... Subsequent analysis showed a decrease in the concentration of urate upon reaction with the BSA radical, while the BSA radical in the presence of poly(Glu-Ala-Tyr) resulted in increased formation of the characteristic protein oxidation product, dityrosine. Reaction between the BSA radical and a linoleic acid...

  6. OpenCL programming guide

    CERN Document Server

    Munshi, Aaftab; Mattson, Timothy G; Fung, James; Ginsburg, Dan

    2011-01-01

    Using the new OpenCL (Open Computing Language) standard, you can write applications that access all available programming resources: CPUs, GPUs, and other processors such as DSPs and the Cell/B.E. processor. Already implemented by Apple, AMD, Intel, IBM, NVIDIA, and other leaders, OpenCL has outstanding potential for PCs, servers, handheld/embedded devices, high performance computing, and even cloud systems. This is the first comprehensive, authoritative, and practical guide to OpenCL 1.1 specifically for working developers and software architects. Written by five leading OpenCL authorities, OpenCL Programming Guide covers the entire specification. It reviews key use cases, shows how OpenCL can express a wide range of parallel algorithms, and offers complete reference material on both the API and OpenCL C programming language. Through complete case studies and downloadable code examples, the authors show how to write complex parallel programs that decompose workloads across many different devices. They...

  7. Electron attachment to fluorocarbon radicals

    Science.gov (United States)

    Shuman, Nicholas

    2014-10-01

    Most plasma environments contain populations of short-lived species such as radicals, the chemistry of which can have significant effects on the overall chemistry of the system. However, few experimental measurements of the kinetics of electron attachment to radicals exist due to the inherent difficulties of working with transient species. Calculations from first principles have been attempted, but are arduous and, because electron attachment is so sensitive to the specifics of the potential surface, their accuracy has not been established. Electron attachment to small fluorocarbon radicals is particularly important, as the data are needed for predictive modeling of plasma etching of semiconductor materials, a key process in the industrial fabrication of microelectronics. We have recently developed a novel flowing afterglow technique to measure several types of otherwise difficult to study plasma processes, including thermal electron attachment to radicals. Variable Electron and Neutral Density Attachment Mass Spectrometry (VENDAMS) exploits dissociative electron attachment in a weakly ionized plasma as a radical source. Here, we apply VENDAMS to a series of halofluorocarbon precursors in order to measure the kinetics of thermal electron attachment to fluorocarbon radicals. Results are presented for CF2, CF3, C2F5,C2F3,1-C3F7, 2-C3F7, and C3F5 from 300 K to 900 K. Both the magnitude and the temperature dependences of rate coefficients as well as product branching between associative and dissociative attachment are highly system specific; however, thermal attachment to all species is inefficient, never exceeding 5% of the collision rate. The data are analyzed using a recently developed kinetic modeling approach, which uses extended Vogt-Wannier theory as a starting point, accounts for dynamic effects such as coupling between the electron and nuclear motions through empirically validated functional forms, and finally uses statistical theory to determine the fate of

  8. Radical carbonylations using a continuous microflow system

    Directory of Open Access Journals (Sweden)

    Takahide Fukuyama

    2009-07-01

    Full Text Available Radical-based carbonylation reactions of alkyl halides were conducted in a microflow reactor under pressurized carbon monoxide gas. Good to excellent yields of carbonylated products were obtained via radical formylation, carbonylative cyclization and three-component coupling reactions, using tributyltin hydride or TTMSS as a radical mediator.

  9. Oxygen free radicals in rheumatoid arthritis

    NARCIS (Netherlands)

    P. Biemond (Pieter)

    1986-01-01

    textabstractCurrent knowledge strongly suggests that oxygen free radicals are involved in the pathogenesis of RA. Additional information about the mechanism of free radical attack is necessary in order to find out if interaction with the mechanism of free radical damage can be used in the treatment

  10. Spin-coupling in ferric metalloporphyrin radical cation complexes: Mössbauer and susceptibility studies

    Science.gov (United States)

    Lang, George; Boso, Brian; Erler, Brian S.; Reed, Christopher A.

    1986-03-01

    The ferric metalloporphyrin π-radical cation complexes Fe(III) (OClO3)2 (TPP.) and [Fe(III) Cl (TPP.)] [SbCl6] were examined in microcrystalline form by Mössbauer spectroscopy and magnetic susceptometry over a range of temperatures and applied fields. All measurements on the six-coordinate Fe(OClO3)2 (TPP.) were consistent with isolated molecules having an S=5/2 iron site with zero field splitting (12 cm-1) S2z that is ferromagnetically coupled to the S=1/2 porphyrin radical by an energy term (-110 cm-1) Sṡs. Thus the ground state is overall spin-3. In the five-coordinate [FeCl (TPP.)] [SbCl6] the susceptibility is in reasonable agreement with the results of a calculation based on zero field splitting (12 cm-1) S2z for the S=5/2 iron and antiferromagnetic coupling (200 cm-1) Sṡs with the radical to give an overall spin-2 ground state. However, the Mössbauer measurements require a more complicated model having the same large intramolecular iron-radical coupling, a smaller zero field splitting (3 cm-1) S2z, and weak intermolecular antiferromagnetic coupling between heme pairs given by (32 cm-1) s1ṡs2 or, equivalently, (0.65 cm-1) S1ṡS2. A slightly improved correspondence with the measured susceptibility results. The intermolecular antiferromagnetic coupling probably results from crystallization of the [FeCl (TPP.)]+ cations in face-to-face dimers as observed in other closely related five-coordinate iron (III) porphyrins.

  11. Kinetics of the ClO + HO2 reaction over the temperature range T = 210-298 K.

    Science.gov (United States)

    Ward, Michael K M; Rowley, David M

    2016-02-17

    The rate coefficient for the atmospherically important radical reaction: which leads to ozone depletion, has been studied over the temperature range T = 210-298 K and at ambient pressure p = 760 ± 20 Torr. The reaction was studied using laser flash photolysis radical generation coupled with broadband charge coupled device absorption spectroscopy employing a two-dimensional charge-coupled-device (CCD) detection system. ClO radicals were generated following the photolysis of Cl2 and Cl2O gas mixtures diluted in nitrogen and oxygen. ClO radicals were monitored using broadband fingerprinting of their characteristic vibronic (A(2)Π ← X(2)Π) spectral structure, representing a definitive monitoring of this radical. Addition of hydroperoxy radical precursors to the gas mixture (methanol and oxygen) subsequently led to a competition for photolytically generated Cl atoms and a simultaneous prompt formation of both ClO and HO2 radicals. Detailed analysis and modelling of the radical production routes provided a degree of constraint into numerical integration simulations which were then used to interrogate and fit to ClO temporal profiles to extract the rate coefficient k1. The ambient temperature (T = 298 K) rate coefficient reported is k1 = (8.5 ± 1.5) × 10(-12) cm(3) molecule(-1) s(-1). The rate coefficient, k1, is described by the Arrhenius expression:where errors are 1σ statistical only. This significant rate coefficient is greater than previously reported, with a stronger negative temperature dependence than previously observed. Consequently this suggests that the contribution of to ozone loss, in particular at mid-latitudes might be currently underestimated in models. This work reports atmospheric pressure kinetic parameters for this reaction which are greater than those reported from low pressure studies, perhaps supporting ClO and HO2 association as predicted by previous theoretical studies of this process and highlighting the need for further pressure

  12. DNA binding hydroxyl radical probes

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Vicky J.; Konigsfeld, Katie M.; Aguilera, Joe A. [Department of Radiology, University of California at San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0610 (United States); Milligan, Jamie R., E-mail: jmilligan@ucsd.edu [Department of Radiology, University of California at San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0610 (United States)

    2012-01-15

    The hydroxyl radical is the primary mediator of DNA damage by the indirect effect of ionizing radiation. It is a powerful oxidizing agent produced by the radiolysis of water and is responsible for a significant fraction of the DNA damage associated with ionizing radiation. There is therefore an interest in the development of sensitive assays for its detection. The hydroxylation of aromatic groups to produce fluorescent products has been used for this purpose. We have examined four different chromophores, which produce fluorescent products when hydroxylated. Of these, the coumarin system suffers from the fewest disadvantages. We have therefore examined its behavior when linked to a cationic peptide ligand designed to bind strongly to DNA. - Highlights: > Examined four aromatic groups as a means to detect hydroxyl radicals by fluorescence. > Coumarin system suffers from the fewest disadvantages. > Characterized its reactivity when linked to a hexa-arginine peptide.

  13. 76 FR 59067 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2B16 (CL-601-3A, CL-601-3R, and CL-604...

    Science.gov (United States)

    2011-09-23

    ... ``significant rule'' under the DOT Regulatory Policies and Procedures (44 FR 11034, February 26, 1979); and 3.... Model CL-600-2B16 (CL- 601-3A, CL-601-3R, and CL-604 Variants) Airplanes AGENCY: Federal Aviation...) events have occurred where the Air-Driven Generator (ADG) failed to provide power on CL-600-2B19...

  14. An MCM modeling study of nitryl chloride (ClNO2) impacts on oxidation, ozone production and nitrogen oxide partitioning in polluted continental outflow

    OpenAIRE

    T. P. Riedel; G. M. Wolfe; Danas, K. T.; J. B. Gilman; W. C. Kuster; Bon, D. M; Vlasenko, A.; Li, S.-M.; E. J. Williams; B. M. Lerner; P. R. Veres; Roberts, J.M.; J. S. Holloway; Lefer, B; S. S. Brown

    2014-01-01

    Nitryl chloride (ClNO2) is produced at night by reactions of dinitrogen pentoxide (N2O5) on chloride containing surfaces. ClNO2 is photolyzed during the morning hours after sunrise to liberate highly reactive chlorine atoms (Cl·). This chemistry takes place primarily in polluted environments where the concentrations of N2O5 precursors (nitrogen oxide radicals and ozone) are high, though it likely occurs in remote regions at lower intensities. Recent field measurements hav...

  15. Radical-scavenging Activity of Natural Methoxyphenols vs. Synthetic Ones using the Induction Period Method

    OpenAIRE

    Seiichiro Fujisawa; Ichiro Yokoe; Mariko Ishihara; Norihisa Okada; Toshiko Atsumi; Yoshinori Kadoma

    2007-01-01

    The radical-scavenging activities of the synthetic antioxidants 2-allyl-4-X-phenol (X=NO2, Cl, Br, OCH3, COCH3, CH3, t-(CH3)3, C6H5) and 2,4-dimethoxyphenol, and the natural antioxidants eugenol and isoeugenol, were investigated using differential scanning calorimetry (DSC) by measuring their anti-1,1-diphenyl-2-picrylhydrazyl (DPPH) radical activity and the induction period for polymerization of methyl methacrylate (MMA) initiated by thermal decomposition of 2,2'-azobisisobutyronitrile (AIBN...

  16. Free radicals and Dupuytren's contracture.

    OpenAIRE

    Murrell, G. A.; Francis, M. J.; Bromley, L.

    1987-01-01

    The concentration of substrate expressed as hypoxanthine capable of reacting with xanthine oxidase to release superoxide free radicals (O2-) was measured in control and Dupuytren's contracture palmar fascia. In Dupuytren's contracture palmar fascia the concentration of hypoxanthine was six times that of control and was greatest in "nodular" areas. Xanthine oxidase activity was also detected in Dupuytren's contracture palmar fascia. These results suggest a greater potential for hypoxanthine-xa...

  17. Geoscientists and the Radical Middle

    Science.gov (United States)

    Tinker, S. W.

    2015-12-01

    Addressing the great challenges facing society requires industry, government, and academia to work together. I call this overlap space, where compromises are made and real solutions determined, the Radical Middle. Radical because it can appear at times as if the loudest and most publicly influential voices lie outside of the actual solution space, content to provoke but not problem-solve. One key area where geoscientists can play a lead role in the Radical Middle is in the overlap between energy, the environment, and the economy. Globally, fossil fuels still represent 85% of the aggregate energy mix. As existing conventional oil and natural-gas reservoir production continues to slowly decline, unconventional reservoirs, led today by shale and other more expensive resources, will represent a growing part of the oil and gas production mix. Many of these unconventional reservoirs require hydraulic fracturing. The positive economic impact of hydraulic fracturing and associated natural gas and oil production on the United States economy is well documented and undeniable. Yet there are environmental concerns about fracking, and some states and nations have imposed moratoria. This energy-environment-economy space is ideal for leadership from the geosciences. Another such overlap space is the potential for geoscience leadership in relations with China, whose economy and global presence continue to expand. Although China is building major hydropower and natural-gas power plants, as well as nuclear reactors, coal is still king—with the associated environmental impacts. Carbon sequestration—onshore in brine and to enhance oil recovery, as well as offshore—could prove viable. It is vital that educated and objective geoscientists from industry, government, and academia leave their corners and work together in the Radical Middle to educate the public and develop and deliver balanced, economically sensible energy and environmental strategies.

  18. Osazone anion radical complex of rhodium(III).

    Science.gov (United States)

    Patra, Sarat Chandra; Biswas, Manas Kumar; Maity, Amarendra Nath; Ghosh, Prasanta

    2011-02-21

    One electron paramagnetic parent osazone complex of rhodium of type trans-Rh(L(NHPh)H(2))(PPh(3))(2)Cl(2) (1), defined as an osazone anion radical complex of rhodium(III), trans-Rh(III)(L(NHPh)H(2)(•-))(PPh(3))(2)Cl(2), 1((t-RhL•)), with a minor contribution (∼2%) of rhodium(II) electromer, trans-Rh(II)(L(NHPh)H(2))(PPh(3))(2)Cl(2), 1((t-Rh•L)), and their nonradical congener, trans-[Rh(III)(L(NHPh)H(2))(PPh(3))(2)Cl(2)]I(3) ([t-1](+)I(3)(-)), have been isolated and are substantiated by spectra, bond parameters, and DFT calculations on equivalent soft complexes [Rh(L(NHPh)H(2))(PMe(3))(2)Cl(2)] (3) and [Rh(L(NHPh)H(2))(PMe(3))(2)Cl(2)](+) (3(+)). 1 is not stable in solution and decomposes to [t-1](+) and a new rhodium(I) osazone complex, [Rh(I)(L(NHPh)H(2))(PPh(3))Cl] (2). 1 absorbs strongly at 351 nm due to MLCT and LLCT, while [t-1](+) and 2 absorb moderately in the range of 300-450 nm, respectively, due to LMCT and MLCT elucidated by TD-DFT calculations on 3((t-RhL•)), [t-3](+), and Rh(I)(L(NHPh)H(2))(PMe(3))Cl (4). EPR spectra of solids at 295 and 77 K, and dichloromethane-toluene frozen glass at 77 K of 1 are similar with g = 1.991, while g = 2.002 for the solid at 25 K. The EPR signal of 1 in dichloromethane solution is weaker (g = 1.992). In cyclic voltammetry, 1 displays two irreversible one electron transfer waves at +0.13 and -1.22 V, with respect to Fc(+)/Fc coupling, due to oxidation of 1((t-RhL•)) to [t-1](+) at the anode and reduction of rhodium(III) to rhodium(II), i.e., [t-1](+) to electromeric 1((t-Rh•L)) at the cathode. PMID:21261283

  19. Efficiencies of fragmentation of glycosaminoglycan chloramides of the extracellular matrix by oxidizing and reducing radicals: potential site-specific targets in inflammation?

    Science.gov (United States)

    Sibanda, Sambulelwe; Akeel, Almabrok; Martin, Stephen W; Paterson, Andrew W J; Edge, Ruth; Al-Assaf, Saphwan; Parsons, Barry J

    2013-12-01

    Hypochlorous acid and its conjugate base, hypochlorite ions, produced under inflammatory conditions, may produce chloramides of glycosaminoglycans, these being significant components of the extracellular matrix (ECM). This may occur through the binding of myeloperoxidase directly to the glycosaminoglycans. The N-Cl group in the chloramides is a potential selective target for both reducing and oxidizing radicals, leading possibly to more efficient and damaging fragmentation of these biopolymers relative to the parent glycosaminoglycans. To investigate the effect of the N-Cl group, we used ionizing radiation to produce quantifiable concentrations of the reducing radicals, hydrated electron and superoxide radical, and also of the oxidizing radicals, hydroxyl, carbonate, and nitrogen dioxide, all of which were reacted with hyaluronan and heparin and their chloramides in this study. PAGE gels calibrated for molecular weight allowed the consequent fragmentation efficiencies of these radicals to be calculated. Hydrated electrons were shown to produce fragmentation efficiencies of 100 and 25% for hyaluronan chloramide (HACl) and heparin chloramide (HepCl), respectively. The role of the sulfate group in heparin in the reduction of fragmentation can be rationalized using mechanisms proposed by M.D. Rees et al. (J. Am. Chem. Soc.125:13719-13733; 2003), in which the initial formation of an amidyl radical leads rapidly to a C-2 radical on the glucosamine moiety. This is 100% efficient at causing glycosidic bond breakage in HACl but only 25% efficient in HepCl, the role of the sulfate group being to favor the nonfragmentary routes for the C-2 radical. The weaker reducing agent, the superoxide radical, did not cause fragmentation of either HACl or HepCl although kinetic reactivity had been demonstrated in earlier studies. Experiments using the oxidizing radicals, hydroxyl and carbonate, both potential in vivo species, showed significant increases in fragmentation efficiencies for

  20. LETTING GO: DE-RADICALIZATION IN EGYPT

    Directory of Open Access Journals (Sweden)

    Zeynep Kaya

    2016-03-01

    Full Text Available The literature on the causes of how terrorist organizations are formed and how counter terrorism measures can be more effective is immense. What is novel in terrorism literature is de-radicalization in terrorist organizations. This paper hopes to shed light on the de-radicalization process in terrorist organizations based in Egypt. In order to achieve that goal, the first part of the paper will deal with the de-radicalization process. The second part will briefly describe the major radical terrorist organizations that are effective in Egypt. The last part will combine the two parts and bring in suggestions on the de-radicalization process itself. Terrorism and de-radicalization are complicated threats to nearly all societies. Therefore, it is important to go beyond security and intelligence approaches and take proactive measures. It is best to view what is de-radicalization and how it can be achieved.

  1. Oxidative stress, free radicals and protein peroxides.

    Science.gov (United States)

    Gebicki, Janusz M

    2016-04-01

    Primary free radicals generated under oxidative stress in cells and tissues produce a cascade of reactive secondary radicals, which attack biomolecules with efficiency determined by the reaction rate constants and target concentration. Proteins are prominent targets because they constitute the bulk of the organic content of cells and tissues and react readily with many of the secondary radicals. The reactions commonly lead to the formation of carbon-centered radicals, which generally convert in vivo to peroxyl radicals and finally to semistable hydroperoxides. All of these intermediates can initiate biological damage. This article outlines the advantages of the application of ionizing radiations to studies of radicals, with particular reference to the generation of desired radicals, studies of the kinetics of their reactions and correlating the results with events in biological systems. In one such application, formation of protein hydroperoxides in irradiated cells was inhibited by the intracellular ascorbate and glutathione.

  2. VEGF secretion during hypoxia depends on free radicals-induced Fyn kinase activity in mast cells

    International Nuclear Information System (INIS)

    Research highlights: → Bone marrow-derived mast cells (BMMCs) secrete functional VEGF but do not degranulate after Cobalt chloride-induced hypoxia. → CoCl2-induced VEGF secretion in mast cells occurs by a Ca2+-insensitive but brefeldin A and Tetanus toxin-sensitive mechanism. → Trolox and N-acetylcysteine inhibit hypoxia-induced VEGF secretion but only Trolox inhibits FcεRI-dependent anaphylactic degranulation in mast cells. → Src family kinase Fyn activation after free radical production is necessary for hypoxia-induced VEGF secretion in mast cells. -- Abstract: Mast cells (MC) have an important role in pathologic conditions such as asthma and chronic obstructive pulmonary disease (COPD), where hypoxia conduce to deleterious inflammatory response. MC contribute to hypoxia-induced angiogenesis producing factors such as vascular endothelial growth factor (VEGF), but the mechanisms behind the control of hypoxia-induced VEGF secretion in this cell type is poorly understood. We used the hypoxia-mimicking agent cobalt chloride (CoCl2) to analyze VEGF secretion in murine bone marrow-derived mast cells (BMMCs). We found that CoCl2 promotes a sustained production of functional VEGF, able to induce proliferation of endothelial cells in vitro. CoCl2-induced VEGF secretion was independent of calcium rise but dependent on tetanus toxin-sensitive vesicle-associated membrane proteins (VAMPs). VEGF exocytosis required free radicals formation and the activation of Src family kinases. Interestingly, an important deficiency on CoCl2-induced VEGF secretion was observed in Fyn kinase-deficient BMMCs. Moreover, Fyn kinase was activated by CoCl2 in WT cells and this activation was prevented by treatment with antioxidants such as Trolox and N-acetylcysteine. Our results show that BMMCs are able to release VEGF under hypoxic conditions through a tetanus toxin-sensitive mechanism, promoted by free radicals-dependent Fyn kinase activation.

  3. Inland Concentrations of Cl2 and ClNO2 in Southeast Texas Suggest Chlorine Chemistry Significantly Contributes to Atmospheric Reactivity

    Directory of Open Access Journals (Sweden)

    Cameron B. Faxon

    2015-10-01

    Full Text Available Measurements of molecular chlorine (Cl2, nitryl chloride (ClNO2, and dinitrogen pentoxide (N2O5 were taken as part of the DISCOVER-AQ Texas 2013 campaign with a High Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS using iodide (I- as a reagent ion. ClNO2 concentrations exceeding 50 ppt were regularly detected with peak concentrations typically occurring between 7:00 a.m. and 10:00 am. Hourly averaged Cl2 concentrations peaked daily between 3:00 p.m. and 4:00 p.m., with a 29-day average of 0.9 ± 0.3 (1σ ppt. A day-time Cl2 source of up to 35 ppt∙h−1 is required to explain these observations, corresponding to a maximum chlorine radical (Cl• production rate of 70 ppt∙h−1. Modeling of the Cl2 source suggests that it can enhance daily maximum O3 and RO2• concentrations by 8%–10% and 28%–50%, respectively. Modeling of observed ClNO2 assuming a well-mixed nocturnal boundary layer indicates O3 and RO2• enhancements of up to 2.1% and 38%, respectively, with a maximum impact in the early morning. These enhancements affect the formation of secondary organic aerosol and compliance with air quality standards for ozone and particulate matter.

  4. MBiO{sub 2}Cl (M=Sr, Ba) as novel photocatalysts: Synthesis, optical property and photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Hongwei, E-mail: hhw@cugb.edu.cn; Wang, Shuobo; Zhang, Yihe, E-mail: zyh@cugb.edu.cn; Han, Xu

    2015-02-15

    Novel quaternary photocatalysts MBiO{sub 2}Cl (M=Sr, Ba) have been successfully developed for efficient photodecomposition of RhB. Their photocatalytic mechanism was also investigated. - Highlights: • Two Bi-based compounds SrBiO{sub 2}Cl and BaBiO{sub 2}Cl were explored as photocatalysts. • They were successfully synthesized by a solid-state reaction. • RhB can be effectively photodecomposed by SrBiO{sub 2}Cl and BaBiO{sub 2}Cl under UV light. • ·OH radicals serving as active species play important roles in degradation process. - Abstract: Two Bi-based compounds SrBiO{sub 2}Cl and BaBiO{sub 2}Cl were successfully synthesized by a solid-state reaction and investigated as new photocatalysts for the first time. Their microstructures and optical properties were characterized by XRD, SEM and DRS. The band gaps of SrBiO{sub 2}Cl and BaBiO{sub 2}Cl were separately determined to be 3.52 and 3.71 eV, and their E{sub CB} and E{sub VB} were also estimated. The photocatalytic activities of the as-prepared samples were evaluated by photodecomposition of rhodamine B (RhB) in aqueous solution. The results revealed that both SrBiO{sub 2}Cl and BaBiO{sub 2}Cl can be used as effective photocatalysts under UV irradiation, and SrBiO{sub 2}Cl exhibits a higher photocatalytic activity than BaBiO{sub 2}Cl, which was also verified by the PL spectra. Terephthalic acid photoluminescence probing technique (TA-PL) demonstrated that ·OH radicals serving as active species play an important role in photooxidative degradation of RhB over SrBiO{sub 2}Cl and BaBiO{sub 2}Cl. Moreover, a larger amount of ·OH radicals generation was observed over SrBiO{sub 2}Cl, which is in agreement with its higher photocatalytic activity.

  5. 75 FR 68728 - Airworthiness Directives; Bombardier, Inc. Model CL-215-1A10 (CL-215), CL-215-6B11 (CL-215T...

    Science.gov (United States)

    2010-11-09

    ... Procedures (44 FR 11034, February 26, 1979); and 3. Will not have a significant economic impact, positive or.... Model CL-215-1A10 (CL- 215), CL-215-6B11 (CL-215T Variant), and CL-215-6B11 (CL-415 Variant) Airplanes...: * * * * * Seven cases of on-ground hydraulic accumulator screw cap or end cap failure have been experienced on...

  6. 76 FR 41653 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2A12 (CL-601) and CL-600-2B16 (CL-601-3A...

    Science.gov (United States)

    2011-07-15

    ... products. That NPRM was published in the Federal Register on January 5, 2011 (76 FR 477). That NPRM...; 2. Is not a ``significant rule'' under the DOT Regulatory Policies and Procedures (44 FR 11034.... Model CL-600-2A12 (CL- 601) and CL-600-2B16 (CL-601-3A, CL-601-3R, and CL-604 Variants) Airplanes...

  7. ClEST cluster :Cl_contig0243 [ClEST

    Lifescience Database Archive (English)

    Full Text Available Cl_contig0243 barrier-to-autointegration factor Cimex lectularius nuclear gene 428 ...TAATAAATACAGTATGATGTGCG fb29038 fs25084 mb23031 3 barrier to autointegration factor [Rhodnius prolixus] AEL79235 5.9E-56 GO:0003677 ...

  8. ClEST cluster :Cl_singleton0416 [ClEST

    Lifescience Database Archive (English)

    Full Text Available Cl_singleton0416 ornithine aminotransferase Cimex lectularius nuclear gene 438 TATC...CAGTTTGCCGAGTATATCACCCGTTATTT fb20049 1 PREDICTED: probable ornithine aminotransferase-like [Glycine max] XP_003531161 4.30167E-26 GO:0008483 ...

  9. ClEST cluster :Cl_singleton2093 [ClEST

    Lifescience Database Archive (English)

    Full Text Available Cl_singleton2093 selenoprotein t Cimex lectularius nuclear gene 435 GAGAAGGAGATTCCG...GAGACGGGAAGAATA mb12059 1 selenoprotein T [Glossina morsitans morsitans] ADD19835 7.29481E-59 GO:0045454 GO:0008430 GO:0005575 ...

  10. ClEST cluster :Cl_contig0231 [ClEST

    Lifescience Database Archive (English)

    Full Text Available Cl_contig0231 bcl2 adenovirus e1b 19 kda protein-interacting Cimex lectularius nucl...AGCCGTCCGGACCAATTTCCACCAAAGGATTGGAAACTGAGGCATCCGGCTCGGAAAACTCTCTCAATACGCACGAC fs06082 fw15056 mb10031 3 BCL2/adenovirus

  11. Simultaneous occurrence of three different valence tautomers in meso-vinylruthenium-modified zinc porphyrin radical cations.

    Science.gov (United States)

    Chen, Jing; Wuttke, Evelyn; Polit, Walther; Exner, Thomas; Winter, Rainer F

    2013-03-01

    The mixed-valent radical cation of a styrylruthenium-modified meso-tetraarylzinc porphyrin forms a mixture of three different valence tautomers (VTs) in CH2Cl2 or 1,2-C2H4Cl2 solutions. One of these VTs has the charge and spin delocalized over the porphyrin and the styrylruthenium moieties, while the other two display charge and spin localization on just one of the different redox sites. The relative amounts of the three different VTs were determined by EPR and IR spectroscopies at variable temperatures, while delocalization in the ground state was confirmed by DFT calculations.

  12. Enantiopure Radical Cation Salt Based on Tetramethyl-Bis(ethylenedithio-Tetrathiafulvalene and Hexanuclear Rhenium Cluster

    Directory of Open Access Journals (Sweden)

    Flavia Pop

    2016-01-01

    Full Text Available Electrocrystallization of the (S,S,S,S enantiomer of tetramethyl-bis(ethylenedithio-tetrathiafulvalene donor 1 in the presence of the dianionic hexanuclear rhenium (III cluster [Re6S6Cl8]2− affords a crystalline radical cation salt formulated as [(S-1]2·Re6S6Cl8, in which the methyl substituents of the donors adopt an unprecedented all-axial conformation. A complex set of intermolecular TTF···TTF and cluster···TTF interactions sustain an original tridimensional architecture.

  13. Investigation of the electron spin resonance of matrix isolated ClO

    International Nuclear Information System (INIS)

    The matrix isolation of ClO in a CO2 matrix is investigated with the aim of providing a detection method for ClO in the stratosphere. Of main concern is the identification and interpretation of the so far unkown ESR-spectrum of matrixisolated ClO. After trapping of ClO in a CO2 matrix at 10 K a highly anisotropic ESR-spectrum is observed which can be attributed to ClO. The shape and the g-values of the spectrum are characteristic for a 2PIsub(3/2) groundstate. Some minor structure discernible on the spectrum can be related to ClO at different trapping sites. After annealing the sample at T > 45 K, the radical concentration diminishes and the gsub(perpendicular to) peak splits into four peaks which correspond to the hyperfinesplitting of ClO. The values of the g and A tensors are determined by comparing the experimental spectrum with computer simulated spectra. In a simple crystal field model these values are compared with molecular parameters of ClO deduced from gas phase spectra. (orig.)

  14. Reactivity of OH radicals with chlorobenzoic acids-A pulse radiolysis and steady-state radiolysis study

    DEFF Research Database (Denmark)

    Zona, Robert; Solar, Sonja; Getoff, Nikola;

    2010-01-01

    The reactions of OH radicals with 2-, 3-, 4-chlorobenzoic acids (ClBzA) and chlorobenzene (ClBz), k(OH+substrates)=(4.5−6.2)×109 dm3 mol−1 s−1, have been studied by pulse radiolysis in N2O saturated solutions. The absorption maxima of the OH-adducts were in the range of 320−340 nm. Their decay wa...... to degradation. The order for the efficiency of dehalogenation was 4->2->3-ClBzA. Several primary radiolytic products could be detected by HPLC. To evaluate the toxicity of final products a bacterial bioluminescence test was carried out....

  15. Online radicalization: the net or the netizen?

    Directory of Open Access Journals (Sweden)

    Femi Richard Omotoyinbo

    2014-10-01

    Full Text Available Purpose - Radicalization has gained some unusual prominence in the academic circles; maintaining a generic existence not only in the political sector. And with the advent of the Information Communication Technology (ICT, radicalization has begun to have some virtual dimension even in the remotest of human communities. This study seeks to mobilize a universal awareness on the collective urgency to oppose Online Radicalization (a radicalization that happens through the internet due to its propensity to engendering conflicts. It also aims at identifying the principal cause of online radicalization and steer a clear course for a practical reversal in the systems of online radicalization.Design/methodology/approach - The study is divided into three primary parts. The general notion of radicalization is the focus of the first part; which is further analysed into the levels of online radicalization with its accompanying developments and segments. The second part utilizes analytic and historical method to pinpoint the principal cause of online radicalization amidst the suspected causal factors (the Net and the Netizen. The final part analytically focuses on the Netizen (a user/citizen of the internet as the primary cause of online radicalization, and how the global community can bring about a corresponding change in the Net by the application of some measures on the Netizen.Findings - By virtue of the analytic plus historical methods employed by this study; it was initially identified that radicalization is basically having two versions which are online and offline. Further emphasis on the online version reveals that its existence is only made possible by the availability of the internet (the Net. Since the Net is a global phenomenon online radicalization is considered to be worldwide: a menace of globalization. However, the study later indicated that the Net is a facilitator and a cause of online radicalization. A view was deduced that the Netizen is

  16. Effect of free radicals released from pulmonary alveolar phagocytes on development of radiation pneumonia in rats

    International Nuclear Information System (INIS)

    Measuring the hydroxyproline (HyP) content in rat lungs and the chemiluminescence (CL) of bronchus alveolar lavage fluid cell (BALFC) at 0.5, 1 and 2 months after irradiation with 60Co γ-rays respectively, we found that the amount of BALFC and its CL stimulated by zymosan and the pulmonary HyP content were apparently increased after irradiation, and these alternations took a favourable turn when selenium was supplemented to irradiated rats, suggesting that selenium protected the rats from radiation injury of lung. In addition, we found that there were certain interrelations between the multiplication of pulmonary fibrocytes and the free radicals released from accumulated BALFC in pulmonary alveoli, indicating that the free radicals produced from alveolar phagocytes may be an important factor in development of rat radiation pneumonia

  17. Radical conservatism and Danish imperialism

    DEFF Research Database (Denmark)

    2013-01-01

    on the basis of a close reading of their imperialist program in the pamphlet Danmark Udslettes! from 1918. Rige had been a vague term for the larger Danish polity that originated in a pre-national conceptualization of the polity as a realm. The article suggests that rige-as-realm was translated by the radical...... to signify the ambition of being a great power, the spiritual elevation of the nation through the transcendence of the decaying liberal modernity. The program addressed the tension between a conservative political attitude and modernity and thus signified a kind of reactionary modernism, which rejected...

  18. Aromatic-radical oxidation chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Glassman, I.; Brezinsky, K. [Princeton Univ., NJ (United States)

    1993-12-01

    The research effort has focussed on discovering an explanation for the anomalously high CO{sub 2} concentrations observed early in the reaction sequence of the oxidation of cyclopentadiene. To explain this observation, a number of plausible mechanisms have been developed which now await experimental verification. One experimental technique for verifying mechanisms is to probe the reacting system by perturbing the radical concentrations. Two forms of chemical perturbation of the oxidation of cyclopentadiene were begun during this past year--the addition of NO{sub 2} and CO to the reacting mixture.

  19. Laser spectroscopy of hydrocarbon radicals

    Energy Technology Data Exchange (ETDEWEB)

    Chen, P. [Harvard Univ., Cambridge, MA (United States)

    1993-12-01

    The author reports the application of supersonic jet flash pyrolysis to the specific preparation of a range of organic radicals, biradicals, and carbenes in a skimmed molecular beam. Each species was produced cleanly and specifically, with little or no secondary reactions by the thermal dissociation of appropriately designed and synthesized organic precursors. Photoelectron spectra of the three isomeric C{sub 3}H{sub 2} carbenes, ortho-benzyne, and the {alpha},3-dehydrotoluene biradical, were used to establish adiabatic ionization potentials for use in thermochemical determinations.

  20. Free radical kinetics of irradiated durum wheat

    Science.gov (United States)

    Korkmaz, M.; Polat, M.

    2000-04-01

    In the present work, a detailed ESR investigation of characteristic features and kinetic behaviors at three different temperatures of free radicals produced in a species of durum wheat cultivated in Turkey and irradiated at doses of up to 5 kGy by a γ source, is reported. Unirradiated wheat samples exhibit a weak, single-line ESR signal originating from a radical of unknown structure called radical III in this work. Irradiation produces two more radicals identified as hydroxyalkyl (I) and aldehydalkyl (II) radicals beside radical III. The radicals (I, II and III) follow complicated kinetics. Species I and II initially decay very fast after the irradiation followed by slower decay. Radical half-life times depend on whether they were induced in the crystalline or amorphous fractions of the wheat starch. Activation energy values of the radicals were found to follow the order Ea(III)> Ea(II)> Ea(I). ESR parameters of the radical species were determined by simulating experimental spectra recorded following the irradiation. Room temperature dose-response curves and variations of different spectral parameters between 120 and 390 K were also studied.

