Sample records for alkyl radicals

  1. Interaction between alkyl radicals and single wall carbon nanotubes. (United States)

    Denis, Pablo A


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

  2. Alkyl Radicals as Hydrogen Bond Acceptors: Computational Evidence

    DEFF Research Database (Denmark)

    Hammerum, Steen


    , and gives rise to pronounced shifts of IR stretching frequencies and to increased absorption intensities. The hydrogen bond acceptor properties of alkyl radicals equal those of many conventional acceptors, e.g., the bond length changes and IR red-shifts suggest that tert-butyl radicals are slightly better...

  3. Conformation-specific spectroscopy of alkyl benzyl radicals: Effects of a radical center on the CH stretch infrared spectrum of an alkyl chain (United States)

    Korn, Joseph A.; Tabor, Daniel P.; Sibert, Edwin L.; Zwier, Timothy S.


    An important initial step in the combustion of gasoline and diesel fuels is the abstraction of hydrogen from alkylbenzenes to form resonance-stabilized alkyl benzyl radicals. This work uses, for the first time, double resonance spectroscopy methods to explore the conformation-specific vibronic and infrared spectroscopy of the α-ethylbenzyl (αEtBz) and α-propylbenzyl (αPrBz) radicals. Local mode Hamiltonian modeling enables assignment of the alkyl CH stretch IR spectra, accounting for Fermi resonance that complicates aliphatic alkyl CH stretch IR spectroscopy. The ground state conformational preferences of the ethyl and propyl chains are changed from those in the alkylbenzenes themselves, with global minima occurring for an in-plane orientation of the alkyl chain (trans) about its first dihedral angle (ϕf123, numbers are alkyl C atoms. C1 is CH radical site). This in-plane structure is the only observed conformer for the α-EtBz radical, while two conformers, tt and tg' share this orientation at the first dihedral, but differ in the second (ϕ1234) for the αPrBz radical. The in-plane orientation lowers the local site frequencies of the CH2 group stretches immediately adjacent to the benzylic radical site by about 50 cm-1 relative to those in pure alkyl chains or alkylbenzenes. This effect of the radical site is localized on the first CH2 group, with little effect on subsequent members of the alkyl chain. In the D1 excited electronic state, an out-of-plane orientation is preferred for the alkyl chains, leading to torsional mode Franck-Condon activity in the D0-D1 spectra that is both conformer-specific and diagnostic of the conformational change.

  4. Iodinated (Perfluoro)alkyl Quinoxalines by Atom Transfer Radical Addition Using ortho-Diisocyanoarenes as Radical Acceptors. (United States)

    Leifert, Dirk; Studer, Armido


    A simple method for the preparation of functionalized quinoxalines is reported. Starting from readily accessible ortho-diisocyanoarenes and (perfluoro)alkyl iodides, the quinoxaline core is constructed during (perfluoro)alkylation by atom transfer radical addition (ATRA), resulting in 2-iodo-3-(perfluoro)alkylquinoxalines. The radical cascades are readily initiated either with visible light or by using α,α'-azobisisobutyronitrile (AIBN). The heteroarene products are obtained in high yields (up to 94 %), and the method can be readily scaled up. Useful follow-up chemistry documents the value of the novel radical quinoxaline synthesis.

  5. UV absorption spectra, kinetics and mechanism for alkyl and alkyl peroxy radicals originating from t-butyl alcohol

    DEFF Research Database (Denmark)

    Langer, S.; Ljungström, E.; Sehested, J.


    Alkyl and alkyl peroxy radicals from 1-butyl alcohol (TBA), HOC (CH3)2CH2. and HOC(CH3)2CH2O2. have been studied in the ps phase at 298 K. Two techniques were used: pulse radiolysis UV absorption to measure the spectra and kinetics, and long path-length Fourier transform infrared spectroscopy (FTIR......) to identify and quantify the reaction products. Absorption cross sections were quantified over the wavelength range 220-320 nm. At 240 nm, sigma(HOC(CH3)2CH2) = (2.4 +/- 0.3) x 10(-18) and sigma(HOC(CH3)2CH2O2) = (3.4 +/- 0.5) X 10(-18) cm2 molecule-1 have been obtained. Observed rate constants for the self...

  6. Direct determination of rate constants for coupling between aromatic radical anions and alkyl and benzyl radicals by laser-flash photolysis

    DEFF Research Database (Denmark)

    Lund, T.; Christensen, P.; Wilbrandt, Robert Walter


    Coupling rates between the radicals methyl, n-, sec-, tert-butyl and benzyl (R-.) and the aromatic radical anions of 1,4-dicyanonaphthalene, 9,10-dicyanoanthracene and fluorenone (A(-.)) have been obtained using a new laser-flash photolysis method. The radicals R-. and the radical anions A(-.) were...... generated by a photoinduced electron transfer reaction between the aromatic compound A and the alkyl or benzyl triphenylborate anion RB(Ph)(3)(-). For the first time the rate constants of the coupling reaction between methyl and benzyl radicals with aromatic radical anions have been obtained. For all...... of the radicals and the structure and standard potentials of the aromatic radical anions....

  7. UV absorption spectra and kinetics for alkyl and alkyl peroxy radicals originating from di-tert-butyl ether

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sehested, J.; Langer, S.;


    the wavelength range 220-330 nm. At 240 nm, sigma((CH3)3COC(CH3)2CH2) = (3.6 +/- 0.4) X 10(-18) cm(2) molecule(-1) and at 260 nm, sigma((CH3)3COC(CH3)2CH2) = (3.8 +/- 0.3) X 10(-18) cm(2) molecule(-1) have been obtained. The observed rate constants for the self-reaction of (CH3)(3)COC(CH3)(2)CH2 and (CH3)(3)COC......(CH3)(2)CH2O2 radicals were found to be (2.9 +/- 0.2) X 10(-11) cm(3) molecule(-1) s(-1) and (2.7 +/- 0.2) X 10(-12) cm(3) molecule(-1) s(-1), respectively. For the reaction of the alkyl radical with O-2 in 1 atm pressure of SF6 a rate constant of (7.2 +/- 1.1) X 10(-13) cm(3) molecule(-1) s(-1......) was found. The rate constants for the reaction of the alkyl peroxy radicals with NO and NO2 were determined to be (1.8 +/- 0.2) X 10(-12) and (9.9 +/- 1.3) X 10(-12) cm(3) molecule(-1) s(-1), respectively. As a part of the work the rate constants k(F + DTBE) and k(OH + DTBE) were determined to be (2.6 +/- 0.6...

  8. Generation of free radicals from organic hydroperoxide tumor promoters in isolated mouse keratinocytes. Formation of alkyl and alkoxyl radicals from tert-butyl hydroperoxide and cumene hydroperoxide. (United States)

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


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

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

    Institute of Scientific and Technical Information of China (English)

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


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

  10. Assessing alkyl-, silyl-, and halo-substituent effects on the electron affinities of silyl radicals. (United States)

    Larkin, Joseph D; Bock, Charles W; Schaefer Iii, Henry F


    Neutral anion energy differences for a large class of alpha-substituted silyl radicals have been computed to determine the effect of alkyl, silyl, and halo substituents on their electron affinities. In particular, we report theoretical predictions of the adiabatic electron affinities (AEAs), vertical electron affinities (VEAs), and vertical detachment energies (VDEs) for a series of methyl-, silyl-, and halo-substituted silyl radical compounds. This work utilizes the carefully calibrated DZP++ basis set, in conjunction with the pure BLYP and OLYP functionals, as well as with the hybrid B3LYP, BHLYP, PBE1PBE, MPW1K, and O3LYP functionals. Bromine has the largest effect in stabilizing the anions, and the BLYP/DZP++ AEA for SiBr(3) is 3.29 eV. The other predicted electron affinities are for SiH(3) (1.37 eV), SiH(2)CH(3) (1.09 eV), SiH(2)F (1.54 eV), SiH(2)Cl (1.94 eV), SiH(2)Br (2.05 eV), SiH(2)(SiH(3)) (1.77 eV), SiH(CH(3))(2) (0.92 eV), SiHF(2) (1.86 eV), SiHCl(2) (2.53 eV), SiHBr(2) (2.67 eV), Si(CH(3))(3) (0.86 eV), SiF(3) (2.66 eV), SiCl(3) (3.21 eV), Si(SiH(3))(3) (2.25 eV), and SiFClBr (3.13 eV). For the five silyl radicals where experimental data are available, the BLYP functional gives the most accurate determination of AEAs; the average absolute error is 0.04(1) eV, whereas the corresponding errors for the O3LYP, MPW1K, PBE1PBE, B3LYP, OLYP, and BHLYP functionals are 0.05(8), 0.06(0), 0.06(3), 0.08(5), 0.11(5), and 0.15(3) eV, respectively.

  11. DDQ-promoted dehydrogenation from natural rigid polycyclic acids or flexible alkyl acids to generate lactones by a radical ion mechanism. (United States)

    Ding, Ye; Huang, Zhangjian; Yin, Jian; Lai, Yisheng; Zhang, Shibo; Zhang, Zhiguo; Fang, Lei; Peng, Sixun; Zhang, Yihua


    A novel and facile DDQ-mediated dehydrogenation from natural rigid polycyclic acids or flexible alkyl acids to generate lactones is described. The formation of lactones proceeds by a radical ion mechanism, which has been established by DPPH˙-mediated chemical identification, ESR spectroscopy and an enol intermediate trapping.

  12. Pulse radiolysis study of reactions of alkyl and alkylperoxy radicals originating from methyl tert-butyl ether in the gas phase

    DEFF Research Database (Denmark)

    Langer, S.; Ljungström, E.; Ellermann, T.;


    UV spectra and kinetics for the reactions of alkyl and alkylperoxy radicals from methyl tert-butyl ether (MTBE) were studied in 1 atm of SF6 by the pulse radiolysis-UV absorption technique. UV spectra for the radical mixtures were quantified from 215 to 340 nm. At 240 nm, sigma(R) = (2.6 +/- 0.4) X...... 10(-18) cm(2) molecule(-1) and sigma(RO2) = (4.1 +/- 0.6) X 10(-18) cm(2) molecule(-1) (base e). The rate constant for the self-reaction of the alkyl radicals is (2.5 +/- 1.1) X 10(-11) cm(3) molecule(-1) s(-1). The rate constants for reaction of the alkyl radicals with molecular oxygen...... and the alkylperoxy radicals with NO and NO2 are (9.1 +/- 1.5) X 10(-13), (4.3 +/- 1.6) X 10(-12) and (1.2 +/- 0.3) X 10(-11) cm(3) molecule(-1) s(-1), respectively. The rate constants given above refer to reaction at the tert-butyl side of the molecule....

  13. Theoretical investigation on the kinetics and mechanisms of hydroxyl radical-induced transformation of parabens and its consequences for toxicity: Influence of alkyl-chain length. (United States)

    Gao, Yanpeng; Ji, Yuemeng; Li, Guiying; An, Taicheng


    As emerging organic contaminants (EOCs), the ubiquitous presence of preservative parabens in water causes a serious environmental concern. Hydroxyl radical ((•)OH) is a strong oxidant that can degrade EOCs through photochemistry in surface water environments as well as in advanced oxidation processes (AOPs). To better understand the degradation mechanisms, kinetics, and products toxicity of the preservative parabens in aquatic environments and AOPs, the (•)OH-initiated degradation reactions of the four parabens were investigated systematically using a computational approach. The four studied parabens with increase of alkyl-chain length were methylparaben (MPB), ethylparaben (EPB), propylparaben (PPB), and dibutylparaben (BPB). Results showed that the four parabens can be initially attacked by (•)OH through (•)OH-addition and H-abstraction routes. The (•)OH-addition route was more important for the degradation of shorter alkyl-chain parabens like MPB and EPB, while the H-abstraction route was predominant for the degradation of parabens with longer alkyl-chain for example PPB and BPB. In assessing the aquatic toxicity of parabens and their degradation products using the model calculations, the products of the (•)OH-addition route were found to be more toxic to green algae than original parabens. Although all degradation products were less toxic to daphnia and fish than corresponding parental parabens, they could be still harmful to these aquatic organisms. Furthermore, as alkyl-chain length increased, the ecotoxicity of parabens and their degradation products was found to be also increased.

  14. Evaluation of the Kinetic Data for Intramolecular 1, x-Hydrogen Shifts in Alkyl Radicals and Structure/Reactivity Predictions from the Carbocyclic Model for the Transition State

    Energy Technology Data Exchange (ETDEWEB)

    Poutsma, Marvin L [ORNL


    Experimental and computational kinetic data for the intramolecular 1,x-hydrogen shift in alkyl radicals are compiled in Arrhenius format for x = 2-5. Significant experimental disparity remains, especially for x = 2 and 3. Experimental data for radicals with tert centers or bearing spectator substituents are lacking for all x, and none exist for x = 6. The common use of the strain energy of the unsubstituted (x+1)-carbocycle to coarsely model the activation energy for the 1,x-shift is extended to explore more subtle differences in progressively methyl-substituted systems by use of molecular mechanics estimates of differences in strain between radicals and carbocycles. For x = 5 and 6, a sterically driven increase in E is predicted for shifts in the tert {yields} tert class that apparently runs counter to the behavior of bimolecular hydrogen transfers. In contrast, a sterically driven decrease in E is predicted to result from spectator methyl groups for the prim {yields} prim reaction class for all x. There is no experimental basis to test these predictions; fragmentary computational evidence lends some support to the second but is ambiguous concerning the first. Possible deficiencies in the use of carbocycles as transition state models are discussed.

  15. Synthesis, Crystal Structure, Solid Photochromic Properties and Light-induced Radical Behavior of Bis(3-[alkyl/(palkoxyphenyl)]-3-hydroxyindan-1-on-2-ylidene) Derivatives

    Institute of Scientific and Technical Information of China (English)

    HAN Jie; WANG Chang-Qing; WEI Yong-Heng; PANG Mei-Li; MENG Ji-Ben


    A series of new bis{3-[alkyl/(p-alkoxyphenyl)]-3-hydroxyindan-1-on-2-ylidene} derivatives 1-6 were prepared and characterized fully by 1H NMR, IR, MS and elemental analysis data. The structures of compounds 1, 5 and 6 were confurmed by the single-crystal X-ray diffraction. The photochromic and light-induced properties were examined by means of UV-Vis and electron spin resonance (ESR) spectroscopy methods, respectively. The results show that all the title compounds in this work simultaneously exhibit photochromism in solid state and generate stable free radicals under irradiation with a 200 W high pressure Hg-lamp. Structure-property relationship within these photochromic compounds was discussed in the context of their molecular structures and intra-molecular interactions.