  1. Radical constructivism: Between realism and solipsism

    Science.gov (United States)

    Martínez-Delgado, Alberto

    2002-11-01

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

  2. Detection of a secondary muoniated radical

    Energy Technology Data Exchange (ETDEWEB)

    McCollum, Brett M.; Brodovitch, Jean-Claude [TRIUMF and Department of Chemistry, Simon Fraser University, Burnaby, BC, V5A 1S6 (Canada); Clyburne, Jason A.C. [Department of Chemistry, Saint Mary' s University, Halifax, NS, B3H 3C3 (Canada); Percival, Paul W., E-mail: percival@sfu.c [TRIUMF and Department of Chemistry, Simon Fraser University, Burnaby, BC, V5A 1S6 (Canada); West, Robert [Organosilicon Research Center, University of Wisconsin, Madison, WI 53706 (United States)

    2009-04-15

    Muoniated free radicals are formed by addition of muonium to unsaturated molecules. Successful detection by transverse-field muon spin rotation (muSR) usually requires pure or highly concentrated samples and a muonium reaction rate in excess of 10{sup 9} M{sup -1}s{sup -1} to ensure that the muon spin polarization is coherently transferred to the radical. For this reason muoniated radicals reported to date are all the primary radical products of Mu reaction. Thus, it was expected that Mu addition to a silylene would result in detection of a silyl radical. However, the muon hyperfine constant determined by experiment is much smaller than the value predicted by density functional calculations. Instead, it is consistent with a disilanyl radical, the secondary radical formed by reaction of the initially formed silyl radical with a second silylene molecule. From an analysis of the signal amplitude it was deduced that the second-order rate constant for reaction of the muoniated silyl radical with the parent silylene is 5.7x10{sup 8} M{sup -1}s{sup -1}. This work represents the first example of direct detection of a secondary radical product by transverse-field muSR.

  3. Preoperative Nomogram Predicting the 10-Year Probability of Prostate Cancer Recurrence After Radical Prostatectomy

    OpenAIRE

    Stephenson, Andrew J.; Scardino, Peter T.; Eastham, James A.; Bianco, Fernando J.; Dotan, Zohar A.; Fearn, Paul A.; Michael W Kattan

    2006-01-01

    An existing preoperative nomogram predicts the probability of prostate cancer recurrence, defined by prostate-specific antigen (PSA), at 5 years after radical prostatectomy based on clinical stage, serum PSA, and biopsy Gleason grade. In an updated and enhanced nomogram, we have extended the predictions to 10 years, added the prognostic information of systematic biopsy results, and enabled the predictions to be adjusted for the year of surgery. Cox regression analysis was used to model the cl...

  4. Green light radiation effects on free radicals inhibition in cellular and chemical systems.

    Science.gov (United States)

    Comorosan, Sorin; Polosan, Silviu; Jipa, Silviu; Popescu, Irinel; Marton, George; Ionescu, Elena; Cristache, Ligia; Badila, Dumitru; Mitrica, Radu

    2011-01-10

    Free radicals generation is inhibited through green light (GL) irradiation in cellular systems and in chemical reactions. Standard melanocyte cultures were UV-irradiated and the induced cellular reactive oxygen species (ROS) were quantified by the fluorescence technique. The same cell cultures, previously protected by a 24h GL exposure, displayed a significantly lower ROS production. A simple chemical reaction is subsequently chosen, in which the production of free radicals is well defined. Paraffin wax and mineral oil were GL irradiated during thermal degradation and the oxidation products checked by chemiluminescence [CL] and Fourier transform infrared spectra [FT-IR]. The same clear inhibition of the radical oxidation of alkanes is recorded. A quantum chemistry modeling of these results is performed and a mechanism involving a new type of Rydberg macromolecular systems with implications for biology and medicine is suggested. PMID:20934350

  5. Mechanism of HgCl2 cytotoxicity in cultured mammalian cells.

    Science.gov (United States)

    Cantoni, O; Christie, N T; Swann, A; Drath, D B; Costa, M

    1984-09-01

    Treatment of intact Chinese hamster ovary cells with HgCl2 produced a rapid, concentration-dependent induction of DNA single-strand breaks (SSB) as revealed by alkaline elution analysis. Direct addition of HgCl2 to cell lysates did not result in DNA strand breaks. HgCl2 treatment of cells also caused a rapid leakage of superoxide radicals that were detected in their media by measurement of the reduction of exogenously added cytochrome c. There was a linear relationship between the production of radicals and the induction of DNA strand breaks, and there were also excellent temporal correlations in these parameters. Addition of oxygen radical scavengers, such as the enzymes superoxide dismutase and catalase, to the extracellular media significantly reduced the extent of DNA damage caused by HgCl2 without a similar attenuation of its uptake into cells, as did the autoclaved enzymes. Similarly, addition of radical scavengers such as glycerol or ascorbate inhibited the DNA damage but also reduced the uptake of the metal by almost the same degree. Thus, because of secondary effects on uptake of the metal, the radical scavenger experiments could not address the importance of oxygen radicals in the DNA damage caused by HgCl2. SSB were enhanced when cells were treated with HgCl2 and diethylmaleate or diethyldithiocarbamate, agents that deplete cellular reduced glutathione or inhibit the intracellular activity of superoxide dismutase, respectively. Thus, DNA damage in cells rendered sensitive to radicals was greater when these cultures were subsequently treated with HgCl2. The binding of 203HgCl2 to the DNA of intact Chinese hamster ovary cells was also studied. These studies were made possible by the relatively high stability of Hg(II) interaction with DNA and by utilizing a gentle method of DNA isolation that minimized redistribution of intracellular Hg(II) complexes after cells were lysed. The amount of Hg(II) bound to DNA varied from approximately 7 to 35 Hg atoms per 10

  6. Radical Reactions and Its Synthetic Application

    Institute of Scientific and Technical Information of China (English)

    Takeaki Naito

    2005-01-01

    @@ 1Introduction Strategies involving radical reactions have become preeminent tools in organic synthesis. Free radical-mediated cyclization has developed as a powerful method for preparing various types of cyclic compounds via carbon-carbon bond-forming processes. In order to develop effective and convenient methods for the synthesis of biologically active cyclic amines, we have focused our efforts on radical reactions using aldehydes, ketones,and C-C multiple bonds as a radical precursor and/or an oxime ether, hydrazone, and nitrone as a radical acceptor. In this lecture, I would like to talk on radical addition-cyclization of oxime ether and its application to the synthesis of martinellines.

  7. Hemispheric average Cl atom concentration from 13C/12C ratios in atmospheric methane

    Directory of Open Access Journals (Sweden)

    D. Lowe

    2004-05-01

    Full Text Available Methane is a significant atmospheric trace gas in the context of greenhouse warming and climate change. The dominant sink of atmospheric methane is the hydroxyl radical (OH. Recently, a mechanism for production of chlorine radicals (Cl in the marine boundary layer (MBL via bromine autocatalysis has been proposed. The importance of this mechanism in producing a methane sink is not clear at present because of the difficulty of in-situ direct measurement of Cl. However, the large kinetic isotope effect of Cl compared with OH produces a large fractionation of 13C compared with 12C in atmospheric methane. This property can be used to estimate the likely size of the methane sink attributable to MBL Cl. By taking account of the mixing of MBL air into the free troposphere, we estimate that the global methane sink due to reaction with Cl atoms in the MBL could be as large as 19 Tg yr−1, or about 3.3% of the total CH4 sink.

  8. Radicalization In Pakistan And The Spread Of Radical Islam In Pakistan

    Directory of Open Access Journals (Sweden)

    Bahir ahmad

    2015-08-01

    Full Text Available ABSTRACT It is pertinent to mention that radicalism is not intrinsic to Islam and radical interpretations of the religion or for that matter may occur within any way of life and religion Saikal 2003 and yet the question remains as to why Muslims in certain geographical regions have more radical approaches towards their religion and also that what are the causes of such radicalization. Becoming a radical Muslim is not even a matter of a day nor is it a sudden process. There are several reasons behind making a person radical peaceful angry smiling or tolerant. For knowing the reason behind radicalization or radicals persons one has to understand the causes. Tracing these causes is one of the ways to eliminate such behavior. The first step in the elimination of the radical sentiments in a person is to develop peace in his personality Fair Malhotra amp Shapiro 2010. The chapter which has been addressed here is going to shed light on the roots and symptoms of the radicalism. There will be a brief discussion on how the roots of radicalism can be traced and can be eliminated. The assessment and discussion will be conducted on the parameters of the economy media politics and theology from social cultural point of view. According to the analysis of Ahrari 2000 political factor is one of the major and direct factors which have resulted in causing of the radicalism. These factors however intertwine with one another. Radical actions cannot take place only because of the political factors.

  9. Involvement of free radicals in breast cancer

    OpenAIRE

    Ríos-Arrabal, Sandra; Artacho-Cordón, Francisco; León, Josefa; Román-Marinetto, Elisa; del Mar Salinas-Asensio, María; Calvente, Irene; Núñez, Maria Isabel

    2013-01-01

    Researchers have recently shown an increased interest in free radicals and their role in the tumor microenvironment. Free radicals are molecules with high instability and reactivity due to the presence of an odd number of electrons in the outermost orbit of their atoms. Free radicals include reactive oxygen and nitrogen species, which are key players in the initiation and progression of tumor cells and enhance their metastatic potential. In fact, they are now considered a hallmark of cancer. ...

  10. Quantitative determination of atmospheric hydroperoxyl radical

    Energy Technology Data Exchange (ETDEWEB)

    Springston, Stephen R. (Upton, NY); Lloyd, Judith (Westbury, NY); Zheng, Jun (Stony Brook, NY)

    2007-10-23

    A method for the quantitative determination of atmospheric hydroperoxyl radical comprising: (a) contacting a liquid phase atmospheric sample with a chemiluminescent compound which luminesces on contact with hydroperoxyl radical; (b) determining luminescence intensity from the liquid phase atmospheric sample; and (c) comparing said luminescence intensity from the liquid phase atmospheric sample to a standard luminescence intensity for hydroperoxyl radical. An apparatus for automating the method is also included.

  11. EPR spin trapping of protein radicals

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan; Hawkins, Clare L

    2004-01-01

    Electron paramagnetic resonance (EPR) spin trapping was originally developed to aid the detection of low-molecular-mass radicals formed in chemical systems. It has subsequently found widespread use in biology and medicine for the direct detection of radical species formed during oxidative stress...... and via enzymatic reactions. Over the last 15 years this technique has also found increasing use in detecting and identifying radicals formed on biological macromolecules as a result of either radical reactions or enzymatic processes. Though the EPR signals that result from the trapping of large, slowly...

  12. Near-Ring Radicals and Class Pairs

    Institute of Scientific and Technical Information of China (English)

    L.Godloza; N.J.Groenewald; W.A.Olivier

    2005-01-01

    For near-ring ideal mappings p1 and p2, we investigate radical theoretical properties of and the relationship among the class pairs (p1: p2), (Sp2: Sp1) and (Rp2:Rp1). Conditions on p1 and p2 are given for a general class pair to form a radical class of various types. These types include the Plotkin and KA-radical varieties. A number of examples are shown to motivate the suitability of the theory of Hoehnke-radicals over KA-radicals when radical pairs of near-rings are studied. In particular, it is shown that (pc: P3) forms a KA-radical class, where Pc denotes the class of completely prime nearrings and P3 the class of 3-prime near-rings. This gives another near-ring generalization of the 2-primal ring concept. The theory of radical pairs are also used to show that in general the class of 3-semiprime near-rings is not the semisimple class of the 3-prime radical.

  13. Experimental studies of the kinetics of small polyatomic free radicals in combustion reactions; Moniatomisten radikaalien kinetiikka palamisreaktioissa, kokeellinen tutkimus

    Energy Technology Data Exchange (ETDEWEB)

    Seetula, J. [Helsinki Univ. (Finland). Lab. of Physical Chemistry

    1996-12-01

    The kinetics of the reactions of CH{sub 2}Cl, CHClBr, CH{sub 3}CCl{sub 2} and CCl{sub 3}, with Cl{sub 2} has been investigated in a tubular reactor coupled to a photoionization mass spectrometer. The radicals of interest, R, were generated homogeneously in the reactor by pulse 248 nm exciplex laser photolysis. The decay of R was monitored as a function of Cl{sub 2} concentration under pseudo-first-order condition to determine the rate constant as a function of temperature pressure. The reactions were studied separately over a temperature range up to a temperature of 873 K. The rate constants of CH{sub 2}Cl, CHClBr and CH{sub 3}CCl{sub 2} radicals determined were fitted to three-parameter Arrhenius-type expression (with units of cm{sup 3} molecule{sup -1} s{sup -1}): k(CH{sub 2}Cl) = 1.05x10{sup -16} x (T){sup 1.4} x exp(-357 J mol{sup -1} / RT), k(CHClBr) = 5.83x10{sup -20} x (T){sup 2.3} x exp(-300 J mol{sup -1}/ RT) and k(CH{sub 3}CCl{sub 2}) 1.10x10{sup -}2{sup 6} x (T){sup 4.3} x exp(15000 J mol{sup -1}/ RT). The rate constants CCl{sub 3} radical were fitted to a two-parameter Arrhenius expression (units in cm{sup 3} molecule{sup -1} s{sup -1}): k(CCl{sub 3}) = (8.1 +- 6.7)10{sup -l3} exp[-(25.0 +- 8.7) kJ mol{sup -1}/ RT]. An Arrhenius expression for the reaction of Cl+CCl{sub 4} -> <- CCl{sub 3}+Cl{sub 2} is also obtained from the kinetics of the reaction of CCl{sub 3} radical with Cl{sub 2} combined with the known heat of formation and entropy values of CCl{sub 3} free radical to be as follows (in units cm{sup 3} molecule{sup -1-}5 s{sup -1}): k(Cl+CCl{sub 4}) = (3.9 + 3.2)10{sup -10} exp[-(71 + 9) kJ mol{sup -1}/ RT]. The error limits stated are l{sigma}+Student`s t and base on statistical uncertainties only. (author)

  14. The Games Radicals Play: Special Issue on Free Radicals and Radical Ions

    Directory of Open Access Journals (Sweden)

    John C. Walton

    2015-02-01

    Full Text Available Chemistry and Physics have aptly been described as “most excellent children of Intellect and Art” [1]. Both these “children” engage with many playthings, and molecules rank as one of their first favorites, especially radicals, which are amongst the most lively and exciting. Checking out radicals dancing to the music of entropy round their potential energy ballrooms is surely both entertaining and enlightening. Radicals’ old favorite convolutions are noteworthy, but the new styles, modes and arrangements appearing on the scene are even more interesting. Some of these are ephemeral and enjoy only a brief appearance, others are retro-types reappearing in new guises, still others are genuinely new and “go viral” in the scientific world. This Special Issue of Molecules contains the observations and reflections of a select group of chemists and physicists fascinated by this spectacle. It contains an eclectic mix reflecting on new modes and advances as well as on permutations and combinations that revive mature themes. [...

  15. Inhibitory effects of chitosan on superoxide anion radicals and lipid free radicals

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    With the electron spin resonance (ESR) technique, the inhibitory effects of chitosan on superoxide anion radicals and linoleic acid lipid radicals were found. The inhibitory ratio E for these two kinds of radicals is in proportion to the concentration of chitosan. It was also observed that E for linoleic acid lipid radicals increased with the increase of the degree of deacetylation and decreased with the increase of the molecular weight of chitosan.

  16. Is Radical Innovation Management Misunderstood?

    DEFF Research Database (Denmark)

    Kristiansen, Jimmi Normann; Gertsen, Frank

    2015-01-01

    This paper poses a critical view on radical innovation (RI) management research and practice. The study investigates how expected RI performance influences firms’ under- standing of their RI capability. RI performance is often based on output measures such as market shares or fiscal return....... On the contrary, RI capability building advocates for ex- ploration, learning, and accepting uncertainty. Hence, RI capability building often focuses on the processes of the firms, and not the outcome. Thus, it is argued that the RI capability- building and RI performance expectations are based on different...... managerial orientations. Coupling a discussion of the literature with case findings from four large international firms, this paper identifies a discrepancy between RI capability-building and RI perfor- mance within literature and practice. This is regarded to be a major contributing factor to RI program...

  17. Photoionisation of the tropyl radical

    Directory of Open Access Journals (Sweden)

    Kathrin H. Fischer

    2013-04-01

    Full Text Available We present a study on the photoionisation of the cycloheptatrienyl (tropyl radical, C7H7, using tunable vacuum ultraviolet synchrotron radiation. Tropyl is generated by flash pyrolysis from bitropyl. Ions and electrons are detected in coincidence, permitting us to record mass-selected photoelectron spectra. The threshold photoelectron spectrum of tropyl, corresponding to the X+ 1A1’ ← X 2E2” transition, reveals an ionisation energy of 6.23 ± 0.02 eV, in good agreement with Rydberg extrapolations, but slightly lower than the value derived from earlier photoelectron spectra. Several vibrations can be resolved and are reassigned to the C–C stretch mode ν16+ and to a combination of ν16+ with the ring breathing mode ν2+. Above 10.55 eV dissociative photoionisation of tropyl is observed, leading to the formation of C5H5+ and C2H2.

  18. Students' Ideas and Radical Constructivism

    Science.gov (United States)

    Sánchez Gómez, Pedro J.

    2016-08-01

    In this article, I study, from the point of view of the analytic philosophy of mind, the compatibility of students' ideas studies (SIS) with radical constructivism (RC). I demonstrate that RC is based on a psychology of narrow mental states; that is, the idea that the mental content of an individual can be fully characterised without any reference external to her or him. I show that this fact imposes some severe restrictions to SIS to be incorporated into RC. In particular, I argue that only qualitative studies can comply with the requirement of narrowness. Nevertheless, I propose that quantitative works can be employed as sources of types in order to study token actual students. I use this type-token dichotomy to put forward an outline of a theory of the relation between school contents and mental contents. In this view, token mental contents regarding a given topic can be defined, and probed, only by resorting to typical school contents.

  19. Iron and iron derived radicals

    Energy Technology Data Exchange (ETDEWEB)

    Borg, D.C.; Schaich, K.M.

    1987-04-01

    We have discussed some reactions of iron and iron-derived oxygen radicals that may be important in the production or treatment of tissue injury. Our conclusions challenge, to some extent, the usual lines of thought in this field of research. Insofar as they are born out by subsequent developments, the lessons they teach are two: Think fastexclamation Think smallexclamation In other words, think of the many fast reactions that can rapidly alter the production and fate of highly reactive intermediates, and when considering the impact of competitive reactions on such species, think how they affect the microenvironment (on the molecular scale) ''seen'' by each reactive molecule. 21 refs., 3 figs., 1 tab.

  20. Supporting radical front end innovation

    DEFF Research Database (Denmark)

    Aagaard, Annabeth; Gertsen, Frank

    2011-01-01

    ). Pharmaceutical innovation is unique, as it opposed to most other industries’ product development is science-driven and not customer-driven. In addition, the pharmaceutical FEI, as represented by research, lasts up to 5 years and the entire R&D process constitutes a period of 10-12 years, which is highly...... regulated by external authorities, e.g. The American Food and Drug Administration (FDA). The research aim of this paper is: to contribute to the field of FEI by studying how FEI can be actively supported within the industry specific context of the pharmaceutical industry, and through a conceptual discussion...... of FEI, pharmaceutical FEI and radical innovation. Based on this understanding, empirical research through exploratory and inductive case studies is analyzed. The value added and the contribution of this article to the existing FEI literature is in the study of the theoretical fields of research...

  1. ClEST cluster :Cl_singleton1538 [ClEST

    Lifescience Database Archive (English)

    Full Text Available Cl_singleton1538 dead (asp-glu-ala-asp) box polypeptide 5 Cimex lectularius nuclear...fw14079 1 similar to DEAD/H (Asp-Glu-Ala-Asp/His) box polypeptide 5 (RNA helicase 68kDa) [Xenopus laevis] NP_001079703 6.59566E-23 ...

  2. Kinetics of the self reaction of cyclohexyl radicals.

    Science.gov (United States)

    Loginova, Ksenia A; Knyazev, Vadim D

    2011-08-11

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

  3. Victimology: A Consideration of the Radical Critique.

    Science.gov (United States)

    Friedrichs, David O.

    1983-01-01

    Discusses the emergence of a new radical model in criminology and a new subdisciplinary area of concern, victimology, with roots in Marx and Engels' original formulations. Argues that the radical understanding of victimization provides an important corrective to mainstream approaches and broadens the focus of the concept of victimization. (JAC)

  4. Localization versus delocalization in diamine radical cations

    DEFF Research Database (Denmark)

    Brouwer, A.M.; Wiering, P.G.; Zwier, J.M.;

    1997-01-01

    The optical absorption spectrum of the radical cation of 1,4-diphenylpiperazine 2a shows a strong transition in the near-IR, and only a weak band at 445 nm, in the region where aniline radical cations normally absorb strongly. This indicates that the charge and spin are delocalized over the two...

  5. What Is Radical in School Geography Today?

    Science.gov (United States)

    Morgan, John

    2011-01-01

    This article addresses the question of what "radical school geography" might look like in the present historical moment. It traces the history of a distinctive "radical" tradition in school geography, most prominently associated with the work of John Huckle, who argued for the importance of understanding the content and pedagogy of school…

  6. Radical Behaviorism and Buddhism: Complementarities and Conflicts

    Science.gov (United States)

    Diller, James W.; Lattal, Kennon A.

    2008-01-01

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

  7. Resonance raman studies of phenylcyclopropane radical cations

    NARCIS (Netherlands)

    Godbout, J.T.; Zuilhof, H.; Heim, G.; Gould, I.R.; Goodman, J.L.; Dinnocenzo, J.P.; Myers Kelley, A.

    2000-01-01

    Resonance Raman spectra of the radical cations of phenylcyclopropane and trans-1-phenyl-2-methylcyclopropane are reported. A near-UV pump pulse excites a photosensitizer which oxidizes the species of interest, and a visible probe pulse delayed by 35 ns obtains the spectrum of the radical ion. The tr

  8. Free Radical Mechanisms in Autoxidation Processes.

    Science.gov (United States)

    Simic, Michael G.

    1981-01-01

    Discusses the use of steady-state radiation chemistry and pulse radiolysis for the generation of initial free radicals and formation of peroxy radicals in the autoxidation process. Provides information regarding the autoxidation process. Defines autoxidation reactions and antioxidant action. (CS)

  9. Combined results of searches for the standard model Higgs boson in pp collisions at {radical}(s)=7 TeV

    Energy Technology Data Exchange (ETDEWEB)

    Chatrchyan, S.; Khachatryan, V.; Sirunyan, A.M.; Tumasyan, A. [Yerevan Physics Institute, Yerevan (Armenia); Adam, W.; Bergauer, T.; Dragicevic, M.; Eroe, J.; Fabjan, C.; Friedl, M.; Fruehwirth, R.; Ghete, V.M.; Hammer, J.; Hoch, M.; Hoermann, N.; Hrubec, J.; Jeitler, M.; Kiesenhofer, W.; Krammer, M.; Liko, D. [Institut fuer Hochenergiephysik der OeAW, Wien (Austria); and others

    2012-03-29

    Combined results are reported from searches for the standard model Higgs boson in proton-proton collisions at {radical}(s)=7 TeV in five Higgs boson decay modes: {gamma}{gamma}, bb, {tau}{tau}, WW, and ZZ. The explored Higgs boson mass range is 110-600 GeV. The analysed data correspond to an integrated luminosity of 4.6-4.8 fb{sup -1}. The expected excluded mass range in the absence of the standard model Higgs boson is 118-543 GeV at 95% CL. The observed results exclude the standard model Higgs boson in the mass range 127-600 GeV at 95% CL, and in the mass range 129-525 GeV at 99% CL. An excess of events above the expected standard model background is observed at the low end of the explored mass range making the observed limits weaker than expected in the absence of a signal. The largest excess, with a local significance of 3.1{sigma}, is observed for a Higgs boson mass hypothesis of 124 GeV. The global significance of observing an excess with a local significance {>=}3.1{sigma} anywhere in the search range 110-600 (110-145) GeV is estimated to be 1.5{sigma}(2.1{sigma}). More data are required to ascertain the origin of the observed excess.

  10. Place of Schauta's radical vaginal hysterectomy.

    Science.gov (United States)

    Roy, Michel; Plante, Marie

    2011-04-01

    Women affected by early stage invasive cancer of the cervix are usually treated by surgery. Radical abdominal hysterectomy with pelvic lymphadenectomy is the most widely used technique. Because the morbidity of the abdominal approach can be important, the radical vaginal hysterectomy has gained acceptance in gynaecologic oncology. New instrumentation in laparoscopy also opens the possibility of treating cervical cancer by laparoscopically assisted vaginal radical hysterectomy and also total laparoscopic radical hysterectomy. Before these techniques become widely accepted, it has to be shown that safety and efficacy are comparable with the 'standard' abdominal approach. In this chapter, we review the technique of radical vaginal hysterectomy with pelvic lymphadenectomy and evaluate results of published studies, comparing the abdominal, vaginal and laparoscopic approaches.

  11. Measurement of the absorption cross sections of SiCl_4, SiCl_3, SiCl_2 and Cl at H Lyman-α wavelength

    OpenAIRE

    Mével, R.; Catoire, L.; M. Fikri; Roth, P.

    2013-01-01

    Atomic resonance absorption spectroscopy coupled with a shock tube is a powerful technique for studying high temperature dynamics of reactive systems. Presently, high temperature pyrolysis of SiCl_4–Ar mixtures has been studied behind reflected shock waves. Using time-resolved absorption profiles at 121.6 nm and a detailed reaction model, the absorption cross sections of SiCl_4, SiCl_3, SiCl_2 and Cl have been measured. Results agree well with available data for SiCl_4 and constitute, to our ...

  12. Pilot study of radical hysterectomy versus radical trachelectomy on sexual distress.

    Science.gov (United States)

    Brotto, Lori A; Smith, Kelly B; Breckon, Erin; Plante, Marie

    2013-01-01

    Radical trachelectomy, which leaves the uterus intact, has emerged as a desirable surgical option for eligible women with early-stage cervical cancer who wish to preserve fertility. The available data suggest excellent obstetrical outcomes with radical trachelectomy, and no differences in sexual responding between radical trachelectomy and radical hysterectomy. There is a need to examine the effect of radical hysterectomy on sexual distress given that it is distinct from sexual function. Participants were 34 women diagnosed with early-stage cervical cancer. The authors report 1-month postsurgery data for 29 women (radical hysterectomy group: n = 17, M age = 41.8 years; radical trachelectomy group: n = 12, M age = 31.8 years), and 6-month follow-up data on 26 women. Whereas both groups experienced an increase in sex-related distress immediately after surgery, distress continued to increase 6 months after surgery for the radical hysterectomy group but decreased in the radical trachelectomy group. There were no between-group differences in mood, anxiety, or general measures of health. The decrease in sex-related distress in the radical trachelectomy but not in the radical hysterectomy group suggests that the preservation of fertility may have attenuated sex-related distress. Care providers should counsel women exploring surgical options for cervical cancer about potential sex distress-related sequelae.

  13. clOpenCL - supporting distributed heterogeneous computing in HPC clusters

    OpenAIRE

    Alves, Albano; Rufino, José; Pina, António; Santos, Luis Paulo

    2013-01-01

    Clusters that combine heterogeneous compute device architectures, coupled with novel programming models, have created a true alternative to traditional (homogeneous) cluster computing, allowing to leverage the performance of parallel applications. In this paper we introduce clOpenCL, a platform that supports the simple deployment and efficient running of OpenCL-based parallel applications that may span several cluster nodes, expanding the original single-node OpenCL model. clOpenCL is deploye...

  14. Coupled evolution of BrOx-ClOx-HOx-NOx chemistry during bromine-catalyzed ozone depletion events in the arctic boundary layer

    OpenAIRE

    M. J. Evans; Jacob, Daniel James; Atlas, E.; Cantrell, C; Eisele, F.; Flocke, F.; Fried, A.; Mauldin, R; Ridley, B.; Wert, B; Talbot, R.; Blake, D.; B. Heikes; Snow, J.; Walega, J

    2003-01-01

    Extensive chemical characterization of ozone (O3) depletion events in the Arctic boundary layer during the TOPSE aircraft mission in March–May 2000 enables analysis of the coupled chemical evolution of bromine (BrOx), chlorine (ClOx), hydrogen oxide (HOx) and nitrogen oxide (NOx) radicals during these events. We project the TOPSE observations onto an O3 chemical coordinate to construct a chronology of radical chemistry during O3 depletion events, and we compare this chronology to results from...

  15. Multicomponent versus domino reactions: One-pot free-radical synthesis of β-amino-ethers and β-amino-alcohols

    Directory of Open Access Journals (Sweden)

    Bianca Rossi

    2015-01-01

    Full Text Available Following an optimized multicomponent procedure, an aryl amine, a ketone, and a cyclic ether or an alcohol molecule are assembled in a one-pot synthesis by nucleophilic radical addition of ketyl radicals to ketimines generated in situ. The reaction occurs under mild conditions by mediation of the TiCl4/Zn/t-BuOOH system, leading to the formation of quaternary β-amino-ethers and -alcohols. The new reaction conditions guarantee good selectivity by preventing the formation of secondary products. The secondary products are possibly derived from a competitive domino reaction, which involves further oxidation of the ketyl radicals.

  16. 75 FR 59071 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2B16 (CL-604 Variants (Including CL-605...

    Science.gov (United States)

    2010-09-27

    ... in the Federal Register on June 2, 2010 (75 FR 30740). That NPRM proposed to correct an unsafe...'' under the DOT Regulatory Policies and Procedures (44 FR 11034, February 26, 1979); and 3. Will not have.... Model CL-600-2B16 (CL- 604 Variants (Including CL-605 Marketing Variant)) Airplanes AGENCY:...

  17. Structure and function of collectin liver 1 (CL-L1) and collectin 11 (CL-11, CL-K1)

    DEFF Research Database (Denmark)

    Selman, Lana; Hansen, Soren

    2012-01-01

    to l-fucose and d-mannose, whereas CL-L1 shows preference for d-mannose, d-fucose, N-acetylglucosamine, and surprisingly also d-galactose. CL-11 binds to various microorganisms including Escherichia coli, Candida albicans and Influenza A virus. Polymorphisms in the CL-11 gene (COLEC11) leading...

  18. Mucosal cytokine network in inflammatory bowel disease Akira Andoh,Yuhki Yagi,Makoto Shioya,Atsushi Nishida,Tomoyuki Tsujikawa,Yoshihide Fujiyama Akira Andoh,Yuhki Yagi,Makoto Shioya,

    Institute of Scientific and Technical Information of China (English)

    Atsushi Nishida; Tomoyuki Tsujikawa; Yoshihide FUjiyama; Yuhki Yagi; Makoto Shioya; Akira Andoh

    2008-01-01

    Inflammatory bowel disease(IBD),ulcerative colitis(UC)and Crohn's disease(CD)are characterized by ongoing mucosal inflammation in which dysfunction of the host immunologic response against dietary factors and commensal bacteria is involved.The chronic inflammatory process leads to disruption of the epithelial barrier,and the fcIrmation of epithelial ulceration.This permits easy access for the luminal microbiota and dietary antigens to cells resident in the lamina propria,and stimulates further pathological immune cell responses.Cytokines are essential mediators of the interactions between activated immune cells and nonimmune cells,including epithelial and mesenchymal cells.The clinicaI efficacy of targeting TNF-α clearly indicates that cytokines are the therapeutic targets in IBD patients.In this manuscript,we focus on the biological activities of recently-reported cytokines[Inter-leukin(IL)-17 cytokine family,IL-31 and IL-32],which might play a role through interaction with TNF-α in the pathophysiology of IBD.(C)2008 The WJG Press.All rights reserved.

  19. Customers as Partners in Radical Service Innovation

    DEFF Research Database (Denmark)

    Scupola, Ada; Nicolajsen, Hanne Westh

    2009-01-01

      Purpose- The main purpose of this paper is to investigate customer involvement and related challenges in radical service innovations in engineering consulting services Design/methodology/approach - The paper uses a case study approach and so called rich descriptions to investigate customer...... involvement, roles and related challenges and conditions in radical service innovations.Findings- One main finding is that customers can engage in radical service innovations in engineering consultancy services and may play a decisive role. In doing this they most likely take on all the three user involvement...... in engineering consulting services on the base of an in depth case study of an engineering consultancy. Research paper...

  20. Radical pancreaticoduodenectomy for benign disease.

    LENUS (Irish Health Repository)

    Kavanagh, D O

    2008-01-01

    Whipple\\'s procedure is the treatment of choice for pancreatic and periampullary malignancies. Preoperative histological confirmation of malignancy is frequently unavailable and some patients will subsequently be found to have benign disease. Here, we review our experience with Whipple\\'s procedure for patients ultimately proven to have benign disease. The medical records of all patients who underwent Whipple\\'s procedure during a 15-year period (1987-2002) were reviewed; 112 patients underwent the procedure for suspected malignancy. In eight cases, the final histology was benign (7.1%). One additional patient was known to have benign disease at resection. The mean age was 50 years (range: 30-75). The major presenting features included jaundice (five), pain (two), gastric outlet obstruction (one), and recurrent gastrointestinal haemorrhage (one). Investigations included ultrasound (eight), computerised tomography (eight), endoscopic retrograde cholangiopancreatography (seven; of these, four patients had a stent inserted and three patients had sampling for cytology), and endoscopic ultrasound (two). The pathological diagnosis included benign biliary stricture (two), chronic pancreatitis (two), choledochal cyst (one), inflammatory pseudotumour (one), cystic duodenal wall dysplasia (one), duodenal angiodysplasia (one), and granular cell neoplasm (one). There was no operative mortality. Morbidity included intra-abdominal collection (one), anastomotic leak (one), liver abscess (one), and myocardial infarction (one). All patients remain alive and well at mean follow-up of 41 months. Despite recent advances in diagnostic imaging, 8% of the patients undergoing Whipple\\'s procedure had benign disease. A range of unusual pathological entities can mimic malignancy. Accurate preoperative histological diagnosis may have allowed a less radical operation to be performed. Endoscopic ultrasound-guided fine needle aspirate (EUS-FNA) may reduce the need for Whipple\\'s operation

  1. Radical Pancreaticoduodenectomy for Benign Disease

    Directory of Open Access Journals (Sweden)

    D. O. Kavanagh

    2008-01-01

    Full Text Available Whipple's procedure is the treatment of choice for pancreatic and periampullary malignancies. Preoperative histological confirmation of malignancy is frequently unavailable and some patients will subsequently be found to have benign disease. Here, we review our experience with Whipple's procedure for patients ultimately proven to have benign disease. The medical records of all patients who underwent Whipple's procedure during a 15-year period (1987–2002 were reviewed; 112 patients underwent the procedure for suspected malignancy. In eight cases, the final histology was benign (7.1%. One additional patient was known to have benign disease at resection. The mean age was 50 years (range: 30–75. The major presenting features included jaundice (five, pain (two, gastric outlet obstruction (one, and recurrent gastrointestinal haemorrhage (one. Investigations included ultrasound (eight, computerised tomography (eight, endoscopic retrograde cholangiopancreatography (seven; of these, four patients had a stent inserted and three patients had sampling for cytology, and endoscopic ultrasound (two. The pathological diagnosis included benign biliary stricture (two, chronic pancreatitis (two, choledochal cyst (one, inflammatory pseudotumour (one, cystic duodenal wall dysplasia (one, duodenal angiodysplasia (one, and granular cell neoplasm (one. There was no operative mortality. Morbidity included intra-abdominal collection (one, anastomotic leak (one, liver abscess (one, and myocardial infarction (one. All patients remain alive and well at mean follow-up of 41 months. Despite recent advances in diagnostic imaging, 8% of the patients undergoing Whipple'’s procedure had benign disease. A range of unusual pathological entities can mimic malignancy. Accurate preoperative histological diagnosis may have allowed a less radical operation to be performed. Endoscopic ultrasound–guided fine needle aspirate (EUS-FNA may reduce the need for Whipple's operation in

  2. An experimental and theoretical study of the electronic spectrum of the HBCl free radical

    International Nuclear Information System (INIS)

    Following our previous discovery of the spectra of the HBX (X = F, Cl, and Br) free radicals [S.-G. He, F. X. Sunahori, and D. J. Clouthier, J. Am. Chem. Soc. 127, 10814 (2005)], the A~2A″Π−X~2A′ band systems of the HBCl and DBCl free radicals have been studied in detail. The radicals have been prepared in a pulsed electric discharge jet using a precursor mixture of BCl3 and H2 or D2 in high pressure argon. Laser-induced fluorescence (LIF) and single vibronic level emission spectra have been recorded to map out the ground and excited state vibrational energy levels. The band system involves a linear-bent transition between the two Renner-Teller components of what would be a 2Π electronic state at linearity. We have used high level ab initio theory to calculate the ground and excited state potential energy surfaces and have determined the vibronic energy levels variationally. The theory results were used to assign the LIF spectra which involve transitions from the ground state zero-point level to high vibrational levels of the excited state. The correspondence between theory and experiment, including the transition frequencies, upper state band symmetries, and H, B, and Cl isotope shifts, was used to validate the assignments

  3. Radicalization and the Use of Social Media

    Directory of Open Access Journals (Sweden)

    Robin Thompson

    2011-01-01

    Full Text Available The use of social media tools by individuals and organizations to radicalize individuals for political and social change has become increasingly popular as the Internet penetrates more of the world and mobile computing devices are more accessible. To establish a construct for radicalization,the power and reach of social media will be described so there is common understanding of what social media is and how it is utilized by various individuals and groups. The second section will answer the question of why social media applications are the perfect platform for the radical voice. Finally, the use of social media and its influence in radicalizing populations in Northern Africa and the Middle East during 2011 will be analyzed and recommendations proposed.