  16. Electron transfer properties of alkoxyl radicals. A time-resolved kinetic study of the reactions of the tert-butoxyl, cumyloxyl, and benzyloxyl radicals with alkyl ferrocenes. (United States)

    Bietti, Massimo; DiLabio, Gino A; Lanzalunga, Osvaldo; Salamone, Michela


    A time-resolved kinetic study on the reactions of the tert-butoxyl (t-BuO*), cumyloxyl (CumO*), and benzyloxyl (BnO*) radicals with alkylferrocenes has been carried out in MeCN solution. With all radicals, clear evidence for an electron transfer (ET) process has been obtained, and with the same ferrocene donor, the reactivity has been observed to increase in the order t-BuO* < CumO* < BnO*, with the difference in reactivity approaching 3 orders of magnitude on going from t-BuO* to BnO*. With BnO*, an excellent fit to the Marcus equation has been obtained, from which a value of the reduction potential of BnO* (E degrees(BnO*/BnO(-)) = 0.54 V/SCE) has been derived. The latter value appears, however, to be significantly higher than the previously determined reduction potential values for alkoxyl radicals and in contrast with the differences in the computed solution-phase electron affinities determined for t-BuO*, CumO*, and BnO*, indicating that the reaction of BnO* with ferrocene donors may not be described in terms of a straightforward outer sphere ET mechanism. From these data, and taking into account the available value of the reduction potential for CumO*, a value of E degrees (BnO*/BnO(-)) = -0.10 V/SCE has been estimated. On the basis of computational evidence for the formation of a pi-stacked prereaction complex in the reaction between BnO* and DcMFc, an alternative ET mechanism is proposed for the reactions of both CumO* and BnO*. In these cases, the delocalized nature of the unpaired electron allows for the aromatic ring to act as an electron relay by mediating the ET from the ferrocene donor to the formal oxygen radical center. This hypothesis is also in line with the observation that both BnO* and CumO* react with the ferrocene donors with rate constants that are in all cases at least 2 orders of magnitude higher than those measured for t-BuO*, wherein the radical is well-localized.

  17. Spin trapping of superoxide, alkyl- and lipid-derived radicals with derivatives of the spin trap EPPN. (United States)

    Stolze, Klaus; Udilova, Natascha; Rosenau, Thomas; Hofinger, Andreas; Nohl, Hans


    The N-t-butyl-alpha-phenylnitrone derivative N-2-(2-ethoxycarbonyl-propyl)-alpha-phenylnitrone (EPPN) has recently been reported to form a superoxide spin adduct (t(1/2)=5.25 min at pH 7.0), which is considerably more stable than the respective N-t-butyl-alpha-phenylnitrone or 5,5-dimethylpyrroline N-oxide adducts (t(1/2) approximately 10 and 45s, respectively). In continuation of our previous studies on structure optimization of 5-(ethoxycarbonyl)-5-methyl-1-pyrroline N-oxide derivatives, a series of six different EPPN derivatives was synthesized and characterized by 1H NMR, 13C NMR and IR spectroscopy. The ethoxy group of EPPN was replaced by a propoxy, iso-propoxy, n-butoxy, sec-butoxy, and tert-butoxy moiety, as well as the phenyl by a pyridyl ring. Electron spin resonance spectra and stabilities of the superoxide adducts of the propoxy derivatives were found to be similar to those of the respective EPPN adduct, whereas the electron spin resonance spectra of the superoxide adducts of N-2-(2-ethoxycarbonyl-propyl)-alpha-(4-pyridyl) nitrone and the butoxy derivatives were accompanied by decomposition products. In contrast to the 5-(ethoxycarbonyl)-5-methyl-1-pyrroline N-oxide series, no significant improvement of the superoxide adduct stability could be obtained when the ethoxy group was replaced by other substituents. Carbon centered radical adducts derived from methanol, ethanol, formic acid and linoleic acid hydroperoxide were more stable than those of 5,5-dimethylpyrroline N-oxide, whereas among the alkoxyl radicals only the methoxyl radical adduct could be detected.

  18. A Single-Component Conductor Based on a Radical Gold Dithiolene Complex with Alkyl-Substituted Thiophene-2,3-dithiolate Ligand. (United States)

    Higashino, Toshiki; Jeannin, Olivier; Kawamoto, Tadashi; Lorcy, Dominique; Mori, Takehiko; Fourmigué, Marc


    Alkyl-substituted thiophene-2,3-dithiolate ligands are prepared through a Thio-Claisen rearrangement of 4,5-bis(propargylthio)-1,3-dithiole-2-thione derivatives. The two novel dithiolate ligands, namely, 4,5-dimethyl-thiophene-2,3-dithiolate (α-Me2tpdt) and 4-ethyl-5-methyl-thiophene-2,3-dithiolate (α-EtMetpdt), are engaged in anionic Au(III) square planar complexes formulated as [Au(α-Me2tpdt)2](-) and [Au(α-EtMetpdt)2](-), isolated as Ph4P(+) salts. Monoelectronic oxidation gives the neutral radical complexes [Au(α-Me2tpdt)2](•) and [Au(α-EtMetpdt)2](•). The latter crystallizes into uniform stacks with limited interstack interactions, giving rise to a calculated half-filled band structure. It exhibits a semiconducting behavior with room temperature conductivity of 3 × 10(-3) S cm(-1), indicating that this single-component conductor can be described as a Mott insulator. The different structures observed in [Au(α-EtMetpdt)2](•) and the known [Au(Et-thiazdt)2](•) complex (Et-thiazdt: N-ethyl-thiazoline-2-thione-4,5-dithiolate), despite their very similar shapes, are tentatively attributed to differences in the electronic structures of the ligand skeleton.

  19. Thermochemical properties, DeltafH degrees (298), S degrees (298), and Cp degrees (T), for n-butyl and n-pentyl hydroperoxides and the alkyl and peroxy radicals, transition states, and kinetics for intramolecular hydrogen shift reactions of the peroxy radicals. (United States)

    Zhu, Li; Bozzelli, Joseph W; Kardos, Lisa M


    Alkyl radicals in atmospheric and combustion environments undergo a rapid association with molecular oxygen (3O2) to form an alkyl peroxy radical (ROO*). One important reaction of these peroxy radicals is the intramolecular H-shift (intramolecular abstraction) to form a hydroperoxide alkyl radical (R'*COOH), where the hydroperoxide alkyl radical may undergo chemical activation reaction with O2 and result in chain branching at moderate to low temperatures. The thermochemistry and trends in kinetic parameters for the hydrogen shift reactions from each carbon (4-8-member-ring TST's) in n-butyl and n-pentyl peroxy radicals (CCCCOO* and CCCCCOO*) are analyzed using density functional and ab initio calculation methods. Thermochemical properties, DeltafH degrees (298 K), C-H bond energies, S degrees (298 K), and Cp degrees (T) of saturated linear C4 and C5 aliphatic peroxides (ROOH), as well as the corresponding hydroperoxide alkyl radicals (R'*COOH), are determined. DeltafH degrees (298 K) are obtained from isodesmic reactions and the total energies of the CBS-QB3 and B3LYP computational methods. Contributions to the entropy and the heat capacity from translation, vibration, and external rotation are calculated using the rigid-rotor-harmonic-oscillator approximation based on the CBS-QB3 frequencies and structures. The results indicate that pre-exponential factors, A(T), decrease with the increase of the ring size (4-8-member-ring TS, H-atom included). The DeltaH for 4-, 5-, 6-, and 7-member rings in n-butyl (and n-pentyl) peroxy are 40.8 (40.8), 31.4 (31.5), 20.5 (20.0), 22.6-p (19.4) kcal mol(-1), respectively. The DeltaH for the 8-member ring in n-pentylperoxy is 23.8-p kcal mol(-1), All abstractions are from secondary (-CH2-) groups except those marked (-p), which are from primary sites. Enthalpy and barrier values from the B3LYP/6-311++G(2d,p) and BHandHLYP/6-311G(d,p) methods are compared with CBS-QB3 results. The B3LYP results show good agreement with the higher

  20. Cyclization by intramolecular carbolithiation of alkyl- and vinyllithiums prepared by the action of aromatic radical anions on phenyl thioethers. High stereoselectivity in the cyclization accelerated by an allylic lithium oxyanion. (United States)

    Deng, Kai; Bensari-Bouguerra, Ahlem; Whetstone, Joseph; Cohen, Theodore


    The reductive lithiation of alkyl and vinyl phenyl thioethers by aromatic radical anions is shown to be the most general method yet known for preparing organolithiums capable of intramolecular carbometalation of unactivated alkenes to produce five-membered rings and in one case a four-membered ring (in a far higher yield than known cases). The relative rates of cyclization for alkyllithiums are secondary > tertiary > primary, and the yields are very high. In the secondary case, the stereoselectivity is extremely high, producing a cyclopentylmethyllithium with a trans-2-alkyl substituent. A remarkable finding is that for all of the organolithiums a lithium oxyanionic group in the proximal allylic position to the alkene greatly accelerates the cyclization and leads almost exclusively to a trans relationship between the CH(2)Li group and the OLi group, the opposite relationship from that observed in intramolecular carbolithiations by allyllithiums. A mechanistic rationale for this divergence is discussed. One of the two types of proximal homoallylic lithium oxyanions exerts an analogous effect. An intriguing limitation, even occurring with the highly reactive secondary organolithium and in the presence of an allylic oxyanionic group, is the failure of intramolecular carbolithiation when a methyl group is at the terminus of the alkene.

  1. Spin adducts of several N-2-(2-alkoxycarbonyl-propyl)-alpha-pyridylnitrone derivatives with superoxide, alkyl and lipid-derived radicals. (United States)

    Stolze, Klaus; Udilova, Natascha; Rosenau, Thomas; Hofinger, Andreas; Nohl, Hans


    Several derivatives of N-t-butyl-alpha-phenylnitrone (PBN) such as N-2-(2-ethoxycarbonyl-propyl)-alpha-phenylnitrone (EPPN) have recently been reported to form superoxide spin adducts (t(1/2) ca. 2-7 min at pH 7.0), which are considerably more stable than their respective PBN or DMPO adducts (t(1/2) ca. 10 and 45 s, respectively). In continuation of our studies on structure optimization of EPPN derivatives, a series of 12 novel spin traps with 2-, 3- and 4-pyridinyl substituents was synthesized and fully characterized by 1H NMR, 13C NMR and IR spectroscopy. In addition to the replacement of the phenyl ring by a 2-, 3- or 4-pyridinyl substituent, the ethoxy group of the parent compound EPPN was replaced by either a propoxy, iso-propoxy, or cyclopropylmethoxy moiety. Superoxide adducts of all PPyN derivatives were considerably more stable than those of the respective EPPN derivatives with half-lives ranging from about 6 to 11 min. In addition, alkoxyl radical adducts were also considerably more stable than those of the EPPN series. Hydroxyl radical adducts were not detected, on the other hand, very stable spin adducts were formed from a series of carbon centered radicals, e.g. from the methyl or hydroxymethyl radical. The novel spin traps are offering an alternative to PBN or POBN, especially where the higher stability of oxygen-centered radical adducts is of major importance. All of them can easily be synthesized from commercially available compounds in two or three steps.

  2. Alkylating enzymes. (United States)

    Wessjohann, Ludger A; Keim, Jeanette; Weigel, Benjamin; Dippe, Martin


    Chemospecific and regiospecific modifications of natural products by methyl, prenyl, or C-glycosyl moieties are a challenging and cumbersome task in organic synthesis. Because of the availability of an increasing number of stable and selective transferases and cofactor regeneration processes, enzyme-assisted strategies turn out to be promising alternatives to classical synthesis. Two categories of alkylating enzymes become increasingly relevant for applications: firstly prenyltransferases and terpene synthases (including terpene cyclases), which are used in the production of terpenoids such as artemisinin, or meroterpenoids like alkylated phenolics and indoles, and secondly methyltransferases, which modify flavonoids and alkaloids to yield products with a specific methylation pattern such as 7-O-methylaromadendrin and scopolamine.

  3. Thermochemical properties of methyl-substituted cyclic alkyl ethers and radicals for oxiranes, oxetanes, and oxolanes: C-H bond dissociation enthalpy trends with ring size and ether site. (United States)

    Auzmendi-Murua, Itsaso; Charaya, Sumit; Bozzelli, Joseph W


    Cyclic ethers are an important product from the gas-phase reactions of hydrocarbon radicals with molecular oxygen in the atmospheric chemistry of diolefins and in low to moderate temperature combustion and oxidation reaction systems. They are also important in organic synthesis. Structures, and fundamental thermochemical parameters-enthalpy (ΔH°(f,298)), entropy (S°(298)), and heat capacity (C(p)(T))-have been calculated for a series of cyclic alkyl ethers and their carbon centered radicals. Enthalpies of formation (ΔH°(f,298)) are determined at the B3LYP/6-31G(d,p), B3LYP/6-31G(2d,2p), and CBS-QB3 levels using several work reactions for each species. Entropy (S) and heat capacity (C(p)(T)) values from vibration, translational, and external rotational contributions are calculated using the rigid-rotor-harmonic-oscillator approximation based on the vibration frequencies and structures obtained from the density functional studies. Contributions from the internal methyl rotors are substituted for torsion frequencies. Calculated enthalpies of formation for a series of 12 cyclic ethers and methyl substituted cyclic ethers are in good agreement with available literature values. C-H bond dissociation enthalpies are reported for 28 carbon sites of 3 to 5 member ring cyclic ethers for use in understanding effects of the ring and the ether oxygen on kinetics and stability. Trends in carbon-hydrogen bond energies for the ring and methyl substituents relative to ring size and to distance from the ether group are described.

  4. Mild Catalytic methods for Alkyl-Alkyl Bond Formation

    Energy Technology Data Exchange (ETDEWEB)

    Vicic, David A


    Overview of Research Goals and Accomplishments for the Period 07/01/06 – 06/30/07: Our overall research goal is to transform the rapidly emerging synthetic chemistry involving alkyl-alkyl cross-couplings into more of a mechanism-based field so that that new, rationally-designed catalysts can be performed under energy efficient conditions. Our specific objectives for the previous year were 1) to obtain a proper electronic description of an active catalyst for alkyl-alkyl cross-coupling reactions and 2) to determine the effect of ligand structure on the rate, scope, selectivity, and functional group compatibility of C(sp3)-C(sp3) cross-coupling catalysis. We have completed both of these initial objectives and established a firm base for further studies. The specific significant achievements of the current grant period include: 1) we have performed magnetic and computational studies on (terpyridine)NiMe, an active catalyst for alkyl-alkyl cross couplings, and have discovered that the unpaired electron resides heavily on the terpyridine ligand and that the proper electronic description of this nickel complex is a Ni(II)-methyl cation bound to a reduced terpyridine ligand; 2) we have for the first time shown that alkyl halide reduction by terpyridyl nickel catalysts is substantially ligand based; 3) we have shown by isotopic labeling studies that the active catalyst (terpyridine)NiMe is not produced via a mechanism that involves the formation of methyl radicals when (TMEDA)NiMe2 is used as the catalyst precursor; 4) we have performed an extensive ligand survey for the alkyl-alkyl cross-coupling reactions and have found that electronic factors only moderately influence reactivity in the terpyridine-based catalysis and that the most dramatic effects arise from steric and solubility factors; 5) we have found that the use of bis(dialkylphosphino)methanes as ligands for nickel does not produce active catalysts for cross-coupling but rather leads to bridging hydride

  5. 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)


    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.

  6. Radical chemistry of artemisinin (United States)

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


    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.

  7. Radicals contributing to preirradiation graft polymerization onto porous polyethylene (United States)

    Uezu, Kazuya; Saito, Kyoichi; Furusaki, Shintaro; Sugo, Takanobu; Ishigaki, Isao

    Porous polyethylene hollow fiber was irradiated by an electron beam at 160 kGy and 8 kGy/min. The concentrations of the radicals such as alkyl, allyl and peroxy were determined by analyzing an integral form of ESR spectra. The comparison of the decay of the radicals with and without contact with air demonstrated that the key radical contributing to the preirradiation graft polymerization is the alkyl radical. The decay of the alkyl radical was simulated by the diffusion-controlled model in the spherical crystallites of polyethylene.

  8. Carbonyl Alkyl Nitrates as Trace Constituents in Urban Air (United States)

    Woidich, S.; Gruenert, A.; Ballschmiter, K.


    Organic nitrates, esters of nitric acid, significantly contribute to the entire pool of odd nitrogen (NOY) in the atmosphere. Organic nitrates are formed in NO rich air by degradation of alkanes and alkenes initiated by OH and NO3 radicals during daytime and nighttime, respectively. Bifunctional organonitrates like the alkyl dinitrates and hydroxy alkyl nitrates are formed primarily from alkenes. The two main sources for Alkenes are traffic emissions and naturally occurring terpenes. So far a broad spectrum of alkyl dinitrates and hydroxy alkyl nitrates including six different isoprene nitrates has been identified in urban and marine air (1-3). We report here for the first time about the group of C4 C7 carbonyl alkyl nitrates as trace constituents in urban air collected on the campus of the University of Ulm Germany, and in the downtown area of Salt Lake City, Utah. Air sampling was done by high volume sampling (flow rate 25 m3/h) using a layer of 100 g silica gel (particle diameter 0.2 - 0.5 mm) as adsorbent. The organic nitrates were eluted from the silica gel by pentane/acetone (4:1, w/w) and the extract was concentrated to a volume of 500 µL for a group separation using normal phase HPLC. Final analysis was performed by high resolution capillary gas chromatography with electron capture detection as well as by mass selective detection in the (CH4)NCI mode using NO2- = m/e 46 as the indicator mass. The carbonyl alkyl nitrates were identified by self synthesized reference standards . So far we have identified eight non-branched a-carbonyl alkyl nitrates (vicinal carbonyl alkyl nitrates), two b-carbonyl alkyl nitrates and one g-carbonyl alkyl nitrate with carbon chains ranging from C4 to C7. The mixing ratios are between 0.05 and 0.30 ppt(v) for daytime samples and are two to three times higher for samples taken at night. (1) M. Schneider, O. Luxenhofer, Angela Deißler, K. Ballschmiter: 2C1-C15 Alkyl Nitrates, Benzyl Nitrate, and Bifunctional Nitrates

  9. Method of making alkyl esters (United States)

    Elliott, Brian


    Methods of making alkyl esters are described herein. The methods are capable of using raw, unprocessed, low-cost feedstocks and waste grease. Generally, the method involves converting a glyceride source to a fatty acid composition and esterifying the fatty acid composition to make alkyl esters. In an embodiment, a method of making alkyl esters comprises providing a glyceride source. The method further comprises converting the glyceride source to a fatty acid composition comprising free fatty acids and less than about 1% glyceride by mass. Moreover, the method comprises esterifying the fatty acid composition in the presence of a solid acid catalyst at a temperature ranging firm about C. to about C. to produce alkyl esters, such that at least 85% of the free fatty acids are converted to alkyl esters. The method also incorporates the use of packed bed reactors for glyceride conversion and/or fatty acid esterification to make alkyl esters.


    Institute of Scientific and Technical Information of China (English)

    LIANG Zhaoxi; LI Wen; LI Manfu


    In order to study the effect of alkyl chain length and the polymer effect on the photoreduction behavior of some viologens, a series of alkyl viologen, polyviologen and bisviologen compounds have been synthesized. In the presence of excess 2-propanol, the initial photoreduction of alkyl viologens and polyviologens follow the peudo-second-order reaction, the calculated rate constants are related to the alkyl chain length. In addition, the intramolecular association of radical cations of polyviologens has been found even in dilute solution. However the extent of association is varied with the alkyl chain length. The observed polymer effect of polyviologens in the photoreduction is significant which can be explained in terms of the nature of second order reaction.

  11. ESR study of free radicals in UHMW-PE fiber irradiated by gamma rays

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Yanning [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, PO Box 800-204, Shanghai 201800 (China); College of Chemistry, Jilin Normal University, Jilin 136000 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100049 (China); Wang Mouhua [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, PO Box 800-204, Shanghai 201800 (China); Tang Zhongfeng [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, PO Box 800-204, Shanghai 201800 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100049 (China); Wu Guozhong, E-mail: [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, PO Box 800-204, Shanghai 201800 (China)


    ESR spectra of the trapped radicals in an ultra-high molecular weight polyethylene (UHMW-PE) fiber irradiated by gamma rays showed well-resolved hyperfine splitting at room temperature since the c-axis of the crystallites is aligned with the fiber direction and the radicals are trapped in crystallites. The alkyl radical (-CH{sub 2}-{sup c}entre dotCH-CH{sub 2}-) was the major product after irradiation in vacuum and in air at room temperature. Some of the alkyl radicals converted to allyl radicals (-CH{sub 2}-{sup c}entre dotCH-CH=CH-) and polyenyl radicals (-CH{sub 2}-{sup c}entre dotCH-(CH=CH){sub n}-CH{sub 2}-) during storage in vacuum. Upon storage in air atmosphere, the alkyl radicals decayed by reaction with oxygen. Of particular interest is the very slow decay rate of the alkyl radical trapped in UHMW-PE fiber, the half-life is 26 days in vacuum, and 13 days in air at room temperature, which is about 1/30 and 1/100 of that reported for high density polyethylene (HDPE), respectively. The extremely long lifetime of the alkyl radical is supposed to be caused by the large size of crystallites in UHMW-PE fiber. The rate of radical decay was accelerated by annealing at elevated temperature.

  12. Combustion Pathways of the Alkylated Heteroaromatics: Bond Dissociation Enthalpies and Alkyl Group Fragmentations (United States)

    Hayes, Carrigan J.; Hadad, Christopher M.


    The bond dissociation enthalpies (BDEs) of the alkyl groups of the alkyl-substituted heterocycles have been studied and compiled using DFT methodology, with the intent of modeling the larger heterocyclic functionalities found in coal. DFT results were calibrated against CBS-QB3 calculations, and qualitative trends were reproduced between these methods. Loss of hydrogen at the benzylic position provided the most favorable route to radical formation, for both the azabenzenes and five-membered heterocycles. The ethyl derivatives had lower BDE values than the methyl derivatives due to increased stabilization of the corresponding radicals. Calculated spin densities correlated well with bond dissociation enthalpies for these compounds, while geometric effects were minimal with respect to the heterocycles themselves. Temperature effects on the bond dissociation enthalpies were minor, ranging by about 5 kcal/mol from 298 to 2000 K; the free energies of reaction dropped significantly over the same range due to entropic effects. Monocyclic heteroaromatic rings were seen to replicate the chemistry of multicyclic heteroaromatic systems.

  13. How are radicals (re)generated in photochemical ATRP? (United States)

    Ribelli, Thomas G; Konkolewicz, Dominik; Bernhard, Stefan; Matyjaszewski, Krzysztof


    The polymerization mechanism of photochemically mediated Cu-based atom-transfer radical polymerization (ATRP) was investigated using both experimental and kinetic modeling techniques. There are several distinct pathways that can lead to photochemical (re)generation of Cu(I) activator species or formation of radicals. These (re)generation pathways include direct photochemical reduction of the Cu(II) complexes by excess free amine moieties and unimolecular reduction of the Cu(II) complex, similar to activators regenerated by electron-transfer (ARGET) ATRP processes. Another pathway is photochemical radical generation either directly from the alkyl halide, ligand, or via interaction of ligand with either monomer or with alkyl halides. These photochemical radical generation processes are similar to initiators for continuous activator regeneration (ICAR) ATRP processes. A series of model experiments, ATRP reactions, and kinetic simulations were performed to evaluate the contribution of these reactions to the photochemical ATRP process. The results of these studies indicate that the dominant radical (re)generation reaction is the photochemical reduction of Cu(II) complexes by free amines moieties (from amine containing ligands). The unimolecular reduction of the Cu(II) deactivator complex is not significant, however, there is some contribution from ICAR ATRP reactions involving the interaction of alkyl halides and ligand, ligand with monomer, and the photochemical cleavage of the alkyl halide. Therefore, the mechanism of photochemically mediated ATRP is consistent with a photochemical ARGET ATRP reaction dominating the radical (re)generation.

  14. Synthesis of tetrahydrokhusitone. Annulation of the cyclohexane ring by free radical and carbanionic sequence of reactions

    Directory of Open Access Journals (Sweden)



    Full Text Available The synthesis of norcadinane sesquiterpene tetrahydrokhusitone 1 has been achieved by a new method for annulation of cyclohexane ring involving a sequence of free radical d-alkylation of the non-activated carbon atom and intramolecular carbanionic alkylation. (–-Menthol was used as the starting compound.

  15. Organic photoredox catalysis for the oxidation of silicates: applications in radical synthesis and dual catalysis. (United States)

    Lévêque, Christophe; Chenneberg, Ludwig; Corcé, Vincent; Ollivier, Cyril; Fensterbank, Louis


    Metal free photooxidation of alkyl bis(catecholato)silicates with the organic dye 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyano-benzene (4CzIPN) allows the smooth formation of alkyl radicals. The latter can be efficiently engaged either with radical acceptors to provide homolytic addition products or in photoredox/nickel dual catalysis reactions to obtain cross-coupling products.

  16. Ion-radical intermediates of the radiation-chemical transformations of organic carbonates (United States)

    Shiryaeva, Ekaterina S.; Sosulin, Ilya S.; Saenko, Elizaveta V.; Feldman, Vladimir I.


    The spectral features and reactions of ion-radical intermediates produced from organic carbonates in low-temperature matrices were investigated by EPR spectroscopy and quantum-chemical calculations. It was shown that radical cations of diethyl carbonate and dimethyl carbonate underwent intramolecular hydrogen transfer to yield alkyl-type species, as was suggested previously. Meanwhile, radical cation of EC demonstrates a ring cleavage even at 77 K, while radical cation of PC is probably intrinsically stable and undergo an ion-molecule reaction with a neighboring neutral molecule in dimers or associates. Radical anions were obtained in glassy matrices of diethyl ether or perdeuteroethanol. The radical anions of linear carbonates show photoinduced fragmentation to yield the corresponding alkyl radicals; such process may also occur directly under radiolysis. Radical anions of cyclic carbonates are relatively stable and yield only trace amounts of fragmentation products under similar conditions.

  17. Synthesis and Antioxidant Activity of Alkyl Nitroderivatives of Hydroxytyrosol

    Directory of Open Access Journals (Sweden)

    Elena Gallardo


    Full Text Available A series of alkyl nitrohydroxytyrosyl ether derivatives has been synthesized from free hydroxytyrosol (HT, the natural olive oil phenol, in order to increase the assortment of compounds with potential neuroprotective activity in Parkinson’s disease. In this work, the antioxidant activity of these novel compounds has been evaluated using Ferric Reducing Antioxidant Power (FRAP, 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid diammonium salt (ABTS, and Oxygen Radical Scavenging Capacity (ORAC assays compared to that of nitrohydroxytyrosol (NO2HT and free HT. New compounds showed variable antioxidant activity depending on the alkyl side chain length; compounds with short chains (2–4 carbon atoms maintained or even improved the antioxidant activity compared to NO2HT and/or HT, whereas those with longer side chains (6–8 carbon atoms showed lower activity than NO2HT but higher than HT.

  18. Distribution coefficients of purine alkaloids in water-ammonium sulfate-alkyl acetate-dialkyl phthalate systems (United States)

    Korenman, Ya. I.; Krivosheeva, O. A.; Mokshina, N. Ya.


    The distribution of purine alkaloids (caffeine, theobromine, theophylline) was studied in the systems: alkyl acetates-dialkyl phtalate-salting-out agent (ammonium sulfate). The quantitative characteristics of the extraction-distribution coefficients ( D) and the degree of extraction ( R, %) are calculated. The relationships between the distribution coefficients of alkaloids and the length of the hydrocarbon radical in the molecule of alkyl acetate (dialkyl phtalate) are determined. The possibility of predicting the distribution coefficients is demonstrated.

  19. 40 CFR 721.9892 - Alkylated urea. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...


    Institute of Scientific and Technical Information of China (English)

    张雅文; 沈宗旋; 陆军


    Ethyl acetamidomalonate was alkylated using three alkylating agents, both by microtwave irradiation of a mixture of the malonate,the alkylating agent, potassium carbonate,TEBA,and DMF for 0.5 to 1.5 min and by heating a solution of the malonate, sodium ethoxide, and the alkylatlng agent in ethanol for several hours. The two metlmds gave comparable results.

  1. Radical prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Sønksen, Jens; Jakobsen, Henrik


    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. Methods of making alkyl esters (United States)

    Elliott, Brian


    A method comprising contacting an alcohol, a feed comprising one or more glycerides and equal to or greater than 2 wt % of one or more free fatty acids, and a solid acid catalyst, a nanostructured polymer catalyst, or a sulfated zirconia catalyst in one or more reactors, and recovering from the one or more reactors an effluent comprising equal to or greater than about 75 wt % alkyl ester and equal to or less than about 5 wt % glyceride.

  3. Pathways of arachidonic acid peroxyl radical reactions and product formation with guanine radicals. (United States)

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


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

  4. Amine synthesis via iron-catalysed reductive coupling of nitroarenes with alkyl halides (United States)

    Cheung, Chi Wai; Hu, Xile


    (Hetero)Aryl amines, an important class of organic molecules in medicinal chemistry, are most commonly synthesized from anilines, which are in turn synthesized by hydrogenation of nitroarenes. Amine synthesis directly from nitroarenes is attractive due to improved step economy and functional group compatibility. Despite these potential advantages, there is yet no general method for the synthesis of (hetero)aryl amines by carbon-nitrogen cross-coupling of nitroarenes. Here we report the reductive coupling of nitroarenes with alkyl halides to yield (hetero)aryl amines. A simple iron catalyst enables the coupling with numerous primary, secondary and tertiary alkyl halides. Broad scope and high functional group tolerance are demonstrated. Mechanistic study suggests that nitrosoarenes and alkyl radicals are involved as intermediates. This new C-N coupling method provides general and step-economical access to aryl amines.