  4. Magnetic Trapping of Cold Methyl Radicals

    CERN Document Server

    Liu, Yang; Djuricanin, Pavle; Zhou, Sida; Zhong, Wei; Mittertreiner, Tony; Carty, David; Momose, Takamasa

    2016-01-01

    We have demonstrated that a supersonic beam of methyl radicals (CH3) in the ground rotational state of both para and ortho species has been slowed down to a standstill with a magnetic molecular decelerator, and successfully captured spatially in an anti-Helmholtz magnetic trap for > 1 s. The translational temperature of the trapped CH3 radicals was about 200 mK. The methyl radical is a non-polar polyatomic molecule, which is predicted to be an ideal system for further cooling below 1 mK via sympathetic cooling with ultracold atoms. In addition, it is a highly reactive intermediate that plays an important role in various processes in cold environments such as planetary atmospheres and the interstellar medium. The demonstrated trapping capability of methyl radicals opens up various possibilities for realizing ultracold ensembles of molecules towards Bose-Einstein condensation of polyatomic molecules and investigations of reactions governed by quantum statistics.

  5. Rigid Ideals and Radicals of Ore Extensions

    Institute of Scientific and Technical Information of China (English)

    Chan Yong Hong; Tai Keun Kwak; S. Tariq Rizvi

    2005-01-01

    For an endomorphism σ of a ring R, Krempa called σ a rigid endomorphism if aσ(a) = 0 implies a= 0 for a ∈ R. A ring R is called rigid if there exists a rigid endomorphism of R. In this paper, we extend the σ-rigid property of a ring R to an ideal of R. For a σ-ideal Ⅰ of a ring R, we call Ⅰ a σ-rigid ideal if aσ(a) ∈Ⅰ implies a ∈Ⅰ for a ∈ R. We characterize σ-rigid ideals and study related properties. The connections of the prime radical and the upper nil radical of R with the prime radical and the upper nil radical of the Ore extension R[x; σ, δ], respectively, are also investigated.

  6. Customers as Partners in Radical Service Innovation

    DEFF Research Database (Denmark)

    Scupola, Ada; Nicolajsen, Hanne Westh

    2009-01-01

    ongoing collaboration where creativity and trial and error are crucial. These needs require new ways of communicating and interacting between customer and consultants. Originality/value- This article is original because it generates new insights into conditions and challenges in radical innovations in......  Purpose- The main purpose of this paper is to investigate customer involvement and related challenges in radical service innovations in engineering consulting services Design/methodology/approach - The paper uses a case study approach and so called rich descriptions to investigate customer...... involvement, roles and related challenges and conditions in radical service innovations.Findings- One main finding is that customers can engage in radical service innovations in engineering consultancy services and may play a decisive role. In doing this they most likely take on all the three user involvement...

  7. Neo-liberal Governing of 'Radicals'

    DEFF Research Database (Denmark)

    Lindekilde, Lasse

    2012-01-01

    The Danish government’s counter-radicalization Action Plan of 2009 had intended and unintended effects. Primarily targeting Danish Muslims, it employs neoliberal governmentality approaches of governance through individual support and response, information and knowledge, empowerment, surveillance ...

  8. Innovation Type, Radicalness, and the Adoption Process.

    Science.gov (United States)

    Damanpour, Fariborz

    1988-01-01

    Reviews studies on the impact of organizational factors on the adoption of innovations along three dimensions (innovation type, innovation radicalness, and stages of adoption), finding considerable agreement. Proposes a research agenda for future studies. (SR)

  9. Optimal pain management for radical prostatectomy surgery

    DEFF Research Database (Denmark)

    Joshi, Grish P; Jaschinski, Thomas; Bonnet, Francis;

    2015-01-01

    BACKGROUND: Increase in the diagnosis of prostate cancer has increased the incidence of radical prostatectomy. However, the literature assessing pain therapy for this procedure has not been systematically evaluated. Thus, optimal pain therapy for patients undergoing radical prostatectomy remains ...... invasive surgical procedures. Finally, while we wait for appropriate procedure specific evidence from publication of adequate studies assessing optimal pain management after radical prostatectomy, we propose a basic analgesic guideline....... treatments studied improved pain relief and/or reduced opioid requirements. However, there were significant differences in the study designs and the variables evaluated, precluding quantitative analysis and consensus recommendations. CONCLUSIONS: This systematic review reveals that there is a lack...... of evidence to develop an optimal pain management protocol in patients undergoing radical prostatectomy. Most studies assessed unimodal analgesic approaches rather than a multimodal technique. There is a need for more procedure-specific studies comparing pain and analgesic requirements for open and minimally...

  10. Radical-Local Teaching and Learning

    DEFF Research Database (Denmark)

    Hedegaard, Mariane; Chaiklin, Seth

    , and Aidarova. The second half of the book addresses the central concern of radical-local teaching and learning - how to relate educational practices to children's specific historical and cultural conditions. The experiment was conducted for an academic year in an afterschool programme in the East Harlem......Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded...... radical-local teaching and learning approach. The first half of the book introduces the idea of radical-local teaching and learning and develops the theoretical background for this perspective, drawing on the cultural-historical research tradition, particularly from Vygotsky, El'konin, Davydov...

  11. Fast beam studies of free radical photodissociation

    Energy Technology Data Exchange (ETDEWEB)

    Neumark, D.M. [Lawrence Berkeley Laboratory, CA (United States)

    1993-12-01

    The authors have developed a novel technique for studying the photodissociation spectroscopy and dynamics of free radicals. In these experiments, radicals are generated by laser photodetachment of a fast (6-8 keV) mass-selected negative ion beam. The resulting radicals are photodissociated with a second laser, and the photofragments are collected and detected with high efficiency using a microchannel plate detector. The overall process is: ABC{sup -} {yields} ABC + e{sup -} {yields} A + BC, AB + C. Two types of fragment detection schemes are used. To map out the photodissociation cross-section of the radical, the photodissociation laser is scanned and the total photofragment yield is measured as a function of wavelength. In other experiments, the photodissociation frequency is fixed and the photofragment masses, kinetic energy release, and scattering angle is determined for each photodissociation event.

  12. Biodegradation of the Nitramine Explosive CL-20

    OpenAIRE

    Trott, Sandra; Nishino, Shirley F.; Hawari, Jalal; Spain, Jim C.

    2003-01-01

    The cyclic nitramine explosive CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) was examined in soil microcosms to determine whether it is biodegradable. CL-20 was incubated with a variety of soils. The explosive disappeared in all microcosms except the controls in which microbial activity had been inhibited. CL-20 was degraded most rapidly in garden soil. After 2 days of incubation, about 80% of the initial CL-20 had disappeared. A CL-20-degrading bacterial strain, Agrobact...

  13. Spectroelectrochemistry of EuCl3 in four molten salt eutectics; 3 LiCl – NaCl, 3 LiCl – 2 KCl, LiCl – RbCl, and 3 LiCl – 2 CsCl; at 873 K

    Energy Technology Data Exchange (ETDEWEB)

    Schroll, Cynthia A.; Chatterjee, Sayandev; Levitskaia, Tatiana G.; Heineman, William R.; Bryan, Samuel A.

    2016-05-17

    Key electrochemical properties affecting pyroprocessing of nuclear fuel were examined in four eutectic melts using using Eu3+/2+ as a representative probe. We report the electrochemical and spectroelectrochemical behavior of EuCl3 in four molten salt eutectics (3 LiCl – NaCl, 3 LiCl – 2 KCl, LiCl – RbCl and 3 LiCl – 2 CsCl) at 873 K. Cyclic voltammetry was used to determine the redox potential for Eu3+/2+ and the applied potentials for spectroelectrochemistry. Single step chronoabsorptometry and thin-layer spectroelectrochemistry were used to obtain the number of electrons transferred, redox potentials and diffusion coefficients for Eu3+ in each eutectic melt. The redox potentials determined by thin-layer spectroelectrochemistry were extremely close to those obtained using cyclic voltammetry. The redox potential for Eu3+/2+ was most positive in the 3 LiCl - NaCl melt, showed a negative shift in the 3 LiCl - 2 KCl melt, and was the most negative in the LiCl - RbCl and 3 LiCl - 2 CsCl eutectics. The diffusion coefficient for Eu3+ followed this same trend; it was the largest in the 3 LiCl - NaCl melt and the smallest in the LiCl - RbCl and 3 LiCl - 2 CsCl melts. The basic one-electron reversible electron transfer for Eu3+/2+ was not changed by melt composition.

  14. Mechanism of the Initial Thermal Decomposition of CL-20 via Molecular Dynamics Simulation%CL-20初始热分解反应机理的分子动力学计算

    Institute of Scientific and Technical Information of China (English)

    张力; 陈朗; 王晨; 伍俊英

    2012-01-01

    基于Reaxff反应力场,采用NPT、NVT系综和Berendsen方法,通过分子动力学计算研究了不同密度和温度下CL-20单分子和超晶胞的初始热解路径.结果表明,CL-20分子中的两种N-NO2键能生成NO2·自由基.单分子CL-20初始热分解中,两种不同类型的N-NO2化学键均能发生断裂生成NO2·自由基和R-(NO2)n(n≤5)碎片,NO2·自由基形成N2O4,N2O4分解为NO、NO3等碎片或重新生成两个NO2·自由基,NO2·自由基与其他中间体发生反应生成N2、HNO3等碎片.CL-20超晶胞的热解初始反应路径与单分子的初始热解反应路径相同,但由于非键相互作用,使得生成NO2·自由基的总量减少.超晶胞CL-20发生热解反应生成的HNO3碎片会继续分解成H2O和N2O5等碎片.%The initial thermal decomposition pathways of supercell structure and signal molecule of CL-20 explosive at various densities and temperatures were studied by molecular dynamics simulations, using Reaxff force field and NPT, NVT ensemble and Berendsen methods. The results show that two types of N—NO2 bond in CL-20 molecule can both form NO2 · radical. The initial pathway of CL-20 molecule is only the N—NO2 dissociation to form NO2 radical fragments and R - (NO2)n (n≤5), then two NO2 · radical fragments quickly form N2O4 , N2O4 could be broken to form NO and NO3 or return to two NO2 · radical fragments, the NO2 · radical and other intermediate fragments form the products as N2 and HNO3. The initial thermal decomposition pathway of supercell is the same with the initial thermal decomposition pathway of signal molecule, but because of the no bond interacting in the CL-20 solid, the number of NO2 · radical is less than the number of NO2 · radical from CL-20 molecule. HNO3 molecules, the thermal fragments of CL-20 supercell, can be decomposed to H2O and N2O5.

  15. Reactions Between Humic Acid Solutions and Excessive ClO2 or Cl2

    Institute of Scientific and Technical Information of China (English)

    GE Yuan-xin; ZHU Zhi-liang; MA Hong-mei; ZHAO Jian-fu

    2007-01-01

    Reactions between humic acid solutions and excessive ClO2 or Cl2 have been investigated. Under various experimental conditions, the removal efficiency of TOC, UV254 and A140 from humic acid solutions were examined. The relationship between the removal efficiency and the consumption of ClO2 or Cl2 was discussed. The results showed that the maximum demand of ClO2 was 2.19 mg/mg TOC for the humic acid solution under the experimental conditions, and that of Cl2 was 1.88 mg/mg TOC. The variation tendency of ClO2 consumption was similar to that of Cl2. TOC of humic acid solutions decreased 15.2% and 15.6% after the reaction with ClO2 or Cl2 respectively. Under the experimental conditions, 21.4% of unsaturated bonds and 52.8% of humic acid color were removed by ClO2 in 168 h. As for Cl2, removal efficiency of unsaturated bonds and humic acid color were 16.8% and 41.7% respectively. Larger molecules from humic acid were oxidized to smaller molecules by ClO2 and Cl2. Higher oxidation potential of ClO2 than that of Cl2 was also indicated by variation of UV254/A410 ratios. The similar tendency, that exhibited faster variation in the initial 24 h, existed for all the research factors.

  16. un clúster empresarial

    Directory of Open Access Journals (Sweden)

    Laura Marcela López Posada

    2006-01-01

    Full Text Available Los clústeres empresariales se han constituido en mecanismos para impulsar la competitividad de sectores en regiones y tradicionalmente han sido analizados desde la perspectiva económica (por su aporte en variables macroeconómicas, pero para su consolidación todo conglomerado empresarial requiere la comprensión de relaciones sociales, culturales y políticas. Resulta difícil estudiar estas relaciones desde teorías organizacionales tradicionales como la estructuralista o la contingencial, y se debe recurrir a otras perspectivas como el neoinstitucionalismo sociológico, enfoque que es utilizado en la presente investigación. La investigación fundamento del artículo se hizo en un sector considerado dinámico para el eje cafetero como es el de herramientas, la cual fue abordada desde un enfoque cualitativo mediante la aplicación de dos guías de entrevista semiestructurada (se aplicaron a treinta empresas de la cadena productiva y a nueve entidades de apoyo, diario de campo y análisis de fuentes documentales. Se concluye que en el clúster predominan el individualismo, la descon- fianza y la ausencia de elementos identitarios, simultáneamente con fuertes lazos comerciales y prácticas de gestión que se han institucionalizado por procesos isomórficos.

  17. Catalytic Radical Domino Reactions in Organic Synthesis

    Science.gov (United States)

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

    2014-01-01

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

  18. Project Radicalization: Why do "they" hate "us"?

    OpenAIRE

    Eggert, Lasse; Foged, Mathias; Jensen, Martin

    2014-01-01

    The phenomenon of global terrorism is still not fully understood by the international community whether within the contingents of public decision-makers, security agencies and researchers. Radicalization as explanation and analytical tool for understanding terrorism has relatively recently gained new prominence. In this project the question of which discourses can be found in the scientific material within the research field of terrorism and radicalization is addressed. A sample of scientifi...

  19. Radicalization and the Use of Social Media

    OpenAIRE

    Robin Thompson

    2011-01-01

    The use of social media tools by individuals and organizations to radicalize individuals for political and social change has become increasingly popular as the Internet penetrates more of the world and mobile computing devices are more accessible. To establish a construct for radicalization,the power and reach of social media will be described so there is common understanding of what social media is and how it is utilized by various individuals and groups. The second section will answer the q...

  20. Free Radicals, Antioxidants in Disease and Health

    OpenAIRE

    Pham-Huy, Lien Ai; He, Hua; Pham-Huy, Chuong

    2008-01-01

    Free radicals and oxidants play a dual role as both toxic and beneficial compounds, since they can be either harmful or helpful to the body. They are produced either from normal cell metabolisms in situ or from external sources (pollution, cigarette smoke, radiation, medication). When an overload of free radicals cannot gradually be destroyed, their accumulation in the body generates a phenomenon called oxidative stress. This process plays a major part in the development of chronic and degene...

  1. Dissociations of copper(II)-containing complexes of aromatic amino acids: radical cations of tryptophan, tyrosine, and phenylalanine.

    Science.gov (United States)

    Siu, Chi-Kit; Ke, Yuyong; Guo, Yuzhu; Hopkinson, Alan C; Siu, K W Michael

    2008-10-14

    The dissociations of two types of copper(II)-containing complexes of tryptophan (Trp), tyrosine (Tyr), or phenylalanine (Phe) are described. The first type is the bis-amino acid complex, [Cu(II)(M)(2)].(2+), where M = Trp, Tyr, or Phe; the second [Cu(II)(4Cl-tpy)(M)].(2+), where 4Cl-tpy is the tridendate ligand 4'-chloro-2,2':6',2''-terpyridine. Dissociations of the Cu(ii) bis-amino acid complexes produce abundant radical cation of the amino acid, M.(+), and/or its secondary products. By contrast, dissociations of the 4Cl-tpy-bearing ternary complexes give abundant M.(+) only for Trp. Density functional theory (DFT) calculations show that for Tyr and Phe, amino-acid displacement reactions by H(2)O and CH(3)OH (giving [Cu(II)(4Cl-tpy)(H(2)O)].(2+) and [Cu(II)(4Cl-tpy)(CH(3)OH)].(2+)) are energetically more favorable than dissociative electron transfer (giving M.(+) and [Cu(I)(4Cl-tpy)](+)). The fragmentation pathway common to all these [Cu(II)(4Cl-tpy)(M)].(2+) ions is the loss of NH(3). DFT calculations show that the loss of NH(3) proceeds via a "phenonium-type" intermediate. Dissociative electron transfer in [Cu(II)(4Cl-tpy)(M-NH(3))].(2+) results in [M-NH(3)].(+). The [Phe-NH(3)] (+) ion dissociates facilely by eliminating CO(2) and giving a metastable phenonium-type ion that rearranges readily into the styrene radical cation.

  2. Biodegradation of the nitramine explosive CL-20.

    Science.gov (United States)

    Trott, Sandra; Nishino, Shirley F; Hawari, Jalal; Spain, Jim C

    2003-03-01

    The cyclic nitramine explosive CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) was examined in soil microcosms to determine whether it is biodegradable. CL-20 was incubated with a variety of soils. The explosive disappeared in all microcosms except the controls in which microbial activity had been inhibited. CL-20 was degraded most rapidly in garden soil. After 2 days of incubation, about 80% of the initial CL-20 had disappeared. A CL-20-degrading bacterial strain, Agrobacterium sp. strain JS71, was isolated from enrichment cultures containing garden soil as an inoculum, succinate as a carbon source, and CL-20 as a nitrogen source. Growth experiments revealed that strain JS71 used 3 mol of nitrogen per mol of CL-20. PMID:12620886

  3. LiYbCl4(THF4

    Directory of Open Access Journals (Sweden)

    Lukas Richtera

    2011-06-01

    Full Text Available The title compound, di-μ-chlorido-dichlorido-1κ2Cl-tetrakis(tetrahydrofuran-1κ2O,2κ2O-lithiumytterbium(III, [LiYbCl4(C4H8O4], was prepared by the reaction of YbCl3(THF3 with LiCl in THF (THF is tetrahydrofuran. The central motif of the structure is a Yb(μ-Cl2Li ring. The Yb atom is hexacoordinated to four Cl atoms and two THF molecules oriented in a trans fashion. The Li atom has a tetrahedral environment and is coordinated to two Cl atoms and two THF molecules. No intermolecular interactions other than van der Waals forces were observed. Two of the THF molecules are disordered over two positions.

  4. Radioprotective thermally generated free-radical dextrins

    Institute of Scientific and Technical Information of China (English)

    Piotr TOMASIK; Oskar MICHALSKI; Ewa BIDZINSKA; Antonina CEBULSKA-WASILEWSKA; Krystyna DYREK; Maciej FIEDOROWICZ; Pawel OLKO

    2008-01-01

    Effect of doses of the X-ray radiation from 0 to 400 Gy upon granular cornstarch and dextrins (British gums, BG) thermally generated from it at 230-300℃ was recognized with quantitative EPR and IR ab-sorption spectroscopy, molecular mass distribution in the depolymerization products, Scanning Elec-tron Microscopy, and X-ray diffractometry. Fractal analysis of the profiles of molecular mass distribu-tion showed that the depolymerization involved debranching of amylopectin. Roasting of cornstarch produced BG which differed in concentration and EPR parameters of stable free radicals from BG generated by X-ray radiation. Two types of stable free radicals, with Gaussian and Lorentzian shapes of EPR signals, were recognized. The shapes of the signals and temperature dependence on free radical intensity indicated exchanging interactions of the antiferromagnetic type, causing partial quenching of the spins at -196℃ (77K). Upon X-ray irradiation, new radicals were generated, the number and stability of which strongly depended on the types of radicals present before irradiation. These radicals slowly ceased because of a repolymerization of BG on storage.

  5. Inactivation of Bacillus atrophaeus by OH radicals

    Science.gov (United States)

    Ono, Ryo; Yonetamari, Kenta; Tokumitsu, Yusuke; Yonemori, Seiya; Yasuda, Hachiro; Mizuno, Akira

    2016-08-01

    The inactivation of Bacillus atrophaeus by OH radicals is measured. This study aims to evaluate the bactericidal effects of OH radicals produced by atmospheric-pressure nonthermal plasma widely used for plasma medicine; however, in this study, OH radicals are produced by vacuum ultraviolet (VUV) photolysis of water vapor instead of plasma to allow the production of OH radicals with almost no other reactive species. A 172 nm VUV light from a Xe2 excimer lamp irradiates a He–H2O mixture flowing in a quartz tube to photodissociate H2O to produce OH, H, O, HO2, H2O2, and O3. The produced reactive oxygen species (ROS) flow out of the quartz tube nozzle to the bacteria on an agar plate and cause inactivation. The inactivation by OH radicals among the six ROS is observed by properly setting the experimental conditions with the help of simulations calculating the ROS densities. A 30 s treatment with approximately 0.1 ppm OH radicals causes visible inactivation.

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

    Science.gov (United States)

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

    2016-01-01

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

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

    Science.gov (United States)

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

    2016-07-01

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

  8. Thermodynamic Optimization of DyCl3 -NaCl System

    Institute of Scientific and Technical Information of China (English)

    叶信宇; 孙益民; 张静; 谈君君

    2005-01-01

    In this paper, the phase diagram of the DyCl3 -NaCl system is optimized and calculated with CALPHAD ( calculation of phase diagram ) technology. A set of thermodynamic functions of compounds Na3 DyCl6, NaDyCl4, and NaDY2 Cl7 have been optimized and calculated based on an interactive computer-assisted analysis. The optimized thermodynamic parameters, calculated phase diagram and experimental phase diagram are thermodynamically serf-consistent.

  9. A DFT Study of R-X Bond Dissociation Enthalpies of Relevance to the Initiation Process of Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Gillies, Malcolm Bjørn; Matyjaszewski, Krzysztof; Norrby, Per-Ola;

    2003-01-01

    DFT calculations at the B3P86/6-31G** level have been carried out to derive the bond dissociation energies (BDE) and free energies for a number of R-X systems (X ) Cl, Br, I, N3, and S2-CNMe2) that have been or can potentially be used as initiators for atom transfer radical polymerization (ATRP)....

  10. Characterization and free radical scavenging activity of rapeseed meal polysaccharides WPS-1 and APS-2.

    Science.gov (United States)

    Zhu, Jianfei; Wu, Moucheng

    2009-02-11

    Two major polysaccharide fractions, WPS-1 and APS-2, were isolated from water-soluble and alkali-soluble extracts of Huaza No. 4 rapeseed meal with a stepwise procedure of D3520 macroporous adsorption resin column chromatography, ethanol precipitation, and DE-52 cellulose column chromatography. Physicochemical properties of the polysaccharides were determined by chemical methods, high -performance liquid chromatography (HPLC), gel permeation chromatography (GPC), and Fourier transform infrared spectrometry (FT-IR). The chemiluminescence (CL) method was used to investigate the free radical scavenging activity of the polysaccharide fractions. The polysaccharides were primarily polymers of arabinose, galactose, and glucose, associated with protein portions consisting of 13 different amino acids. The average molecular masses of WPS-1 and APS-2 were 7.20 x 10(5) and 1.61 x 10(5) Da, respectively. Compared with APS-2, WPS-1 was more effective at scavenging superoxide radical (O(2)(*-)) and hydroxyl radical (HO(*)), but less effective at scavenging hydrogen peroxide (H(2)O(2)). In decreasing order, the free radical scavenging activity of WPS-1 and APS-2 toward reactive oxygen species (ROS) was H(2)O(2) > HO(*) > O(2)(*-).

  11. ESR study on carboxymethyl chitosan radicals in an aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Saiki, Seiichi, E-mail: saiki.seiichi@jaea.go.j [Graduate School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656 (Japan); Quantum Beam Science Directorate, Japan Atomic Energy Agency, 1233 Watanuki, Takasaki, Gunma 370-1292 (Japan); Nagasawa, Naotsugu; Hiroki, Akihiro; Morishita, Norio; Tamada, Masao [Quantum Beam Science Directorate, Japan Atomic Energy Agency, 1233 Watanuki, Takasaki, Gunma 370-1292 (Japan); Muroya, Yusa; Kudo, Hisaaki [Graduate School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656 (Japan); Katsumura, Yosuke [Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656 (Japan); Advanced Science Research Center, Japan Atomic Energy Agency, 2-4 Shirakata-Shirane, Tokai, Naka, Ibaraki 319-1195 (Japan)

    2010-03-15

    Carboxymethyl chitosan (CMCTS) at a highly concentrated aqueous solution forms hydrogel by ionizing irradiation. To study on radiation-induced reaction mechanism of CMCTS in an aqueous solution, CMCTS radicals formed by reactions with OH radical were observed by ESR method. As a result of ESR spectral analysis, CMCTS radicals were identified as radicals on carboxymethyl groups.

  12. Atom transfer radical polymerization (ATRP) and organometallic mediated radical polymerization (OMRP) of styrene mediated by diaminobis(phenolato)iron(II) complexes: a DFT study.

    Science.gov (United States)

    Poli, Rinaldo; Shaver, Michael P

    2014-07-21

    This study has addressed the radical polymerization of styrene mediated by the diaminobis(phenolate) complexes [Fe(O-2,4-Y2C6H2-5-CH2)2NCH2CH2NMe2], abbreviated as [Fe(II)]. The system is known to be well controlled when Y = Cl but not when Y = alkyl. The control was proposed to occur by a dual ATRP+OMRP mechanism. We have used DFT calculations to address the Y = Cl and Y = CH3 systems. The growing radical chain, ATRP dormant chain, and OMRP dormant chain were simplified to PhCH(CH3)(•), PhCH(CH3)-Cl, and [PhCH(CH3)-Fe(III)]. The idealized ATRP activation/deactivation equilibrium involves [Fe(III)-Cl] (I(Y)) and PhCH(CH3)(•) on the active side and [Fe(II)] (II(Y)) and PhCH(CH3)-Cl on the dormant side, whereas the OMRP activation/deactivation relates [Fe(II)] and PhCH(CH3)(•) with [PhCH(CH3)-Fe(III)] (III(Y)). A benchmarking of various functionals against the known spin properties of alkylporphyriniron(III) shows B3PW91* to be a suitable functional. For the purpose of bond dissociation energy calculations, a dispersion correction was made (B3PW91*-D3). For both Y systems, the ground state is a spin sextet for I, a spin quintet for II, and a spin quartet for III. The calculations show a greater energy cost for the ATRP activation process involving Cl atom addition to II(Cl) to yield I(Cl) (7.2 kcal/mol) relative to the process transforming II(Me) to I(Me) (2.1 kcal/mol). On the other hand, the alkyl addition transforming II to III provides slightly greater stabilization for II(Cl) (27.1 kcal/mol) than for II(Me) (26.1 kcal/mol). As a result, both ATRP and OMRP trapping processes provide greater stabilization for the Y = Cl system, in agreement with the observed better control. The charge analysis attributes these minor but determining energy differences to the inductive electron withdrawing effect of the phenolato Cl substituents. The ATRP and OMRP activation/deactivation pathways have been analyzed in relation to the spin state change; they show in each case

  13. Synthesis of polystyrene with high melting temperature through BDE/CuCl catalyzed polymerization

    Institute of Scientific and Technical Information of China (English)

    WAN; Xiaolong

    2001-01-01

    Lecomte, P., Drapier, I., Dubios, P. et al., Controlled radical polymerization of methyl methacrylate in the presence of palladium acetate, triphenyl phosphine, and carbon tetrachloride, Macromolecules, 1997, 30: 7631.[12]Kotani, Y., Kamigaito, Y., Sawamoto, M., Re(V)-mediated living radical polymerization of styrene: ReO2I(PPh3)2/RI initiating system, Macromolecules, 1999, 32: 2420.[13]Makino, T., Tokunaga, E., Hogen-Esch, T. E., Controlled atom transfer radical polymerizations of methyl methacrylate under micellar conditions, Polym. Prep., 1998, 39(1): 288.[14]Gaynor, S. G., Qiu, J., Matyjaszewski, K., Controlled/"living" radical polymerization applied to water-borne system, Macromolecule, 1998, 31: 5951.[15]Qiu, J., Gaynor, S. G., Matyjaszewski, K., Controlled/"living" radical polymerization of n-butyl methacrylate by reverse atom transfer radical polymerization, Macromolecules, 1999, 32: 2872.[16]Shipp, D. A., McMurtry, G. P., Gaynor, S. G. et al., Water-borne block copolymer synthesis and a simple and effective one-pot synthesis of acrylate-methacrylate block copolymers by atom transfer radical polymerization, Polym. Prep., 1999, 40(2): 448.[17]Nishikawa, T., Kamigaito, M., Sawamoto, M., Living radical polymerization in water and alcohols: suspension polymerization of methyl methacrylate with RuCl2(PPh3)3 complex, Macromolecules, 1999, 32: 2204.[18]Wan, X. L., Ying, S. K., "Living" radical emulsion polymerization of styrene under Cu0/Bpy/CCl4 and CuCl2/Bpy/AIBN system, Chinese J. Polym. Sci., 2000, (1): 27.[19]Wan, X. L., Ying, S. K., Controlled radical polymerization catalyzed by Cu/BDE complex in water medium, 1. Polymerization of styrene and synthesis of poly(St-b-MMA), J. Appl. Polym. Sci., 2000, 75(1): 802.[20]Wan, X. L., Ying, S. K., Synthesis of block copolymers by emulsion "living"/controlled radical polymerization of vinyl monomers in sequence, Polym. Prep., 1999, 40: 1055.[21]Keller, R. N., Wycoff, H. D., The synthesis

  14. Theoretical study of the reactivity trends in the Cl-abstraction reactions of CHCl3 + CHX·−/CX$_{2}^{·−}$ (X = Cl, Br and I)

    Indian Academy of Sciences (India)

    Jun Xi Liang; Zhi Yuan Geng; Yong Cheng Wang

    2011-09-01

    To better understand how and to what extent the halosubstituted carbene radical anions effect the chlorine abstraction of CHCl3, a detailed theoretical investigation has been performed at the UMP2/6-311++G (d, p)/RECP level of theory. The model system CHCl3+CHX·−/CX$^{·−}_{2}$ (X = Cl, Br, and I) has been chosen for the present study. According to the detailed discussions of geometries and energetics of the optimized stationary points, our theoretical findings suggest that the Cl-abstraction reactions by CHX·− are energetically favourable, indicating the less massive substitution X in CHX·− the easier abstraction reaction, as compared to those by CX$^{·−}_{2}$, which are energetically unfavourable and would be endothermic.

  15. OH Radical and a Drizzling Water Jet Production from the Ball-Lightning Discharge in Water

    Science.gov (United States)

    Maeyama, Mitsuaki; Tanaka, Yasutomo

    The ball lightning, or fireball discharge using the typical electrode configuration was reported to produce a long-living spherical plasmoid with radius exceed 10 cm at atmospheric pressure. In this study, we investigated the relationship between a optical output emitted from OH radicals and discharge conditions of the ball-lightning electrode configuration, and discussed its possibility to the water treatment process. As a results, in both polarity cases of the charged voltage V0, a ball-lightning discharge and the optical emission from OH radicals as a major radiation can be generated on the condition |V0| > 4 kV in tap water. Furthermore, an intensive upward water jet from the rod electrode is observed in case of positive polarity and in 0.2% NaCl solution, which is composed of drizzling water drops near the rod electrode.

  16. 76 FR 34014 - Airworthiness Directives; Bombardier, Inc. Model CL-215-1A10, CL-215-6B11 (CL-215T Variant), and...

    Science.gov (United States)

    2011-06-10

    ... Procedures (44 FR 11034, February 26, 1979); and 3. Will not have a significant economic impact, positive or.... Model CL-215-1A10, CL- 215-6B11 (CL-215T Variant), and CL-215-6B11 (CL-415 Variant) Airplanes AGENCY.... Model CL-215-1A10 airplanes, serial numbers 1051 through 1125 inclusive; Model CL-215- 6B11...

  17. DFT and ENDOR Study of Bixin Radical Cations and Neutral Radicals on Silica-Alumina.

    Science.gov (United States)

    Tay-Agbozo, Sefadzi S; Krzyaniak, Matthew D; Bowman, Michael K; Street, Shane; Kispert, Lowell D

    2015-06-18

    Bixin, a carotenoid found in annatto (Bixa orellana), is unique among natural carotenoids by being water-soluble. We stabilized free radicals from bixin on the surface of silica-alumina (Si-Al) and characterized them by pulsed electron-nuclear double resonance (ENDOR). DFT calculations of unpaired electron spin distribution for various bixin radicals predict the EPR hyperfine couplings. Least-square fitting of experimental ENDOR spectra by spectra calculated from DFT hyperfine couplings characterized the radicals trapped on Si-Al. DFT predicts that the trans bixin radical cation is more stable than the cis bixin radical cation by 1.26 kcal/mol. This small energy difference is consistent with the 26% trans and 23% cis radical cations in the ENDOR spectrum. The remainder of the ENDOR spectrum is due to several neutral radicals formed by loss of a H(+) ion from the 9, 9', 13, or 13' methyl group, a common occurrence in all water-insoluble carotenoids previously studied. Although carboxyl groups of bixin strongly affect its solubility relative to other natural carotenoids, they do not alter properties of its free radicals based on DFT calculations and EPR measurements which remain similar to typical water-insoluble carotenoids. PMID:25333911

  18. How Radical is a Radical Innovation? An Outline for a Computational Approach

    NARCIS (Netherlands)

    Kasmire, J.; Korhonen, J.M.; Nikolic, I.

    2012-01-01

    Radical innovations prompt significant subsequent technological development and exhibit novelty and “architectural” innovation, i.e. rearranging the way design elements are put together in a system. Thus, radical innovations often serve as the foundation for new technological systems, industries or

  19. Heterogeneous computing with OpenCL

    CERN Document Server

    2013-01-01

    Heterogeneous Computing with OpenCL teaches OpenCL and parallel programming for complex systems that may include a variety of device architectures: multi-core CPUs, GPUs, and fully-integrated Accelerated Processing Units (APUs) such as AMD Fusion technology. Designed to work on multiple platforms and with wide industry support, OpenCL will help you more effectively program for a heterogeneous future. Written by leaders in the parallel computing and OpenCL communities, this book will give you hands-on OpenCL experience to address a range of fundamental parallel algorithms. The authors explore memory spaces, optimization techniques, graphics interoperability, extensions, and debugging and profiling. Intended to support a parallel programming course, Heterogeneous Computing with OpenCL includes detailed examples throughout, plus additional online exercises and other supporting materials.

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

    Science.gov (United States)

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

    2015-11-01

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

  1. Modeling Radicalization Phenomena in Heterogeneous Populations.

    Science.gov (United States)

    Galam, Serge; Javarone, Marco Alberto

    2016-01-01

    The phenomenon of radicalization is investigated within a mixed population composed of core and sensitive subpopulations. The latest includes first to third generation immigrants. Respective ways of life may be partially incompatible. In case of a conflict core agents behave as inflexible about the issue. In contrast, sensitive agents can decide either to live peacefully adjusting their way of life to the core one, or to oppose it with eventually joining violent activities. The interplay dynamics between peaceful and opponent sensitive agents is driven by pairwise interactions. These interactions occur both within the sensitive population and by mixing with core agents. The update process is monitored using a Lotka-Volterra-like Ordinary Differential Equation. Given an initial tiny minority of opponents that coexist with both inflexible and peaceful agents, we investigate implications on the emergence of radicalization. Opponents try to turn peaceful agents to opponents driving radicalization. However, inflexible core agents may step in to bring back opponents to a peaceful choice thus weakening the phenomenon. The required minimum individual core involvement to actually curb radicalization is calculated. It is found to be a function of both the majority or minority status of the sensitive subpopulation with respect to the core subpopulation and the degree of activeness of opponents. The results highlight the instrumental role core agents can have to hinder radicalization within the sensitive subpopulation. Some hints are outlined to favor novel public policies towards social integration. PMID:27166677

  2. Analysis of radicals induced in irradiated foods

    International Nuclear Information System (INIS)

    By electron spin resonance (ESR) spectroscopy, we revealed free radicals in γ-ray irradiated foods; black pepper, green coffee bean and ginseng. We also analyzed the decay behavior of radiation induced free radicals during storage of irradiated foods. The ESR spectrum of experimental irradiated foods consists of a sextet signal centered at g=2.0 and a singlet signal at the same g-value position and a singlet signal at g=4.0. The singlet signal at g=2.0 is originated from organic free radicals and its peak intensity showed the dependence of γ-ray irradiation dose levels. The signal intensity was decreased during storage. Only after 3 hours of radiation treatment the peak intensity was decreased fast and after that the intensity was decreased slowly. The relaxation times, T1 and T2, of radiation induced free radicals showed the variations before and after irradiation. During long time storage period it was shown that T1 was increased and T2 was decreased. By analysis of decay process using the simulation methods based on the theory of reaction speed, it is considered that at least two kinds of radicals were induced in irradiated foods during long time storage. (author)

  3. Modeling Radicalization Phenomena in Heterogeneous Populations

    Science.gov (United States)

    2016-01-01

    The phenomenon of radicalization is investigated within a mixed population composed of core and sensitive subpopulations. The latest includes first to third generation immigrants. Respective ways of life may be partially incompatible. In case of a conflict core agents behave as inflexible about the issue. In contrast, sensitive agents can decide either to live peacefully adjusting their way of life to the core one, or to oppose it with eventually joining violent activities. The interplay dynamics between peaceful and opponent sensitive agents is driven by pairwise interactions. These interactions occur both within the sensitive population and by mixing with core agents. The update process is monitored using a Lotka-Volterra-like Ordinary Differential Equation. Given an initial tiny minority of opponents that coexist with both inflexible and peaceful agents, we investigate implications on the emergence of radicalization. Opponents try to turn peaceful agents to opponents driving radicalization. However, inflexible core agents may step in to bring back opponents to a peaceful choice thus weakening the phenomenon. The required minimum individual core involvement to actually curb radicalization is calculated. It is found to be a function of both the majority or minority status of the sensitive subpopulation with respect to the core subpopulation and the degree of activeness of opponents. The results highlight the instrumental role core agents can have to hinder radicalization within the sensitive subpopulation. Some hints are outlined to favor novel public policies towards social integration. PMID:27166677

  4. Modeling Radicalization Phenomena in Heterogeneous Populations.

    Directory of Open Access Journals (Sweden)

    Serge Galam

    Full Text Available The phenomenon of radicalization is investigated within a mixed population composed of core and sensitive subpopulations. The latest includes first to third generation immigrants. Respective ways of life may be partially incompatible. In case of a conflict core agents behave as inflexible about the issue. In contrast, sensitive agents can decide either to live peacefully adjusting their way of life to the core one, or to oppose it with eventually joining violent activities. The interplay dynamics between peaceful and opponent sensitive agents is driven by pairwise interactions. These interactions occur both within the sensitive population and by mixing with core agents. The update process is monitored using a Lotka-Volterra-like Ordinary Differential Equation. Given an initial tiny minority of opponents that coexist with both inflexible and peaceful agents, we investigate implications on the emergence of radicalization. Opponents try to turn peaceful agents to opponents driving radicalization. However, inflexible core agents may step in to bring back opponents to a peaceful choice thus weakening the phenomenon. The required minimum individual core involvement to actually curb radicalization is calculated. It is found to be a function of both the majority or minority status of the sensitive subpopulation with respect to the core subpopulation and the degree of activeness of opponents. The results highlight the instrumental role core agents can have to hinder radicalization within the sensitive subpopulation. Some hints are outlined to favor novel public policies towards social integration.

  5. Formation of semiquinone radical anion and free radical scavenging reactions of plumbagin. A pulse radiolysis study

    International Nuclear Information System (INIS)

    Kinetics and mechanism of scavenging of reducing free radicals by plumbagin (5-hydroxy-2-methyl-1,4-naphthoquinone) are studied using pulse radiolysis technique. It scavenged superoxide radical, hydroxyethyl radical and hydrated electron with bimolecular rate constants of 8.9 × 107, 2.3 × 109 and 1.6 × 1010 M-1 s-1, respectively in aqueous-alcohol medium. Plumbagin also scavenged linoleic acid peroxyl radical and tyrosyl radical with bimolecular rate constants of 1.0 × 108 and 7.0 × 106 M-1 s-1, respectively. Further, redox properties of plumbagin and its transients are studied using standard redox couples and cyclic voltammetry. (author)

  6. On the ClC halogen bond: a rotational study of CF3Cl-CO.

    Science.gov (United States)

    Caminati, Walther; Evangelisti, Luca; Feng, Gang; Giuliano, Barbara M; Gou, Qian; Melandri, Sonia; Grabow, Jens-Uwe

    2016-07-21

    The rotational spectra of two isotopologues (CF3(35)Cl-CO and CF3(37)Cl-CO) of the CF3Cl-CO adduct have been investigated and analyzed using supersonic-jet Fourier transform microwave spectroscopy, and found to have the features of a symmetric top. Rotational, centrifugal distortion, and nuclear quadrupole ((35)Cl and (37)Cl) coupling constants have been precisely obtained from high-resolution measurements. The two subunits of the complex are held together via a ClC halogen bond interaction. Information on the internal dynamics and the dissociation energy of the complex is provided. PMID:27049637

  7. Evaluation of the Relative Importance of Radical Sources in Determining the Regional Tropospheric Oxidation Capacity in the Seoul Metropolitan Area

    Science.gov (United States)

    Jeong, D.; Sanchez, D.; Blake, D. R.; Kim, D. S.; Lee, G.; Lee, M.; Jung, J.; Ahn, J.; Cho, G.; Guenther, A. B.; Kim, S.

    2015-12-01

    We will discuss oxidation capacity in the boundary layer of the Seoul Metropolitan Area (SMA) by analyzing a comprehensive field observational datasets of trace gases, radicals, and radical precursors. Two intensive field observations will be discussed. From mid-May to mid-June of 2015, we conducted a field observation in the middle of Seoul, representing a region with high anthropogenic emissions and photochemistry near the source region. We deployed an identical suite of instrumentation (i.e., CO, NOX, O3, SO2, VOCs, ClNO2, HONO, and PANs) at Taehwa Research Forest (TRF), ~ 50 km from the center of Seoul in early September of 2015. The site has been characterized as an ideal region in probing roles of biogenic VOCs (BVOCs) in a moderately polluted regional background. Therefore, the comparisons between two datasets will allow us to assess regional oxidation capacity of a megacity surrounded by forests, which is a typical set-up in the East Asian region. The main focus of the discussion was to investigate the following: (i) relative impact of nighttime radical reservoirs (i.e., HONO and ClNO2) in the morning radical budget in the urban and suburban environments and (ii) relative importance of unconstrained primary and recycling (e.g., BVOC oxidation) OH production at the isoprene dominated TRF region. An observationally constrained box model with detailed VOC chemical oxidation schemes (e.g., MCM) will be used for the comprehensive evaluations.

  8. Resveratrol products resulting by free radical attack

    Energy Technology Data Exchange (ETDEWEB)

    Bader, Yvonne; Quint, R.M. [Section Radiation Biology, Department of Nutritional Sciences, Faculty of Life Sciences, University of Vienna, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Getoff, Nikola [Section Radiation Biology, Department of Nutritional Sciences, Faculty of Life Sciences, University of Vienna, UZAII, Althanstrasse 14, A-1090 Vienna (Austria)], E-mail: nikola.getoff@univie.ac.at

    2008-06-15

    Trans-resveratrol (trans-3,4',5-trihydroxystilbene; RES), which is contained in red wine and many plants, is one of the most relevant and extensively investigated stilbenes with a broad spectrum of biological activities. Among other duties, RES has been reported to have anti-carcinogenetic activities, which could be attributed to its antioxidant properties. The degradation of RES was studied under various conditions. The products (aldehydes, carboxylic acids, etc.) generated from RES by the attack of free radicals were registered as a function of the radical concentration (absorbed radiation dose). Based on the obtained data it appears that the OH radicals are initiating the rather complicated process, which involves of the numerous consecutive reactions. A possible starting reaction mechanism is presented.

  9. Resveratrol products resulting by free radical attack

    Science.gov (United States)

    Bader, Yvonne; Quint, R. M.; Getoff, Nikola

    2008-06-01

    Trans-resveratrol ( trans-3,4',5-trihydroxystilbene; RES), which is contained in red wine and many plants, is one of the most relevant and extensively investigated stilbenes with a broad spectrum of biological activities. Among other duties, RES has been reported to have anti-carcinogenetic activities, which could be attributed to its antioxidant properties. The degradation of RES was studied under various conditions. The products (aldehydes, carboxylic acids, etc.) generated from RES by the attack of free radicals were registered as a function of the radical concentration (absorbed radiation dose). Based on the obtained data it appears that the OH radicals are initiating the rather complicated process, which involves of the numerous consecutive reactions. A possible starting reaction mechanism is presented.

  10. Radiation chemistry of aromatic dimer radical cations

    International Nuclear Information System (INIS)

    π-π Interactions of aromatic molecules are paid attention much in many fields, especially biology, chemistry, and applied physics, represented as protein, DNA, electron donor-accepter complexes, charge transfers, and self assembly molecules. Aromatic molecules including benzene rings are the simplest case to study the π-π interactions. To interpret the charge resonance (CR) structure in the dimer radical cations, spectroscopic and ESR methods have been carried out. The spectroscopic study on the dimer radical ion of molecules with two chromophores would be profitable to identify the electronic and configurational properties. In this article, dynamics of the dimer radical cation of benzenes, polystyrenes, and resist polymers is described on the basis of direct observation of CR band by the nanosecond pulse radiolysis and low temperature γ-radiolysis methods. (author)

  11. Exploring how lead users develop radical innovation

    DEFF Research Database (Denmark)

    Lettl, Christopher; Gemuenden, Hans Georg; Hienerth, C.

    2008-01-01

    in order to transform their radically new solutions into functional prototypes and then to convince established manufacturers of the technological and market potential of their innovations. Using a comparative case study design in the high-tech field of medical equipment technology, we find that individual...... lead users as surgeons launch entrepreneurial activities and bridge periods in which established medical equipment manufacturers would not risk investing in radical innovations. By doing so, lead users create the conditions usually provided in manufacturer-initiated lead user projects, including...... the supply of diversified knowledge, the development and coordination of a network for further development of the innovation, and initial tests of technical or market feasibility. Our findings have implications for manufacturing firms that wish to design radical innovation projects with (individual) lead...

  12. Effects of NaCl and NH4Cl on the initial atmospheric corrosion of zinc

    International Nuclear Information System (INIS)

    Effects of NaCl and NH4Cl on the initial atmospheric corrosion of zinc were investigated via quartz crystal microbalance (QCM) in laboratory at 80% RH and 25 deg C. The results show that both NaCl and NH4Cl can accelerate the initial atmospheric corrosion of zinc. The combined effect of NaCl and NH4Cl on the corrosion of zinc is greater than that caused by NH4Cl and less than that caused by NaCl. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy and electron dispersion X-ray analysis (SEM/EDAX) were used to characterize the corrosion products of zinc. (NH4)2ZnCl4, Zn5(OH)8Cl2 . H2O and ZnO present on zinc surface in the presence of NH4Cl while Zn5(OH)8Cl2 . H2O and ZnO are the dominant corrosion products on NaCl-treated zinc surface. Probable mechanisms are presented to explain the experimental results

  13. 76 FR 66620 - Airworthiness Directives; Bombardier, Inc. Model CL-215-1A10, CL-215-6B11 (CL-215T Variant), and...

    Science.gov (United States)

    2011-10-27

    ... Procedures (44 FR 11034, February 26, 1979); and 3. Will not have a significant economic impact, positive or.... Model CL-215-1A10, CL- 215-6B11 (CL-215T Variant), and CL-215-6B11 (CL-415 Variant) Airplanes AGENCY... comments. SUMMARY: We are adopting a new airworthiness directive (AD) for certain Bombardier, Inc. Model...

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

    Science.gov (United States)

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

    2014-02-28

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

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

    Science.gov (United States)

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

    2014-02-01

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

  16. Free Radicals in Adolescent Varicocele Testis

    OpenAIRE

    Carmelo Romeo; Giuseppe Santoro

    2014-01-01

    We examine the relationship between the structure and function of the testis and the oxidative and nitrosative stress, determined by an excessive production of free radicals and/or decreased availability of antioxidant defenses, which occur in the testis of adolescents affected by varicocele. Moreover, the effects of surgical treatment on oxidative stress were provided. We conducted a PubMed and Medline search between 1980 and 2014 using “adolescent,” “varicocele,” “free radicals,” “oxidative...

  17. Photodynamically generated bovine serum albumin radicals

    DEFF Research Database (Denmark)

    Silvester, J A; Timmins, G S; Davies, Michael Jonathan

    1998-01-01

    Porphyrin-sensitized photoxidation of bovine serum albumin (BSA) results in oxidation of the protein at (at least) two different, specific sites: the Cys-34 residue giving rise to a thiyl radical (RS.); and one or both of the tryptophan residues (Trp-134 and Trp-214) resulting in the formation...... of tertiary carbon-centred radicals and disruption of the tryptophan ring system. In the case of porphyrins such as hematoporphyrin, which bind at specific sites on BSA, these species appear to arise via long-range transfer of damage within the protein structure, as the binding site is some distance from...

  18. Resonance ionization detection of combustion radicals

    Energy Technology Data Exchange (ETDEWEB)

    Cool, T.A. [Cornell Univ., Ithaca, NY (United States)

    1993-12-01

    Fundamental research on the combustion of halogenated organic compounds with emphasis on reaction pathways leading to the formation of chlorinated aromatic compounds and the development of continuous emission monitoring methods will assist in DOE efforts in the management and disposal of hazardous chemical wastes. Selective laser ionization techniques are used in this laboratory for the measurement of concentration profiles of radical intermediates in the combustion of chlorinated hydrocarbon flames. A new ultrasensitive detection technique, made possible with the advent of tunable VUV laser sources, enables the selective near-threshold photoionization of all radical intermediates in premixed hydrocarbon and chlorinated hydrocarbon flames.

  19. Radical Islamism and Migrant Integration in Denmark

    DEFF Research Database (Denmark)

    Goli, Marco; Rezaei, Shahamak

    2011-01-01

    It has been suggested that alienation and failed integration may be causes of “Homegrown Radical Islamism” in Western societies. Western countries often expect that migrants and their descendants residing there as citizens will embrace or support common democratic ideals as a predicate for – or c......It has been suggested that alienation and failed integration may be causes of “Homegrown Radical Islamism” in Western societies. Western countries often expect that migrants and their descendants residing there as citizens will embrace or support common democratic ideals as a predicate...

  20. Elementary reaction allyl radical with oxygen

    Institute of Scientific and Technical Information of China (English)

    DONG Feng; KONG Fanao

    2003-01-01

    The elementary reaction between allyl radical with oxygen molecule wasexperimentally investigated. The allyl radical was produced via laser photolysis of C3H5Br in gaseous phase. Nascent vibrational excited products HCO, CO2, CH3CHO and HCOOH were recorded by the time- resolved Fourier transform infrared spectroscopy. The product channels of C2H5+CO2, CH3CHO+HCO, and HCOOH + C2H3 have been identified. The vibrational populations of product CO2 are obtained by spectral simulation. A mechanism forming a series of three-membered ring-struc- ture intermediates is suggested.

  1. Secondary radicals derived from chloramines of apolipoprotein B-100 contribute to HOCl-induced lipid peroxidation of low-density lipoproteins

    DEFF Research Database (Denmark)

    Hazell, L J; Davies, Michael Jonathan; Stocker, R

    1999-01-01

    component to be the major site of attack, whereas others describe extensive lipid peroxidation. The present study addresses this controversy. The results obtained are consistent with the hypothesis that radical-induced oxidation of LDL's lipids by HOCl is a secondary reaction, with most HOCl consumed via...... rapid, non-radical reaction with apolipoprotein B-100. Subsequent incubation of HOCl-treated LDL gives rise to lipid peroxidation and antioxidant consumption in a time-dependent manner. Similarly, with myeloperoxidase/H2O2/Cl- (the source of HOCl in vivo), protein oxidation is rapid and followed...... by an extended period of lipid peroxidation during which further protein oxidation does not occur. The secondary lipid peroxidation process involves EPR-detectable radicals, is attenuated by a radical trap or treatment of HOCl-oxidized LDL with methionine, and occurs less rapidly when the lipoprotein...

  2. Structure model and synthesis of NdCl3-FeCl3-graphite intercalation compounds

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The distribution of the elements and microstructure of NdCl3-FeCl3-graphite intercalation compounds (GICs) were shown by scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS). The results show that Nd element intercalates into graphite, forming NdCl3-FeCl3-GICs, and the distribution of Nd and Fe is nearly even. On the basis of the data, a structure model for RECl3-GICs was founded, and the characteristic layer distance and the index of interval energy were calculated. The calculated results agree with experimental ones, and the relative errors are ±2%. Thus it can be seen that the (111) face is optimal direction for intercalation reaction of TbCl3 LuCl3, and the (001) face is that for LaCl3 GdCl3, because of the lowest interval energy.

  3. Glutathione--hydroxyl radical interaction: a theoretical study on radical recognition process.

    Directory of Open Access Journals (Sweden)

    Béla Fiser

    Full Text Available Non-reactive, comparative (2 × 1.2 μs molecular dynamics simulations were carried out to characterize the interactions between glutathione (GSH, host molecule and hydroxyl radical (OH(•, guest molecule. From this analysis, two distinct steps were identified in the recognition process of hydroxyl radical by glutathione: catching and steering, based on the interactions between the host-guest molecules. Over 78% of all interactions are related to the catching mechanism via complex formation between anionic carboxyl groups and the OH radical, hence both terminal residues of GSH serve as recognition sites. The glycine residue has an additional role in the recognition of OH radical, namely the steering. The flexibility of the Gly residue enables the formation of further interactions of other parts of glutathione (e.g. thiol, α- and β-carbons with the lone electron pair of the hydroxyl radical. Moreover, quantum chemical calculations were carried out on selected GSH/OH(• complexes and on appropriate GSH conformers to describe the energy profile of the recognition process. The relative enthalpy and the free energy changes of the radical recognition of the strongest complexes varied from -42.4 to -27.8 kJ/mol and from -21.3 to 9.8 kJ/mol, respectively. These complexes, containing two or more intermolecular interactions, would be the starting configurations for the hydrogen atom migration to quench the hydroxyl radical via different reaction channels.

  4. CL møder sptogfagsdidaktikken

    DEFF Research Database (Denmark)

    Pedersen, Michael Svendsen

    2011-01-01

    I artiklen diskuteres den didaktiske kontekst for brugen af CL (Cooperative Learning) i sprogundervisningen. Indledningsvis stilles følgende spørgsmål: Hvor kommer de indholdsfrie CL-strukturer fra, og hvad sker der når man inddrager dem i sprogundervisningen? I besvarelsen af disse spørgsmål...

  5. Some Properties of CL-space and Almost CL-space%关于CL-空间和几乎CL-空间的一些性质

    Institute of Scientific and Technical Information of China (English)

    卢允照

    2006-01-01

    讨论具有"平坦性"凸性单位球结构的Banach空间的一些性质.首先根据CL-空间的定义证明了Banach空间l1是CL-空间.通过证明l31和l3∞具有非CL-子空间证明了维数大于2的CL空间不具继承性,即具有非CL-子空间,另外,总结了有限维CL-空间与其它一些Banach空间类的等价性.最后讨论了CL-空间和几乎CL-空间包含Banach空间c0与l1的一些性质以及实对偶空间成为几乎CL-空间的两个必要条件.

  6. Al/Cl2 molten salt battery

    Science.gov (United States)

    Giner, J.

    1972-01-01

    Molten salt battery has been developed with theoretical energy density of 5.2 j/kg (650 W-h/lb). Battery, which operates at 150 C, can be used in primary mode or as rechargeable battery. Battery has aluminum anode and chlorine cathode. Electrolyte is mixture of AlCl3, NaCl, and some alkali metal halide such as KCl.

  7. Atmospheric production rate of {sup 36}Cl

    Energy Technology Data Exchange (ETDEWEB)

    Parrat, Y.; Hajdas, W.; Baltensperger, U.; Synal, H.A.; Kubik, P.W.; Gaeggeler, H.W. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Suter, M. [Eidgenoessische Technische Hochschule, Zurich (Switzerland)

    1997-09-01

    Using experimental cross sections, a new calculation of the atmospheric production rate of {sup 36}Cl was carried out. A mean production rate of 20 atoms m{sup -2}s{sup -1} was obtained, which is lower than mean {sup 36}Cl deposition rates. (author) 2 figs., 7 refs.

  8. Low-temperature combustion chemistry of n-butanol: principal oxidation pathways of hydroxybutyl radicals.

    Science.gov (United States)

    Welz, Oliver; Zádor, Judit; Savee, John D; Sheps, Leonid; Osborn, David L; Taatjes, Craig A

    2013-11-21

    Reactions of hydroxybutyl radicals with O2 were investigated by a combination of quantum-chemical calculations and experimental measurements of product formation. In pulsed-photolytic Cl-initiated oxidation of n-butanol, the time-resolved and isomer-specific product concentrations were probed using multiplexed tunable synchrotron photoionization mass spectrometry (MPIMS). The interpretation of the experimental data is underpinned by potential energy surfaces for the reactions of O2 with the four hydroxybutyl isomers (1-hydroxybut-1-yl, 1-hydroxybut-2-yl, 4-hydroxybut-2-yl, and 4-hydroxybut-1-yl) calculated at the CBS-QB3 and RQCISD(T)/cc-pV∞Z//B3LYP/6-311++G(d,p) levels of theory. The observed product yields display substantial temperature dependence, arising from a competition among three fundamental pathways: (1) stabilization of hydroxybutylperoxy radicals, (2) bimolecular product formation in the hydroxybutyl + O2 reactions, and (3) decomposition of hydroxybutyl radicals. The 1-hydroxybut-1-yl + O2 reaction is dominated by direct HO2 elimination from the corresponding peroxy radical forming butanal as the stable coproduct. The chemistry of the other three hydroxybutylperoxy radical isomers mainly proceeds via alcohol-specific internal H-atom abstractions involving the H atom from either the -OH group or from the carbon attached to the -OH group. We observe evidence of the recently reported water elimination pathway (Welz et al. J. Phys. Chem. Lett. 2013, 4 (3), 350-354) from the 4-hydroxybut-2-yl + O2 reaction, supporting its importance in γ-hydroxyalkyl + O2 reactions. Experiments using the 1,1-d2 and 4,4,4-d3 isotopologues of n-butanol suggest the presence of yet unexplored pathways to acetaldehyde.

  9. Cs3ScCl6

    Directory of Open Access Journals (Sweden)

    Matthew D. Ward

    2014-06-01

    Full Text Available Crystals of tricaesium scandium(III hexachloride were obtained as a side product from the reaction of U, SnCl2, Sc, and S in a CsCl flux at 1073 K. Cs3ScCl6 crystallizes in the Rb3YCl6 structure type. The asymmetric unit comprises three Cs sites, two Sc sites, and six Cl sites, all of which have site symmetry 1, except for the two Sc sites that have site symmetries of 2 and -1, respectively. The structure is composed of isolated [ScCl6]3− octahedra that are surrounded by Cs+ cations. Two Cs+ cations have interactions with eight Cl− anions, while the third has interactions with ten Cl− anions.

  10. Tandem catalysis of ring-closing metathesis/atom transfer radical reactions with homobimetallic ruthenium–arene complexes

    Directory of Open Access Journals (Sweden)

    Yannick Borguet

    2010-12-01

    Full Text Available The tandem catalysis of ring-closing metathesis/atom transfer radical reactions was investigated with the homobimetallic ruthenium–indenylidene complex [(p-cymeneRu(μ-Cl3RuCl(3-phenyl-1-indenylidene(PCy3] (1 to generate active species in situ. The two catalytic processes were first carried out independently in a case study before the whole sequence was optimized and applied to the synthesis of several polyhalogenated bicyclic γ-lactams and lactones from α,ω-diene substrates bearing trihaloacetamide or trichloroacetate functionalities. The individual steps were carefully monitored by 1H and 31P NMR spectroscopies in order to understand the intimate details of the catalytic cycles. Polyhalogenated substrates and the ethylene released upon metathesis induced the clean transformation of catalyst precursor 1 into the Ru(II–Ru(III mixed-valence compound [(p-cymeneRu(μ-Cl3RuCl2(PCy3], which was found to be an efficient promoter for atom transfer radical reactions under the adopted experimental conditions.

  11. Discourses of postmodern epistemology: Radical impetus lost?

    OpenAIRE

    Mueller, Martin

    2006-01-01

    Exhibiting a highly divisive agenda postmodernism has created profound chasms across scientific communities. In development studies its radical impetus has translated into the postdevelopment perspective which violently repudiates the modernist development project. This paper crystallises two distinct discourses of working upon the epistemological raw material of postmodernism: an exclusivist discourse, which reinforces the chasm by isolating postmodernism, and an inclusivist discourse, which...

  12. Identity and Islamic Radicalization in Western Europe

    NARCIS (Netherlands)

    S.M. Murshed (Syed); S. Pavan (Sara)

    2009-01-01

    textabstractThis paper argues that both socio-economic disadvantage and political factors, such as the West’s foreign policy with regard to the Muslim world, along with historical grievances, play a part in the development of Islamic radicalized collective action in Western Europe. We emphasise the

  13. Radical Negativity: Music Education for Social Justice

    Science.gov (United States)

    McLaren, Peter

    2011-01-01

    According to Hedges (2010), the real enemies of the liberal class are radical thinkers such as Noam Chomsky and Ralph Nader, iconoclastic intellectuals who possess the moral autonomy to defy the power elite. While this author agrees with Hedges, he would take this argument even further. In this article, the author argues that the real enemy of…

  14. Neglected Side Effects After Radical Prostatectomy

    DEFF Research Database (Denmark)

    Frey, Anders Ullmann; Sønksen, Jens; Fode, Mikkel

    2014-01-01

    INTRODUCTION: A series of previously neglected sexually related side effects to radical prostatectomy (RP) has been identified over the recent years. These include orgasm-associated incontinence (OAI), urinary incontinence in relation to sexual stimulation (UISS), altered perception of orgasm, or...

  15. Radical recombinations in acetylene-air flames

    NARCIS (Netherlands)

    Zeegers, P.J.Th.; Alkemade, C.T.J.

    1965-01-01

    In this paper an analysis is given of the behaviour of excess radical concentrations, H, OH and O as a function of height above the reaction zone in premixed acetylene-air flames at 2–200° to 2400°K and 1 atmosphere pressure. The intensity was measured of the Li resonance line which is related to th

  16. Designed metalloprotein stabilizes a semiquinone radical.

    Science.gov (United States)

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

    2016-04-01

    Enzymes use binding energy to stabilize their substrates in high-energy states that are otherwise inaccessible at ambient temperature. Here we show that a de novo designed Zn(II) metalloprotein stabilizes a chemically reactive organic radical that is otherwise unstable in aqueous media. The protein binds tightly to and stabilizes the radical semiquinone form of 3,5-di-tert-butylcatechol. Solution NMR spectroscopy in conjunction with molecular dynamics simulations show that the substrate binds in the active site pocket where it is stabilized by metal-ligand interactions as well as by burial of its hydrophobic groups. Spectrochemical redox titrations show that the protein stabilized the semiquinone by reducing the electrochemical midpoint potential for its formation via the one-electron oxidation of the catechol by approximately 400 mV (9 kcal mol(-1)). Therefore, the inherent chemical properties of the radical were changed drastically by harnessing its binding energy to the metalloprotein. This model sets the basis for designed enzymes with radical cofactors to tackle challenging chemistry. PMID:27001731

  17. Designed metalloprotein stabilizes a semiquinone radical

    Science.gov (United States)

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

    2016-04-01

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

  18. Ultraviolet photodissociation dynamics of the phenyl radical

    International Nuclear Information System (INIS)

    Ultraviolet (UV) photodissociation dynamics of jet-cooled phenyl radicals (C6H5 and C6D5) are studied in the photolysis wavelength region of 215-268 nm using high-n Rydberg atom time-of-flight and resonance enhanced multiphoton ionization techniques. The phenyl radicals are produced from 193-nm photolysis of chlorobenzene and bromobenzene precursors. The H-atom photofragment yield spectra have a broad peak centered around 235 nm and are in good agreement with the UV absorption spectra of phenyl. The H + C6H4 product translational energy distributions, P(ET)'s, peak near ∼7 kcal/mol, and the fraction of average translational energy in the total excess energy, T>, is in the range of 0.20-0.35 from 215 to 268 nm. The H-atom product angular distribution is isotropic. The dissociation rates are in the range of 107-108 s-1 with internal energy from 30 to 46 kcal/mol above the threshold of the lowest energy channel H +o-C6H4 (ortho-benzyne), comparable with the rates from the Rice-Ramsperger-Kassel-Marcus theory. The results from the fully deuterated phenyl radical are identical. The dissociation mechanism is consistent with production of H +o-C6H4, as the main channel from unimolecular decomposition of the ground electronic state phenyl radical following internal conversion of the electronically excited state.

  19. Support for radical left ideologies in Europe

    NARCIS (Netherlands)

    Visser, Mark; Lubbers, Marcel; Kraaykamp, Gerbert; Jaspers, Eva

    2014-01-01

    This article examines support for radical left ideologies in 32 European countries. It thus extends the relatively scant empirical research available in this field. The hypotheses tested are derived mainly from group-interest theory. Data are deployed from the 2002-2010 European Social Surveys (N=17

  20. Radical Change: Digital Age Literature and Learning.

    Science.gov (United States)

    Dresang, Eliza T.; McClelland, Kathryn

    1999-01-01

    Describes the concept of radical change, a theoretical construct that identifies and explains books with characteristics reflecting the types of interactivity, connectivity, and access that permeate the emerging digital society. Highlights innovative ways that authors, illustrators, and designers incorporate these features into books for…

  1. User involvement competence for radical innovation

    DEFF Research Database (Denmark)

    Lettl, Christopher

    2007-01-01

    focuses on the involvement of such users that are in the position to play an active role as inventors and (co)-developers. A multiple case study analysis was conducted in the field of medical technology. Five radical innovation projects within four firms were selected including medical robots and computer...

  2. Radical Welfare State Retrenchment: A Comparative Analysis

    DEFF Research Database (Denmark)

    Starke, Peter

    as electoral suicide, but this changed in the 1980s when Margaret Thatcher's government began a series of cutbacks in the UK. During the 1990s, the New Zealand government announced the most radical social benefit cutbacks the country had ever seen. Examining these cases in detail, and contrasting them...

  3. Ruthenium, rhodium, osmium, and iridium complexes of osazones (osazones = bis-arylhydrazones of glyoxal): radical versus nonradical states.

    Science.gov (United States)

    Patra, Sarat Chandra; Weyhermüller, Thomas; Ghosh, Prasanta

    2014-03-01

    Phenyl osazone (L(NHPh)H2), phenyl osazone anion radical (L(NHPh)H2(•-)), benzoyl osazone (L(NHCOPh)H2), benzoyl osazone anion radical (L(NHCOPh)H2(•-)), benzoyl osazone monoanion (L(NCOPh)HMe(-)), and anilido osazone (L(NHCONHPh)HMe) complexes of ruthenium, osmium, rhodium, and iridium of the types trans-[Os(L(NHPh)H2)(PPh3)2Br2] (3), trans-[Ir(L(NHPh)H2(•-))(PPh3)2Cl2] (4), trans-[Ru(L(NHCOPh)H2)(PPh3)2Cl2] (5), trans-[Os(L(NHCOPh)H2)(PPh3)2Br2] (6), trans- [Rh(L(NHCOPh)H2(•-))(PPh3)2Cl2] (7), trans-[Rh(L(NHCOPh)HMe(-))(PPh3)2Cl]PF6 ([8]PF6), and trans-[Ru(L(NHCONHPh)HMe)(PPh3)2Cl]Cl ([9]Cl) have been isolated and compared (osazones = bis-arylhydrazones of glyoxal). The complexes have been characterized by elemental analyses and IR, mass, and (1)H NMR spectra; in addition, single-crystal X-ray structure determinations of 5, 6, [8]PF6, and [9]Cl have been carried out. EPR spectra of 4 and 7 reveal that in the solid state they are osazone anion radical complexes (4, gav = 1.989; 7, 2.028 (Δg = 0.103)), while in solution the contribution of the M(II) ions is greater (4, gav = 2.052 (Δg = 0.189); 7, gav = 2.102 (Δg = 0.238)). Mulliken spin densities on L(NHPh)H2 and L(NHCOPh)H2 obtained from unrestricted density functional theory (DFT) calculations on trans-[Ir(L(NHPh)H2)(PMe3)2Cl2] (4(Me)) and trans-[Rh(L(NHCOPh)H2)(PMe3)2Cl2] (7(Me)) in the gas phase with doublet spin states authenticated the existence of L(NHPh)H2(•-) and L(NHCOPh)H2(•-) anion radicals in 4 and 7 coordinated to iridium(III) and rhodium(III) ions. DFT calculations on trans-[Os(L(NHPh)H2)(PMe3)2Br2] (3(Me)), trans-[Os(L(NHCOPh)H2)(PMe3)2Br2] (6(Me)), and trans-[Ru(L(NHCONHPh)HMe(-))(PMe3)2Cl] [9(Me)](+) with singlet spin states established that the closed-shell singlet state (CSS) solutions of 3, 5, 6, and [9]Cl are stable. The lower value of M(III)/M(II) reduction potentials and lower energy absorption bands corroborate the higher extent of mixing of d orbitals with the π* orbital

  4. Hitos de la perspectiva molar del condicionamiento clásico

    OpenAIRE

    Andrés M. Pérez Acosta; Jairo A. Rozo; Herbert T. Baquero

    2003-01-01

    En este artículo se revisan los acontecimientos históricos fundamentales en la teoría del condicionamiento clásico como fenómeno psicológico comportamental o cognoscitivo, es decir, desde una perspectiva molar, en oposición a una perspectiva molecular, que es propia de las neurociencias. Se analizan los siguientes acontecimientos o hitos: la teoría reflexológica de Vladimir Bechterev, la perspectiva conductista radical de B. F. Skinner, el modelo de Rescorla y Wagner (1972),...

  5. Isotope Effects in the Reactions of Chloroform Isotopologues with Cl, OH and OD

    DEFF Research Database (Denmark)

    Nilsson, Elna Johanna Kristina; Johnson, Matthew Stanley; Nielsen, Claus J.

    2009-01-01

    The kinetic isotope effects in the reactions of CHCl3, CDCl3, and 13CHCl3 with Cl, OH, and OD radicals have been determined in relative rate experiments at 298 ( 1 K and atmospheric pressure monitored by long path FTIR spectroscopy. The spectra were analyzed using a nonlinear least-squares spectral......, respectively. The reaction rate coefficients of the two elementary vapor phase reactions including the 2H and 13C kinetic isotope effects were calculated using improved canonical variational theory with small curvature tunneling (ICVT/SCT) and the results compared with experimental data....

  6. Investigation of the formation of benzoyl peroxide, benzoic anhydride, and other potential aerosol products from gas-phase reactions of benzoylperoxy radicals

    Science.gov (United States)

    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.

  7. Roles of external and cellular Cl- ions on the activation of an apical electrodiffusional Cl- pathway in toad skin.

    Science.gov (United States)

    Procopio, J; Lacaz-Vieira, F

    1990-07-01

    This study is concerned with the short-circuit current, Isc, responses of the Cl(-)-transporting cells of toad skin submitted to sudden changes of the external Cl- concentration, [Cl]o. Sudden changes of [Cl]o, carried out under apical membrane depolarization, allowed comparison of the roles of [Cl]o and [Cl]cell on the activation of the apical Cl- pathways. Equilibration of short-circuited skins symmetrically in K-Ringer's solutions of different Cl- concentrations permitted adjustment of [Cl]cell to different levels. For a given Cl- concentration (in the range of 11.7 to 117 mM) on both sides of a depolarized apical membrane, this structure exhibits a high Cl- permeability, P(Cl)apical. On the other hand, for the same range of [Cl]cell but with [Cl]o = 0, P(Cl)apical is reduced to negligible values. These observations indicate that when the apical membrane is depolarized P(Cl)apical is modulated by [Cl]o; in the absence of external Cl- ions, intracellular Cl- is not sufficient to activate P(Cl)apical. Computer simulation shows that the fast Cl- currents induced across the apical membrane by sudden shifts of [Cl]o from a control equilibrium value strictly follow the laws of electrodiffusion. For each experimental group, the computer-generated Isc versus [( Cl]cell - [Cl]o) curve which best fits the experimental data can only be obtained by a unique pair of P(Cl)apical and Rb (resistance of the basolateral membrane), thus allowing the calculation of these parameters. The electrodiffusional behavior of the net Cl- flux across the apical membrane supports the channel nature of the apical Cl- pathways in the Cl(-)-transporting cells. Cl- ions contribute significantly to the overall conductance of the basolateral membrane even in the presence of a high K concentration in the internal solution. PMID:1698229

  8. The magnetic susceptibility of graphite biintercalated with CoCl2 and GaCl3

    OpenAIRE

    Rosenman, I.; Batallan, F.; Simon, Ch.; Hachim, L.