  5. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name). (United States)


    ... alkyl esters (generic name). 721.1875 Section 721.1875 Protection of Environment ENVIRONMENTAL... esters (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  6. New insight into the spatiotemporal variability and source apportionments of C1-C4 alkyl nitrates in Hong Kong (United States)

    Ling, Zhenhao; Guo, Hai; Simpson, Isobel Jane; Saunders, Sandra Maria; Lam, Sean Ho Man; Lyu, Xiaopu; Blake, Donald Ray


    C1-C4 alkyl nitrates (RONO2) were measured concurrently at a mountain site, Tai Mo Shan (TMS), and an urban site, Tsuen Wan (TW), at the base of the same mountain in Hong Kong from September to November 2010. Although the levels of parent hydrocarbons were much lower at TMS (p Pearl River delta (PRD) region. In contrast to TW, the alkyl nitrate levels measured at TMS mainly resulted from the photooxidation of the parent hydrocarbons at TW during mesoscale circulation, i.e., valley breezes, corresponding to 52-86 % of the alkyl nitrate levels at TMS. Furthermore, regional transport from the inland PRD region made significant contributions to the levels of alkyl nitrates (˜ 58-82 %) at TMS in the non-meso scenario, resulting in similar levels of alkyl nitrates observed at the two sites. The simulation of secondary formation pathways using a photochemical box model found that the reaction of alkyl peroxy radicals (RO2) with nitric oxide (NO) dominated the formation of RONO2 at both sites, and the formation of alkyl nitrates contributed negatively to O3 production, with average reduction rates of 4.1 and 4.7 pptv pptv-1 at TMS and TW, respectively.

  7. Enhanced Synthesis of Alkyl Amino Acids in Miller's 1958 H2S Experiment (United States)

    Parker, Eric T.; Cleaves, H. James; Callahan, Michael P.; Dworkin, James P.; Glavin, Daniel P.; Lazcano, Antonio; Bada, Jeffrey L.


    Stanley Miller's 1958 H2S-containing experiment, which included a simulated prebiotic atmosphere of methane (CH4), ammonia (NH3), carbon dioxide (CO2), and hydrogen sulfide (H2S) produced several alkyl amino acids, including the alpha-, beta-, and gamma-isomers of aminobutyric acid (ABA) in greater relative yields than had previously been reported from his spark discharge experiments. In the presence of H2S, aspariic and glutamic acids could yield alkyl amino acids via the formation of thioimide intermediates. Radical chemistry initiated by passing H2S through a spark discharge could have also enhanced alkyl amino acid synthesis by generating alkyl radicals that can help form the aldehyde and ketone precursors to these amino acids. We propose mechanisms that may have influenced the synthesis of certain amino acids in localized environments rich in H2S and lightning discharges, similar to conditions near volcanic systems on the early Earth, thus contributing to the prebiotic chemical inventory of the primordial Earth.

  8. Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer (United States)

    Choi, Gilbert J.; Zhu, Qilei; Miller, David C.; Gu, Carol J.; Knowles, Robert R.


    Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process—a subset of the classical Hofmann-Löffler-Freytag reaction—amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using

  9. Process for the preparation of alkyl glycosides

    NARCIS (Netherlands)

    De Goede, A.T.J.; Van der Leij, I.G.; Van der Heijden, A.M.; Van Rantwijk, F.; Van Bekkum, H.


    Abstract of WO 9636640 (A2) The present invention relates to a process for the preparation of alkyl glycosides by reacting an alcohol with a saccharide or a lower-alkyl glycoside in the presence of a catalyst, wherein the catalyst is a mesoporous silica-based molecular sieve material. This proce

  10. Ignorance Radicalized

    Directory of Open Access Journals (Sweden)

    Gergo Somodi


    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.

  11. Exchanging Alkyl Groups through Unstrained C-C Bond Cleavage in the Presence of a Copper Catalyst. (United States)

    Wada, Masaru; Noda, Yushi; Nishikata, Takashi


    Although numerous reports exist on strained C-C bond cleavage reactions in aryl substitutions, the cleavage methodology for unstrained C-C bonds in alkylation reactions has not yet been established. We found that unstrained allylic C-C bonds can be cleaved using α-radicals to form C(sp(3) )-C(sp(3) ) bonds in the presence of a copper catalyst. In this reaction, the property of leaving and loading radicals is very important for radical fragmentations. In this paper, we investigated the effects of these properties in cleavage reactions for unstrained C-C bonds.

  12. Section i: Thermodynamic Properties of Hydrocarbon Radicals, Peroxy Hydrocarbon and Peroxy Chlorohydrocarbon Molecules and Radicals. Section II. Kinetics and Reaction Mechanisms For: (1) Chloroform Pyrolysis and Oxidation; (2) Benzene and Toluene Oxidation Under Atmospheric Conditions. (United States)

    Lay, Tsan-Horng


    Alkyl radicals are important active intermediates in gas phase photochemistry and combustion reaction systems. With the exception of a limited number of the most elementary radicals, accurate thermodynamic properties of alkyl radicals are either not available or only rough estimations exist. An H atom Bond Increment approach is developed and a data base is derived, for accurately estimating thermodynamic properties (Delta H_{f }^circ298, S ^circ298 and Cp(T)) for generic classes of hydrocarbon radical species. Reactions of alkyl radicals with molecular oxygen are one of the major reaction paths for these radicals in atmospheric photochemistry, oxidation of hydrocarbon liquids and combustion process. Alkyl hydroperoxides are subsequently formed through the alkyl peroxy radicals reactions with varied chemical species present in the reaction system. Thermodynamic properties of the alkyl hydroperoxides and related radicals are therefore frequently required in gas phase modeling and kinetic studies on these systems. The thermodynamic properties of alkyl hydroperoxides, alkyl peroxy radicals and hydroperoxyl-1-ethyl radicals including the species with fluorine and chlorine substituents on the alpha-carbon are evaluated using molecular orbital calculations. Chloroform is used as a model chlorocarbon system with high Cl/H ratio to investigate thermal decomposition processes of chlorocarbons in oxidative and pyrolytic reaction environments. A detailed reaction mechanism is developed to describe the important features of products and reagent loss and is shown to predict the experimental data well. Reaction pathways and rate constants are developed for CCl _3, CCl_2 and rm C_2Cl_3 radical addition to O_2 and combination with O, OH HO_2 and ClO. The reversible addition reaction of OH radical with benzene to form the hydroxyl-2,4-cyclohexadienyl (benzene -OH) adduct and the subsequent reactions of this benzene -OH adduct with O_2 are important initial steps for the

  13. Alkylation of organic aromatic compounds (United States)

    Smith, L.A. Jr.


    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  14. Reactivity patterns of transition metal hydrides and alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Jones, W.D. II


    The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/sub 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.

  15. Kinetics of UV curable alkyl 3-mercaptopropionate-vinyl silizane

    Institute of Scientific and Technical Information of China (English)

    Jiale SONG; Lixin CHEN; Yazhou WANG; Weiwei CHEN; Rumin WANG


    Photopolymerization of vinyl-containing liquid silizane preceramic monomers copolymerized with thiol monomers, based on a step-growth radical polymerization mechanism, is a novel, rapid, inexpensive and simple tech-nique for producing preceramic structures from liquid pre-cursors. The kinetics of alkyl 3-mercptopropionate-vinyl silizane under UV irradiation is investigated by using real-time Fourier transform infrarcd (FT-IR) and photo-dif-ferential scanning calorimetry (photo-DSC). The experi-mental results show preliminarily that: (1) about 80% conversion of vinyl group has been achieved in the pres-ence of a low concentration photoinitiator under UV irra-diation; (2) by increasing the functionalities of the thiol group, the peak rate of copolymerization increases and the final conversion of the vinyl group decreases; (3) the copolymerization is primarily a bimolecular radical ter-mination process; (4) the copolymerization is first-order, i.e., its rate is proportional to the vinyl group concentra-tion and independent of the concentration of thiol group.

  16. Reactions of Hydroxyalkyl Radicals with Cysteinyl Peptides in a NanoESI Plume (United States)

    Stinson, Craig A.; Xia, Yu


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

  17. Growing up Radical: Investigation of Benzyl-Like Radicals with Increasing Chain Lengths (United States)

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


    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.

  18. A radical approach to radical innovation


    Deichmann, Dirk; van der Ende, Jan


    textabstractInnovation pays. Amazon, Apple, Facebook, Google – nearly every one of today’s most successful companies has a talent for developing radical new ideas. But how best to encourage radical initiative taking from employees, and does their previous success or failure at it play a role?

  19. Superoxide Anion Radical Scavenging Ability of Quaternary Ammonium Salt of Chitosan

    Institute of Scientific and Technical Information of China (English)

    Xiao Yan ZHU; Jian Min WU; Zhi Shen JIA


    A series of N-alkyl or N-aryl chitosan quaternary ammonium salt were prepared using 96% deacetylated chitosan. Their scavenging activities against superoxide anion radical were investigated by chemiluminescence. The IC50 values of these compounds range from 280 to 880 μg/mL, which should be attributed to their different substitutes.

  20. Biodegradation of alkylates under less agitated aquifer conditions

    Institute of Scientific and Technical Information of China (English)

    Jay J.Cho; Makram T.Suidan; Albert D.Venosa


    The biodegradability of three alkylates (2,3-dimethylpentane,2,4-dimethylpentane and 2,2,4-trimethylpentane) under less agitated aquifer conditions was investigated in this study.All three alkylates biodegraded completely under these conditions regardless of the presence or absence of ethanol or benzene,toluene,ethylbenzene,and xylenes (BTEX) in the feed.In the presence of ethanol,alkylates degradation was not inhibited by ethanol.However,alkylates degraded more slowly in the presence of BTEX suggesting competitive inhibition to microbial utilization of alkylates.In the sterile controls,alkylates concentrations remained unchanged throughout the experiments.


    Institute of Scientific and Technical Information of China (English)

    GUO Xinqiu; QIU Kunyuan; FENG Xinde


    Effects of N-alkyl substituted ethylenediamine derivatives on vinyl polymerization using persulfate as initiator were studied. The apparent kinetic equations and overall activation energies of acrylamide polymerization were determined using the above mentioned system as initiator. The promoting activities of diamine > primary diamine. Diamines having methyl groups as the substituent on their nitrogen atom possess higher promoting activity than that of having larger alkyl groups.The initialfree radicals produced through the redox reaction of persulfate and diamines were studied by spin strapping technique and ESR spectroscopy. The results obtained confirm the fact that the initial free radicals of the diamine species can initiate vinyl polymerization and become the amino end group of the resulting polymers.

  2. Comparative study of the antioxidant activities of some lipase-catalyzed alkyl dihydrocaffeates synthesized in ionic liquid. (United States)

    Gholivand, Somayeh; Lasekan, Ola; Tan, Chin Ping; Abas, Faridah; Wei, Leong Sze


    The solubility limitations of phenolic acids in many lipidic environments are now greatly improved by their enzymatic esterification in ionic liquids (ILs). Herein, four different ILs were tested for the esterification of dihydrocaffeic acid with hexanol and the best IL was selected for the synthesis of four other n-alkyl esters with different chain-lengths. The effect of alkyl chain length on the anti-oxidative properties of the resulted purified esters was investigated using β-carotene bleaching (BCB) and free radical scavenging method DPPH and compared with butylated hydroxytoluene (BHT) as reference compound. All four esters (methyl, hexyl, dodecyl and octadecyl dihydrocaffeates) exhibited relatively strong radical scavenging abilities. The scavenging activity of the test compounds was in the following order: methyl ester>hexyl ester⩾dodecyl ester>octadecyl ester>BHT while the order for the BCB anti-oxidative activity was; BHT>octadecyl ester>dodecyl ester>hexyl ester>methyl ester.

  3. Chiral Alkyl Halides: Underexplored Motifs in Medicine

    Directory of Open Access Journals (Sweden)

    Bálint Gál


    Full Text Available While alkyl halides are valuable intermediates in synthetic organic chemistry, their use as bioactive motifs in drug discovery and medicinal chemistry is rare in comparison. This is likely attributable to the common misconception that these compounds are merely non-specific alkylators in biological systems. A number of chlorinated compounds in the pharmaceutical and food industries, as well as a growing number of halogenated marine natural products showing unique bioactivity, illustrate the role that chiral alkyl halides can play in drug discovery. Through a series of case studies, we demonstrate in this review that these motifs can indeed be stable under physiological conditions, and that halogenation can enhance bioactivity through both steric and electronic effects. Our hope is that, by placing such compounds in the minds of the chemical community, they may gain more traction in drug discovery and inspire more synthetic chemists to develop methods for selective halogenation.

  4. Fourier transform infrared absorption spectroscopy of jet-cooled radicals (United States)

    Rohrs, Henry W.; Wickham-Jones, C. Tom; Ellison, G. Barney; Berry, David; Argrow, Brian M.


    We describe an experiment that couples a high-resolution Fourier transform spectrometer (FTS) to a supersonic jet of radicals. A 1-mm-i.d. cylindrical SiC nozzle is resistively heated to 1500 K in order to decompose organic precursors and generate expansions of jet-cooled radicals. We have used this apparatus to pyrolyze alkyl nitrites to make alkoxy and nitric oxide radicals. The residence time of radicals in this hot nozzle is roughly 20 μs RONO→ΔRO+NO. We use the FTS to detect the IR absorption of the product NO (ν0=1876.1 cm-1) at resolutions as fine as 0.005 cm-1 FWHM. We observe the product NO from the pyrolysis of CH3CH2ONO to be rotationally cooled to roughly 50 K. The IR spectra indicate that the optical path length is about 3/4 cm and that the nitrites pyrolyze to produce approximately 1014 NO radicals cm-3 some 9 mm downstream from the nozzle. Our spectrometer is capable of detecting an absorption signal of 0.1% over a bandwidth of 100 cm-1 at 0.005 cm-1 resolution. Depending on the infrared cross section of the radical, this implies that we are able to monitor diatomic radical densities of roughly 5×1012 cm-3 (quantum state)-1.

  5. Radical theory of rings

    CERN Document Server

    Gardner, JW


    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

  6. [Lavoisier and radicals]. (United States)

    Lafont, Olivier


    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.

  7. Alkylation of Chitosan as Nerve Conduit Biomaterial

    Institute of Scientific and Technical Information of China (English)

    邓劲光; 公衍道; 程明愚; 赵南明; 张秀芳


    Chitosan under physiological conditions is a degradable and biocompatible biomaterial with a wide variety of useful physicochemical properties. However, as a nerve conduit biomaterial, its solubility was very low, so chitosan was modified chemically to enhance its solubility. The free amino groups of long molecular chains in chitosan are responsible for its solubility, and the solubility could be adjusted by controlling the free amidogen capacity with N-alkylation. The results show that the solubility of N-alkylation chitosan is increased to 10%, which is an increase of 500%.