    1986-01-01

    We present the first results of magnetic susceptibility on CoCl2-GaCl 3 biintercalated in graphite, and compare them with those obtained in second stage CoCl2-graphite. A fit by a power law above the maximum of the susceptibility present two regimes : in the high temperature one, the γ values are high and even higher in the CoCl2-GaCl 3 compound. This indicates that the three-dimensional coupling is lower in the biintercalation compound. In the low temperature regime, near the transition, the...

  9. Free Radicals in Superfluid Liquid Helium Nanodroplets: A Pyrolysis Source for the Production of Propargyl Radical

    CERN Document Server

    Küpper, J; Miller, R E; K\\"upper, Jochen; Merritt, Jeremy M.; Miller, Roger E.

    2002-01-01

    An effusive pyrolysis source is described for generating a continuous beam of radicals under conditions appropriate for the helium droplet pick-up method. Rotationally resolved spectra are reported for the $\

  10. THE RADICAL ONLINE: INDIVIDUAL RADICALIZATION PROCESSES AND THE ROLE OF THE INTERNET

    Directory of Open Access Journals (Sweden)

    Daniel Koehler

    2014-12-01

    Full Text Available This paper examines in detail the role of the Internet in individual radicalization processes of eight German former right-wing extremists. Applying Grounded Theory methodology the qualitative interviews were analyzed in several coding and re-coding phases. The findings are integrated into the existing literature afterwards. Besides well known factors, such as more effective communication, anonymity and better networking opportunities, this study found evidence that the Internet is a major driving factor to establish and foster the development of radical contrast societies (cf. Koehler, 2015 transmitting radical and violent ideologies and translating them into political activism. As a venue for information exchange, ideological development and training, the individual radicalization process was characteristically shaped or even made possible through the Internet. This paper also shows the high value of qualitative research regarding the topic in contrast to usually employed quantitative analysis of webpage content.

  11. Monolignol radical-radical coupling networks in western red cedar and Arabidopsis and their evolutionary implications

    Science.gov (United States)

    Kim, Myoung K.; Jeon, Jae-Heung; Davin, Laurence B.; Lewis, Norman G.

    2002-01-01

    The discovery of a nine-member multigene dirigent family involved in control of monolignol radical-radical coupling in the ancient gymnosperm, western red cedar, suggested that a complex multidimensional network had evolved to regulate such processes in vascular plants. Accordingly, in this study, the corresponding promoter regions for each dirigent multigene member were obtained by genome-walking, with Arabidopsis being subsequently transformed to express each promoter fused to the beta-glucuronidase (GUS) reporter gene. It was found that each component gene of the proposed network is apparently differentially expressed in individual tissues, organs and cells at all stages of plant growth and development. The data so obtained thus further support the hypothesis that a sophisticated monolignol radical-radical coupling network exists in plants which has been highly conserved throughout vascular plant evolution.

  12. Charge transfer from 2-aminopurine radical cation and radical anion to nucleobases: A pulse radiolysis study

    Energy Technology Data Exchange (ETDEWEB)

    Manoj, P. [School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686 560, Kerala (India); Mohan, H. [Radiation Chemistry and Chemical Dynamics Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Mittal, J.P. [Radiation Chemistry and Chemical Dynamics Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Manoj, V.M. [School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686 560, Kerala (India); Aravindakumar, C.T. [School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686 560, Kerala (India)], E-mail: CT-Aravindakumar@rocketmail.com

    2007-01-08

    Pulse radiolysis study has been carried out to investigate the properties of the radical cation of 2-aminopurine (2AP) and the probable charge transfer from the radical cation and radical anion of 2AP to natural nucleobases in aqueous medium. The radical cation of 2AP was produced by the reaction of sulfate radical anion (SO{sub 4}{sup dot-}). The time resolved absorption spectra obtained by the reaction of SO{sub 4}{sup dot-} with 2AP at neutral pH have two distinct maxima at 380 and 470nm and is assigned to the formation of a neutral radical of the form 2AP-N{sup 2}(-H){sup dot} (k{sub 2}=4.7x10{sup 9}dm{sup 3}mol{sup -1}s{sup -1} at pH 7). This neutral radical is formed from the deprotonation reaction of a very short-lived radical cation of 2AP. The transient absorption spectra recorded at pH 10.2 have two distinct maxima at 400 and 480nm and is assigned to the formation of a nitrogen centered radical (2AP-N(9){sup dot}). As the hole transport from 2AP to guanine is a highly probable process, the reaction of SO{sub 4}{sup dot-} is carried out in the presence of guanosine, adenosine and inosine. The spectrum obtained in the presence of guanosine was significantly different from that in the absence and it showed prominent absorption maxima at 380 and 470nm, and a weak broad maximum centered around 625nm which match well with the reported spectrum of a neutral guanine radical (G(-H){sup dot}). The electron transfer reaction from the radical anion of 2AP to thymine (T), cytidine (Cyd) and uridine (Urd) was also investigated at neutral pH. Among the three pyrimidines, only the transient spectrum in the presence of T gave a significant difference from the spectral features of the electron adduct of 2AP, which showed a prominent absorption maximum at 340nm and this spectrum is similar to the electron adduct spectrum of T. The preferential reduction of thymine by 2AP{sup dot-} and the oxidation of guanosine by 2AP{sup dot+} clearly follow the oxidation

  13. A novel LiCl-BaCl2:Eu2+ eutectic scintillator for thermal neutron detection

    Science.gov (United States)

    Wu, Yuntao; Lukosi, Eric D.; Zhuravleva, Mariya; Lindsey, Adam C.; Melcher, Charles L.

    2015-10-01

    A natLiCl-BaCl2:Eu2+ eutectic scintillator was synthesized by the vertical Bridgman method aiming at the application of thermal neutron detection. The molar ratio of LiCl and BaCl2 was 75.1/24.9, which corresponds to the eutectic composition in the LiCl-BaCl2 system. The grown eutectic showed a periodic microstructure of BaCl2:Eu2+ and LiCl phases with 2-3 μm thickness. The α-particle induced radioluminescence spectrum of the scintillator showed an intense emission peak at 406 nm due to the Eu2+ 5d1→4f emission from the BaCl2:Eu2+ phase and an additional weak emission peak at 526 nm. The scintillation decay time was 412 ns. LiCl-BaCl2:Eu2+ eutectic samples exhibited non-correlated neutron detection efficiency and light yield as a function of crystal length, suggesting material non-uniformities within the boule. The relative light yield was equal to or greater than that of Nucsafe lithium glass. Gamma-ray exposures indicate that gamma/neutron threshold discrimination for higher energy gamma-rays will be limited.

  14. Spectroscopy of free radicals and radical containing entrance-channel complexes in superfluid helium nanodroplets

    OpenAIRE

    Küpper, J.; Merritt, J.

    2007-01-01

    The spectroscopy of free radicals and radical containing entrance-channel complexes embedded in superfluid helium nano-droplets is reviewed. The collection of dopants inside individual droplets in the beam represents a micro-canonical ensemble, and as such each droplet may be considered an isolated cryo-reactor. The unique properties of the droplets, namely their low temperature (0.4 K) and fast cooling rates ( ~ 1016 K s-1)provides novel opportunities for the formation and high-resolution st...

  15. Environmentally Persistent Free Radicals (EPFRs) - 2. Are Free Hydroxyl Radicals Generated in Aqueous Solutions?

    OpenAIRE

    Khachatryan, Lavrent; Dellinger, Barry

    2011-01-01

    A chemical spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), in conjunction with electron paramagnetic resonance (EPR) spectroscopy was employed to measure the production of hydroxyl radical (.OH) in aqueous suspensions of 5% Cu(II)O/silica (3.9% Cu) particles containing environmentally persistent free radicals (EPFRs) of 2-monochlorophenol (2-MCP). The results indicate: 1) a significant differences in accumulated DMPO-OH adducts between EPFR containing particles and non-EPFR control sample...

  16. Unbound states of 32Cl and the 31S(p,\\gamma)32Cl reaction rate

    CERN Document Server

    Matoš, M; Linhardt, L E; Bardayan, D W; Nesaraja, C D; Clark, J A; Deibel, C M; O'Malley, P D; Parker, P D

    2011-01-01

    The 31S(p,\\gamma)32Cl reaction is expected to provide the dominant break-out path from the SiP cycle in novae and is important for understanding enrichments of sulfur observed in some nova ejecta. We studied the 32S(3He,t)32Cl charge-exchange reaction to determine properties of proton-unbound levels in 32Cl that have previously contributed significant uncertainties to the 31S(p,\\gamma)32Cl reaction rate. Measured triton magnetic rigidities were used to determine excitation energies in 32Cl. Proton-branching ratios were obtained by detecting decay protons from unbound 32Cl states in coincidence with tritons. An improved 31S(p,\\gamma)32Cl reaction rate was calculated including robust statistical and systematic uncertainties.

  17. Nitryl chloride as a 'new' radical source and its role in production of ozone in polluted troposphere: an overview of the results from four field campaigns in China

    Science.gov (United States)

    Wang, Tao; Tham, Yee Jun; Xue, Likun; Wang, Zhe; Wang, Xinfeng; Wang, Weihao; Wang, Hao; Yun, Hui; Lu, Keding; Shao, Min; Louie, Peter K. K.; Blake, Donald R.; Brown, Steven S.; Zhang, Yuanhang

    2016-04-01

    Nitryl chloride (ClNO2) - a trace gas produced from heterogeneous reactions of dinitrogen pentoxide (N2O5) on aerosols containing chorine - can significantly affect radical budget and concentrations of ozone and other secondary pollutants. However, the abundance, formation kinetics, and impact of ClNO2are not fully understood under different environmental conditions. This presentation gives an overview of recent field campaigns of ClNO2 and related chemical constituents in China, including one at a mountain top (957 m a.s.l) in Hong Kong of South China in winter 2013 and three in North China (urban Ji'nan, semi-rural Wangdu, and Mt Tai (1534 m a.s.l)) in summer 2014. ClNO2 and N2O5 were measured with a chemical ionization mass spectrometry (CIMS) system with iodide as the primary ions. Ambient concentrations of several hundreds ppts and up to 4.7 ppbv of ClNO2were observed in these locations, suggesting existence of elevated ClNO2 in both coastal and inland atmospheres of China. Measurements in North China exhibited generally low concentrations of N2O5, indicative of its fast uptake of on aerosols under aerosol and humid conditions. Indications of anthropogenic sources of chloride were observed at all these sites. The impact of photolysis of ClNO2 on radical budget and ozone enhancement was assessed with a MCM model which was updated with detailed chlorine chemistry and constrained by measurement data for the southern and a northern site. The results show that the ClNO2 could increase ozone production by 2-16% in the following day. Overall, our study re-affirms the need to include ClNO2 related reactions in photochemical models for prediction of ground-level ozone in polluted environments.

  18. Radical Scavenging Activities of Tannin Extracted from Amaranth (Amaranthus caudatus L.).

    Science.gov (United States)

    Jo, Hyeon-Ju; Chung, Kang-Hyun; Yoon, Jin A; Lee, Kwon-Jai; Song, Byeong Chun; An, Jeung Hee

    2015-06-01

    This study investigates the bioactivity of tannin from amaranth (Amaranthus caudatus L.) extracts. The antioxidant activities of the extracts from amaranth leaves, flowers, and seeds were evaluated. Tannin from leaves of amaranth has been evaluated for superoxide scavenging activity by using DPPH and ABTS(+) analysis, reducing power, protective effect against H2O2-induced oxidative damage in L-132 and BNL-CL2 cells, and inhibition of superoxide radical effects on HL-60 cells. At a concentration of 100 μg/ml, tannin showed protective effects and restored cell survival to 69.2% and 41.8% for L-132 and BNL-CL2 cells, respectively. Furthermore, at the same concentration, tannin inhibited 41% of the activity of the superoxide radical on HL-60 cells and 43.4% of the increase in nitric oxide levels in RAW 264.7 cells. The expression levels of the antioxidant-associated protein SOD-1 were significantly increased in a concentration-dependent manner in RAW 264.7 cells treated with tannin from amaranth leaves. These results suggest that tannin from the leaves of Amaranthus caudatus L. is a promising source of antioxidant component that can be used as a food preservative or nutraceutical. PMID:25639718

  19. Role of oxygen free radicals in patients with acute pancreatitis

    OpenAIRE

    Park, Byung Kyu; Chung, Jae Bock; Lee, Jin Heon; Suh, Jeong Hun; Park, Seung Woo; Song, Si Young; Kim, Hyeyoung; Kim, Kyung Hwan; Kang, Jin Kyung

    2003-01-01

    AIM: The generation of oxygen free radicals has been implicated in the pathogenesis of experimental pancreatitis. The aim of this study was to determine the role of oxygen free radicals in patients with acute pancreatitis.

  20. Self-Assembled Monolayers of a Multifunctional Organic Radical

    NARCIS (Netherlands)

    Crivillers, Núria; Mas-Torrent, Marta; Perruchas, Sandrine; Roques, Nans; Vidal-Gancedo, José; Veciana, Jaume; Rovira, Concepció; Basabe-Desmonts, Lourdes; Ravoo, Bart Jan; Crego-Calama, Mercedes; Reinhoudt, David N.

    2007-01-01

    A radical switch: Covalent and noncovalent interactions have been used to functionalize silicon oxide surfaces with polychlorotriphenylmethyl radicals, which are electroactive and can be reversibly reduced or oxidized to nonmagnetic and nonfluorescent species. Thus, the self-assembled monolayers beh

  1. Inguinal hernia developed after radical retropubic surgery for prostate cancer

    OpenAIRE

    Chung, Choon Sik; Jeong, Gyu Young; Kim, Seung Han; Lee, Dong Keun

    2013-01-01

    Purpose In this retrospective study, we aimed to compare the clinical characteristics of inguinal hernia developed after radical retropubic surgery for prostate cancer to the hernia without previous radical prostatectomy. Methods Twenty-three patients (group A) who had radical retropubic surgery for prostate cancer underwent laparoscopic or open tension-free inguinal hernia repair from March 2007 to February 2011. Nine hundred and forty patients (group B) without previous radical retropubic s...

  2. The Serbian Radical movement 1881-1903: A historical aspect

    OpenAIRE

    Protić Milan St.

    2005-01-01

    Focusing on the initial stage (until 1903) of the Serbian Radical movement the paper attempts to delineate and explicate the main phases of its political maturation. In its initial stage Serbian Radicalism passed through several significant phases. The earliest phase (1869-80) may be named the period of rudimentary Radicalism. The movement was unorganized and oscillated between the ideas of socialism, anarchism and peasant democracy. The year 1881 saw the founding of the Radical Party as the ...

  3. Free radicals, antioxidants and functional foods: Impact on human health

    OpenAIRE

    Lobo, V.; Patil, A.; A Phatak; N Chandra

    2010-01-01

    In recent years, there has been a great deal of attention toward the field of free radical chemistry. Free radicals reactive oxygen species and reactive nitrogen species are generated by our body by various endogenous systems, exposure to different physiochemical conditions or pathological states. A balance between free radicals and antioxidants is necessary for proper physiological function. If free radicals overwhelm the body's ability to regulate them, a condition known as oxidative stress...

  4. AcEST: CL39Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL39Contig1 913 36 Adiantum capillus-veneris contig: CL39contig1 sequence. Link to clone list Show CL39C...ontig1 Contig ID CL39Contig1 Length 913 Number of clones 36 Definition Adiantum capillus-veneris contig: CL39c

  5. AcEST: CL1509Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL1509Contig1 1477 3 Adiantum capillus-veneris contig: CL1509contig1 sequence. Link... to clone list Show CL1509Contig1 Contig ID CL1509Contig1 Length 1477 Number of clones 3 Definition Adiantum... capillus-veneris contig: CL1509contig1 sequence. Link to clone list Link to clone list Clone ID BP916497 DK

  6. AcEST: CL89Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL89Contig1 651 21 Adiantum capillus-veneris contig: CL89contig1 sequence. Link to clone list Show CL89C...ontig1 Contig ID CL89Contig1 Length 651 Number of clones 21 Definition Adiantum capillus-veneris contig: CL89c

  7. AcEST: CL49Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL49Contig1 701 14 Adiantum capillus-veneris contig: CL49contig1 sequence. Link to clone list Show CL49C...ontig1 Contig ID CL49Contig1 Length 701 Number of clones 14 Definition Adiantum capillus-veneris contig: CL49c

  8. AcEST: CL59Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL59Contig1 769 28 Adiantum capillus-veneris contig: CL59contig1 sequence. Link to clone list Show CL59C...ontig1 Contig ID CL59Contig1 Length 769 Number of clones 28 Definition Adiantum capillus-veneris contig: CL59c

  9. AcEST: CL227Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL227Contig1 1060 9 Adiantum capillus-veneris contig: CL227contig1 sequence. Link to clone list Show CL2...27Contig1 Contig ID CL227Contig1 Length 1060 Number of clones 9 Definition Adiantum capillus-veneris contig: CL2

  10. AcEST: CL22Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL22Contig1 1518 45 Adiantum capillus-veneris contig: CL22contig1 sequence. Link to clone list Show CL2...2Contig1 Contig ID CL22Contig1 Length 1518 Number of clones 45 Definition Adiantum capillus-veneris contig: CL2

  11. AcEST: CL267Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL267Contig1 922 8 Adiantum capillus-veneris contig: CL267contig1 sequence. Link to clone list Show CL2...67Contig1 Contig ID CL267Contig1 Length 922 Number of clones 8 Definition Adiantum capillus-veneris contig: CL2

  12. AcEST: CL270Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL270Contig1 687 7 Adiantum capillus-veneris contig: CL270contig1 sequence. Link to clone list Show CL2...70Contig1 Contig ID CL270Contig1 Length 687 Number of clones 7 Definition Adiantum capillus-veneris contig: CL2

  13. AcEST: CL265Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL265Contig1 1000 8 Adiantum capillus-veneris contig: CL265contig1 sequence. Link to clone list Show CL2...65Contig1 Contig ID CL265Contig1 Length 1000 Number of clones 8 Definition Adiantum capillus-veneris contig: CL2

  14. AcEST: CL230Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL230Contig1 829 9 Adiantum capillus-veneris contig: CL230contig1 sequence. Link to clone list Show CL2...30Contig1 Contig ID CL230Contig1 Length 829 Number of clones 9 Definition Adiantum capillus-veneris contig: CL2

  15. AcEST: CL29Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL29Contig1 903 40 Adiantum capillus-veneris contig: CL29contig1 sequence. Link to clone list Show CL2...9Contig1 Contig ID CL29Contig1 Length 903 Number of clones 40 Definition Adiantum capillus-veneris contig: CL2

  16. AcEST: CL253Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL253Contig1 644 8 Adiantum capillus-veneris contig: CL253contig1 sequence. Link to clone list Show CL2...53Contig1 Contig ID CL253Contig1 Length 644 Number of clones 8 Definition Adiantum capillus-veneris contig: CL2

  17. AcEST: CL204Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL204Contig1 503 2 Adiantum capillus-veneris contig: CL204contig1 sequence. Link to clone list Show CL2...04Contig1 Contig ID CL204Contig1 Length 503 Number of clones 2 Definition Adiantum capillus-veneris contig: CL2

  18. Generation and propagation of radical reactions on proteins

    DEFF Research Database (Denmark)

    Hawkins, C L; Davies, Michael Jonathan

    2001-01-01

    The oxidation of proteins by free radicals is thought to play a major role in many oxidative processes within cells and is implicated in a number of human diseases as well as ageing. This review summarises information on the formation of radicals on peptides and proteins and how radical damage may...

  19. Hybrid radical energy storage device and method of making

    Energy Technology Data Exchange (ETDEWEB)

    Gennett, Thomas; Ginley, David S.; Braunecker, Wade; Ban, Chunmei; Owczarczyk, Zbyslaw

    2016-04-26

    Hybrid radical energy storage devices, such as batteries or electrochemical devices, and methods of use and making are disclosed. Also described herein are electrodes and electrolytes useful in energy storage devices, for example, radical polymer cathode materials and electrolytes for use in organic radical batteries.

  20. Biochemistry and pathology of radical-mediated protein oxidation

    DEFF Research Database (Denmark)

    Dean, R T; Fu, S; Stocker, R;

    1997-01-01

    Radical-mediated damage to proteins may be initiated by electron leakage, metal-ion-dependent reactions and autoxidation of lipids and sugars. The consequent protein oxidation is O2-dependent, and involves several propagating radicals, notably alkoxyl radicals. Its products include several catego...

  1. α-Carbonyl Radical Cyclizatio n in Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Intramolecular radical cyclization reactions are now used routinely to synthesize carbocyclic and heterocyclic structures. We have reported that α-carbonyl radicals 1, generated from the corresponding iodo ketones or enones, underwent intramolecular radical cyclization smoothly to afford products 2.1, 2,3

  2. On Sensitivity of HE CL-20

    Institute of Scientific and Technical Information of China (English)

    Yu. V. Sheikov; L. A. Andrievskikh; V. G. Vasipenko; S. A. Vakhmistrov; N. N. Zhbanova; V. B. Kosolapov; L.V.Fomicheva

    2004-01-01

    @@ 1 Introduction Recently a series of publications appeared in literature devoted to study of properties of hexanitrohexaazaisowurtzitan( CL-20), which is considered as an explosive with performance higher than that of HMX, and which has moderate sensitivity[1].

  3. Equations for calculation of NaCl/( NaCl + CaCl2 ) ratios and salinities from hydrohalite-melting and ice-melting temperatures in the H2O-NaCl-CaCl2 system%利用H2O-NaCl-CaCl2体系水盐化合物和冰的融化温度计算NaCl/(NaCl+CaCl2)比值和盐度的方程

    Institute of Scientific and Technical Information of China (English)

    Guoxiang Chi; Pei Ni

    2007-01-01

    The composition of fluid inclusions in the H2O-NaCl-CaCl2 system has been generally graphically estimated using the melting temperatures of hydrohalite ( Tm-HH ) and ice ( Tm-ice ). Here we present two equations that can be used to calculate the relative proportion of NaCl ( i. e. , NaCt/[ NaCl + CaCl2 ], or XNaCl) and the total salinity ( i. e. , NaCl + CaCl2, wt% ) for fluid inclusions with ice as the last melting phase. XNaCl can be calculated from Tm-HH using the following equation:y= ( a + bx)-1/c where y is XNaCl, x is Tm-HH, a =0. 33124402, b = -0.031518028, and c =0. 22932736. In the cases where only Tm-ice is measured and Tm-HH is not known, Tm-ice can be used as the maximum possible Tm-HH to calculate the maximum value of XNaCl using the above equation. In these cases, the following equation can be used to calculate the maximum total salinity: y = (a +bx +cx2) -1 where y is salinity, x is Tm-HH, a = 0. 057184817, b = 0. 00078565757, and c = 5. 7262766E-6. Because the isothems in the field of ice are sub-parallel to the NaCl-CaCl2 binary side in the H2O-NaCl-CaCl2 ternary system, the errors in salinity calculation introduced by the above approximation are small ( less than 2 wt% ). A Windows program for calculation of XNacl and salinity is available at: http ://uregina. ca/~ chiguox.

  4. Radical radiotherapy for carcinoma of the vulva

    International Nuclear Information System (INIS)

    A study was made of 58 patients with carcinoma of the vulva treated by radical radiotherapy between 1965 and 1982. The choice of treatment technique was influenced by site and extent of disease as well as the general condition of the patient. The crude 5-year survival was 26% (15/58). Local control was achieved in 40% of cases and was associated with tumour size of 4 cm or less. Radionecrosis occurred in nine cases but none of these required surgical intervention. Surgery remains the treatment of choice for carcinoma of the vulva. This report emphasizes that radical radiotherapy has a curative potential in those cases considered unsuitable for surgery and that the necrosis type and rate are within the limits of acceptable morbidity. (author)

  5. Freedom Now! Radical Jazz and Social Movements

    Directory of Open Access Journals (Sweden)

    Przemysław Pluciński

    2014-01-01

    Full Text Available Music is obviously not only an aesthetic phenomenon. It is embeddedin a dense network of social relations. However, its social involvementis rather ambiguous, particularly since the second half of the twentiethcentury. On the one hand, music is one of the main elements of culturalcapitalism and a part of the system of domination. On the other hand,music provokes, (coproduces or possibly strengthens and coexists witha number of counterdiscourses and social projects of counterhegemoniccharacter.The main objective of the paper is to examine relationships between both, revolutionary jazz and revolutionary social movements, namely the civil rights movement, but above all radical movements, especially black power movement. The crucial questions I am interested in are problems of selforganization, performative social practices, as well as alternatives elaborated by radical-oriented jazz circles in various social dimensions, for instance economic or symbolic.

  6. Regularities and Radicals in Near-rings

    Institute of Scientific and Technical Information of China (English)

    N.J. Groenewald

    2002-01-01

    Let F be a regularity for near-rings and F(R) the largest FR-regular ideal in R. In the first part of this paper, we introduce the concepts of maximal Fmodular ideals and F-primitive near-rings to characterize F(R) for any near-ring regularity F. Under certain conditions, F(R) is equal to the intersection of all the maximal F-modular ideals of R. As examples, we apply this to the different analogs of the Brown-McCoy radicals and also the Behrens radicals. In the last part of this paper, we show that for certain regularities, the class of F-primitive near-rings forms a special class.

  7. Radical radiotherapy for carcinoma of the vulva

    Energy Technology Data Exchange (ETDEWEB)

    Slevin, N.J.; Pointon, R.C.S.

    1989-02-01

    A study was made of 58 patients with carcinoma of the vulva treated by radical radiotherapy between 1965 and 1982. The choice of treatment technique was influenced by site and extent of disease as well as the general condition of the patient. The crude 5-year survival was 26% (15/58). Local control was achieved in 40% of cases and was associated with tumour size of 4 cm or less. Radionecrosis occurred in nine cases but none of these required surgical intervention. Surgery remains the treatment of choice for carcinoma of the vulva. This report emphasizes that radical radiotherapy has a curative potential in those cases considered unsuitable for surgery and that the necrosis type and rate are within the limits of acceptable morbidity.

  8. Anion photoelectron spectroscopy of radicals and clusters

    Energy Technology Data Exchange (ETDEWEB)

    Travis, Taylor R.

    1999-12-16

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying {sup 2}{Sigma} and {sup 2}{Pi} states of C{sub 2n}H (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C{sub 2}H and C{sub 4}H. Other radicals studied include NCN and I{sub 3}. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I{sub 3} revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  9. EPR study of free radicals in bread

    Science.gov (United States)

    Yordanov, Nicola D.; Mladenova, Ralitsa

    2004-05-01

    The features of the recorded EPR spectra of paramagnetic species formed in bread and rusk are reported. The appearance of free radicals in them is only connected with their thermal treatment since the starting materials (flour and grains) exhibit very weak EPR signal. The obtained EPR spectra are complex and indicate that: (i) the relative number of paramagnetic species depends on the temperature and treating time of the raw product; (ii) the g-values are strongly temperature dependent with a tendency to coincide at t≥220 °C. Because of the relatively low (150-220 °C) temperature of thermal treatment, the studied free radicals can be assumed to appear in the course of the browning (Maillard) reaction and not to the carbonization of the material.

  10. Editorial: RADICALISM AND POLITICS OF RELIGION

    Directory of Open Access Journals (Sweden)

    Editorial Al-Jami'ah: Journal of Islamic Studies

    2008-02-01

    Full Text Available Radical Islamism has become the “sexiest” issue in the international scholarship of religion since the September 11 tragedy in 2001. It has been associated with a number of terrorist attacks not only in the West but also in Muslim countries. Every single of radical Islamism has caught the interest of not only scholars and policy makers but also general public. Interestingly, the general assumption that religion is the source of peace has been seriously challenged, not by non-religious communities, but by the violent practices of particular religious groups, however small they are. Indeed, there are certain groups striving for Islam but by using acts which could give awful image on Islam itself and against humanity.

  11. Lipid modification processes induced by thiyl radicals

    Science.gov (United States)

    Mihaljević, Branka; Bujak, Ivana Tartaro

    2016-07-01

    Polyunsaturated fatty acid (PUFA) oxidation by thiyl radicals (RS•) is believed to be responsible for some of the biological radiation damage. At the same time, RS• can cause isomerization of PUFA double bonds with the formation of trans isomers. The aim of this study was to better understand the competition between lipid peroxidation and geometrical isomerization processes in biomimetic model system of linoleic acid in the presence of 2-mercaptoethanol using irradiation as a method for free radicals generation. In air-equilibrated conditions the propagation of lipid peroxidation was dominant up to the dose of 400 Gy, after which at higher doses up to 10 kGy the termination occurred with the predominance of geometrical isomerization. This study revealed that undesirable and permanent lipid modifications are possible at higher irradiation doses which should be considered in the planning of irradiation treatment of foods and feeds with high content of lipids and sulfur compounds.

  12. Prediction of CL-20 chemical degradation pathways, theoretical and experimental evidence for dependence on competing modes of reaction

    Energy Technology Data Exchange (ETDEWEB)

    Qasim, Mohammad M.; Fredrickson, Herbert L.; Honea, P.; Furey, John; Leszczynski, Jerzy; Okovytyy, S.; Szecsody, Jim E.; Kholod, Y.

    2005-10-01

    Highest occupied and lowest unoccupied molecular orbital energies, formation energies, bond lengths and FTIR spectra all suggest competing CL-20 degradation mechanisms. This second of two studies investigates recalcitrant, toxic, aromatic CL-20 intermediates that absorb from 370 to 430 nm. Our earlier study (Struct. Chem., 15, 2004) revealed that these intermediates were formed at high OH- concentrations via the chemically preferred pathway of breaking the C-C bond between the two cyclopentanes, thereby eliminating nitro groups, forming conjugated π bonds, and resulting in a pyrazine three-ring aromatic intermediate. In attempting to find and make dominant a more benign CL-20 transformation pathway, this current research validates hydroxylation results from both studies and examines CL-20 transformations via photo-induced free radical reactions. This article discusses CL-20 competing modes of degradation revealed through: computational calculation; UV/VIS and SF spectroscopy following alkaline hydrolysis; and photochemical irradiation to degrade CL-20 and its byproducts at their respective wavelengths of maximum absorption.

  13. Prediction of CL-20 chemical degradation pathways, theoretical and experimental evidence for dependence on competing modes of reaction.

    Science.gov (United States)

    Qasim, M; Fredrickson, H; Honea, P; Furey, J; Leszczynski, J; Okovytyy, S; Szecsody, J; Kholod, Y

    2005-10-01

    Highest occupied and lowest unoccupied molecular orbital energies, formation energies, bond lengths and FTIR spectra all suggest competing CL-20 degradation mechanisms. This second of two studies investigates recalcitrant, toxic, aromatic CL-20 intermediates that absorb from 370 to 430 nm. Our earlier study (Struct. Chem., 15, 2004) revealed that these intermediates were formed at high OH(-) concentrations via the chemically preferred pathway of breaking the C-C bond between the two cyclopentanes, thereby eliminating nitro groups, forming conjugated pi bonds, and resulting in a pyrazine three-ring aromatic intermediate. In attempting to find and make dominant a more benign CL-20 transformation pathway, this current research validates hydroxylation results from both studies and examines CL-20 transformations via photo-induced free radical reactions. This article discusses CL-20 competing modes of degradation revealed through: computational calculation; UV/VIS and SF spectroscopy following alkaline hydrolysis; and photochemical irradiation to degrade CL-20 and its byproducts at their respective wavelengths of maximum absorption. PMID:16272046

  14. OpenCL programming using Python syntax

    OpenAIRE

    Massimo Di Pierro

    2013-01-01

    We describe ocl, a Python library built on top of p yOpenCL and numpy. It allows programming GPU devices using Python. Python functions which ar e marked up using the provided decorator, are converted into C99/OpenCL and compil ed using the JIT at runtime. This approach lowers the barrier to entry to programming GPU devices since it requires only Python syntax and no external compilation or linkin g steps. The resulting Pyth...

  15. How Hume's Philosophy Informed Radical Behaviorism.

    Science.gov (United States)

    Nuzzolilli, Andrew E; Diller, James W

    2015-05-01

    The present paper analyzes consistencies between the philosophical systems of David Hume and B. F. Skinner, focusing on their conceptualization of causality and attitudes about scientific behavior. The ideas that Hume initially advanced were further developed in Skinner's writings and shaped the behavior-analytic approach to scientific behavior. Tracing Skinner's logical antecedents allows for additional historical and philosophical clarity when examining the development of radical behaviorism.

  16. The radical of a vertex operator algebra

    OpenAIRE

    Dong, C.; Li, H.; Mason, G.; Montague, P

    1996-01-01

    The radical $J(V)$ of a vertex operator algebra $V$ is defined to be the subspace of $V$ consisting of vectors $v$ such that the zero mode $o(v)=0$ on $V$ where $o(v)=v_{wt v-1}$ if $v$ is homogeneous. We establish various facts about $o(v),$ including the determination of $J(V)$ which is shown to be essentially equal to $(L(0)+L(-1))V.$

  17. EARLY POSTOPERATIVE COMPLICATIONS AFTER RADICAL CYSTECTOMY

    Directory of Open Access Journals (Sweden)

    V. O. Mager

    2014-08-01

    Full Text Available Radical cystectomy (RCE is associated with a considerable number of early postoperative complications as before. Based on 10 years’ experience, this paper demonstrates the frequency (33.9 % and types of early complications following RCE, as well as postoperative mortality (5.5 % and its resulting causes. Although postoperative mortality is relatively low today, the frequency of early postoperative complications remains high as before.

  18. EI igualitarismo radical de John Rawls

    OpenAIRE

    Rodríguez Zepeda, Jesús

    2004-01-01

    The main purpose of this paper is to offer an interpretation of the canonical statement of justice as fairness (A Theory of Justice) as a deeply egalitarian, even radical, argument. In order to do so, the categories of justice as fairness strongly related to the egalitarian and distributive meaning of the rawlsian liberal model and, specifically, those aimed to solve the problem of social justice, are accurately revised, namely, the fair equality of opportunity and the diff...

  19. The Electronic Dissertation: A less radical approach

    OpenAIRE

    Andre Costopoulos

    1999-01-01

    Cornelius Holtorf's article in Internet Archaeology, Issue 6 (1999) is a strident call for a radical application of hypermedia techniques to archaeological publishing. Like Holtorf, I recently produced and submitted a Ph.D. dissertation on electronic medium entitled Simulation and Modelling for Anthropological Archaeology (Costopoulos, 1999). My experience of the process, however, was quite different from Holtorf's. While his work concentrates on the hypertextuality of electronic media, mine ...

  20. AQUEOUS STABLE FREE RADICAL POLYMERIZATION PROCESSES

    Institute of Scientific and Technical Information of China (English)

    Andrea R. Szkurhan; Michael K. Georges

    2004-01-01

    An overview of aqueous polymerizations, which include emulsion, miniemulsion and suspension polymerizations,under stable free radical polymerization (SFRP) conditions is presented. The success of miniemulsion and suspension SFRP polymerizations is contrasted with the difficulties associated with obtaining a stable emulsion polymerization. A recently developed unique microprecipitation technique is referenced as a means of making submicron sized particles that can be used to achieve a stable emulsion SFRP process.

  1. "JCE" Classroom Activity Connections: NaCl or CaCl[subscript 2], Smart Polymer Gel Tells More

    Science.gov (United States)

    Chen, Yueh-Huey; Lin, Jia-Ying; Wang, Yu-Chen; Yaung, Jing-Fun

    2010-01-01

    This classroom activity connection demonstrates the differences between the effects of NaCl (a salt of monovalent metal ions) and CaCl[subscript 2] (a salt of polyvalent metal ions) on swollen superabsorbent polymer gels. Being ionic compounds, NaCl and CaCl[subscript 2] both collapse the swollen polymer gels. The gel contracted by NaCl reswells…

  2. Radiocarbon dating and the 36Cl/Cl evolution of three Great Artesian Basin wells at Dalhousie, South Australia

    Science.gov (United States)

    Abu Risha, Usama A.