  8. Enhancement of alkylation catalysts for improved supercritical fluid regeneration (United States)

    Ginosar, Daniel M.; Petkovic, Lucia


    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  9. Antioxidant properties and efficacies of synthesized alkyl caffeates, ferulates, and coumarates

    DEFF Research Database (Denmark)

    Sørensen, Ann-Dorit Moltke; Durand, Erwann; Laguerre, Mickaël


    Caffeic, ferulic, and coumaric acids were lipophilized with saturated fatty alcohols (C1-C20). The antioxidant properties of these hydroxycinnamic acids and their alkyl esters were evaluated in various assays. Furthermore, the antioxidant efficiency of the compounds was evaluated in a simple o....../w microemulsion using the conjugated autoxidizable triene (CAT) assay. All evaluated phenolipids had radical scavenging, reducing power, and metal chelating properties. Only caffeic acid and caffeates were able to form a complex with iron via their catechol group in the phenolic ring. In the o/w emulsion...

  10. Contemporary Radical Prostatectomy

    Directory of Open Access Journals (Sweden)

    Qiang Fu


    Full Text Available Purpose. Patients diagnosed with clinically localized prostate cancer have more surgical treatment options than in the past. This paper focuses on the procedures' oncological or functional outcomes and perioperative morbidities of radical retropubic prostatectomy, radical perineal prostatectomy, and robotic-assisted laparoscopic radical prostatectomy. Materials and Methods. A MEDLINE/PubMed search of the literature on radical prostatectomy and other new management options was performed. Results. Compared to the open procedures, robotic-assisted radical prostatectomy has no confirmed significant difference in most literatures besides less blood loss and blood transfusion. Nerve sparing is a safe means of preserving potency on well-selected patients undergoing radical prostatectomy. Positive surgical margin rates of radical prostatectomy affect the recurrence and survival of prostate cancer. The urinary and sexual function outcomes have been vastly improved. Neoadjuvant treatment only affects the rate of positive surgical margin. Adjuvant therapy can delay and reduce the risk of recurrence and improve the survival of the high risk prostate cancer. Conclusions. For the majority of patients with organ-confined prostate cancer, radical prostatectomy remains a most effective approach. Radical perineal prostatectomy remains a viable approach for patients with morbid obesity, prior pelvic surgery, or prior pelvic radiation. Robot-assisted laparoscopic prostatectomy (RALP has become popular among surgeons but has not yet become the firmly established standard of care. Long-term data have confirmed the efficacy of radical retropubic prostatectomy with disease control rates and cancer-specific survival rates.

  11. The Synthesis of 6-Alkyl-5-Fluorouracil Derivatives

    Institute of Scientific and Technical Information of China (English)


    6-alkyl-5-fluorouracil derivatives (5a~5f) were synthesized by facile alkylation of lithiation of 5-fluorouracil derivatives with mthyl iodide (MeI) or alkyl trifluoromethanesulfonate (ROTf) in yield of 42~58%. We found that the methylated product was ethyl-substituted derivatives, not methyl-substituted derivatives.

  12. Amberlyst-15 catalyzed synthesis of alkyl/aryl/heterocyclic phosphonates

    Institute of Scientific and Technical Information of China (English)

    U.M. Rao Kunda; V.N. Reddy Mudumala; C.S. Reddy Gangireddy; B.R. Nemallapudi; K.N. Sandip; S.R. Cirandur


    A novel and efficient procedure for the synthesis of alkyl phosphonates through one pot condensation of alkyl halide and tri-alkyl/aryl phosphite in the presence of Amberlyst-15 as catalyst under solvent free conditions was applied. It demonstrated several advantages such as good yields of products, simple operation, convenient separation and inexpensive catalyst.


    A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

  14. 40 CFR 721.10087 - Substituted alkyl phosphine oxide (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl phosphine oxide... Specific Chemical Substances § 721.10087 Substituted alkyl phosphine oxide (generic). (a) Chemical... as substituted alkyl phosphine oxide (PMN P-06-332) is subject to reporting under this section...

  15. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  16. 40 CFR 721.2825 - Alkyl ester (generic name). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl ester (generic name). 721.2825... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance alkyl ester (PMN P-84-968) is subject to reporting under this...

  17. 40 CFR 721.8700 - Halogenated alkyl pyridine. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkyl pyridine. 721.8700... Substances § 721.8700 Halogenated alkyl pyridine. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkyl pyridine (PMN P-83-237)...

  18. Polypyrrole Doped with Alkyl Benzene Sulphonates

    DEFF Research Database (Denmark)

    Bay, Lasse; Mogensen, Naja; Skaarup, Steen;


    The properties of polypyrrole (PPy) are to a large extent determined by the condition of synthesis and especially by the counterion incorporated as dopant during synthesis. In this work, PPy doped with different alkyl benzenesulfonates are compared. The polymer films are prepared by constant curr...

  19. Forgotten Radicals in Biology



    Redox reactions play key roles in intra- and inter-cellular signaling, and in adaptative processes of tissues towards stress. Among the major free radicals with essential functions in cells are reactive oxygen species (ROS) including superoxide anion (O2 •-), hydroxyl radical (•OH) and reactive nitrogen species (RNS) such as nitric oxide (•NO). In this article, we review the forgotten and new radicals with potential relevance to cardiovascular pathophysiology. Approximately 0.3% of O2 •- pres...

  20. Inhibition and Promotion of Pyrolysis by Hydrogen Sulfide (H2S) and Sulfanyl Radical (SH)

    DEFF Research Database (Denmark)

    Zeng, Zhe; Altarawneh, Mohammednoor; Oluwoye, Ibukun


    This study resolves the interaction of sulfanyl radical (SH) with aliphatic (C1–C4) hydrocarbons, using CBS-QB3 based calculations. We obtained the C–H dissociation enthalpies and located the weakest link in each hydrocarbon. Subsequent computations revealed that, H abstraction by SH from......, an alkyl radical readily abstracts H atom from H2S, with H2S acting as a potent scavenger for alkyl radicals in combustion processes. That is, these reactions proceed in the opposite direction than those involving SH and alkene or alkyne species, exhibiting shallow barriers and strong spontaneity. Our...... processes. For the three groups of hydrocarbon, Evans–Polanyi plots display linear correlations between the bond dissociation enthalpies of the abstracted hydrogens and the relevant activation energies. In the case of methane, we demonstrated that the reactivity of SH radicals toward abstracting H atoms...

  1. Identification of chemical structure and free radical scavenging activity of diphlorethohydroxycarmalol isolated from a brown alga, Ishige okamurae. (United States)

    Heo, Soo-Jin; Kim, Jong-Pyung; Jung, Won-Kyo; Lee, Nam-Ho; Kang, Hahk-Soo; Jun, Eun-Mi; Park, Soon-Hye; Kang, Sung-Myung; Lee, Young-Jae; Park, Pyo-Jam; Jeon, You-Jin


    To obtain a natural antioxidant from a marine biomass, this study investigated the antioxidative activity of methanolic extracts from the marine brown alga, Ishige okamurae collected off Jeju Island. A potent free radical scavenging activity was detected in the ethyl acetate fraction containing polyphenolic compounds, and the potent antioxidant elucidated as a kind of phlorotannin, diphlorethohydroxycarmalol, by NMR and mass spectroscopic data. The free radical scavenging activities of the diphlorethohydroxycarmalol were investigated in relation to 1,1-diphenyl-2-picrylhydrazyl (DPPH), alkyl, and hydroxyl radicals using an electron spin resonance (ESR) system. The diphlorethohydroxycarmalol was found to scavenge DPPH (IC50=3.41 microM) and alkyl (IC50=4.92 microM) radicals more effectively than the commercial antioxidant, ascorbic acid. Therefore, these results present diphlorethohydroxycarmalol as a new phlorotannin with a potent antioxidative activity that could be useful in cosmetics, foods, and pharmaceuticals.

  2. Assessing the reactivity of sodium alkyl-magnesiates towards quinoxaline: single electron transfer (SET) vs. nucleophilic alkylation processes. (United States)

    Livingstone, Zoe; Hernán-Gómez, Alberto; Baillie, Sharon E; Armstrong, David R; Carrella, Luca M; Clegg, William; Harrington, Ross W; Kennedy, Alan R; Rentschler, Eva; Hevia, Eva


    By exploring the reactivity of sodium butyl-magnesiate (1) supported by the bulky chelating silyl(bisamido) ligand {Ph2Si(NAr*)2}(2-) (Ar* = 2,6-iPr2-C6H3) towards Quinoxaline (Qx), the ability of this bimetallic system to effectively promote SET processes has been disclosed. Thus 1 executes the single-electron reduction of Qx affording complex (2) whose structure in the solid state contains two quinaxolyl radical anions Qx˙ stabilised within a dimeric magnesiate framework. Combining multinuclear NMR and EPR measurements with DFT calculations, new insights into the constitution of 2 in solution and its magnetic behaviour have been gained. Further evidence on the SET reactivity of 1 was found when it was reacted with nitroxyl radical TEMPO which furnished contacted ion pair sodium magnesiate [(Ph2Si(NAr*)2)Mg(TEMPO(-))Na(THF)3] (4) where both metals are connected by an alkoxide bridge, resulting from reduction of TEMPO. The role that the different ligands present in 1 can play in these new SET reactions has also been assessed. Using an amination approach, the Bu group in 1 can be replaced by the more basic amide TMP allowing the isolation of (3) which was characterised by multinuclear NMR and X-ray crystallography. (1)H NMR monitoring of the reaction of 3 with Qx showed its conversion to 2, leaving the hydrogen atoms of the heterocycle untouched. Contrastingly, using sodium homoalkyl magnesiate [NaMg(CH2SiMe3)3] (5) led to the chemoselective C2 alkylation of this heterocycle, suggesting that the presence of the steric stabiliser {Ph2Si(NAr*)2}(2-) on the mixed-metal reagent is required in order to facilitate the Qx reduction.

  3. Orgasm after radical prostatectomy

    NARCIS (Netherlands)

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


    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

  4. The Radicalization Puzzle [video


    Mohammed Hafez; Center for Homeland Defense and Security Naval Postgraduate School


    This 20 minute lecture, by Dr. Mohammad Hafez of the Naval Postgraduate School examines the driving factors behind the process of radicalization, turning seemingly ordinary men and women into potential terrorists. The lecture is based on the article "The Radicalization Puzzle: A Theoretical Synthesis of Empirical Approaches to Homegrown Extremism" in Studies in Conflict and Terrorism, by Mohammad Hafez and Creighton Mullins.

  5. Deuterium Substitution used as a Tool for Investigating Mechanisms of Gas-Phase Free-Radical Reactions (United States)

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


    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.

  6. Evidence for production of oxidizing radicals by the particulate O-2-forming system from human neutrophils. (United States)

    Tauber, A I; Gabig, T G; Babior, B M


    The particulate O-2-forming system from human neutrophils was found to oxidize methional and 2-keto-4-methylthiobutyric acid (KMB) to ethylene, indicating the formation by this system of strongly oxidizing radicals. Conforming this interpretation was the observation that ethylene production was inhibited by the radical scavengers benzoate, ethanol, and mannitol. Ethylene production was also sharply reduced by superoxide dismutase, implicatin O-2 as a precursor of oxidizing radicals. In our system catalase only partially inhibited ethylene generation from either methional or KMB, suggesting that oxidizing radicals are generated at least in part by the reacton of O-2 with compounds other than H2O2. We propose that in neutrophils oxidizing radicals are formed in a reaction between O-2 and a peroxide according to the following equation: O-2 + ROOH leads to RO . + OH- + O2, in which ROOH may be hydrogen peroxide, an alkyl peroxide, or an acyl peroxide (i.e., a peroxy acid).

  7. Alkyl- and fluoroalkyltrialkoxysilanes for wettability modification

    Energy Technology Data Exchange (ETDEWEB)

    Dopierala, Katarzyna, E-mail: [Institute of Chemical Technology and Engineering, Poznan University of Technology, Pl. Marii Skłodowskiej-Curie 2, Poznań 60-965 (Poland); Maciejewski, Hieronim [Poznań Science and Technology Park, Rubież 46, Poznań 61-612 (Poland); Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, Poznań 60-780 (Poland); Karasiewicz, Joanna [Poznań Science and Technology Park, Rubież 46, Poznań 61-612 (Poland); Prochaska, Krystyna [Institute of Chemical Technology and Engineering, Poznan University of Technology, Pl. Marii Skłodowskiej-Curie 2, Poznań 60-965 (Poland)


    Alkyl- and fluoroalkyltriethoxysilanes were investigated as potential surface modifiers. Many aspects concerning trialkoxysilanes were discussed, starting from hydrolysis of silanes in water solutions, the effect of this hydrolysis on the surface tension, wettability of the modified surface to the morphology of the modified surface. Surface tension and contact angle measurements as well as scanning electron microscopy were used to characterise alkyl- and fluoroalkyltriethoxysilanes and their ability to modify the wettability of glass. The effect of such modification was superhydrophobic surface with high values of contact angles. Superhydrophobic behaviour was observed as a result of two-step modification providing increased surface roughness thanks to the use of different size silica particles and surface chemical modification with fluorosilane molecules.

  8. Salvage robotic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Samuel D Kaffenberger


    Full Text Available Failure of non-surgical primary treatment for localized prostate cancer is a common occurrence, with rates of disease recurrence ranging from 20% to 60%. In a large proportion of patients, disease recurrence is clinically localized and therefore potentially curable. Unfortunately, due to the complex and potentially morbid nature of salvage treatment, radical salvage surgery is uncommonly performed. In an attempt to decrease the morbidity of salvage therapy without sacrificing oncologic efficacy, a number of experienced centers have utilized robotic assistance to perform minimally invasive salvage radical prostatectomy. Herein, we critically evaluate the existing literature on salvage robotic radical prostatectomy with a focus on patient selection, perioperative complications and functional and early oncologic outcomes. These results are compared with contemporary and historical open salvage radical prostatectomy series and supplemented with insights we have gained from our experience with salvage robotic radical prostatectomy. The body of evidence by which conclusions regarding the efficacy and safety of robotic salvage radical prostatectomy can be drawn comprises fewer than 200 patients with limited follow-up. Preliminary results are promising and some outcomes have been favorable when compared with contemporary open salvage prostatectomy series. Advantages of the robotic platform in the performance of salvage radical prostatectomy include decreased blood loss, short length of stay and improved visualization. Greater experience is required to confirm the long-term oncologic efficacy and functional outcomes as well as the generalizability of results achieved at experienced centers.

  9. Ascorbic Acid-Initiated Tandem Radical Cyclization of N-Arylacrylamides to Give 3,3-Disubstituted Oxindoles

    Directory of Open Access Journals (Sweden)

    Sheng Liu


    Full Text Available An ascorbic acid-promoted and metal-free tandem room temperature cyclization of N-arylacrylamides with 4-nitrobenzenediazonium generated in situ was developed. This reaction proceeds smoothly through a radical mechanism and provides an environmentally friendly alternative approach to biologically active 3-alkyl-3-benzyloxindoles, avoiding the use of excess oxidants and light irradiation.