    2016-06-01

    The use of 14C (half-life = 5,730 years) in modeling the evolution of the 36Cl/Cl ratios in groundwater is reported for the first time. The complexity of the Cl-36Cl system due to the occurrence of different Cl and 36Cl sources and the difficulty of the determination of the initial groundwater 36Cl/Cl ratios have raised concerns about the reliability of using 36Cl (half-life = 301 thousand years, a) as a groundwater-dating tool. This work uses groundwater 14C age as a calibrating parameter of the Cl-36Cl/Cl decay-mixing models of three wells from the southwestern Great Artesian Basin (GAB), Australia. It aims to allow for the different sources of Cl and 36Cl in the southwestern GAB aquifer. The results show that the initial Cl concentrations range from 245 to 320 mg/l and stable Cl is added to groundwater along flowpaths at rates ranging from 1.4 to 3.5 mg/l/ka. The 36Cl content of the groundwater is assumed to be completely of atmospheric origin. The samples have different Cl-36Cl/Cl mixing-decay models reflecting recharge under different conditions as well as the heterogeneity of the aquifer.

  3. Phase diagrams for the binary systems NdCl3-LiCl and PrCl3-LiCl

    OpenAIRE

    Kim, I; 岡本芳浩

    1999-01-01

    NdCl3-LiCl及びPrCl3-LiClの各2成分系の相状態を、200~800circCの範囲における示差熱分析及び急冷したサンプルの室温X線回折によって調べた。NdCl3-LiCl系では、31mol%NdCl3の組成に共晶(456circC)が見られたのに加えて、包晶点(467circC)の存在が観測された。一方、PrCl3-LiCl系では同じく31mol%PrCl3の組成に共晶(464circC)が見いだされたのみで包晶の存在は確認されなかった。これらの結晶をもとに、各2成分系の状態図を作成した。...

  4. Radical correction of Budd-Chiari syndrome

    Institute of Scientific and Technical Information of China (English)

    LI Xiao-qiang; WANG Zhong-gao; MENG Qing-you; SANG Hong-fei; QIAN Ai-min; DUAN Peng-fei; RONG Jian-jie

    2007-01-01

    Background Interventional therapy is widely accepted as the first choice for the treatment of the Budd-Chiari syndrome,but the use of radical correctional therapy should not be discarded. This study describes radical correction by controlling bleeding from distal end of pathological segment of the inferior vena cava (IVC) and discusses potential surgical errors and postoperative complications.Methods Of the 216 patients in the study, 78 were treated with simple membranectomy, 64 with dissection of the pathological segment of the IVC and vascular prosthesis or pericardial patch plasty, 60 with resection of the pathological segment of the IVC and orthotopic graft transplantation with vascular prosthesis, and 14 with resection of the occlusive main hepatic vein and its upper IVC, hepatic venous outflow plasty and vascular prosthesis orthotopic graft transplantation from the hepatic venous entrance to the IVC of right atrial ostium.Results Except 14 cases who were discharged after hepatic vein outflow plasty, four cases died postoperatively, and 198 patients were discharged without complications. The symptoms of 15 patients were relieved partially and 2 without any change. There were no deaths intraoperatively. Of the 112 cases who were followed up for 72 months, 13 suffered from a relapse.Conclusions Radical correction is a beneficial therapy in the treatment of Budd-Chiari syndrome.

  5. Radical induction theory of ulcerative colitis

    Institute of Scientific and Technical Information of China (English)

    Jay Pravda

    2005-01-01

    To propose a new pathogenesis called Radical Induction to explain the genesis and progression of ulcerative colitis (UC). UC is an inflammatory bowel disease. Colonic inflammation in UC is mediated by a buildup of white blood cells (WBCs) within the colonic mucosal lining; however,to date there is no answer for why WBCs initially enter the colonic mucosa to begin with. A new pathogenesis termed "Radical Induction Theory" is proposed to explain this and states that excess un-neutralized hydrogen peroxide, produced within colonic epithelial cells as a result of aberrant cellular metabolism, diffuses through cell membranes to the extracellular space where it is converted to the highly damaging hydroxyl radical resulting in oxidative damage to structures comprising the colonic epithelial barrier. Once damaged, the barrier is unable to exclude highly immunogenic fecal bacterial antigens from invading the normally sterile submucosa. This antigenic exposure provokes an initial immune response of WBC infiltration into the colonic mucosa. Once present in the mucosa,WBCs are stimulated to secrete toxins by direct exposure to fecal bacteria leading to mucosal ulceration and bloody diarrhea characteristic of this disease.

  6. Removal of NOx by radical injection

    Institute of Scientific and Technical Information of China (English)

    LIN He; GAO Xiang; LUO Zhongyang; CEN Kefa; PEI Meixiang; HUANG Zhen

    2004-01-01

    Removal of NOx ( DeNOx, NOx is the total of NO and NO2) from flue gas by radical injection has been investigated . The discharge characteristics were examined and the steady streamer corona was acquired by adjusting the nozzle gases properly. It was found that an increase in the voltage resulted in a decrease in the NO concentration and the concentration of the NO2 increased at low voltages but decreased as the voltage rose to a certain level. The DeNOx efficiency increased as the applied voltage rose and reached a maximum of 70% when the voltage approached the breakdown voltage. The hypothetical mechanism of NOx removal suggested that the radicals formed in the discharge process converted the NO and NO2 into acidic species. The Monte Carlo method was used to calculate the rate coefficients and the productivity of the radicals, and then the concentrations of both NO and NO2 and the DeNOx efficiencies were calculated with chemical kinetics. The calculated DeNOx efficiencies were comparable with the experimental DeNOx efficiencies at low voltages, but were lower at high voltages.

  7. [Free radicals and hepatic ischemia-reperfusion].

    Science.gov (United States)

    Szijártó, Attila

    2015-11-22

    The critical importance of the ischemic-reperfusive injury is well documented with regards to numerous organs and clinical conditions. Oxygen free radicals play a central role in the mediation of the injury, which dominantly influences the prevalence of postoperative complications, (long term) organ damage, and the potential manifestation of systemic reactions. The both anatomically and pathophysiologically unique ischemic-reperfusive injury of the liver, which is expressively vulnerable to free radicals, is of utmost importance in liver surgery. Several techniques (adaptive maneuvers, chemical agents) are known to ameliorate the reperfusive injury. Based on the prior research of the workgroup of the author, the aim of the current article is to overview the set of measures capable of attenuating ischemic-reperfusive injury (ischemic preconditioning, -perconditioning, administration of adenosine, -inosine, -levosimendan, and -poly-ADP-ribose-polymerase inhibitor), with special attention to the ischemic-reperfusive injury of the liver, as well as the special pathophysiological role of free radicals in mediating hepatic damage.

  8. Complications of Radical Cystectomy and Orthotopic Reconstruction

    Directory of Open Access Journals (Sweden)

    Wei Shen Tan

    2015-01-01

    Full Text Available Radical cystectomy and orthotopic reconstruction significant morbidity and mortality despite advances in minimal invasive and robotic technology. In this review, we will discuss early and late complications, as well as describe efforts to minimize morbidity and mortality, with a focus on ileal orthotopic bladder substitute (OBS. We summarise efforts to minimize morbidity and mortality including enhanced recovery as well as early and late complications seen after radical cystectomy and OBS. Centralisation of complex cancer services in the UK has led to a fall in mortality and high volume institutions have a significantly lower rate of 30-day mortality compared to low volume institutions. Enhanced recovery pathways have resulted in shorter length of hospital stay and potentially a reduction in morbidity. Early complications of radical cystectomy occur as a direct result of the surgery itself while late complications, which can occur even after 10 years after surgery, are due to urinary diversion. OBS represents the ideal urinary diversion for patients without contraindications. However, all patients with OBS should have regular long term follow-up for oncological surveillance and to identify complications should they arise.

  9. Global modelling of the ClNO2 production impact on tropospheric nitrogen oxides and main oxidants

    Science.gov (United States)

    Cuevas Rodríguez, Carlos Alberto; Brown, Steven S.; Lamarque, Jean-Francoise; Saiz-Lopez, Alfonso; Kinnison, Douglas E.; Lopez-Hilfiker, Felipe; Thornton, Joel A.; Jaegle, Lyatt; Fibiger, Dorothy; McDuffie, Erin E.; Sullivan, Amy P.; Weber, Rodney J.; Dibb, Jack

    2016-04-01

    Heterogeneous uptake of dinitrogen pentoxide, N2O5, to aerosol is one of the most important reactions controlling the global budget of nitrogen oxides, with subsequent impacts on oxidants such as ozone and hydroxyl radical. Most chemistry global models assume that this uptake proceeds through hydrolysis to produce nitric acid, effectively a terminal sink for nitrogen oxides. However, recent field studies have shown that the yield of nitryl chloride, ClNO2, from N2O5 uptake is significant in many locations. Because ClNO2 photolyzes subsequent to its nighttime production to recycle NO2 and produce atomic chlorine, a potent oxidant, the impact of heterogeneous N2O5 uptake and the role of ClNO2 on the scale distribution of oxidants need to be re-assessed. Here we present global simulations using the chemistry-climate model CAM-Chem, including a state of the art halogen chemistry scheme and different assumptions for the magnitude and spatial distribution of ClNO2 yields from N2O5. The model shows a significant effect of ClNO2 production on tropospheric ozone, hydroxyl radical and peroxyacyl nitrates (PAN) during northern hemisphere late winter and early spring. Simulations are compared to observations from recent field campaigns, including ClNO2 and N2O5 from the Wintertime INvestigation of Transport, Emissions and Reactivity (WINTER) study on the NSF / NCAR C-130 aircraft on the U.S. East Coast in February and March of 2015.

  10. Electric conductivity of PCl5-ZrCl4, PCl5-TaCl5, and PCl5-MoCl5 molten mixtures

    International Nuclear Information System (INIS)

    When mixing individual molecular melts of PCl5 with ZrCl4, TaCl5 or with MoCl5, an essential (by several orders) increase in electric conductivity (up to 0.02-0.1 Ohm-1·cm-1), which stems, in all probability, from the appearance of complex ions PCl4+, ZrCl5-, ZrCl62-, TaCl5- and MoCl6- in the molten mixtures as a result of chemical interaction

  11. Reduction behavior of cerium(Ⅲ) ions in NaCl-2CsCl melt

    Institute of Scientific and Technical Information of China (English)

    QI Xue; ZHU Hongmin

    2005-01-01

    The cathodic process of cerium(Ⅲ) ions in NaCl-2CsCl melt was studied by cyclic voltammetry and square wave voltammetry with tungsten and gold electrodes at 873 K. The two electroanalytical methods yield similar results. The cathodic process of cerium(Ⅲ) ions consists of two reversible steps: Ce3+ + e-= Ce2+ and Ce2+ + 2e-= Ce. The half wave potentials of Ce3+/Ce2+ and Ce2+/Ce were determined as -2.525 V vs. Cl2/Cl- and -2.975 V vs. Cl2/Cl-, respectively. The diffusion coefficient of Ce3+ was also determined as 5.5 × 10-5 cm2·s-1.

  12. Reactivity of chlorine radical with submicron palmitic acid particles: kinetic measurements and products identification

    Directory of Open Access Journals (Sweden)

    M. Mendez

    2013-06-01

    Full Text Available The heterogeneous reaction of Cl. radicals with sub-micron palmitic acid (PA particles was studied in an aerosol flow tube in the presence or in the absence of O2. Fine particles were generated by homogeneous condensation of PA vapors and introduced in the reactor where chlorine atoms are produced by photolysis of Cl2 using UV lamps surrounding the reactor. The effective reactive uptake coefficient (γ has been determined from the rate loss of PA measured by GC/MS analysis of reacted particles as a function of the chlorine exposure. In the absence of O2, γ = 14 ± 5 indicates efficient secondary chemistry involving Cl2. GC/MS analyses have shown the formation of monochlorinated and polychlorinated compounds in the oxidized particles. Although, the PA particles are solid, the complete mass can be consumed. In the presence of oxygen, the reaction is still dominated by secondary chemistry but the propagation chain length is smaller than in the absence of O2 which leads to an uptake coefficient γ = 3 ± 1. In the particulate phase, oxocarboxylic acids and dicarboxylic acids are identified by GC/MS. Formation of alcohols and monocarboxylic acids are also suspected. All these results show that solid organic particles could be efficiently oxidized by gas-phase radicals not only on their surface, but also in bulk by mechanisms which are still unclear. Furthermore the identified reaction products are explained by a chemical mechanism showing the pathway of the formation of more functionalized products. They help to understand the aging of primary tropospheric aerosol containing fatty acids.

  13. Growing up Radical: Investigation of Benzyl-Like Radicals with Increasing Chain Lengths

    Science.gov (United States)

    Korn, Joseph A.; Jawad, Khadija M.; Hewett, Daniel M.; Zwier, Timothy S.

    2015-06-01

    Combustion processes involve complex chemistry including pathways leading to polyaromatic hydrocarbons (PAHs) from small molecule precursors. Resonance stabilized radicals (RSRs) likely play an important role in the pathways to PAHs due to their unusual stability. Benzyl radical is a prototypical RSR that is stabilized by conjugation with the phenyl ring. Earlier work on α-methyl benzyl radical showed perturbations to the spectroscopy due to a hindered methyl rotor. If the alkyl chain is lengthened then multiple conformations become possible. This talk will discuss the jet-cooled spectroscopy of α-ethyl benzyl radical and α-propyl benzyl radical produced from the discharge of 1-phenyl propanol and 1-phenyl butanol respectively. Electronic spectra were obtained via resonant two-photon ionization, and IR spectra were obtained by resonant ion-dip infrared spectroscopy. Kidwell, N. M.; Reilly, N. J.; Nebgen, B.; Mehta-Hurt, D. N.; Hoehn, R. D.; Kokkin, D. L.; McCarthy, M. C.; Slipchenko, L. V.; Zwier, T. S. The Journal of Physical Chemistry A 2013, 117, 13465.

  14. Peroxy radical chemistry and OH radical production during the NO3-initiated oxidation of isoprene

    Directory of Open Access Journals (Sweden)

    P. O. Wennberg

    2012-01-01

    Full Text Available Peroxy radical reactions (RO2 + RO2 from the NO3-initiated oxidation of isoprene are studied with both gas chromatography and a chemical ionization mass spectrometry technique that allows for more specific speciation of products than in previous studies of this system. We find high nitrate yields (>~80%, consistent with other studies. We further see evidence of significant hydroxyl radical (OH formation in this system, which we propose comes from RO2 + HO2 reactions with a yield of ~42–62%. An additional OH source is the second generation oxidation of the nitrooxyhydroperoxide, which produces OH and a dinitrooxyepoxide with a yield of ~35%. The branching ratio of the radical propagating, carbonyl- and alcohol-forming, and dimer-forming channels of the RO2 + RO2 reaction are found to be ~18–38%, ~59–77%, and ~3–4%, respectively. HO2 formation in this system is lower than has been previously assumed. Addition of RO2 to isoprene is suggested as a possible route to the formation of several isoprene dimer compounds (ROOR. The nitrooxy, allylic, and C5 peroxy radicals present in this system exhibit different behavior than the limited suite of peroxy radicals that have been studied to date.

  15. Characterization of the interaction between collectin 11 (CL-11, CL-K1) and nucleic acids

    DEFF Research Database (Denmark)

    Henriksen, Maiken Lumby; Brandt, Jette; Iyer, Sinduja S C;

    2013-01-01

    to changes in ionic strength and pH. Competition studies show that CL-11 binds to nucleic acids and carbohydrates via separate binding-sites and oligomericity appears crucial for binding activity. Combined interaction with DNA and mannan strongly increases binding avidity. By surface plasmon resonance we...... estimate the dissociation constant for the binding between CL-11 and double stranded DNA oligonucleotides to KD=9-20nM. In an in vitro assay we find that CL-11 binds to DNA coated surfaces, which leads to C4b deposition via MASP-2. We propose that CL-11, e.g. via complement, may play a role in response...

  16. Electrochemical Deposition of Aluminum from NaCl-AlCl3 Melts

    DEFF Research Database (Denmark)

    Li, Qingfeng; Hjuler, H. A.; Berg, Rolf W.;

    1990-01-01

    Electrochemical deposition of aluminum from NaAlCl4 melts saturated with NaCl onto a glassy carbon electrode at175°C has been studied by voltammetry, chronoamperometry, and constant current deposition. The deposition of aluminumwas found to proceed via a nucleation/growth mechanism, and the nucle......Electrochemical deposition of aluminum from NaAlCl4 melts saturated with NaCl onto a glassy carbon electrode at175°C has been studied by voltammetry, chronoamperometry, and constant current deposition. The deposition of aluminumwas found to proceed via a nucleation/growth mechanism...

  17. Covalently Bound Nitroxyl Radicals in an Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Hughes, Barbara K.; Braunecker, Wade A.; Bobela, David C.; Nanayakkara, Sanjini U.; Reid, Obadiah G.; Johnson, Justin C.

    2016-09-15

    A series of covalent organic framework (COF) structures is synthesized that possesses a tunable density of covalently bound nitroxyl radicals within the COF pores. The highest density of organic radicals produces an electron paramagnetic resonance (EPR) signal that suggests the majority of radicals strongly interact with other radicals, whereas for smaller loadings the EPR signals indicate the radicals are primarily isolated but with restricted motion. The dielectric loss as determined from microwave absorption of the framework structures compared with an amorphous control suggests that free motion of the radicals is inhibited when more than 25% of available sites are occupied. The ability to tune the mode of radical interactions and the subsequent effect on redox, electrical, and optical characteristics in a porous framework may lead to a class of structures with properties ideal for photoelectrochemistry or energy storage.

  18. Molecular Recognition of Metal Complexes by DNA: A Comparative Study of the Interactions of the Parent Complexes [PtCl(TERPY)]Cl and [AuCl(TERPY)]Cl 2 with Double Stranded DNA

    OpenAIRE

    Luigi Messori; Giordana Marcon; Alessio Innocenti; Enzo Gallori; Marco Franchi; Pierluigi Orioli

    2005-01-01

    The interactions of the parent complexes [AuCl(Terpy)]Cl2 and [PtCl(Terpy)]Cl with DNA were analysed by various physicochemical methods. Surprisingly, these metal complexes produce different interaction patterns with DNA in spite of their profound structural similarity. Indeed, important modifications are detected in the characteristic UV-Vis bands of [PtCl(Terpy)]Cl upon addition of ct-DNA, while the spectrum of [AuCl(Terpy)]Cl2 is almost unaffected. Gel electrophoresis studies confirm these...

  19. A tese da "nova clivagem" e a base social do apoio à direita radical

    Directory of Open Access Journals (Sweden)

    Pippa Norris

    2005-03-01

    Full Text Available A ascensão da direita radical está aberta a múltiplas interpretações. A questão abordada neste artigo é saber se muitos desses partidos criaram uma base social duradoura entre os eleitores e, se assim for, quais setores sociais apresentam maior probabilidade de apoiá-los. A primeira parte discute os marcos teóricos alternativos oferecidos pelos trabalhos clássicos dos anos 1950 e 1960, a tese da "nova clivagem social" comum durante a última década e a teoria do desalinhamento partidário. Em seguida, o artigo analisa hipóteses concorrentes sobre a base social do voto na direita radical em quinze países, usando dados retirados do Survey Social Europeu de 2002 e do Estudo Comparativo de Sistemas Eleitorais, 1996-2001. A segunda parte trata do papel de indicadores socioeconômicos, enquanto a terceira parte examina a duradoura diferença entre os sexos e os padrões geracionais de apoio. A conclusão considera as implicações desses resultados para compreender a base da popularidade da direita radical e para a estabilidade e longevidade desses partidos.The rise of the radical right is open to multiple interpretations. The question addressed in this paper is whether many of these parties have fostered an enduring social base among core voters and, if so, which social sectors are most likely to support them. The first part discusses the alternative theoretical frameworks provided by the classic accounts of the 1950s and 1960s, the "new social cleavage" thesis common during the last decade, and the theory of partisan dealignment. Then, it compares evidence to analyze rival hypotheses about the social basis of the radical right vote across fifteen nations, using data drawn from the European Social Survey, 2002, and the Comparative Study of Electoral Systems, 1996-2001. The second part focuses upon the role of socioeconomic indicators, while the third part considers the enduring gender gap and patterns of generational support. The

  20. Even free radicals should follow some rules: a guide to free radical research terminology and methodology.

    Science.gov (United States)

    Forman, Henry Jay; Augusto, Ohara; Brigelius-Flohe, Regina; Dennery, Phyllis A; Kalyanaraman, Balaraman; Ischiropoulos, Harry; Mann, Giovanni E; Radi, Rafael; Roberts, L Jackson; Vina, Jose; Davies, Kelvin J A

    2015-01-01

    Free radicals and oxidants are now implicated in physiological responses and in several diseases. Given the wide range of expertise of free radical researchers, application of the greater understanding of chemistry has not been uniformly applied to biological studies. We suggest that some widely used methodologies and terminologies hamper progress and need to be addressed. We make the case for abandonment and judicious use of several methods and terms and suggest practical and viable alternatives. These changes are suggested in four areas: use of fluorescent dyes to identify and quantify reactive species, methods for measurement of lipid peroxidation in complex biological systems, claims of antioxidants as radical scavengers, and use of the terms for reactive species.

  1. Investigation of the O+allyl addition/elimination reaction pathways from the OCH(2)CHCH(2) radical intermediate.

    Science.gov (United States)

    Fitzpatrick, Benjamin L; Lau, Kai-Chung; Butler, Laurie J; Lee, Shih-Huang; Lin, Jim Jr-Min

    2008-08-28

    These experiments study the preparation of and product channels resulting from OCH(2)CHCH(2), a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3 nm produces chlorine atoms and c-OCH(2)CHCH(2) radicals; these undergo a facile ring opening to the OCH(2)CHCH(2) radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8 eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33 kcalmol. To elucidate the product channels resulting from the OCH(2)CHCH(2) radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C(3)H(4)O (acrolein)+H, C(2)H(4)+HCO (formyl radical), and H(2)CO (formaldehyde)+C(2)H(3). A small signal from C(2)H(2)O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at me=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C(2)H(5)+CO, does not contribute significantly to the product branching. The higher internal energy onset of the acrolein+H product channel is consistent with the relative barriers en route to

  2. Formation of a porphyrin pi-cation radical in the fluoride complex of horseradish peroxidase.

    Science.gov (United States)

    Farhangrazi, Z S; Sinclair, R; Powers, L; Yamazaki, I

    1995-11-21

    Horseradish peroxidase (HRP) was oxidized by IrCl6(2-) to a mixture of compounds I and II, the rate of oxidation and the ratio of the mixture being greatly affected by pH (Hayashi & Yamazaki, 1979). Oxidation of HRP by IrCl6(2-) in the presence of fluoride was significantly accelerated. This resulted in the formation of a new compound which is a ferric fluoride complex containing a porphyrin pi-cation radical. The spectrum of the new compound showed a decreased absorption band in the Soret region and a broad band at 570 nm; which was converted to that of the original ferric fluoride complex by addition of ascorbate or hydroquinone. Addition of cyanide slowed down the oxidation of HRP by IrCl6(2-), and the oxidation product was the same as that obtained in the absence of cyanide. Compound I was formed when H2O2 was added to HRP in the presence of fluoride or cyanide. The one-electron reduction potential (Eo') of the oxidized HRP-fluoride complex was measured at several pH values, the Eo' value at pH 7 being 861 +/- 4 mV. The ratio of delta Eo' to delta pH was 49 mV/pH unit.

  3. Radical hysterectomy with adjuvant radiotherapy versus radical radiotherapy for FIGO stage IIB cervical cancer

    International Nuclear Information System (INIS)

    The goal of this study was to compare treatment outcomes for Federation of Gynecology and Obstetrics (FIGO) stage IIB cervical carcinoma patients receiving radical surgery followed by adjuvant postoperative radiotherapy versus radical radiotherapy. Medical records of FIGO stage IIB cervical cancer patients treated between July 2008 and December 2011 were retrospectively reviewed. A total of 148 patients underwent radical hysterectomy with pelvic lymph node dissection followed by adjuvant radiotherapy (surgery-based group). These patients were compared with 290 patients that received radical radiotherapy alone (RT-based group). Recurrence rates, progression-free survival (PFS), overall survival (OS), local control rates, and treatment-related complications were compared for these two groups. Similar rates of recurrence (16.89% vs. 12.41%, p = 0.200), PFS (log-rank, p = 0.211), OS (log-rank, p = 0.347), and local control rates (log-rank, p = 0.668) were observed for the surgery-based group and the RT-based group, respectively. Moreover, the incidence of acute grade 3–4 gastrointestinal reactions and late grade 3–4 lower limb lymphedema were significantly higher for the surgery-based group versus the RT-based group. Cox multivariate analyses found no significant difference in survival outcome between the two groups, and tumor diameter and histopathology were identified as significant prognostic factors for OS. Radical radiotherapy was associated with fewer treatment-related complications and achieved comparable survival outcomes for patients with FIGO stage IIB cervical cancer compared to radical hysterectomy followed by postoperative radiotherapy

  4. Ginsenoside Rb1 directly scavenges hydroxyl radical and hypochlorous acid.

    Science.gov (United States)

    Lü, Jian-Ming; Weakley, Sarah M; Yang, Zhen; Hu, Ming; Yao, Qizhi; Chen, Changyi

    2012-01-01

    Reactive oxygen species (ROS) have been implicated in a variety of inflammatory diseases including cardiovascular disease (CVD), cancer, diabetes, Alzheimer's disease, autism, cataracts and aging. When endogenous mechanisms for the maintenance of redox homeostasis are overwhelmed, dietary intake of antioxidants contributes substantially to balancing the body's oxidant/antioxidant status. Ginsenosides are thought to be primarily responsible for the pharmacological effect of P. ginseng root extracts on oxidative stress and inflammation. However, little is known about the underlying antioxidant mechanisms of individual ginsenoside; specifically, the reactivity of ginsenoside Rb1 with ROS has not been well studied. We found that Rb1 can significantly and selectively reduce hydroxyl radical (●OH) and hypochlorous acid (HOCl), two of the strongest ROS, with unique molecular mechanisms in a cell-free system. Rb1 directly scavenges the ●OH and protects plasmid DNA from damage induced by ●OH. ●OH likely attacks the double bond on the side chain of Rb1 as well as hydrogen atoms adjacent to the -OH groups, including those of sugar moieties. Rb1 also shows a high reactivity to HOCl and effectively inhibits HOCl-induced tyrosine chlorination in a cell free system. HOCl is added to the double bond of Rb1; the -Cl group and -OH group of HOCl possibly bond at C-24 and C-25 of Rb1 based on the regioselectivity of Markovnikov's Rule. To our knowledge, this is the first demonstration that ginsenoside Rb1 scavenges HOCl and protects tyrosine from HOCl-induced chlorination. Thus, this study reveals unique antioxidant mechanisms of individual ginsenoside Rb1, which may contribute to the pharmacological effect of P. ginseng and to the development of effective strategies for clinical applications of ginsenosides.

  5. Spectroscopy of free radicals and radical containing entrance-channel complexes in superfluid helium nano-droplets

    CERN Document Server

    K"upper, J; K\\"upper, Jochen; Merritt, Jeremy M.

    2006-01-01

    The spectroscopy of free radicals and radical containing entrance-channel complexes embedded in superfluid helium nano-droplets is reviewed. The collection of dopants inside individual droplets in the beam represents a micro-canonical ensemble, and as such each droplet may be considered an isolated cryo-reactor. The unique properties of the droplets, namely their low temperature (0.4 K) and fast cooling rates ($\\sim10^{16}$ K s$^{-1}$) provides novel opportunities for the formation and high-resolution studies of molecular complexes containing one or more free radicals. The production methods of radicals are discussed in light of their applicability for embedding the radicals in helium droplets. The spectroscopic studies performed to date on molecular radicals and on entrance / exit-channel complexes of radicals with stable molecules are detailed. The observed complexes provide new information on the potential energy surfaces of several fundamental chemical reactions and on the intermolecular interactions pres...

  6. Studies of radiation-produced radicals and radical ions. Progress report, September 1, 1982-August 31, 1983

    International Nuclear Information System (INIS)

    During the past year, radiation chemical and solid-state ESR techniques were combined to generate and characterize novel radical ions. Observations have been made on a variety of metastable organometallic radical cations derived from Group IV B metal alkyls. Matrix interactions have been discovered between radical cations and the Freon solvent. The radical cation formed from ethylene oxide is the ring-opened 2-oxa-trimethylene cation with a symmetrical C/sub 2v/ planar structure. The CF3CCl2 radical was formed after γ irradiation of the CF3CCl3 (Freon) matrix. Very large long-range proton hyperfine couplings were found in radical cations of carbonyl compounds. The C8F8- ion was studied in MTHF glass, using ESR. Two new inorganic radicals, SF4- and SF4O-, were discovered

  7. Thermal study of HNIW (CL-20)

    Energy Technology Data Exchange (ETDEWEB)

    Turcotte, R.; Vachon, M.; Kwok, Q.S.M.; Wang, R.; Jones, D.E.G.

    2005-04-01

    The addition of energetic material HNIW (also known as CL-20) to propellants or explosive can increase the performance parameters of explosives such as specific impulse, ballistics and detonation velocity. This study used differential scanning calorimetry (DSC), thermogravimetry (TG), accelerating rate calorimetry (ARC), heat flow calorimetry (HFC) and simultaneous TG-DTA-FTIR-MS measurements to investigate the thermal properties of HNIW (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-tetracyclo-5.5.0.0{sup 5,9}.0{sup 3,=} 1{sup 1}]-dodecane). The study examined the solid-solid phase transistions and the reversibility of these phase transitions. The effects of various heating rates on the mass loss of CL-20 and its onset temperature was also examined along with its thermal stability and its behaviour at various pressures of argon. This paper outlined the experimental procedures and summarized the kinetic parameters, thermal decomposition, and evolved gases. Each experiment indicates the multi-step thermal decomposition of CL-20 and its autocatalytic behaviour. CL-20 lost about 85 per cent of its initial mass during the decomposition and its onset temperature was found to vary with the heating rate. Decomposition of CL-20 resulted in the formation of gaseous products such as NO{sub 2}, N{sub 2}O, NO, CO{sub 2}, CO, HCN, HCOOH, HNCO, and water and other carbonaceous products. 28 refs., 4 tabs., 17 figs.

  8. Spectroscopy of free-base N-confused tetraphenylporphyrin radical anion and radical cation.

    Science.gov (United States)

    Alemán, Elvin A; Manríquez Rocha, Juan; Wongwitwichote, Wongwit; Godínez Mora-Tovar, Luis Arturo; Modarelli, David A

    2011-06-23

    The radical anions and radical cations of the two tautomers (1e and 1i) of 5,10,15,20-tetraphenyl N-confused free-base porphyrin have been studied using a combination of cyclic voltammetry, steady state absorption spectroscopy, and computational chemistry. N-Confused porphyrins (NCPs), alternatively called 2-aza-21-carba-5,10,15,20-tetraphenylporphyrins or inverted porphyrins, are of great interest for their potential as building blocks in assemblies designed for artificial photosynthesis, and understanding the absorption spectra of the corresponding radical ions is paramount to future studies in multicomponent arrays where electron-transfer reactions are involved. NCP 1e was shown to oxidize at a potential of E(ox) 0.65 V vs Fc(+)|Fc in DMF and reduce at E(red) -1.42 V, while the corresponding values for 1i in toluene were E(ox) 0.60 V and E(red) -1.64 V. The geometries of these radical ions were computed at the B3LYP/6-31+G(d)//B3LYP/6-31G(d) level in the gas phase and in solution using the polarizable continuum model (PCM). From these structures and that of H(2)TPP and its corresponding radical ions, the computed redox potentials for 1e and 1i were calculated using the Born-Haber cycle. While the computed reduction potentials and electron affinities were in excellent agreement with the experimental reduction potentials, the calculated oxidation potentials displayed a somewhat less ideal relationship with experiment. The absorption spectra of the four radical ions were also measured experimentally, with radical cations 1e(•+) and 1i(•+) displaying significant changes in the Soret and Q-band regions as well as new low energy absorption bands in the near-IR region. The changes in the absorption spectra of radical anions 1e(•-) and 1i(•-) were not as dramatic, with the changes occurring only in the Soret and Q-band regions. These results were favorably modeled using time-dependent density functional calculations at the TD-B3LYP/6-31+G(d)//B3LYP/6-31G

  9. Mixed views about radical life extension

    Directory of Open Access Journals (Sweden)

    Allen Alvarez

    2015-05-01

    Full Text Available Background: Recent studies on public attitudes toward life extension technologies show a mix of ambivalence toward and support for extending the human lifespan (Partridge 2009; Dragojlovic 2013; Funk et al. 2013. Attitudes toward genetic modification of organisms and technological enhancements may be used to categorize individuals according to political or ideological orientation such as technoprogressive or conservative (Hughes 2010 and it could be easy to assume that these categories are related to more general categorizations related to culture, e.g. between Traditional and Secular-rational values in the World Values Survey (Ingelhart & Welzel 2010. This paper discusses how attitudes toward aspects of radical life extension may be related to cultural values as revealed in an online deliberative survey among university students conducted between January 2012 to January 2013. Survey results suggest that attitudes toward radical life extension tend to be mixed among groups categorized as Traditional, Secular-rational, Survivalist, and Self-expressionist. The study explored the relation between responses of 326 university students to 5 key questions on radical life extension (RLE and the cultural values they tend to favor as indicated by their response to 20 statements from the World Values Survey. Design and Method: The survey consisted of 3 stages: an online pre-discussion survey, face-to-face discussion, and post-discussion survey. After completing the 5 main survey questions in stage 1, participants were presented two additional questionnaires: one on cultural attitudes using 20 statements from the 2004-2008 World Values Survey (WVS and another on health attitudes with 12 statements from Dutta-Bergman’s 2004 study. In stage 2, participants were engaged in a face-to-face discussion in class focusing on their responses to the five key questions. After the discussion, they were invited to reconsider the choices and reasons they posted in stage

  10. RISE OF RADICALIZATION IN THE GLOBAL VILLAGE. ONLINE RADICALIZATION VS. IN-PERSON RADICALIZATION - IS THERE A DIFFERENCE?

    Directory of Open Access Journals (Sweden)

    Tanja Dramac Jiries

    2016-03-01

    Full Text Available In the vicinity of open space, some authors have called the “dark web” the perfect “breeding grounds” for generating conditions for seeds of extremism to thrive and grow. The perceived anonymity and vast information databases found here present a perfect incubator for terrorist activity. Academics and policymakers alike are as well convinced that such an open space filled with recruiter masterminds is perfectly adept at embracing the unadoptable, unconventional, or socially unfit into terrorist or jihadi organizations. Nevertheless, regardless of organizations, modernization and adoption of new technological methods in which one can obtain ideas and information, many individuals are still and to a great extent, influenced by face-to-face interactions. Intimate environments of a religious institution, somewhat of a home-like feeling in community gathering center, can equally impact a person, as can the internet and its vast informational influence. For the reason of contributing to understand the radicalization in the Global Village, this article will examine differences in online and in-person radicalization and illustrate it with some examples and attempt to make a comparison between two different exposures to information and its effects on young individuals.

  11. Isoprene, sulphoxy radical-anions and acidity

    Directory of Open Access Journals (Sweden)

    K. J. Rudziński

    2008-12-01

    Full Text Available Transformation of isoprene coupled with autoxidation of SIV in aqueous solutions was studied experimentally and by chemical-kinetic modelling over broad range of solution acidities (pH=3–9 to complement the research on aqueous-phase and heterogeneous transformation of isoprene reported recently by many laboratories. Isoprene significantly slowed down the autoxidation in acidic and basic solutions, and accelerated it slightly in neutral solutions. Simultaneously, production of sulphate ions and formation of solution acidity were significantly reduced. Formation of sulphite and sulphate derivatives of isoprene – sulphurous acid mono-(2-methyl-4-oxo-but-2-enyl ester (m/z=162.9, sulphurous acid mono-(4-hydroxy-2-methyl-but-2-enyl ester (m/z=164.9, sulphuric acid mono-(2-methyl-4-oxo-but-2-enyl ester (m/z=178.9, sulphuric acid mono-(4-hydroxy-2-methyl-but-2-enyl ester (m/z=180.9 – was indicated by mass spectroscopic analysis of post-reaction mixtures. The results of experiments were explained by changes in a subtle quantitative balance of three superimposed processes whose rates depended in different manner on the acidity of reacting solutions – the scavenging of sulphoxy radicals by isoprene, the formation of sulphoxy radicals during further reactions of isoprene radicals, and the autoxidation of SIV itself. A chemical mechanism based on this idea was explored numerically to show good agreement with experimental data. Interaction of isoprene with sulphur(IV species and oxygen can possibly result in formation of new organosulphate components of atmospheric aerosols and waters, and influence distribution of reactive sulphur and oxygen species in isoprene-emitting organisms exposed to SIV pollutants.

  12. Effects of Montelukast on free radical production in whole blood and isolated human polymorphonuclear neutrophils (PMNs) in asthmatic children

    Science.gov (United States)

    Al Saadi, Muslim M.; Meo, Sultan Ayoub; Mustafa, Ali; Shafi, Ahmed; Tuwajri, Ali S. Al

    2011-01-01

    Montelukast is a highly selective leukotriene-receptor antagonist (LTRA). It is widely used in the treatment of bronchial asthma, primarily as an adjunct to corticosteroids. Reactive oxygen species (ROSs) play an important role in the pathogenesis of asthma and oxidative stress contributing to the initiation and worsening of inflammatory respiratory disorders, such as asthma. Antioxidant drugs may have a role in minimizing or preventing damage in asthmatic children. The aim of this study was to assess the antioxidant effect of montelukast on the production of free radicals in the whole blood and polymorphonuclear neutrophils (PMNs) in asthmatic children. A group of 48 (38 males and 10 females), apparently healthy asthmatic children were recruited with ages ranging between 6 and 14 years. In asthmatic children, base line (premedication) and post medication free radicals activity in the whole blood and polymorphonuclear neutrophils (PMNs) was determined by measuring chemiluminescence (CL) response through chemiluminescence luminometer. Free radical productions were significantly decreased in the whole blood, when stimulated with Phorbol Myristate Acetate (p < 0.04) and Opsonised Zymosan (p < 0.05). The free radicals were also significantly decreased in isolated polymorphonuclear neutrophils (PMNs) when stimulated with Opsonised Zymosan (p < 0.05) after the post medication treatment of montelukast in asthmatic children. Montelukast decreased the reactive oxygen species production, both in the whole blood as well as isolated PMNs in asthmatic children. PMID:23960762

  13. Key contributors: Ernst von Glasersfeld's radical constructivism

    Science.gov (United States)

    Tobin, Kenneth

    2007-07-01

    This article reviews the significance of the contributions of Ernst von Glasersfeld to research in science education, especially through his theoretical contributions on radical constructivism. As a field shaper, Glasersfeld's subversive ideas catalyzed debate in the science education community and fuelled transformation of many facets including research methods, ways of thinking about teaching and learning, curriculum, and science teacher education. Perturbations emanating from the debates on constructivism forged new pathways that led to the development and use of many of the sociocultural frameworks employed by authors in Cultural Studies of Science Education.

  14. [URINARY DISCOMFORTS IN PATIENTS AFTER RADICAL PROSTATECTOMY].

    Science.gov (United States)

    Al'-Shukri, S Kh; Ananiĭ, I A; Amdiĭ, R E; Kuz'min, I V

    2015-01-01

    The authors showed the result of complication treatment of lower urinary tracts in 128 patients with localized prostate cancer. The patients underwent radical prostatectomy. Urinary discomforts included enuresis, urinary incontinence in postoperative period. Abnormalities of urine outflow due to urethral stricture were revealed in 6 (4,6%) patients by the 6 month after operation. These complications required surgical treatment. Urinary incontinence was noted in 20 (15,6%) patients in this period. It was stressful urinary incontinence in 16 (12,6%) and urgent - in 4 (3%). Patents with stressful urinary difficulty were advised to use the conservative treatment (pelvic floor muscle training and electrostimulation), but in case of inefficiency - surgical treatment.

  15. Autoethnographic Mother-Writing: Advocating Radical Specificity

    Directory of Open Access Journals (Sweden)

    Patty Sotirin

    2010-01-01

    Full Text Available In considering the similarities between "momoirs"--popular memoirs written by mothers about motherhood experiences--and evocative autoethnographic mother-writing, I argue that differentiating these two forms of intimate observation and personal narrative requires a rethinking of autoethnographic practice. Specifically, I draw on the work of Gilles Deleuze to advocate for a radical specificity in autoethnographic writing. Thinking the autoethnographic narrative in terms of specificities and differences encourages us to think creatively about personal experiences and cultural relations beyond what is shared and communicable.

  16. Radical Nature of C-Lignin

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-10-03

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

  17. Rehabilitation of erectile function following radical prostatectomy

    Institute of Scientific and Technical Information of China (English)

    Andrew R. McCullough

    2008-01-01

    The concept of muscle rehabilitation after nerve injury is not a novel idea and is practiced in many branches of medicine, including urology. Bladder rehabilitation after spinal cord injury is universally practiced. The erectile dysfunction (ED) experienced after radical prostatectomy (RP) is increasingly recognized as being primarily neurogenic followed by secondary penile smooth muscle (SM) changes. There is unfortunately no standard approach to penile rehabilitation after RP because controlled prospective human studies are not available. This article reviews the epidemiology, experimental pathophysiological models, rationale for penile rehabilitation, and currently published rehabilitation strategies.

  18. Superzoom. Italia y el compromiso radical

    OpenAIRE

    Parga Prado, Marcos

    2015-01-01

    Italy: the new domestic landscape, la ambiciosa exposición que en 1972 tuvo lugar en el MoMA, supone la consagración y a la vez escenifica la muerte de lo que algunos críticos acababan de catalogar como Arquitectura Radical, término con el que intentaban unificar el trabajo de un heterogéneo y atomizado grupo de arquitectos, principalmente italianos, comprometidos con el replanteamiento total de la definición y objetivos de la disciplina. Se ponía fin así a un corto pero intenso periodo d...

  19. Resonance Raman study of benzyl radical

    DEFF Research Database (Denmark)

    Langkilde, F.W.; Bajdor, K.; Wilbrandt, R.

    1992-01-01

    Time-resolved resonance Raman spectra are obtained of benzyl radicals created by laser flash photolysis of benzylchloride and diphenylacetone in solution. The spectra are obtained in resonance with the intense 2 2A2-1 B-2(2) transition of benzyl. The strong Raman bands are assigned to totally...... symmetric a1 modes. The remaining observed bands are tentatively assigned to fundamental modes of b1, a2, and b2 symmetry, and to overtones and combinations. The resonance Raman spectra are found to be quite different from previous fluorescence spectra of benzyl, and the origins of these differences are...

  20. Intermediate-range chemical ordering of cations in molten RbCl-AgCl

    Energy Technology Data Exchange (ETDEWEB)

    Tahara, S. [Department of Physics and Earth Sciences, Faculty of Science, University of the Ryukyus, Okinawa 903-0213 (Japan); Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), Hyogo 679-5198 (Japan); Kawakita, Y. [J-PARC Center, Japan Atomic Energy Agency (JAEA), Ibaraki 319-1195 (Japan); Shimakura, H. [Faculty of Pharmacy, Niigata University of Pharmacy and Applied Life Sciences, Niigata 956-8603 (Japan); Ohara, K. [Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), Hyogo 679-5198 (Japan); Fukami, T. [Department of Physics and Earth Sciences, Faculty of Science, University of the Ryukyus, Okinawa 903-0213 (Japan); Takeda, S. [Department of Physics, Faculty of Sciences, Kyushu University, Fukuoka 812-8581 (Japan)

    2015-07-28

    A first sharp diffraction peak (FSDP) is observed in the X-ray total structure factor of a molten mixture of RbCl-AgCl, while both pure melts of RbCl and AgCl do not exhibit FSDP individually. Molecular dynamics simulations were performed to investigate the origin of the FSDP with the polarizable ion model (PIM). Coexistence of covalent Ag–Cl and ionic Rb–Cl bonds leads the system to evolve intermediate range ordering, which is simulated by introducing the induced polarization in different ways between Ag–Cl with fully polarizable treatment based on Vashishta-Raman potential and Rb–Cl with suppression over-polarization in the nearest neighbor contribution based on Born-Meyer potential. The partial structure factors for both the Ag–Ag and Rb–Rb correlations, S{sub AgAg}(Q) and S{sub RbRb}(Q), show a positive contribution to the FSDP, while S{sub AgRb}(Q) for the Ag–Rb correlation exhibits a negative contribution, indicating that Ag and Rb ions are distributed in an alternating manner within the intermediate-range length scale. The origin of the intermediate-range chemical ordering of cations can be ascribed to the preferred direction of the dipole moments of anions in the PIM.

  1. SnCl2/TiCl3-Mediated Deoximation of Oximes in an Aqueous Solvent

    Directory of Open Access Journals (Sweden)

    Tsung-Hsun Chuang

    2012-03-01

    Full Text Available A simple procedure for SnCl2/TiCl3-mediated deoximation of ketoximes in an aqueous solvent is reported. Under the conditions developed in this effort, various ketones and aldehydes are produced in good to excellent yields.

  2. Intermediate-range chemical ordering of cations in molten RbCl-AgCl

    International Nuclear Information System (INIS)

    A first sharp diffraction peak (FSDP) is observed in the X-ray total structure factor of a molten mixture of RbCl-AgCl, while both pure melts of RbCl and AgCl do not exhibit FSDP individually. Molecular dynamics simulations were performed to investigate the origin of the FSDP with the polarizable ion model (PIM). Coexistence of covalent Ag–Cl and ionic Rb–Cl bonds leads the system to evolve intermediate range ordering, which is simulated by introducing the induced polarization in different ways between Ag–Cl with fully polarizable treatment based on Vashishta-Raman potential and Rb–Cl with suppression over-polarization in the nearest neighbor contribution based on Born-Meyer potential. The partial structure factors for both the Ag–Ag and Rb–Rb correlations, SAgAg(Q) and SRbRb(Q), show a positive contribution to the FSDP, while SAgRb(Q) for the Ag–Rb correlation exhibits a negative contribution, indicating that Ag and Rb ions are distributed in an alternating manner within the intermediate-range length scale. The origin of the intermediate-range chemical ordering of cations can be ascribed to the preferred direction of the dipole moments of anions in the PIM

  3. Repensando a psicologia clínica

    OpenAIRE

    Rita Petrarca Teixeira

    1997-01-01

    Este estudo pretende refletir acerca de alguns aspectos da Psicologia Clínica tais como sua constituição histórica, as concepções de homem subliminares e os pressupostos epistemológicos que vigoram no ensino acadêmico da Psicologia Clínica. Para tanto, analisamos os planos de ensino das disciplinas denominadas Psicologia Clínica de uma universidade do sul do país, a partir do Método de Análise de Conteúdo (Bardin, 1988). As principais conclusões apontam para distorções e limitações no escopo ...

  4. Acetyl radical generation in cigarette smoke: Quantification and simulations

    Science.gov (United States)

    Hu, Na; Green, Sarah A.

    2014-10-01

    Free radicals are present in cigarette smoke and can have a negative effect on human health. However, little is known about their formation mechanisms. Acetyl radicals were quantified in tobacco smoke and mechanisms for their generation were investigated by computer simulations. Acetyl radicals were trapped from the gas phase using 3-amino-2, 2, 5, 5-tetramethyl-proxyl (3AP) on solid support to form stable 3AP adducts for later analysis by high-performance liquid chromatography (HPLC), mass spectrometry/tandem mass spectrometry (MS-MS/MS) and liquid chromatography-mass spectrometry (LC-MS). Simulations were performed using the Master Chemical Mechanism (MCM). A range of 10-150 nmol/cigarette of acetyl radical was measured from gas phase tobacco smoke of both commercial and research cigarettes under several different smoking conditions. More radicals were detected from the puff smoking method compared to continuous flow sampling. Approximately twice as many acetyl radicals were trapped when a glass fiber particle filter (GF/F specifications) was placed before the trapping zone. Simulations showed that NO/NO2 reacts with isoprene, initiating chain reactions to produce hydroxyl radical, which abstracts hydrogen from acetaldehyde to generate acetyl radical. These mechanisms can account for the full amount of acetyl radical detected experimentally from cigarette smoke. Similar mechanisms may generate radicals in second hand smoke.

  5. Lipid radicals: Properties and detection by spin trapping

    International Nuclear Information System (INIS)

    Unsaturated lipids are rapidly oxidized to toxic products such as lipid hydroperoxides, especially when transition metals such as iron or copper are present. In a Fenton-type reaction Fe2+ converts lipid hydroperoxides to the very short-lived lipid alkoxyl radicals. The reaction was started upon the addition of Fe2+ to an aqueous linoleic acid hydroperoxide (LOOH) emulsion and the spin trap in the absence of oxygen. Even when high concentrations of spin traps were added to the incubation mixture, only secondary radical adducts were detected, probably due to the rapid rearrangement of the primary alkoxyl radicals. With the commercially available nitroso spin trap MNP we observed a slightly immobilized ESR spectrum with only one hydrogen splitting, indicating the trapping of a methinyl fragment of a lipid radical. With DMPO or 5-diethoxyphosphoryl-5-methyl-1-pyrroline N-oxide (DEPMPO) adducts were detected with carbon-centered lipid radical, with acyl radical, and with the hydroxyl radical. We also synthesized lipophilic derivatives of the spin trap DEPMPO in order to detect lipid radical species generated in the lipid phase. With all spin traps studied a lipid-derived carbon-centered radical was obtained in the anaerobic incubation system Fe2+/LOOH indicating the trapping of a lipid radical, possibly generated as a secondary reaction product of the primary lipid alkoxyl radical formed. Under aerobic conditions an SOD-insensitive oxygen-centered radical adduct was formed with DEPMPO and its lipophilic derivatives. The observed ESR parameters were similar to those of alkoxyl radical adducts, which were independently synthesized in model experiments using Fe3+-catalyzed nucleophilic addition of methanol or t-butanol to the respective spin trap. (author)

  6. Increase the Degradation Efficiency of Organic Pollutants With a Radical Scavenger(Cl-)in a Novel Photoelectrocatalytic Reactor

    Institute of Scientific and Technical Information of China (English)

    Tai Cheng AN; Wen Bing ZHANG; Gui Ying LI; Jia Mo FU; Guo Ying SHENG

    2004-01-01

    Photoelectrocatalytic degradation performance of quinoline in saline water was investigated using a new-designed continuous flow three-dimensional electrode-packed bed photocatalytic reactor.It is interesting to find that chloride ion has an obvious enhancement effect rather than a scavenging effect on the photoelectrocatalytic degradation of quinoline, and create a kinetic synergetic effect in the photoelectrocatalytic reactor.

  7. Método Clínico: Método Clínico?

    OpenAIRE

    Aguiar Fernando

    2001-01-01

    Este artigo retoma a noção de método clínico, situando-a no contexto da psicologia clínica francesa. Por sua vez, a psicologia clínica francesa não pode ser examinada historicamente senão em sua relação com a psicanálise. A estreita conjunção entre psicologia clínica e psicanálise, formulada na França nos termos de uma "unidade da psicologia", inclui a noção de método clínico. Tendo assim uma derivação eminentemente psicanalítica, essa noção é hoje mais do que nunca contestada, ou mesmo disto...

  8. Polychloride monoanions from [Cl3]- to [Cl9]- : a Raman spectroscopic and quantum chemical investigation.

    Science.gov (United States)

    Brückner, Robin; Haller, Heike; Ellwanger, Mathias; Riedel, Sebastian

    2012-04-27

    Polychloride monoanions stabilized by quaternary ammonium salts are investigated using Raman spectroscopy and state-of-the-art quantum-chemical calculations. A regular V-shaped pentachloride is characterized for the [N(Me)(4)][Cl(5)] salt, whereas a hockey-stick-like structure is tentatively assigned for [N(Et)(4)][Cl(2)⋅⋅⋅Cl(3)(-)]. Increasing the size of the cation to the quaternary ammonium salts [NPr(4)](+) and [NBu(4)](+) leads to the formation of the [Cl(3)](-) anion. The latter is found to be a pale yellow liquid at about 40 °C, whereas all the other compounds exist as powders. Further to these observations, the novel [Cl(9)](-) anion is characterized by low-temperature Raman spectroscopy in conjunction with quantum-chemical calculations. PMID:22461376

  9. Fragment Coupling with Tertiary Radicals Generated by Visible-Light Photocatalysis.

    Science.gov (United States)

    Jamison, Christopher R; Overman, Larry E

    2016-08-16

    Convergent synthesis strategies in which a target molecule is prepared by a branched approach wherein two or more complex fragments are combined at a late stage are almost always preferred over a linear approach in which the overall yield of the target molecule is eroded by the efficiency of each successive step in the sequence. As a result, bimolecular reactions that are able to combine complex fragments in good yield and, where important, with high stereocontrol are essential for implementing convergent synthetic strategies. Although intramolecular reactions of carbon radicals have long been exploited to assemble polycyclic ring systems, bimolecular coupling reactions of structurally complex carbon radicals have rarely been employed to combine elaborate fragments in the synthesis of structurally intricate molecules. We highlight in this Account recent discoveries from our laboratories that demonstrate that bimolecular reactions of structurally elaborate tertiary carbon radicals and electron-deficient alkenes can unite complex fragments in high yield using nearly equimolar amounts of the two coupling partners. Our discussion begins by considering several aspects of the bimolecular addition of tertiary carbon radicals to electron-deficient alkenes that commend these transformations for the union of structurally complex, sterically bulky fragments. We then discuss how in the context of synthesizing rearranged spongian diterpenoids we became aware of the exceptional utility of coupling reactions of alkenes and tertiary carbon radicals to unite structurally complex synthetic intermediates. Our initial investigations exploit the early report of Okada that N-(acyloxy)phthalimides reductively fragment at room temperature in the presence of visible light and catalytic amounts of the photocatalyst Ru(bpy)3Cl2 to form carbon radicals that react with alkenes. We show that this reaction of a tertiary radical precursor and an enone can combine two elaborate enantioenriched

  10. OpenCL programming by example

    CERN Document Server

    Banger, Ravishekhar

    2013-01-01

    This book follows an example-driven, simplified, and practical approach to using OpenCL for general purpose GPU programming.If you are a beginner in parallel programming and would like to quickly accelerate your algorithms using OpenCL, this book is perfect for you! You will find the diverse topics and case studies in this book interesting and informative. You will only require a good knowledge of C programming for this book, and an understanding of parallel implementations will be useful, but not necessary.

  11. Molecular dynamics simulations for pure epsilon-CL-20 and epsilon-CL-20-based PBXs.

    Science.gov (United States)

    Xu, Xiao-Juan; Xiao, He-Ming; Xiao, Ji-Jun; Zhu, Wei; Huang, Hui; Li, Jin-Shan

    2006-04-13

    Molecular dynamics has been employed to simulate the well-known high energy density compound epsilon-CL-20 (hexanitrohexaazaisowurtzitane) crystal and 12 epsilon-CL-20-based PBXs (polymer bonded explosives) with four kinds of typical fluorine polymers, i.e., polyvinylidenedifluoride, polychlorotrifluoroethylene, fluorine rubber (F(2311)), and fluorine resin (F(2314)) individually. The elastic coefficients, isotropic mechanical properties (tensile moduli, bulk moduli, shear moduli, and poission's ratios), and bonding energy are first reported for epsilon-CL-20 crystal and epsilon-CL-20-based polymer bonded explosives (PBXs). The mechanical properties of epsilon-CL-20 can be effectively improved by blending with a small amount of fluorine polymers, and the whole effect of the adding fluorine polymers to improve mechanical properties of PBXs along the three crystalline surfaces of epsilon-CL-20 is found to be (100) approximately (001) > (010). The interaction between each of the crystalline surfaces and each of the fluorine polymers is different, and the ordering of binding energy for the three surfaces is (001) > (100) > (010); F(2314) always has the strongest binding ability with the three different surfaces. F(2314) can best improve the ductibility and tenacity of PBX when it is positioned on epsilon-CL-20 (001) crystal surface. The calculations on detonation performances for pure epsilon-CL-20 crystal and the four epsilon-CL-20-based PBXs show that adding a small amount of fluorine polymer into pure epsilon-CL-20 will lower detonation performance, but each detonation parameter of the obtained PBXs is still excellent. PMID:16599487

  12. Effect of halide ions and carbonates on organic contaminant degradation by hydroxyl radical-based advanced oxidation processes in saline waters.

    Science.gov (United States)

    Grebel, Janel E; Pignatello, Joseph J; Mitch, William A

    2010-09-01

    Advanced oxidation processes (AOPs) generating nonselective hydroxyl radicals (HO*) provide a broad-spectrum contaminant destruction option for the decontamination of waters. Halide ions are scavengers of HO* during AOP treatment, such that treatment of saline waters would be anticipated to be ineffective. However, HO* scavenging by halides converts HO* to radical reactive halogen species (RHS) that participate in contaminant destruction but react more selectively with electron-rich organic compounds. The effects of Cl-, Br-, and carbonates (H2CO3+HCO3-+CO3(2-)) on the UV/H2O2 treatment of model compounds in saline waters were evaluated. For single target organic contaminants, the impact of these constituents on contaminant destruction rate suppression at circumneutral pH followed the order Br->carbonates>Cl-. Traces of Br- in the NaCl stock had a greater effect than Cl- itself. Kinetic modeling of phenol destruction demonstrated that RHS contributed significantly to phenol destruction, mitigating the impact of HO* scavenging. The extent of treatment efficiency reduction in the presence of halides varied dramatically among different target organic compounds. Destruction of contaminants containing electron-poor reaction centers in seawater was nearly halted, while 17beta-estradiol removal declined by only 3%. Treatment of mixtures of contaminants with each other and with natural organic matter (NOM) was evaluated. Although NOM served as an oxidant scavenger, conversion of nonselective HO* to selective radicals due to the presence of anions enhanced the efficiency of electron-rich contaminant removal in saline waters by focusing the oxidizing power of the system away from the NOM toward the target contaminant. Despite the importance of contaminant oxidation by halogen radicals, the formation of halogenated byproducts was minimal. PMID:20681567

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

    Science.gov (United States)

    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

  14. Electronic paramagnetic resonance (EPR) for the study of ascorbyl radical and lipid radicals in marine organisms.

    Science.gov (United States)

    González, Paula Mariela; Aguiar, María Belén; Malanga, Gabriela; Puntarulo, Susana

    2013-08-01

    Electron paramagnetic resonance (EPR) spectroscopy detects the presence of radicals of biological interest, such as ascorbyl radical (A(•)) and lipid radicals. A(•) is easily detectable by EPR even in aqueous solution at room-temperature. Under oxidative conditions leading to changes in total ascorbate (AH(-)) content, the A(•)/AH(-) ratio could be used to estimate early oxidative stress in the hydrophilic milieu. This methodology was applied to a wide range of aquatic systems including algae, sea urchin, limpets, bivalves and fish, under physiological and oxidative stress conditions as well. The A(•)/AH(-) ratio reflected the state of one part of the oxidative defense system and provided an early and simple diagnosis of environmental stressing conditions. Oxidative damage to lipids was assessed by the EPR-sensitive adduct formation that correlates well with cell membrane damage with no interference from other biological compounds. Probe instability, tissue metabolism, and lack of spin specificity are drawback factors for employing EPR for in vivo determination of free radicals. However, the dependability of this technique, mostly by combining it with other biochemical strategies, enhances the value of these procedures as contributors to the knowledge of oxidative condition in aquatic organisms. PMID:23485428

  15. European radicals and the 'Third World’: imagined solidarities and radical networks, 1958-1973

    NARCIS (Netherlands)

    R. Gildea; J. Mark; N. Pas

    2011-01-01

    This article addresses the importance of Third Worldism/tiersmondisme as a source of inspiration for European radicals on both sides of the Iron Curtain 1958-73, focusing on the cases of France, the Netherlands and Hungary. Using both oral history and archival material, it considers the decline of d

  16. Radical Reform Within a Liberal and Democratic Framework? Rawls and the Radical Critique of Schooling.

    Science.gov (United States)

    Claus, John F.

    1981-01-01

    The radical critique of American education portrays the schools as perpetuators of ethnic, social, and racial inequalities because they do not alter existing class relations. John Rawls' theory of social justice is discussed as an alternative approach to this situation that remains firmly grounded in the liberal tradition. (PP)

  17. Assessment of Free Radical Scavenging Activity of Dimethylglycine Sodium Salt and Its Role in Providing Protection against Lipopolysaccharide-Induced Oxidative Stress in Mice.

    Science.gov (United States)

    Bai, Kaiwen; Xu, Wen; Zhang, Jingfei; Kou, Tao; Niu, Yu; Wan, Xiaoli; Zhang, Lili; Wang, Chao; Wang, Tian

    2016-01-01

    In the present study, the free radical scavenging activities (against 1,1-diphenyl-2-pierylhydrazy (DPPH), 2,2'-Azinobis-(3-ethylbenzthiazoline-6- sulphonate) (ABTS+), Hydrogen peroxide (H2O2)) of dimethylglycine sodium salt (DMG-Na) were measured and compared with those of Trolox (6-hydroxy-2, 5, 7, 8-tetramethylchroman-2-carboxylic acid), a commonly used antioxidant. The radical scavenging activities of DMG-Na were found to be the highest at 40 mg/ml. In Experiment 2, gastric intubation in mice with 12 mg DMG-Na/0.3 ml sterile saline solution significantly increased (P effect of 12 mg DMG-Na/0.3 ml sterile saline solution, which showed the highest antioxidant capacity, was further studied using a mice model. In Experiment 3, the mice CL (CON+ lipopolysaccharide (LPS)) group showed a significant decrease (P stress by enhancing the free radical scavenging capacity, and increasing the activity of antioxidant defense system. PMID:27171376

  18. AcEST: CL889Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL889Contig1 598 4 Adiantum capillus-veneris contig: CL889contig1 sequence. Link to clone list Show CL889C...ontig1 Contig ID CL889Contig1 Length 598 Number of clones 4 Definition Adiantum capil

  19. AcEST: CL959Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL959Contig1 659 4 Adiantum capillus-veneris contig: CL959contig1 sequence. Link to clone list Show CL959C...ontig1 Contig ID CL959Contig1 Length 659 Number of clones 4 Definition Adiantum capil

  20. AcEST: CL49Contig2 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL49Contig2 1080 13 Adiantum capillus-veneris contig: CL49contig2 sequence. Link to clone list Show CL49C...ontig2 Contig ID CL49Contig2 Length 1080 Number of clones 13 Definition Adiantum capil

  1. AcEST: CL719Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL719Contig1 679 4 Adiantum capillus-veneris contig: CL719contig1 sequence. Link to clone list Show CL719C...ontig1 Contig ID CL719Contig1 Length 679 Number of clones 4 Definition Adiantum capil

  2. AcEST: CL469Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL469Contig1 501 6 Adiantum capillus-veneris contig: CL469contig1 sequence. Link to clone list Show CL469C...ontig1 Contig ID CL469Contig1 Length 501 Number of clones 6 Definition Adiantum capil

  3. AcEST: CL359Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL359Contig1 717 7 Adiantum capillus-veneris contig: CL359contig1 sequence. Link to clone list Show CL359C...ontig1 Contig ID CL359Contig1 Length 717 Number of clones 7 Definition Adiantum capil

  4. AcEST: CL779Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL779Contig1 980 4 Adiantum capillus-veneris contig: CL779contig1 sequence. Link to clone list Show CL779C...ontig1 Contig ID CL779Contig1 Length 980 Number of clones 4 Definition Adiantum capil

  5. AcEST: CL609Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL609Contig1 522 5 Adiantum capillus-veneris contig: CL609contig1 sequence. Link to clone list Show CL609C...ontig1 Contig ID CL609Contig1 Length 522 Number of clones 5 Definition Adiantum capil

  6. AcEST: CL99Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL99Contig1 1138 14 Adiantum capillus-veneris contig: CL99contig1 sequence. Link to clone list Show CL99C...ontig1 Contig ID CL99Contig1 Length 1138 Number of clones 14 Definition Adiantum capil

  7. AcEST: CL539Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL539Contig1 774 5 Adiantum capillus-veneris contig: CL539contig1 sequence. Link to clone list Show CL539C...ontig1 Contig ID CL539Contig1 Length 774 Number of clones 5 Definition Adiantum capil

  8. The role of CuCl on the mechanism of dibenzo-p-dioxin formation from poly-chlorophenol precursors: A computational study.

    Science.gov (United States)

    Fernández Pulido, Yoana; Suárez, Ernesto; López, Ramón; Menéndez, M Isabel

    2016-02-01

    A computational study is performed for the elucidation of the role played by CuCl in the condensation of two polychlorophenol molecules to yield PCDDs. The mechanism found consists of six sequential steps, which allow the final recuperation of the CuCl molecule, and applies for phenol molecules with an ortho chlorine. In the temperature range of 453-473 K (previously reported as adequate to diminish PCDDs formation in the post-combustion area), CuCl is able to softly retain chlorophenol molecules, mainly those less chlorinated. After a first HCl release, Cu(I) remains bonded to phenol oxygen atom, thus avoiding the formation of phenoxy radicals and the subsequent radical processes. A temperature raise up to 1200 K destabilizes the initial CuCl-chlorophenol complexes and causes that the rate limiting step change from the formation of the first oxygen bridge to HCl elimination. It has been checked that tetra and penta-chlorophenols undergo essentially the same reaction process of 2-chlorophenol. In view of our results and trying to arrive at a practical way to diminish the rate of formation of PCDDs, we propose that an extra addition of powdered CuCl to the post-combustion zone, cooled down to temperatures lower than 473 K, could act as an inhibitor in the formation of these pollutants. PMID:26684925

  9. Constructing Bi24O31Cl10/BiOCl heterojunction via a simple thermal annealing route for achieving enhanced photocatalytic activity and selectivity

    Science.gov (United States)

    Liu, Xiaoyan; Su, Yiguo; Zhao, Qihang; Du, Chunfang; Liu, Zhiliang

    2016-06-01

    This work reports on the construction of a Bi24O31Cl10/BiOCl heterojunction via a simple thermal annealing method. The X-ray diffraction (XRD) results indicated that the phase transformation from BiOCl to Bi24O31Cl10 could be realized during the thermal annealing process. The high-resolution transmission electron microscopy (HRTEM) images, X-ray photoelectron spectroscopy (XPS) binding energy shifts, Raman spectra and Fouier transform infrared spectroscopy (FT-IR) spectra confirmed the formation of the Bi24O31Cl10/BiOCl heterojunction. The obtained Bi24O31Cl10/BiOCl photocatalyst showed excellent conversion efficiency and selectivity toward photocatalytic conversion of benzyl alcohol to benzaldehyde under visible light irradiation. The radical scavengers and electron spin resonance (ESR) results suggested that the photogenerated holes were the dominant reactive species responsible for the photocatalytic oxidation of benzyl alcohol and superoxide radicals were not involved in the photocatalytic process. The in-situ generation of Bi24O31Cl10/BiOCl heterojunction may own superior interfacial contact than the two-step synthesized heterojunctions, which promotes the transfer of photogenerated charge carriers and is favorable for excellent photocatalytic activities.

  10. Fast beam studies of free radical photodissociation

    Energy Technology Data Exchange (ETDEWEB)

    Cyr, D R [Lawrence Berkeley Lab., CA (United States)

    1993-11-01

    The photodissociation of free radicals is studied in order to characterize the spectroscopy and dissociation dynamics of the dissociative electronic states in these species. To accomplish this, a novel method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with a highly complementary form of photofragment translational spectroscopy. The optical spectroscopy of transitions to dissociative states is determined by monitoring the total photofragment yield as a function of dissociation photon energy. Branching ratios to various product channels, internal energy distributions of the fragments, bond dissociation energies, and the translational energy-dependent photofragment recoil angular distributions are then determined at selected excitation energies. A detailed picture of the dissociation dynamics can then be formulated, allowing insight concerning the interactions of potential energy surfaces involved in the dissociation. After an introduction to the concepts and techniques mentioned above, the experimental apparatus used in these experiments is described in detail. The basis and methods used in the treatment of data, especially in the dissociation dynamics experiments, are then put forward.

  11. Free radical facilitated damage of ungual keratin.

    Science.gov (United States)

    Khengar, Rajeshree H; Brown, Marc B; Turner, Rob B; Traynor, Matthew J; Holt, Katherine B; Jones, Stuart A

    2010-09-01

    Thioglycolic acid (TA) and urea hydrogen peroxide (urea H(2)O(2)) are thought to disrupt alpha-keratin disulfide links in the nail. However, optimal clinical use of these agents to improve the treatment of nail disorders is currently hindered by a lack of fundamental data to support their mechanism of action. The aim of this study was to investigate how the redox environment of ungual keratin, when manipulated by TA and urea H(2)O(2), influenced the properties of the nail barrier. Potentiometric and voltammetric measurements demonstrated that urea H(2)O(2) obeyed the Nernst equation for a proton coupled one-electron transfer redox process while TA underwent a series of redox reactions that was complicated by electrode adsorption and dimer formation. The functional studies demonstrated that nail permeability, measured through TBF penetration (38.51+/-10.94 microg/cm(2)/h) and nail swelling (244.10+/-14.99% weight increase), was greatest when relatively low concentrations of the thiolate ion were present in the applied solution. Limiting the thiolate ion to low levels in the solution retards thiolate dimerisation and generates thiyl free radicals. It appeared that this free radical generation was fundamental in facilitating the redox-mediated keratin disruption of the ungual membrane. PMID:20550963

  12. Radical cystectomy: Analysis of postoperative course

    Directory of Open Access Journals (Sweden)

    Jeremić Dimitrije

    2010-01-01

    Full Text Available Background/Aim. Radical cystectomy is a method of choice in the therapy of infiltrative bladder cancer. The aim of this research was to analyze postoperative course after radical cystectomy (length of hospitalization, most frequent complications and utilization of antibiotics and transfusions. Methods. We analyzed the records of 82 patients operated on in the Department of Urology, Clinical Center of Vojvodina, in a three-year period. In order to aquire data World Health Organization (WHO has developed Anatomical Therapeutic Chemical/Defined Daily Dose (ATC/DDD methodology. Defined daily dose (DDD is the assumed average maintenance dose per day for a drug use for its main indication. Results. Continent urinary derivation was preformed in 23.15% cases. Postoperative complications occurred in 18.29% of patients. Average blood utilization was 2.19 units. Blood utilization for continent derivations (n = 48 was 4.6 units, and incontinent ones 3.36 units. Totally 159.33 DDD/100 bed days were used. Conclusion. When preforming continent derivation there is a significant increase in blood utilization. Frequency of postoperative complications correlates to those reported in the literature.

  13. Free radical facilitated damage of ungual keratin.

    Science.gov (United States)

    Khengar, Rajeshree H; Brown, Marc B; Turner, Rob B; Traynor, Matthew J; Holt, Katherine B; Jones, Stuart A

    2010-09-01

    Thioglycolic acid (TA) and urea hydrogen peroxide (urea H(2)O(2)) are thought to disrupt alpha-keratin disulfide links in the nail. However, optimal clinical use of these agents to improve the treatment of nail disorders is currently hindered by a lack of fundamental data to support their mechanism of action. The aim of this study was to investigate how the redox environment of ungual keratin, when manipulated by TA and urea H(2)O(2), influenced the properties of the nail barrier. Potentiometric and voltammetric measurements demonstrated that urea H(2)O(2) obeyed the Nernst equation for a proton coupled one-electron transfer redox process while TA underwent a series of redox reactions that was complicated by electrode adsorption and dimer formation. The functional studies demonstrated that nail permeability, measured through TBF penetration (38.51+/-10.94 microg/cm(2)/h) and nail swelling (244.10+/-14.99% weight increase), was greatest when relatively low concentrations of the thiolate ion were present in the applied solution. Limiting the thiolate ion to low levels in the solution retards thiolate dimerisation and generates thiyl free radicals. It appeared that this free radical generation was fundamental in facilitating the redox-mediated keratin disruption of the ungual membrane.

  14. Modeling Radicalization Phenomena in Heterogeneous Populations

    CERN Document Server

    Galam, Serge

    2015-01-01

    The phenomenon of radicalization is investigated within an heterogeneous population composed of a core subpopulation, sharing a way of life locally rooted, and a recently immigrated subpopulation of different origins with ways of life which can be partly in conflict with the local one. While core agents are embedded in the country prominent culture and identity, they are not likely to modify their way of life, which make them naturally inflexible about it. On the opposite, the new comers can either decide to live peacefully with the core people adapting their way of life, or to keep strictly on their way and oppose the core population, leading eventually to criminal activities. To study the corresponding dynamics of radicalization we introduce a 3-state agent model with a proportion of inflexible agents and a proportion of flexible ones, which can be either peaceful or opponent. Assuming agents interact via weighted pairs within a Lotka-Volterra like Ordinary Differential Equation framework, the problem is an...