  10. Enzymatic Synthesis of Palm Alkyl Ester Using Dialkyl Carbonate as an Alkyl Donors

    Directory of Open Access Journals (Sweden)

    Roila Awang


    Full Text Available Problem statement: Though efficient in terms of reaction yield and time, the chemical approach to synthesizing alkyl ester has drawback such as difficulties in the recovery of glycerol and the need for removal of salt residue. On the other hand, biocatalyst allow for synthesis of specific alkyl esters and easy recovery of glycerol. However, the solvent-free alcoholysis, does not give high conversion. The same problem was also found when ethyl or methyl acetate was used as acyl acceptors. Approach: Lipase catalyzed transesterification of oil and dialkyl carbonate was predicted to give higher conversion in solvent free reaction system. Results: Alkyl esters were synthesized enzymatically to overcome the problems associated with chemical processes. In this study, dialkyl carbonates were used as an alkyl donor for the production of alkyl ester. Nine commercial lipases were tested for their suitability for the reaction system. Among the lipase tested, Novozym 435 was chosen for optimization study because of their higher activity. In a solvent-free reaction system, the ester formation using dialkyl carbonate was 6 times higher than using ethanol and methanol. The effect of various reaction parameters such as temperature, amount of enzyme, organic solvent and structure of substrates were studied to determine optimal condition. The optimal conditions of ester formation were reaction temperature at 60°C, reaction time at 8 h, enzyme amount of 10% (w/w of oil and 0.2% wt added water. Conclusion: Solvent-free lipase catalyzed transesterification of palm kernel oil and dialkyl carbonates gave higher conversion of ester compared to the reaction using short chain alcohol as an alkyl donors.

  11. Effects of alkyl parabens on plant pathogenic fungi. (United States)

    Ito, Shinsaku; Yazawa, Satoru; Nakagawa, Yasutaka; Sasaki, Yasuyuki; Yajima, Shunsuke


    Alkyl parabens are used as antimicrobial preservatives in cosmetics, food, and pharmaceutical products. However, the mode of action of these chemicals has not been assessed thoroughly. In this study, we determined the effects of alkyl parabens on plant pathogenic fungi. All the fungi tested, were susceptible to parabens. The effect of linear alkyl parabens on plant pathogenic fungi was related to the length of the alkyl chain. In addition, the antifungal activity was correlated with the paraben-induced inhibition of oxygen consumption. The antifungal activity of linear alkyl parabens likely originates, at least in part, from their ability to inhibit the membrane respiratory chain, especially mitochondrial complex II. Additionally, we determined that some alkyl parabens inhibit Alternaria brassicicola infection of cabbage.

  12. Radical prostatectomy - discharge (United States)

    ... to 6 months. You will learn exercises (called Kegel exercises) that strengthen the muscles in your pelvis. ... Radical prostatectomy Retrograde ejaculation Urinary incontinence Patient Instructions Kegel exercises - self-care Suprapubic catheter care Urinary catheters - ...

  13. Oxidative Umpolung α‐Alkylation of Ketones

    DEFF Research Database (Denmark)

    Shneider, O. Svetlana; Pisarevsky, Evgeni; Fristrup, Peter;


    We disclose a hypervalent iodine mediated α-alkylative umpolung reaction of carbonyl compounds with dialkylzinc as the alkyl source. The reaction is applicable to all common classes of ketones including 1,3-dicarbonyl compounds and regular ketones via their lithium enolates. The α......-alkylated carbonyl products are formed in up to 93% yield. An ionic mechanism is inferred based on meticulous analysis, NMR studies, trapping and crossover experiments, and computational studies....

  14. Radical Addition to Iminium Ions and Cationic Heterocycles

    Directory of Open Access Journals (Sweden)

    Johannes Tauber


    Full Text Available Carbon-centered radicals represent highly useful reactive intermediates in organic synthesis. Their nucleophilic character is reflected by fast additions to electron deficient C=X double bonds as present in iminium ions or cationic heterocycles. This review covers diverse reactions of preformed or in situ-generated cationic substrates with various types of C-radicals, including alkyl, alkoxyalkyl, trifluoromethyl, aryl, acyl, carbamoyl, and alkoxycarbonyl species. Despite its high reactivity, the strong interaction of the radical’s SOMO with the LUMO of the cation frequently results in a high regioselectivity. Intra- and intermolecular processes such as the Minisci reaction, the Porta reaction, and the Knabe rearrangement will be discussed along with transition metal and photoredox catalysis or electrochemical methods to generate the odd-electron species.

  15. Isolation of a Cyclic (Alkyl(aminogermylene

    Directory of Open Access Journals (Sweden)

    Liliang Wang


    Full Text Available A 1,4-addition of a dichlorogermylene dioxane complex with α,β-unsaturated imine 1 gave a dichlorogermane derivative 2 bearing a GeC3N five-membered ring skeleton. By reducing 2 with KC8, cyclic (alkyl(aminogermylene 3 was synthesized and fully characterized. Germylene 3 readily reacted with TEMPO, N2O and S8, producing the 1:2 adduct 4, the oxo-bridged dimer 5 and the sulfido-bridged dimer 6, respectively.

  16. New Bioactive Alkyl Sulfates from Mediterranean Tunicates

    Directory of Open Access Journals (Sweden)

    Marialuisa Menna


    Full Text Available Chemical investigation of two species of marine ascidians, Aplidium elegans and Ciona edwardsii, collected in Mediterranean area, led to isolation of a series of alkyl sulfates (compounds 1–5 including three new molecules 1–3. Structures of the new metabolites have been elucidated by spectroscopic analysis. Based on previously reported cytotoxic activity of these type of molecules, compounds 1–3 have been tested for their effects on the growth of two cell lines, J774A.1 (BALB/c murine macrophages and C6 (rat glioma in vitro. Compounds 1 and 2 induced selective concentration-dependent mortality on J774A.1 cells.

  17. Free Radical Reactions in Food. (United States)

    Taub, Irwin A.


    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…

  18. Alkyl nitrate production and persistence in the Mexico City Plume

    Directory of Open Access Journals (Sweden)

    G. Sachse


    Full Text Available Alkyl and multifunctional nitrates (ΣANs have been observed to be a significant fraction of NOy in a number of different chemical regimes. Their formation is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. ΣANs also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Numerous studies have investigated the role of nitrate formation from biogenic compounds. Less attention has been paid to the role ΣANs may play in the complex mixtures of hydrocarbons typical of urban settings. Measurements of ΣANs, NO2, total peroxy nitrates (ΣPNs, HNO3 and a wide suite of hydrocarbons were obtained from the NASA DC-8 aircraft during spring of 2006 in and around Mexico City and the Gulf of Mexico. ΣANs were observed to be 10–20% of NOy in the Mexico City plume and to increase in importance with increased photochemical age. We describe three conclusions: 1 Correlations of ΣANs with odd-oxygen (Ox indicate a stronger role for ΣANs in the photochemistry of Mexico City than is expected based on currently accepted photochemical mechanisms, 2 ΣAN formation suppresses peak ozone production rates by as much as 30% in the near-field of Mexico City and 3 ΣANs play a comparable role to ΣPNs in the export of NOy to the Gulf Region.

  19. Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs

    Directory of Open Access Journals (Sweden)

    Fabrice Chemla


    Full Text Available The formation of alkylidenezinc carbenoids by 1,4-addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with β-(propargyloxyenoates having pendant iodo- and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is fully stereoselective at −30 °C and arises from a formal anti-selective carbozincation reaction. Upon warming, the zinc carbenoid is stereochemically labile and isomerizes to its more stable form.

  20. Gangs, Terrorism, and Radicalization

    Directory of Open Access Journals (Sweden)

    Scott Decker


    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.

  1. Sexuality Following Radical Prostatectomy

    DEFF Research Database (Denmark)

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


    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...

  2. An overview of the properties of fatty acid alkyl esters (United States)

    Fatty acid alkyl esters of plant oils, especially in the form of methyl esters, have numerous applications with fuel use having received the most attention in recent times due to the potential high volume. Various properties imparted by neat fatty acid alkyl esters have been shown to influence fuel ...

  3. 40 CFR 721.840 - Alkyl substituted diaromatic hydrocarbons. (United States)


    ... hydrocarbons. 721.840 Section 721.840 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.840 Alkyl substituted diaromatic hydrocarbons. (a) Chemical substance... alkyl substituted di-aro-matic hydrocarbons (PMN P-91-710) is subject to reporting under this...

  4. 40 CFR 721.2155 - Alkoxyamino-alkyl-coumarin (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkoxyamino-alkyl-coumarin (generic... Substances § 721.2155 Alkoxyamino-alkyl-coumarin (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  5. 40 CFR 721.10073 - Modified alkyl acrylamide (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified alkyl acrylamide (generic... Specific Chemical Substances § 721.10073 Modified alkyl acrylamide (generic). (a) Chemical substance and... acrylamide (PMN P-05-536) is subject to reporting under this section for the significant new uses...

  6. Polyfluorinated alkyl phosphate ester surfactants - current knowledge and knowledge gaps

    DEFF Research Database (Denmark)

    Taxvig, Camilla; Rosenmai, Anna Kjerstine; Vinggaard, Anne Marie


    information on fluorochemicals. Polyfluorinated alkyl phosphate ester surfactants (PAPs) belong to the group of polyfluorinated alkyl surfactants. They have been detected in indoor dust and are widely used in food-contact materials, from which they have the ability to migrate into food. Toxicological data...

  7. One-step selective synthesis of branched 1-O-alkyl-glycerol/diglycerol monoethers by catalytic reductive alkylation of ketones

    Institute of Scientific and Technical Information of China (English)

    DAYOUB; Wissam; LEMAIRE; Marc


    Branched 1-O-alkyl glycerol and diglycerol monoethers were obtained in good yields and high selectivity by a straightforward catalytic reductive alkylation of glycerol with relevant ketones in the presence of 0.5 mol% of Pd/C under 10 bar of hydrogen pressure using a Brφnsted acid as the co-catalyst.

  8. Beyond Radical Educational Cynicism. (United States)

    Wood, George H.


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

  9. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali


    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.

  10. Electromeric rhodium radical complexes

    NARCIS (Netherlands)

    Puschmann, F.F.; Harmer, J.; Stein, D.; Rüegger, H.; de Bruin, B.; Grützmacher, H.


    Radical changes: One single P-Rh-P angle determines whether the odd electron in the paramagnetic complex [Rh(trop2PPh)(PPh3)] is delocalized over the whole molecule (see picture, blue) or is localized on the P—Rh unit (red). The two energetically almost degenerate electromers exist in a fast equilib

  11. Violent Radicalization in Europe

    DEFF Research Database (Denmark)

    Dalgaard-Nielsen, Anja


    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. Radical School Reform. (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…

  13. 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...

  14. On Radical Feminism

    Institute of Scientific and Technical Information of China (English)



    <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

  15. Intramolecular Homolytic Substitution with Amidyl Radicals: A Free-Radical Synthesis of Ebselen and Related Analogues. (United States)

    Fong, Mei C.; Schiesser, Carl H.


    Irradiation of a water-cooled benzene solution of pyridine-2-thioneoxycarbonyl (PTOC) imidate esters 9 derived from N-butyl-2-(benzylseleno)benzamide (6, R = Bu), 2-(benzylseleno)-N-hexylbenzamide (6, R = Hex), N-benzyl-2-(benzylseleno)benzamide (6, R = Bn), and 2-(benzylseleno)-N-cyclohexylbenzamide (6, R = c-Hex) with a 250-W low-pressure mercury lamp affords the corresponding 1,2-benzisoselenazol-3(2H)-ones (1) in yields of 81-91% (R = primary alkyl) and 45% (R = c-Hex). Presumably, these transformations involve formation of amidyl radicals 2 which undergo subsequent intramolecular homolytic substitution at the selenium atom with expulsion of a benzyl radical. PTOC imidate esters derived from 2-(benzylseleno)benzanilide (6, R = Ph) and 2-(benzylseleno)-N-tert-butylbenzamide (6, R = t-Bu) were unable to be prepared in this manner. 1,2-Benzisoselenazol-3(2H)-ones (1, R = Ph, Hex, i-Pr, t-Bu) could also be prepared in 76-85% yield by reaction of the corresponding 2,2'-diselenobis(benzamide) (15) with benzoyl or tert-butyl peroxide. The mechanisms of these transformations are discussed.

  16. A comparison of transition state of phenol in H-atom abstraction by methyl and methylperoxyl radicals

    Institute of Scientific and Technical Information of China (English)

    SUN YouMin; WU JunSen; LIU ChengBu


    DFT method was employed to locate transition state for H-atom transfer from phenol by methyl radical and methylperoxyl radical. The reaction pathway energy profiles and the structure of transition state show that a common feature is the out-of-plane structure of the transition state: in contrast to the energetic minima of a hydrogen-bonded intermediate, the hydrogen bond in transition structures is considerably twisted out of the aromatic ring. From the values of enthalpy (△H) and activation energy (Ea)obtained, it is found that the rate of the reaction of peroxyl radical with phenolic antioxidant is higher than that of alkyl radical with antioxidant. Spin density distributions show that the electron transmission is between methyl (methylperoxyl) radical and phenol.

  17. Detection of a branched alkyl molecule in the interstellar medium: iso-propyl cyanide

    CERN Document Server

    Belloche, Arnaud; Müller, Holger S P; Menten, Karl M


    The largest non-cyclic molecules detected in the interstellar medium (ISM) are organic with a straight-chain carbon backbone. We report an interstellar detection of a branched alkyl molecule, iso-propyl cyanide (i-C3H7CN), with an abundance 0.4 times that of its straight-chain structural isomer. This detection suggests that branched carbon-chain molecules may be generally abundant in the ISM. Our astrochemical model indicates that both isomers are produced within or upon dust grain ice mantles through the addition of molecular radicals, albeit via differing reaction pathways. The production of iso-propyl cyanide appears to require the addition of a functional group to a non-terminal carbon in the chain. Its detection therefore bodes well for the presence in the ISM of amino acids, for which such side-chain structure is a key characteristic.

  18. Organomontmorillonites Modified with 2-Methacryloyloxy Ethyl Alkyl Dimethyl Ammonium Bromide

    Institute of Scientific and Technical Information of China (English)

    WANG Jian-quan; WU Wen-hui


    Organomontmorillonites (organo-MMT) were synthesized by means of montmorillonites (MMT) modified with a series of 2-methacryloyloxy ethyl alkyl dimethyl ammonium bromide (MAAB) having different alkyl chain lengths as cationic surfactants through a cationic exchanging reaction, and were characterized by FTIR, TG, elemental analysis, and XRD. The microenvironment of the organic interlayer such as the orientation and arrangement of the alkyl chains of MAAB, as well as the properties of nanocomposite hydrogels, were also investigated. The amount of organic components absorbed on interlayer and the basal spacing of organo-MMT both increase with the increasing of alkyl length of MAAB. When carbon number of alkyl chain is in the region of 8 to 14, the alkyl chains between layers would adopt a disordered gauche conformation; while the carbon number is 16, an ordered all-trans conformation with a vertical orientation would be found together with the disordered gauche conformation according to the results of XRD and FTIR. Due to the difference of microenvironment of organic interlayer, the Young's moduli of the nanocomposite hydrogels increased as the alkyl chains of MAAB became longer.

  19. Probability and radical behaviorism (United States)

    Espinosa, James M.


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

  20. Probability and radical behaviorism


    Espinosa, James M.


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

  1. Radical chic, javisst!

    NARCIS (Netherlands)

    Hartle, J.F.


    Det är lätt att raljera över engagerade människor, i synnerhet när engagemanget framstår som ytligt och chict snarare än grundläggande och autentiskt. Men vad ligger bakom ett sådant avfärdande? Johan Frederik Hartle läser om Tom Wolfes klassiska essä "Radical Chic" och visar hur Wolfe −− genom att

  2. Women and radicalization


    Badran, Margot


    The paper focuses on women and radicalization within the context of Muslim societies (majority, minority, and half Muslim) societies and groups, mainly in Asia and Africa. The basic argument advanced in this paper is that Islamic feminism with its gender-egalitarian discourse and practices has a major role to play in the empowerment of Muslim women—and of men and society as a whole—and should be brought to bear in devising policy, strategy, and tools.

  3. Radical substitution with azide

    DEFF Research Database (Denmark)

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


    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....


    Energy Technology Data Exchange (ETDEWEB)

    Kent M. Ervin, Principal Investigator


    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.

  5. [Radical prostatectomy - pro robotic]. (United States)

    Gillitzer, R


    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.

  6. Palladium-catalyzed regioselective decarboxylative alkylation of arenes and heteroarenes with aliphatic carboxylic acids. (United States)

    Premi, Chanchal; Dixit, Ankit; Jain, Nidhi


    An unprecedented Pd(OAc)2-catalyzed decarboxylative alkylation of unactivated arenes, with aliphatic carboxylic acids as inexpensive alkyl sources, is reported. The alkylation, controlled by the directing group, is regioselective, shows high functional group tolerance, and provides mild access to alkylated indolines, 2-phenylpyridines, and azobenzenes under solvent-free conditions in moderate to high yields.

  7. 21 CFR 176.120 - Alkyl ketene dimers. (United States)


    ... derived from the fatty acids of animal or vegetable fats and oils. (b) The alkyl ketene dimers are used as... HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: PAPER AND PAPERBOARD COMPONENTS Substances...

  8. Alkyl resorcinols in grains from plants from the family Gramineae

    Directory of Open Access Journals (Sweden)

    Grzegorz Kubus


    Full Text Available 5-n-alkylresorcinols were found in 22 of the 27 studied species of grasses. In Agropyron caninum and Bromus macrostachys only the content of alkyl resorcinols was determined, in Agropyron repens, Bromus mollis and Elymus arenarius the composition of alkyl resorcinol homologues was also established. When calculated per gram of dry mass of air-dried grains, the content of alkyl resorcinols was found to be: in the genus Agropyron - approximately 715 µg, in the genus Bromus approximately 60 µg and in Elymus arenarius, 272 µg. The homologues of alkyl resorcinods in the studied genera of grasses differ from the homologues found in wheat or rye by their greater content of long-chain fractions.

  9. Safety assessment of alkyl benzoates as used in cosmetics. (United States)

    'Becker, Lillian C; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan


    The functions of alkyl benzoates in cosmetics include fragrance ingredients, skin-conditioning agents--emollient, skin-conditioning agents--miscellaneous, preservatives, solvents, and plasticizers. The Cosmetic Ingredient Review Expert Panel reviewed the relevant animal and human data and noted gaps in the available safety data for some of the alkyl benzoates. Similar structure activity relationships, biologic functions, and cosmetic product usage allowed the available data of many of the alkyl benzoates to be extended to the entire group. Carcinogenicity data were not available, but available data indicated that these alkyl benzoate cosmetic ingredients are not genotoxic. Also benzoic acid and tested component alcohols were not reproductive or developmental toxicants, are not genotoxic in almost all assays, and are not carcinogenic. These ingredients were determined to be safe in the present practices of use and concentration.

  10. Fluorinated Alkyl Ether Epoxy Resin Compositions and Applications Thereof (United States)

    Wohl, Christopher J. (Inventor); Connell, John W. (Inventor); Smith, Joseph G. (Inventor); Siochi, Emilie J. (Inventor); Gardner, John M. (Inventor); Palmieri, Frank M. (Inventor)


    Epoxy resin compositions prepared using amino terminated fluoro alkyl ethers. The epoxy resin compositions exhibit low surface adhesion properties making them useful as coatings, paints, moldings, adhesives, and fiber reinforced composites.

  11. Alkyl chains acting as entropy reservoir in liquid crystalline materials. (United States)

    Sorai, Michio; Saito, Kazuya


    The roles played by the conformational disordering of alkyl chains in determining the aggregation states of matter are reviewed for liquid crystalline materials from a thermodynamic perspective. Entropy, which is one of the most macroscopic concepts but which has a clear microscopic meaning, provides crucial microscopic information for complex systems for which a microscopic description is hard to establish. Starting from structural implication by absolute (third-law) entropy for crystalline solids, the existence of successive phase transitions caused by the successive conformational melting of alkyl chains in discotic mesogens is explained. An experimental basis is given for the "quasi-binary picture" of thermotropic liquid crystals, i.e., the highly disordered alkyl chains behave like a second component (solvent). A novel entropy transfer between the "components" of a molecule and the resulting "alkyl chains as entropy reservoir" mechanism are explained for cubic mesogens.

  12. Iminium Salts by Meerwein Alkylation of Ehrlich’s Aldehyde

    Directory of Open Access Journals (Sweden)

    Gerhard Laus


    Full Text Available 4-(Dimethylaminobenzaldehyde is alkylated at the N atom by dialkyl sulfates, MeI, or Me3O BF4. In contrast, ethylation by Et3O BF4 occurs selectively at the O atom yielding a quinoid iminium ion. 4-(Diethylaminobenzaldehyde is alkylated only at O by either Et or Me oxonium reagent. The iminium salts are prone to hydrolysis giving the corresponding hydrotetrafluoroborates. Five crystal structures were determined.

  13. Time course evaluation of N-nitrosodialkylamines-induced DNA alkylation and oxidation in liver of mosquito fish

    Energy Technology Data Exchange (ETDEWEB)

    Chao, M.-R. [Department of Occupational Safety and Health, Chung Shan Medical University, Taichung 402, Taiwan (China); Institute of Medical and Molecular Toxicology, Chung Shan Medical University, Taichung 402, Taiwan (China); Chang, Y.-Z. [Institute of Medical and Molecular Toxicology, Chung Shan Medical University, Taichung 402, Taiwan (China); Wong, R.-H. [Department of Public Health, Chung Shan Medical University, Taichung 402, Taiwan (China); Hu, C.-W. [Department of Public Health, Chung Shan Medical University, Taichung 402, Taiwan (China)], E-mail:


    Here we simultaneously measured N7-alkylguanines and 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG) in liver of small fish, respectively, to assess the time course of the formation and removal of alkylation and oxidative damage to DNA caused by N-nitrosodialkylamines. Mosquito fish (Gambusia affinis) were killed at various times during (4 days) and post-exposure (16 days) to N-nitrosodimethylamine (NDMA) and N-nitrosodiethylamine (NDEA) alone or their combination with concentrations of 10 and 50 mg/l. The modified guanine adducts were sensitively and selectively quantitated by isotope-dilution LC-MS/MS methods. During exposure, N7-methylguanine (N7-MeG) and N7-ethylguanine (N7-EtG) in liver DNA increased with the duration and dose of N-nitrosodialkylamine exposure, while 8-oxodG was dose-dependently induced within 1 day. It was found that NDMA formed substantially more N7-alkylated guanines and 8-oxodG than NDEA on the basis of adducts formed per micromolar concentration, suggesting that NDMA can be more easily bioactivated than NDEA to form reactive alkylating agents with the concomitant formation of oxygen radicals. After cessation of exposure, N7-alkylguanines remained elevated for 1 day and then gradually decreased over time but still higher than the background levels, even at day 16 (half-lives of 7-8 days). However, 8-oxodG was excised quickly from liver DNA and returned to the background level within 4 days post-exposure (half-lives less than 2 days). Taken together, this study firstly demonstrated that in addition to alkylation, N-nitrosodialkylamines can concurrently cause oxidative damage to DNA in vivo.

  14. Alkyl and phenolic glycosides from Saussurea stella. (United States)

    Wang, Tian-Min; Wang, Ru-Feng; Chen, Hu-Biao; Shang, Ming-Ying; Cai, Shao-Qing


    One alkyl glycoside, saussurostelloside A (1), two phenolic glycosides, saussurostellosides B1 (2) and B2 (3), and 27 known compounds, including eleven flavonoids, seven phenolics, six lignans, one neolignan, one phenethyl glucoside and one fatty acid, were isolated from an ethanol extract of Saussurea stella (Asteraceae). Their structures were elucidated by NMR, MS, UV, and IR spectroscopic analysis. Of the known compounds, (+)-medioresinol-di-O-β-D-glucoside (7), picraquassioside C (10), and diosmetin-3'-O-β-D-glucoside (27) were isolated from the Asteraceae family for the first time, while (+)-pinoresinol-di-O-β-D-glucoside (6), di-O-methylcrenatin (11), protocatechuic acid (14), 1,5-di-O-caffeoylquinic acid (17), formononetin (28), and phenethyl glucoside (29) were isolated from the Saussurea genus for the first time. The anti-inflammatory activities of three new compounds (1-3), five lignans ((-)-arctiin (4), (+)-pinoresinol-4-O-β-D-glucoside (5), (+)-pinoresinol-di-O-β-D-glucoside (6), (+)-medioresinol-di-O-β-D-glucoside (7) and (+)-syringaresinol-4-O-β-D-glucoside (8)), one neolignan (picraquassioside C (10)), and one phenolic glycoside (di-O-methylcrenatin (11)) were evaluated by testing their inhibition of the release of β-glucuronidase from PAF-stimulated neutrophils. Only compound 5 showed moderate inhibition of the release of β-glucuronidase, with an inhibition ratio of 39.1%.

  15. Effects of alkyl substituents of xanthine on phosphodiesterase isoenzymes. (United States)

    Miyamoto, K; Sakai, R; Kurita, M; Ohmae, S; Sanae, F; Sawanishi, H; Hasegawa, T; Takagi, K


    The structure-activity relationships of a series of alkylxanthine derivatives were investigated. The partition coefficient of alkylxanthines enlarged with an elongation of the alkyl chain at the 1-, 3-, or 7-position of xanthine. There was a mild correlation between the apparent partition coefficient and the tracheal relaxant activity or the inhibitory activity on phosphodiesterase (PDE) IV isoenzyme, while the tracheal relaxant activity closely correlated with the PDE IV inhibitory activity. Regarding substituents at different positions, the alkylation at the 3-position increased the inhibitory activity on every PDE isoenzyme. The alkylation at the 1-position potentiated the inhibitory activity on PDE IV with the alkyl chain length, but decreased the activities on other PDE isoenzymes. The alkylation at the 7-position was characteristic in its decrease in inhibitory activity on PDE III. These results suggested that the potency of the inhibitory activity of xanthine derivatives on PDE isoenzymes is not dependent simply upon their hydrophobicity but upon change in the affinity for the active sites on PDE isoenzymes by the introduction of the alkyl group at particular positions of the xanthine skeleton.

  16. Final Technical Report [Development of Catalytic Alkylation and Fluoroalkylation Methods

    Energy Technology Data Exchange (ETDEWEB)

    Vicic, David A.


    In the early stages of this DOE-funded research project, we sought to prepare and study a well-defined nickel-alkyl complex containing tridentate nitrogen donor ligands. We found that reaction of (TMEDA)NiMe2 (1) with terpyridine ligand cleanly led to the formation of (terpyridyl)NiMe (2), which we also determined to be an active alkylation catalyst. The thermal stability of 2 was unlike that seen for any of the active pybox ligands, and enabled a number of key studies on alkyl transfer reactions to be performed, providing new insights into the mechanism of nickel-mediated alkyl-alkyl cross-coupling reactions. In addition to the mechanistic studies, we showed that the terpyridyl nickel compounds can catalytically cross-couple alkyl iodides in yields up to 98% and bromides in yields up to 46 %. The yields for the bromides can be increased up to 67 % when the new palladium catalyst [(tpy’)Pd-Ph]I is used. The best route to the targeted [(tpy)NiBr] (1) was found to involve the comproportionation reaction of [(dme)NiBr{sub 2}] and [Ni(COD){sub 2}] in the presence of two equivalents of terpyridine. This reaction was driven to high yields of product formation (72 % isolated) by the precipitation of 1 from THF solvent.

  17. Catalysis of Radical Reactions: A Radical Chemistry Perspective. (United States)

    Studer, Armido; Curran, Dennis P


    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.

  18. Gnosticism and Radical Feminism

    DEFF Research Database (Denmark)

    Cahana, Jonathan


    and place demand an explanation; my attempt to do so also takes into account the important differences between the gnostic and the radical feminist postures, notably the latter belief in progress and the former nostalgia for an ungendered era. Both the similarities and the differences, however, may offer...... support for approaching Gnosticism as first and foremost a cultural phenomenon (albeit exhibiting religious “symptoms”), and I attempt to show that such an approach can help to solve the recurrent problem of defining Gnosticism....

  19. Antioxidant activity of ferulic acid alkyl esters in a heterophasic system: a mechanistic insight. (United States)

    Anselmi, Cecilia; Centini, Marisanna; Granata, Paola; Sega, Alessandro; Buonocore, Anna; Bernini, Andrea; Facino, Roberto Maffei


    The antioxidant activity of some esters of ferulic acid with the linear fatty alcohols C7, C8 (branched and linear), C9, C11, C12, C13, C15, C16, and C18 has been studied in homogeneous and heterogeneous phases. Whereas in homogeneous phase all of the alkyl ferulates possessed similar radical-scavenging abilities, in rat liver microsomes they showed striking differences, the more effective being C12 (7) (IC50 = 11.03 M), linear C8 (3) (IC50 = 12.40 microM), C13 (8) (IC50 = 18.60 microM), and C9 (5) (IC50 = 19.74 microM), followed by C7 (2), C15 (9), C11 (6), branched C8 (4), C16 (10), and C18 (11) (ferulic acid was the less active, IC50 = 243.84 microM). All of the molecules showed similar partition coefficients in an octanol-buffer system. Three-dimensional studies (NMR in solution, modeling in vacuo) indicate that this behavior might be due to a different anchorage of the molecules with the ester side chain to the microsomal phospholipid bilayer and to a consequent different orientation/positioning of the scavenging phenoxy group outside the membrane surface against the flux of oxy radicals.