  15. Free Radicals and Extrinsic Skin Aging

    Directory of Open Access Journals (Sweden)

    Borut Poljšak

    2012-01-01

    Full Text Available Human skin is constantly directly exposed to the air, solar radiation, environmental pollutants, or other mechanical and chemical insults, which are capable of inducing the generation of free radicals as well as reactive oxygen species (ROS of our own metabolism. Extrinsic skin damage develops due to several factors: ionizing radiation, severe physical and psychological stress, alcohol intake, poor nutrition, overeating, environmental pollution, and exposure to UV radiation (UVR. It is estimated that among all these environmental factors, UVR contributes up to 80%. UV-induced generation of ROS in the skin develops oxidative stress, when their formation exceeds the antioxidant defence ability of the target cell. The primary mechanism by which UVR initiates molecular responses in human skin is via photochemical generation of ROS mainly formation of superoxide anion (O2−•, hydrogen peroxide (H2O2, hydroxyl radical (OH•, and singlet oxygen (1O2. The only protection of our skin is in its endogenous protection (melanin and enzymatic antioxidants and antioxidants we consume from the food (vitamin A, C, E, etc.. The most important strategy to reduce the risk of sun UVR damage is to avoid the sun exposure and the use of sunscreens. The next step is the use of exogenous antioxidants orally or by topical application and interventions in preventing oxidative stress and in enhanced DNA repair.

  16. Fast beam studies of free radical photodissociation

    International Nuclear Information System (INIS)

    The photodissociation of free radicals is studied in order to characterize the spectroscopy and dissociation dynamics of the dissociative electronic states in these species. To accomplish this, a novel method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with a highly complementary form of photofragment translational spectroscopy. The optical spectroscopy of transitions to dissociative states is determined by monitoring the total photofragment yield as a function of dissociation photon energy. Branching ratios to various product channels, internal energy distributions of the fragments, bond dissociation energies, and the translational energy-dependent photofragment recoil angular distributions are then determined at selected excitation energies. A detailed picture of the dissociation dynamics can then be formulated, allowing insight concerning the interactions of potential energy surfaces involved in the dissociation. After an introduction to the concepts and techniques mentioned above, the experimental apparatus used in these experiments is described in detail. The basis and methods used in the treatment of data, especially in the dissociation dynamics experiments, are then put forward

  17. Hegel’s Gesture Towards Radical Cosmopolitanism

    Directory of Open Access Journals (Sweden)

    Shannon Brincat

    2009-09-01

    Full Text Available This is a preliminary argument of a much larger research project inquiring into the relation betweenHegel’s philosophical system and the project of emancipation in Critical International Relations Theory. Specifically, the paper examines how Hegel’s theory of recognition gestures towards a form of radical cosmopolitanism in world politics to ensure the conditions of rational freedom for all humankind. Much of the paper is a ground-clearing exercise defining what is ‘living’ in Hegel’s thought for emancipatory approaches in world politics, to borrow from Croce’s now famous question. It focuses on Hegel’s unique concept of freedom which places recognition as central in the formation of self-consciousness and therefore as a key determinant in the conditions necessary forhuman freedom to emerge in political community. While further research is needed to ascertain the precise relationship between Hegel’s recognition theoretic, emancipation and cosmopolitanism, it is contended that the intersubjective basis of Hegel’s concept of freedom through recognition necessitates some form of radical cosmopolitanism that ensures successful processes of recognition between all peoples, the precise institutional form of which remains unspecified.

  18. Threshold photoelectron spectroscopy of the imidogen radical

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, Gustavo A., E-mail: gustavo.garcia@synchrotron-soleil.fr [Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, BP 48, 91192 Gif sur Yvette (France); Gans, Bérenger [Institut des Sciences Moléculaires d’Orsay, Univ Paris-Sud, CNRS, Bât 210, Univ Paris-Sud, 91405 Orsay Cedex (France); Tang, Xiaofeng [Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, BP 48, 91192 Gif sur Yvette (France); Ward, Michael; Batut, Sébastien [PC2A, Université de Lille 1, UMR CNRS-USTL 8522, Cité Scientifique Bât. C11, F-59655 Villeneuve d’Ascq (France); Nahon, Laurent [Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, BP 48, 91192 Gif sur Yvette (France); Fittschen, Christa [PC2A, Université de Lille 1, UMR CNRS-USTL 8522, Cité Scientifique Bât. C11, F-59655 Villeneuve d’Ascq (France); Loison, Jean-Christophe [ISM, Université de Bordeaux, CNRS, 351 cours de la Libération, 33405 Talence Cedex (France)

    2015-08-15

    We present the threshold photoelectron spectroscopy of the imidogen radical (NH) recorded in the photon energy region up to 1 eV above its first ionization threshold. The radical was produced by reaction of NH{sub 3} and F in a microwave discharge flow-tube and photoionized using vacuum ultraviolet (VUV) synchrotron radiation. A double imaging coincidence spectrometer was used to record mass-selected spectra and avoid contributions from the byproducts present in the reactor and background gas. The energy region includes the ground X{sup +2}Π and first electronically excited a{sup +4}Σ{sup −} states of NH{sup +}. Strong adiabatic transitions and weak vibrational progressions up to v{sup +} = 2 are observed for both electronic states. The rotational profile seen in the origin band has been modeled using existing neutral and cationic spectroscopic constants leading to a precise determination of the adiabatic ionization energy at 13.480 ± 0.002 eV.

  19. Free radicals in synthetic and natural indigo

    Energy Technology Data Exchange (ETDEWEB)

    Troup, G.J.; Hutton, D.R. [Monash University, Clayton, VIC (Australia). Physics Department; Hewitt, D.J. [Monash University, Clayton, VIC (Australia). Chemistry Department; Picollo, M.; Casini, A. [Istituto di Ricerche sulle Onde Elettromagnetiche, Firenze (Italy)

    1998-12-31

    Full text: It has been suggested that ESR could be useful in identifying paint pigments in Medieval and Renaissance paintings, since most of the pigments are mineral. However, there are some plant pigments, such as indigo, which also give ESR signals. Indigo used to be made from two kinds of plants: the indigoferae, and isatis (woad): the indigo from the former was regarded as the more valuable. With the development of organic chemistry, it became possible to synthesise indigo in the late 19th century. Two samples, presumed synthesised, were obtained from two European suppliers, and a sample known to be prepared from a plant was kindly supplied by the National Gallery of Victoria. These were examined by ESR, using a Varian E-12 (X-band: {approx}9.1 GHz) spectrometer at room temperature. All samples showed a broad signal, and a very sharp (free radical) signal in the g=2 region. One of the presumed synthesised samples gave other signals as well, probably from transition metals. The highest free radical signal was from the plant sample. The stability of these signals is still under study, since `indigo` also contains unoxidised, pale yellow, leuco-indigo

  20. EI igualitarismo radical de John Rawls

    Directory of Open Access Journals (Sweden)

    Rodríguez Zepeda, Jesús

    2004-12-01

    Full Text Available The main purpose of this paper is to offer an interpretation of the canonical statement of justice as fairness (A Theory of Justice as a deeply egalitarian, even radical, argument. In order to do so, the categories of justice as fairness strongly related to the egalitarian and distributive meaning of the rawlsian liberal model and, specifically, those aimed to solve the problem of social justice, are accurately revised, namely, the fair equality of opportunity and the difference principle. The paper evaluates the relative weight of each of these categories in the rawlsian argument for social and economic equality.

    El objetivo central de este texto es interpretar la enunciación canónica de la justicia como imparcialidad (la de Una Teoría de la Justicia como un argumento profundamente igualitarista, incluso radical. Para ello concede especial atención a las categorías de la justicia como imparcialidad que proporcionan las señas de identidad igualitaria a su modelo liberal y, en particular, a aquellas que pretenden ofrecer una solución a los problemas de la llamada justicia social como la justa igualdad de oportunidades y el principio de diferencia. El artículo evalúa el peso relativo de cada una de estas categorías en la construcción del argumento rawlsiano a favor de la igualdad social y económica.

  1. Hydroxyl radical induced degradation of ibuprofen

    Energy Technology Data Exchange (ETDEWEB)

    Illés, Erzsébet, E-mail: erzsebet.illes@chem.u-szeged.hu [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary); Takács, Erzsébet [Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary); Dombi, András [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Gajda-Schrantz, Krisztina [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Department of Inorganic and Analytical Chemistry, University of Szeged, Szeged (Hungary); EMPA, Laboratory for High Performance Ceramics, Duebendorf (Switzerland); Rácz, Gergely; Gonter, Katalin; Wojnárovits, László [Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary)

    2013-03-01

    Pulse radiolysis experiments were used to characterize the intermediates formed from ibuprofen during electron beam irradiation in a solution of 0.1 mmol dm{sup −3}. For end product characterization {sup 60}Co γ-irradiation was used and the samples were evaluated either by taking their UV–vis spectra or by HPLC with UV or MS detection. The reactions of {sup ·}OH resulted in hydroxycyclohexadienyl type radical intermediates. The intermediates produced in further reactions hydroxylated the derivatives of ibuprofen as final products. The hydrated electron attacked the carboxyl group. Ibuprofen degradation is more efficient under oxidative conditions than under reductive conditions. The ecotoxicity of the solution was monitored by Daphnia magna standard microbiotest and Vibrio fischeri luminescent bacteria test. The toxic effect of the aerated ibuprofen solution first increased upon irradiation indicating a higher toxicity of the first degradation products, then decreased with increasing absorbed dose. Highlights: ► In hydroxyl radical attack on the ring mainly hydroxylated products form ► The hydrated electron attacks the carboxyl group. ► Oxidative conditions are more effective in ibuprofen decomposition than reductive. ► Ecotoxicity of ibuprofen solution first increases then decreases with irradiation.

  2. Analysis of radicals, radical precursors and chemical transformations for Houston/Texas

    Science.gov (United States)

    Rappenglück, Bernhard; Czader, Beata; Li, Xiangshang

    2015-04-01

    Air quality simulations were performed for the Houston-Galveston-Brazoria area for springtime conditions in May and June of 2009. Meteorological parameters predicted by Weather Research and Forecasting (WRF) model, for which data assimilation with recursive objective analysis was performed, are well simulated most of the time. The Community Multiscale Air Quality (CMAQ) model driven by meteorology from WRF simulates ozone and many other trace species, including radical precursors such as HCHO and HONO, with a satisfactory agreement with observations. While CMAQ satisfactorily captures the daily variations of the OH radical, it sometimes underestimates its high daytime values. Concentrations of HO2 are often underpredicted in polluted air masses and persistently severely underpredicted at low NOx conditions, when the Houston air is affected bymarine air masses. In contrast, concentrations of H2O2 and CH3OOHare almost always overpredicted by the model, the overprediction occurs frequently in the polluted air and occurs always when marine air is encountered. Those mispredictions are consistent despite day-to-day variations in meteorological conditions and emissions and bring into question current representation of radical-related chemistry in the model as radical production and recirculation in the model is overtaken by termination processes and creation ofmore stable compounds, such asH2O2 and CH3OOH. Smaller model biases of H2O2 and peroxides are associated with lower humidity. The relative importance of various photolysis processes as radical sources in the Houston atmosphere was also elucidated. Morning HOx formation is dominated by HONO while ozone contributes the most during midday. HONO contribution to HOx formation is more pronounced at the surface layer where most of it is formed, radical production from ozone is more important at elevated levels where higher concentrations of ozone are observed. Formaldehyde contributes up to 40% and also peaks during midday

  3. Spin polarization transfer by the radical pair mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Zarea, Mehdi, E-mail: m-zarea@northwestern.edu; Ratner, Mark A.; Wasielewski, Michael R. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208-3113 (United States)

    2015-08-07

    In a three-site representation, we study a spin polarization transfer from radical pair spins to a nearby electron or nuclear spin. The quantum dynamics of the radical pair spins is governed by a constant exchange interaction between the radical pair spins which have different Zeeman frequencies. Radical pair spins can recombine to the singlet ground state or to lower energy triplet states. It is then shown that the coherent dynamics of the radical pair induces spin polarization on the nearby third spin in the presence of a magnetic field. The spin polarization transfer depends on the difference between Zeeman frequencies, the singlet and triplet recombination rates, and on the exchange and dipole-dipole interactions between the different spins. In particular, the sign of the polarization depends on the exchange coupling between radical pair spins and also on the difference between singlet and triplet recombination rate constants.

  4. Radical Israeli settlers: ultimate concerns, political goals and violence

    Directory of Open Access Journals (Sweden)

    Jonathan Peste

    2006-01-01

    Full Text Available The focus of this article is the radical and activist parts of the wider Israeli settler community on the West Bank. This Radical Israeli Settler Movement should not be confused with the general settler community in the West Bank, even if the more radical groups often recruit their members from the general settler community. The Radical Israeli Settler Movement today includes groups such as Kach, The Committee for Safety on the Roads and The Jewish Legion. The purpose of this article is to analyse some instances of violence in the radical Israeli settler movement and to identify recurring features and processes in this violence. It will be argued that these features and processes are important factors in understanding why certain movements use violence. It will also be argued that future comparative studies are needed, which include other contexts where similar radical movements have become violent, in order to develop a general theory of ethno-religious movements using political violence.

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

    Science.gov (United States)

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

    2016-04-01

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

  6. The salts of chloronium ions R-Cl(+)-R (R = CH3 or CH2Cl): formation, thermal stability, and interaction with chloromethanes.

    Science.gov (United States)

    Stoyanov, Evgenii S

    2016-05-14

    The interaction of CH3Cl/CD3Cl or CH2Cl2/CD2Cl2 with the carborane acid H(CHB11Cl11) (abbreviated as H{Cl11}) generates the salts of CH3-{Cl11} and CH2Cl-{Cl11} and their deuterio analogs, respectively, which are analogs of the salts of asymmetric chloronium cations. Next, salts of chloronium cations CH3-Cl(+)-CH3, ClCH2-Cl(+)-CH2Cl, and ClCH2-Cl(+)-CH3 and their deuterio analogs were obtained from the above compounds. The asymmetric ClCH2-Cl(+)-CH3 cation was found to be unstable, and at ambient temperature, slowly disproportionated into symmetric cations (CH3)2Cl(+) and (CH2Cl)2Cl(+). At a high temperature (150 °C), disproportionation was completed within 5 minutes, and the resulting cations further decomposed into CH3-{Cl11} and CH2Cl-{Cl11}. The molecular fragment ClCH2-(X) of the compounds (X = {Cl11}, -Cl(+)-CH2Cl, or -Cl(+)-CH3) is involved in exchange reactions with CH2Cl2 and CHCl3, converting into CH3-(X) with the formation of chloroform and CCl4, respectively. PMID:27104946

  7. Free radical-mediated activation of hydrazine derivatives.

    OpenAIRE

    Kalyanaraman, B.; Sinha, B. K.

    1985-01-01

    Hydrazines are known to undergo oxidative activation in several enzymatic systems in vitro. Free radicals or carbonium ions have been proposed as active intermediates during such activation. The toxic effects elicited by hydrazines have also been linked to free radical-mediated activation. In this report, we have reviewed the identification of organic free radicals from hydrazines by direct ESR and ESR-spin trapping.

  8. In vivo detection of radicals in biological reactions.

    OpenAIRE

    Chance, B; G. Gao

    1994-01-01

    In vivo detection of free radicals on a quantitative basis is essential for an establishment of their role in membrane, protein, and cell and tissue damage. This article compares optical methods, including chemiluminescence, electron paramagnetic resonance (EPR) and NMR methods for the study of free radicals and free radical damage, especially reperfusion injury neutrophil accumulation 6 hr after the ischemia/reperfusion insult. The chemiluminescence method is applied to an evaluation of the ...

  9. Management of rectal injury during laparoscopic radical prostatectomy

    OpenAIRE

    Castillo, Octavio A.; Elias Bodden; Gonzalo Vitagliano

    2006-01-01

    PURPOSE: Because laparoscopic radical prostatectomy remains a challenging procedure, rectal injury is always a potential complication. We review the incidence of rectal injuries at our institution in the first 110 consecutive laparoscopic extraperitoneal radical prostatectomies. MATERIALS AND METHODS: Nine (8%) out of the first 110 laparoscopic extraperitoneal radical prostatectomies performed between December 2001 and February 2004, were complicated by rectal injury. Mean patient age was 64....

  10. [Radicalism and feminism: The case of Poulain de la Barre].

    Science.gov (United States)

    Pellegrin, Marie-Frédérique

    2015-12-01

    Early modern radicalism and its criteria are described and defined by Jonathan Israel in various works. Poulain de la Barre, one of the first modern feminist thinkers, first is used by Israel as an example of the so-called radical Enlightenment and finally is rejected as such. This case study exhibed the necessity of questionning the coherence of the required criteria for defining a « radical » thinker, especially when examinating carefully the last paragraph of Spinoza's Political Treatise.

  11. Radicals generated from 2-chloro-5-fluorotoluene by corona discharge

    Science.gov (United States)

    Yi, Eun Hye; Yoon, Young Wook; Lee, Sang Kuk

    2014-06-01

    The generation of molecular radicals in corona discharge was investigated spectroscopically by varying the experimental conditions applied to a substituted toluene precursor. Vibronic emission spectra were observed from the corona discharge of 2-chloro-5-fluorotoluene seeded in a large amount of carrier gas helium. From an analysis of emission spectra observed, it was confirmed that bond dissociation energy plays a key role in radical formation. The possible pathway for the formation of benzyl-type radicals is proposed to explain the observation.

  12. [Radicalism and feminism: The case of Poulain de la Barre].

    Science.gov (United States)

    Pellegrin, Marie-Frédérique

    2015-12-01

    Early modern radicalism and its criteria are described and defined by Jonathan Israel in various works. Poulain de la Barre, one of the first modern feminist thinkers, first is used by Israel as an example of the so-called radical Enlightenment and finally is rejected as such. This case study exhibed the necessity of questionning the coherence of the required criteria for defining a « radical » thinker, especially when examinating carefully the last paragraph of Spinoza's Political Treatise. PMID:26746644

  13. Theoretical Investigation on Radical-Coupling Reactivity of Indolinonic Aminoxyls

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Indolinonic aminoxyls can effectively scavenge various radicals by directly coupling with them or by imitating superoxide dismutase. To better understand the radical-coupling reactions, DFT method B3LYP/6-31G(d,p) was employed to calculate variations of free energy for the coupling reactions and other physico-chemical parameters. The radical-coupling activity difference between aminoxyls was elucidated to a large extent in terms of electronic properties of substituents.

  14. New reagents for detecting free radicals and oxidative stress.

    Science.gov (United States)

    Barzegar Amiri Olia, Mina; Schiesser, Carl H; Taylor, Michelle K

    2014-09-21

    Free radicals and oxidative stress play important roles in the deterioration of materials, and free radicals are important intermediates in many biological processes. The ability to detect these reactive species is a key step on the road to their understanding and ultimate control. This short review highlights recent progress in the development of reagents for the detection of free radicals and reactive oxygen species with broad application to materials science as well as biology.

  15. Positive Effect of Propolis on Free Radicals in Burn Wounds

    OpenAIRE

    Pawel Olczyk; Pawel Ramos; Katarzyna Komosinska-Vassev; Jerzy Stojko; Barbara Pilawa

    2013-01-01

    Concentration and properties of free radicals in the burn wounds treated with propolis were examined by the use of electron paramagnetic resonance spectroscopy. Magnetic spin-spin interactions and complex free radicals structures in wound beds were studied. The results were compared to those obtained for silver sulphadiazine used as a standard pharmaceutical agent. The changes of free radicals in the matrix of injury with time of exposition on these substances were tested. The aim of this stu...

  16. Fabrication and characterization of curcumin-loaded silk fibroin/P(LLA-CL) nanofibrous scaffold

    Science.gov (United States)

    Lian, Yuan; Zhan, Jian-Chao; Zhang, Kui-Hua; Mo, Xiu-Mei

    2014-12-01

    Curcumin exhibited excellent properties including antioxidant, antiinflammatory, antiviral, antibacterial, antifungal, anticancer, and anticoagulant activities. In this study, curcumin was incorporated into silk fibroin (SF)/poly(L-lactic acid- co-e-caprolactone) (P(LLA-CL)) nanofibrous scaffolds via electrospinning, and changes brought about by raising the curcumin content were observed: SEM images showed that the average nanofibrous diameter decreased at the beginning and then increased, and the nanofibers became uniform; FTIR showed that the conformation of SF transforming from random coil form to β-sheet structure had not been induced, while SF conformation converted to β-sheet after being treated with 75% ethanol vapor; XRD results confirmed that the crystal structure of (P(LLA-CL)) had been destroyed; The mechanical test illustrated that nanofibrous scaffolds still maintained good mechanical properties. Further, curcumin-loaded nanofibrous scaffolds were evaluated for drug release, antioxidant and antimicrobial activities in vitro. The results showed that curcumin presented a sustained release behavior from nanofibrous scaffolds and maintained its free radical scavenging ability, and such scaffolds could effectively inhibit S. aureus growth (> 95%). Thus, curcumin-loaded SF/P(LLA-CL) nanofibrous scaffolds might be potential candidates for wound dressing and tissue engineering scaffolds.

  17. Comparison of MALDI-TOF mass spectra of [PdCl(dien]Cl and [Ru(en2Cl2]Cl acquired with different matrices

    Directory of Open Access Journals (Sweden)

    Damnjanović Bojana

    2011-01-01

    Full Text Available In this work, the matrix-assisted laser desorption and ionization time-of-flight (MALDI-TOF mass spectra of two cationic complexes, i.e., [PdCl(dien]Cl and [Ru(en2Cl2]Cl, acquired under different conditions were analyzed. The spectra were recorded with three matrices with or without trifluoroacetic acid (TFA, i.e., two traditional matrices, i.e., 2,5-dihydroxybenzoic acid and α-cyano-hydroxycinnamic acid, and one flavonoid, quercetin. The spectra acquired with quercetin appeared to be the simplest, whereas in the spectra obtained with other matrices, peaks arising either from the addition of matrix molecules or from the fragmentation products were detectable. Addition of TFA did not complicate the spectra of the Pd(II and Ru(III complexes when the traditional matrices were used. On the other hand, the spectra of Pd complex were simpler, whereas the addition of TFA in the case of the Ru complex resulted in a higher number of peaks, some of which could not be identified. Taken together, the results of this study once more emphasize the differences arising in the MALDI-TOF mass spectra of transition metal complexes in dependence on the applied matrix.

  18. AcEST: CL3499Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL3499Contig1 690 2 Adiantum capillus-veneris contig: CL3499contig1 sequence. Link ...to clone list Show CL3499Contig1 Contig ID CL3499Contig1 Length 690 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL3499contig1 sequence. Link to clone list Link to clone list Clone ID DK948868 DK95

  19. AcEST: CL3229Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL3229Contig1 791 2 Adiantum capillus-veneris contig: CL3229contig1 sequence. Link ...to clone list Show CL3229Contig1 Contig ID CL3229Contig1 Length 791 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL3229contig1 sequence. Link to clone list Link to clone list Clone ID DK955761 DK96

  20. AcEST: CL3989Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL3989Contig1 550 2 Adiantum capillus-veneris contig: CL3989contig1 sequence. Link ...to clone list Show CL3989Contig1 Contig ID CL3989Contig1 Length 550 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL3989contig1 sequence. Link to clone list Link to clone list Clone ID DK946923 DK94

  1. AcEST: CL3009Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL3009Contig1 571 2 Adiantum capillus-veneris contig: CL3009contig1 sequence. Link ...to clone list Show CL3009Contig1 Contig ID CL3009Contig1 Length 571 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL3009contig1 sequence. Link to clone list Link to clone list Clone ID BP919782 BP91

  2. AcEST: CL4019Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL4019Contig1 513 2 Adiantum capillus-veneris contig: CL4019contig1 sequence. Link ...to clone list Show CL4019Contig1 Contig ID CL4019Contig1 Length 513 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL4019contig1 sequence. Link to clone list Link to clone list Clone ID BP917846 BP91

  3. AcEST: CL2239Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL2239Contig1 915 2 Adiantum capillus-veneris contig: CL2239contig1 sequence. Link ...to clone list Show CL2239Contig1 Contig ID CL2239Contig1 Length 915 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL2239contig1 sequence. Link to clone list Link to clone list Clone ID BP914517 DK95

  4. AcEST: CL4009Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL4009Contig1 530 2 Adiantum capillus-veneris contig: CL4009contig1 sequence. Link ...to clone list Show CL4009Contig1 Contig ID CL4009Contig1 Length 530 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL4009contig1 sequence. Link to clone list Link to clone list Clone ID BP917355 BP91

  5. AcEST: CL4249Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL4249Contig1 797 2 Adiantum capillus-veneris contig: CL4249contig1 sequence. Link ...to clone list Show CL4249Contig1 Contig ID CL4249Contig1 Length 797 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL4249contig1 sequence. Link to clone list Link to clone list Clone ID DK950942 DK95

  6. AcEST: CL4079Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL4079Contig1 514 2 Adiantum capillus-veneris contig: CL4079contig1 sequence. Link ...to clone list Show CL4079Contig1 Contig ID CL4079Contig1 Length 514 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL4079contig1 sequence. Link to clone list Link to clone list Clone ID BP914721 BP91

  7. AcEST: CL1049Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL1049Contig1 704 3 Adiantum capillus-veneris contig: CL1049contig1 sequence. Link ...to clone list Show CL1049Contig1 Contig ID CL1049Contig1 Length 704 Number of clones 3 Definition Adiantum c...apillus-veneris contig: CL1049contig1 sequence. Link to clone list Link to clone list Clone ID BP919672 DK94

  8. AcEST: CL4179Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL4179Contig1 659 2 Adiantum capillus-veneris contig: CL4179contig1 sequence. Link ...to clone list Show CL4179Contig1 Contig ID CL4179Contig1 Length 659 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL4179contig1 sequence. Link to clone list Link to clone list Clone ID DK946839 DK96

  9. AcEST: CL2939Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL2939Contig1 595 2 Adiantum capillus-veneris contig: CL2939contig1 sequence. Link ...to clone list Show CL2939Contig1 Contig ID CL2939Contig1 Length 595 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL2939contig1 sequence. Link to clone list Link to clone list Clone ID BP912753 BP91

  10. AcEST: CL2869Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL2869Contig1 543 2 Adiantum capillus-veneris contig: CL2869contig1 sequence. Link ...to clone list Show CL2869Contig1 Contig ID CL2869Contig1 Length 543 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL2869contig1 sequence. Link to clone list Link to clone list Clone ID BP917758 BP92

  11. AcEST: CL4169Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL4169Contig1 508 2 Adiantum capillus-veneris contig: CL4169contig1 sequence. Link ...to clone list Show CL4169Contig1 Contig ID CL4169Contig1 Length 508 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL4169contig1 sequence. Link to clone list Link to clone list Clone ID BP918892 BP92

  12. AcEST: CL4189Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL4189Contig1 527 2 Adiantum capillus-veneris contig: CL4189contig1 sequence. Link ...to clone list Show CL4189Contig1 Contig ID CL4189Contig1 Length 527 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL4189contig1 sequence. Link to clone list Link to clone list Clone ID DK953497 DK95

  13. AcEST: CL2199Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL2199Contig1 746 2 Adiantum capillus-veneris contig: CL2199contig1 sequence. Link ...to clone list Show CL2199Contig1 Contig ID CL2199Contig1 Length 746 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL2199contig1 sequence. Link to clone list Link to clone list Clone ID BP913617 DK95

  14. AcEST: CL1929Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL1929Contig1 684 2 Adiantum capillus-veneris contig: CL1929contig1 sequence. Link ...to clone list Show CL1929Contig1 Contig ID CL1929Contig1 Length 684 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL1929contig1 sequence. Link to clone list Link to clone list Clone ID BP913609 BP91

  15. AcEST: CL2179Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL2179Contig1 509 2 Adiantum capillus-veneris contig: CL2179contig1 sequence. Link ...to clone list Show CL2179Contig1 Contig ID CL2179Contig1 Length 509 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL2179contig1 sequence. Link to clone list Link to clone list Clone ID BP920806 BP91

  16. AcEST: CL3249Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL3249Contig1 549 2 Adiantum capillus-veneris contig: CL3249contig1 sequence. Link ...to clone list Show CL3249Contig1 Contig ID CL3249Contig1 Length 549 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL3249contig1 sequence. Link to clone list Link to clone list Clone ID BP914216 BP91

  17. AcEST: CL2109Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL2109Contig1 462 2 Adiantum capillus-veneris contig: CL2109contig1 sequence. Link ...to clone list Show CL2109Contig1 Contig ID CL2109Contig1 Length 462 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL2109contig1 sequence. Link to clone list Link to clone list Clone ID BP917476 BP91

  18. AcEST: CL2269Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL2269Contig1 735 2 Adiantum capillus-veneris contig: CL2269contig1 sequence. Link ...to clone list Show CL2269Contig1 Contig ID CL2269Contig1 Length 735 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL2269contig1 sequence. Link to clone list Link to clone list Clone ID BP915041 BP91

  19. AcEST: CL2379Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL2379Contig1 634 2 Adiantum capillus-veneris contig: CL2379contig1 sequence. Link ...to clone list Show CL2379Contig1 Contig ID CL2379Contig1 Length 634 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL2379contig1 sequence. Link to clone list Link to clone list Clone ID BP914162 DK95

  20. AcEST: CL2009Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL2009Contig1 630 2 Adiantum capillus-veneris contig: CL2009contig1 sequence. Link ...to clone list Show CL2009Contig1 Contig ID CL2009Contig1 Length 630 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL2009contig1 sequence. Link to clone list Link to clone list Clone ID BP917084 BP91

  1. AcEST: CL289Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL289Contig1 1247 8 Adiantum capillus-veneris contig: CL289contig1 sequence. Link to clone list Show CL289C...ontig1 Contig ID CL289Contig1 Length 1247 Number of clones 8 Definition Adiantum cap...illus-veneris contig: CL289contig1 sequence. Link to clone list Link to clone list Clone ID BP918911 DK95600

  2. AcEST: CL3129Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL3129Contig1 736 2 Adiantum capillus-veneris contig: CL3129contig1 sequence. Link ...to clone list Show CL3129Contig1 Contig ID CL3129Contig1 Length 736 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL3129contig1 sequence. Link to clone list Link to clone list Clone ID DK957418 DK96

  3. AcEST: CL119Contig2 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL119Contig2 1799 9 Adiantum capillus-veneris contig: CL119contig2 sequence. Link to clone list Show CL119C...ontig2 Contig ID CL119Contig2 Length 1799 Number of clones 9 Definition Adiantum cap...illus-veneris contig: CL119contig2 sequence. Link to clone list Link to clone list Clone ID BP916247 BP92045

  4. AcEST: CL209Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL209Contig1 887 10 Adiantum capillus-veneris contig: CL209contig1 sequence. Link to clone list Show CL209C...ontig1 Contig ID CL209Contig1 Length 887 Number of clones 10 Definition Adiantum cap...illus-veneris contig: CL209contig1 sequence. Link to clone list Link to clone list Clone ID DK946036 DK94588

  5. AcEST: CL2049Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL2049Contig1 590 2 Adiantum capillus-veneris contig: CL2049contig1 sequence. Link ...to clone list Show CL2049Contig1 Contig ID CL2049Contig1 Length 590 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL2049contig1 sequence. Link to clone list Link to clone list Clone ID BP915153 BP92

  6. AcEST: CL3879Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL3879Contig1 724 2 Adiantum capillus-veneris contig: CL3879contig1 sequence. Link ...to clone list Show CL3879Contig1 Contig ID CL3879Contig1 Length 724 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL3879contig1 sequence. Link to clone list Link to clone list Clone ID BP912314 BP91

  7. AcEST: CL2519Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL2519Contig1 671 2 Adiantum capillus-veneris contig: CL2519contig1 sequence. Link ...to clone list Show CL2519Contig1 Contig ID CL2519Contig1 Length 671 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL2519contig1 sequence. Link to clone list Link to clone list Clone ID DK945822 DK95

  8. AcEST: CL1749Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL1749Contig1 432 3 Adiantum capillus-veneris contig: CL1749contig1 sequence. Link ...to clone list Show CL1749Contig1 Contig ID CL1749Contig1 Length 432 Number of clones 3 Definition Adiantum c...apillus-veneris contig: CL1749contig1 sequence. Link to clone list Link to clone list Clone ID BP918055 BP91

  9. AcEST: CL1859Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL1859Contig1 551 2 Adiantum capillus-veneris contig: CL1859contig1 sequence. Link ...to clone list Show CL1859Contig1 Contig ID CL1859Contig1 Length 551 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL1859contig1 sequence. Link to clone list Link to clone list Clone ID BP911746 BP91

  10. AcEST: CL2629Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL2629Contig1 552 2 Adiantum capillus-veneris contig: CL2629contig1 sequence. Link ...to clone list Show CL2629Contig1 Contig ID CL2629Contig1 Length 552 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL2629contig1 sequence. Link to clone list Link to clone list Clone ID BP916663 BP92

  11. AcEST: CL3749Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL3749Contig1 529 2 Adiantum capillus-veneris contig: CL3749contig1 sequence. Link ...to clone list Show CL3749Contig1 Contig ID CL3749Contig1 Length 529 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL3749contig1 sequence. Link to clone list Link to clone list Clone ID BP912718 BP91

  12. AcEST: CL3239Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL3239Contig1 584 2 Adiantum capillus-veneris contig: CL3239contig1 sequence. Link ...to clone list Show CL3239Contig1 Contig ID CL3239Contig1 Length 584 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL3239contig1 sequence. Link to clone list Link to clone list Clone ID BP914227 BP91

  13. AcEST: CL1679Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL1679Contig1 879 3 Adiantum capillus-veneris contig: CL1679contig1 sequence. Link ...to clone list Show CL1679Contig1 Contig ID CL1679Contig1 Length 879 Number of clones 3 Definition Adiantum c...apillus-veneris contig: CL1679contig1 sequence. Link to clone list Link to clone list Clone ID BP912652 BP91

  14. AcEST: CL3819Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL3819Contig1 519 2 Adiantum capillus-veneris contig: CL3819contig1 sequence. Link ...to clone list Show CL3819Contig1 Contig ID CL3819Contig1 Length 519 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL3819contig1 sequence. Link to clone list Link to clone list Clone ID BP920148 BP92

  15. AcEST: CL4209Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL4209Contig1 573 2 Adiantum capillus-veneris contig: CL4209contig1 sequence. Link ...to clone list Show CL4209Contig1 Contig ID CL4209Contig1 Length 573 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL4209contig1 sequence. Link to clone list Link to clone list Clone ID BP911729 BP91

  16. AcEST: CL139Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL139Contig1 724 15 Adiantum capillus-veneris contig: CL139contig1 sequence. Link to clone list Show CL139C...ontig1 Contig ID CL139Contig1 Length 724 Number of clones 15 Definition Adiantum cap...illus-veneris contig: CL139contig1 sequence. Link to clone list Link to clone list Clone ID BP920076 DK94821

  17. AcEST: CL1109Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL1109Contig1 592 3 Adiantum capillus-veneris contig: CL1109contig1 sequence. Link ...to clone list Show CL1109Contig1 Contig ID CL1109Contig1 Length 592 Number of clones 3 Definition Adiantum c...apillus-veneris contig: CL1109contig1 sequence. Link to clone list Link to clone list Clone ID BP912925 BP91

  18. AcEST: CL3119Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL3119Contig1 745 2 Adiantum capillus-veneris contig: CL3119contig1 sequence. Link ...to clone list Show CL3119Contig1 Contig ID CL3119Contig1 Length 745 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL3119contig1 sequence. Link to clone list Link to clone list Clone ID BP918231 DK95

  19. AcEST: CL2019Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL2019Contig1 584 2 Adiantum capillus-veneris contig: CL2019contig1 sequence. Link ...to clone list Show CL2019Contig1 Contig ID CL2019Contig1 Length 584 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL2019contig1 sequence. Link to clone list Link to clone list Clone ID BP912181 BP91

  20. AcEST: CL3319Contig1 [AcEST

    Lifescience Database Archive (English)

    Full Text Available CL3319Contig1 535 2 Adiantum capillus-veneris contig: CL3319contig1 sequence. Link ...to clone list Show CL3319Contig1 Contig ID CL3319Contig1 Length 535 Number of clones 2 Definition Adiantum c...apillus-veneris contig: CL3319contig1 sequence. Link to clone list Link to clone list Clone ID DK945469 DK94