  20. Depolymerization of coal by oxidation and alkylation; Sanka bunkai to alkyl ka ni yoru sekitan kaijugo

    Energy Technology Data Exchange (ETDEWEB)

    Tomita, H.; Isoda, T.; Kusakabe, K.; Morooka, S. [Kyushu University, Fukuoka (Japan). Faculty of Engineering; Hayashi, J. [Hokkaido University, Sapporo (Japan). Center for Advanced Research of Energy Technology


    Change in depolymerization degree and coal structure was studied for depolymerization treatment of coal in various alcohol containing aqueous hydrogen peroxide. In experiment, the mixture of Yallourn coal, alcohol and aqueous hydrogen peroxide was agitated in nitrogen atmosphere of normal pressure at 70{degree}C for 12 hours. As the experimental result, the methanol solubility of only 5% of raw coal increased up to 35.2% by hydrogen peroxide treatment, while the yield of insoluble matters also decreased from 94% to 62%. Most of the gas produced during treatment was composed of inorganic gases such as CO and CO2, and its carbon loss was extremely decreased by adding alcohol. From the analytical result of carbon loss in hydrogen peroxide treatment, it was clarified that alkylation advances with introduction of alkyl group derived from alcohol into coal by hydrogen peroxide treatment under a coexistence of alcohol, and depolymerization reaction of coal itself is thus promoted by alcohol. 4 refs., 7 figs., 1 tab.

  1. Inhibition and Promotion of Pyrolysis by Hydrogen Sulfide (H2S) and Sulfanyl Radical (SH). (United States)

    Zeng, Zhe; Altarawneh, Mohammednoor; Oluwoye, Ibukun; Glarborg, Peter; Dlugogorski, Bogdan Z


    This study resolves the interaction of sulfanyl radical (SH) with aliphatic (C1-C4) hydrocarbons, using CBS-QB3 based calculations. We obtained the C-H dissociation enthalpies and located the weakest link in each hydrocarbon. Subsequent computations revealed that, H abstraction by SH from the weakest C-H sites in alkenes and alkynes, except for ethylene, appears noticeably exothermic. Furthermore, abstraction of H from propene, 1-butene, and iso-butene displays pronounced spontaneity (i.e., ΔrG° < -20 kJ mol(-1) between 300-1200 K) due to the relatively weak allylic hydrogen bond. However, an alkyl radical readily abstracts H atom from H2S, with H2S acting as a potent scavenger for alkyl radicals in combustion processes. That is, these reactions proceed in the opposite direction than those involving SH and alkene or alkyne species, exhibiting shallow barriers and strong spontaneity. Our findings demonstrate that the documented inhibition effect of hydrogen sulfide (H2S) on pyrolysis of alkanes does not apply to alkenes and alkynes. During interaction with hydrocarbons, the inhibitive effect of H2S and promoting interaction of SH radical depend on the reversibility of the H abstraction processes. For the three groups of hydrocarbon, Evans-Polanyi plots display linear correlations between the bond dissociation enthalpies of the abstracted hydrogens and the relevant activation energies. In the case of methane, we demonstrated that the reactivity of SH radicals toward abstracting H atoms exceeds that of HO2 but falls below those of OH and NH2 radicals.

  2. Bursectomy at radical gastrectomy

    Institute of Scientific and Technical Information of China (English)

    Cuneyt; Kayaalp


    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.

  3. Radically innovative steelmaking technologies (United States)

    Szekely, Julian


    The steel industry is faced with serious problems caused by the increasing cost of energy, labor and capital and by tough overseas competition, employing new highly efficient process plants. The very high cost of capital and of capital equipment renders the construction of new green field site plants, exemplifying the best available technology economically unattractive. For this reason, over the long term the development radically innovative steelmaking technologies appears to be the only satisfactory resolution of this dilemma. The purpose of this article is to present a critical review of some of the radically innovative steelmaking technologies that have been proposed during the past few years and to develop the argument that these indeed do deserve serious consideration at the present time. It should be stressed, however, that these innovative technologies can be implemented only as part of a carefully conceived long range plan, which contains as a subset short term solutions, such as trigger prices improved investment credits, and so forth and intermediate term solutions, such as more extensive use of continuous casting, external desulfurization and selective modernization in general.

  4. A Study on Alkyl Polyglycosides of the Starch

    Institute of Scientific and Technical Information of China (English)

    Wang Qing-ning; Li Chun-lei; Feng Hui-xia; Kang Wen-shu


    The alkyl polyglycosides (APG) is new type the surfactants that is made by regenerationresource of the starch and the grease, since the nineties of 20th century it is energetically exploited ininternational extent. APG not only good in surface activity, but also plenty on bubble, thin greasyand stabilization, there are good decontamination, compatibility, innocuity, not incitation and uniquefunction that organism decomposition of swiftness and downrightness, and so on.APG is to get production that loses one molecule water with half condensation aldehyde hydroxyand sebum alcohol hydroxy under acid catalysis. The production not is one simplicity compound, butis one of sugar polymerization degree, so it is mixture of the alkyl single glucoside, the alkyl twoglucoside and the alkyl three glucoside.Author synthesizes the surfactants of the alkyl polyglycosides, with the oleaster and potato starchand sebum alcohol, that was chosen to use duality system activator of plant acid and p-toluene-sulfoacid for the first time. The adoption way is that the lower alkyl polyglycosides is firstly formed byreaction of lower alcohol with starch then exchanged with high alcohol to obtain APG. The study isto make certain most technics condition, determining capillary tension and the pastern sheafdeepness of critical, calculating HLB value, determining construction by 1R.To synthesize principium:Peroration :[1]Duality system activator of plant acid and p-toluene-sulfo acid is compare idea activator that was the lower alkyl polyglycosides is firstly formed by reaction of lower alcohol with glucose then exchanged with high alcohol to obtain high alkyl polyglycosides. The advantage is that it overcomes agglomeration, there is reaction entirety, high of sugar transform ratio, reaction time short.[2]Most good reaction temperature is 90~ 170℃, the dosage of activator is 0.5%~0.9%, the mated ratio: The APG of glucose basic butane ratio starch is 5:1, the APG of potato starch basic glycol

  5. Effects of alkyl substitutions of xanthine skeleton on bronchodilation. (United States)

    Sakai, R; Konno, K; Yamamoto, Y; Sanae, F; Takagi, K; Hasegawa, T; Iwasaki, N; Kakiuchi, M; Kato, H; Miyamoto, K


    Structure-activity relationships in a series of 1,3,7-trialkyl-xanthine were studied with guinea pigs. Relaxant actions in the tracheal muscle were increased with alkyl chain length at the 1- and 3-positions of the xanthine skeleton, but decreased by alkylation at the 7-position. Positive chronotropic actions in the right atrium were potentiated with 3-alkyl chain length but tended to decrease with 1-alkylation and diminish by 7-substitution. Consequently, while the 1- and 3-substitutions were equally important for the tracheal smooth muscle relaxation, the substitution at the 1-position was more important than the 3-substitution for bronchoselectivity. The 7-alkylation may be significant to cancel heart stimulation. There were good correlations between the smooth muscle relaxant action and the cyclic AMP-PDE inhibitory activity in 3-substituents and the affinity for adenosine (A1) receptors in 1-, 3-, and 7-substituents. This suggests that not only the cyclic AMP-PDE inhibitory activity but also the adenosine antagonistic activity is important in the bronchodilatory effects of alkylxanthines. Among these xanthine derivatives, 1-butyl-3-propylxanthine and its 7-methylated derivative showed high bronchoselectivity in the in vitro and in vivo experiments compared to theophylline and enprofylline and may be new candidates for bronchodilator.

  6. Radicals in Berkeley? (United States)

    Linn, Stuart


    In a previous autobiographical sketch for DNA Repair (Linn, S. (2012) Life in the serendipitous lane: excitement and gratification in studying DNA repair. DNA Repair 11, 595-605), I wrote about my involvement in research on mechanisms of DNA repair. In this Reflections, I look back at how I became interested in free radical chemistry and biology and outline some of our bizarre (at the time) observations. Of course, these studies could never have succeeded without the exceptional aid of my mentors: my teachers; the undergraduate and graduate students, postdoctoral fellows, and senior lab visitors in my laboratory; and my faculty and staff colleagues here at Berkeley. I am so indebted to each and every one of these individuals for their efforts to overcome my ignorance and set me on the straight and narrow path to success in research. I regret that I cannot mention and thank each of these mentors individually.

  7. Reactions of the cumyloxyl radical with secondary amides. The influence of steric and stereoelectronic effects on the hydrogen atom transfer reactivity and selectivity. (United States)

    Salamone, Michela; Basili, Federica; Mele, Riccardo; Cianfanelli, Marco; Bietti, Massimo


    A time-resolved kinetic study of the hydrogen atom transfer (HAT) reactions from secondary alkanamides to the cumyloxyl radical was carried out in acetonitrile. HAT predominantly occurs from the N-alkyl α-C-H bonds, and a >60-fold decrease in kH was observed by increasing the steric hindrance of the acyl and N-alkyl groups. The role of steric and stereoelectronic effects on the reactivity and selectivity is discussed in the framework of HAT reactions from peptides.

  8. Radical chic? Yes we are!


    Hartle, J.F.


    Ever since Tom Wolfe in a classical 1970 essay coined the term "radical chic", upper-class flirtation with radical causes has been ridiculed. But by separating aesthetics from politics Wolfe was actually more reactionary than the people he criticized, writes Johan Frederik Hartle.

  9. 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:


    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.

  10. Melatonin scavenges phenylglyoxylic ketyl radicals. (United States)

    Sersen, F; Vencel, T; Annus, J


    The antioxidant properties of melatonin were tested in this work by EPR technique. It was found that melatonin scavenges phenylglyoxylic ketyl radicals. Its effectiveness was 10-times lower than that of vitamin C. A new method of generation of phenylglyoxylic ketyl radicals by spontaneous decomposition of D,L-2,3-diphenyltartaric acid in propan-2-ol was used.

  11. Safety Assessment of Alkyl PEG Sulfosuccinates as Used in Cosmetics. (United States)

    Johnson, Wilbur; Heldreth, Bart; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan


    The Cosmetic Ingredient Review (CIR) Expert Panel (Panel) reviewed the safety of alkyl polyethylene glycol (PEG) sulfosuccinates, which function in cosmetics mostly as surfactants/cleansing agents. Although these ingredients may cause ocular and skin irritation, dermal penetration is unlikely because of the substantial polarity and molecular size of these ingredients. The Panel considered the negative oral carcinogenicity and reproductive and developmental toxicity data on chemically related laureths (PEG lauryl ethers) and negative repeated dose toxicity and skin sensitization data on disodium laureth sulfosuccinate supported the safety of these alkyl PEG sulfosuccinates in cosmetic products, but. The CIR Expert Panel concluded that the alkyl PEG sulfosuccinates are safe in the present practices of use and concentration when formulated to be nonirritating.

  12. Safety Assessment of Alkyl Ethylhexanoates as Used in Cosmetics. (United States)

    Fiume, Monice; Heldreth, Bart; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan


    The Cosmetic Ingredient Review (CIR) Expert Panel (Panel) assessed the safety of 16 alkyl ethylhexanoates for use in cosmetics, concluding that these ingredients are safe in cosmetic formulations in the present practices of use and concentrations when formulated to be nonirritating. The alkyl ethylhexanoates primarily function as skin-conditioning agents in cosmetics. The highest concentration of use reported for any of the alkyl ethylhexanoates is 77.3% cetyl ethylhexanoate in rinse-off formulations used near the eye, and the highest leave-on use reported is 52% cetyl ethylhexanoate in lipstick formulations. The Panel reviewed available animal and clinical data related to these ingredients, and the similarities in structure, properties, functions, and uses of ingredients from previous CIR assessments on constituent alcohols that allowed for extrapolation of the available toxicological data to assess the safety of the entire group.

  13. Alkylation of imidazole under ultrasound irradiation over alkaline carbons

    Energy Technology Data Exchange (ETDEWEB)

    Costarrosa, L. [Dpto. de Quimica Inorganica y Quimica Tecnica, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia (UNED), C/Senda del Rey, 9, E-28040 Madrid (Spain); Calvino-Casilda, V. [Dpto. de Quimica Inorganica y Quimica Tecnica, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia (UNED), C/Senda del Rey, 9, E-28040 Madrid (Spain); Ferrera-Escudero, S. [Dpto. de Quimica Inorganica y Quimica Tecnica, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia (UNED), C/Senda del Rey, 9, E-28040 Madrid (Spain); Duran-Valle, C.J. [Dpto. de Quimica Inorganica, Facultad de Ciencias, Universidad de Extremadura, Avenida de Elvas s/n, 06071 Badajoz (Spain); Martin-Aranda, R.M. [Dpto. de Quimica Inorganica y Quimica Tecnica, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia (UNED), C/Senda del Rey, 9, E-28040 Madrid (Spain)]. E-mail:


    N-Alkyl-imidazole has been synthesized by sonochemical irradiation of imidazole and 1-bromobutane using alkaline-promoted carbons (exchanged with the binary combinations of Na, K and Cs). The catalysts were characterized by X-ray photoelectron spectroscopy, thermal analysis and N{sub 2} adsorption isotherms. Under the experimental conditions, N-alkyl-imidazoles can be prepared with a high activity and selectivity. It is observed that imidazole conversion increases in parallel with increasing the basicity of the catalyst. The influence of the alkaline promoter, the reaction temperature, and the amount of catalyst on the catalytic activity has been studied. For comparison, the alkylation of imidazole has also been performed in a batch reactor system under thermal activation.

  14. Characterization of alkyl phenols in cashew (Anacardium occidentale) products and assay of their antioxidant capacity. (United States)

    Trevisan, M T S; Pfundstein, B; Haubner, R; Würtele, G; Spiegelhalder, B; Bartsch, H; Owen, R W


    In this study the content of anacardic acids, cardanols and cardols in cashew apple, nut (raw and roasted) and cashew nut shell liquid (CNSL) were analysed. The higher amounts (353.6 g/kg) of the major alkyl phenols, anacardic acids were detected in CNSL followed by cashew fibre 6.1 g/kg) while the lowest (0.65 g/kg) amounts were detected in roasted cashew nut. Cashew apple and fibre contained anacardic acids exclusively, whereas CNSL also contained an abundance of cardanols and cardols. Cashew nut (raw and roasted) also contained low amounts of hydroxy alkyl phenols. Cashew nut shell liquid was used for a basic fractionation of the alkyl phenol classes and the individual anacardic acids, major cardanols and cardols were purified to homogeneity from these fractions by semi-preparative HPLC and definitively identified by nano-ESI-MS-MS, GC-MS and NMR analyses. The hexane extracts (10 mg/ml) of all cashew products tested plus CNSL, displayed significant antioxidant capacity. Cashew nut shell liquid was the more efficient (inhibition=100%) followed by the hexane extract of cashew fibre (94%) and apple (53%). The antioxidant capacity correlated significantly (P4.0 mM). The data shows that of these substances, anacardic-1 was by far the more potent antioxidant (IC50=0.27 mM) compared to cardol-1 (IC50=1.71 mM) and cardanol-1 (IC50>4.0 mM). The antioxidant capacity of anacardic acid-1 is more related to inhibition of superoxide generation (IC50=0.04 mM) and xanthine oxidase (IC50=0.30 mM) than to scavenging of hydroxyl radicals. At present a substantial amount of cashew fibre is mostly used in formulations of animal or poultry feeds. The data presented in this study, indicates that this waste product along with CNSL, both of which contain high contents of anacardic acids, could be better utilized in functional food formulations and may represent a cheap source of cancer chemopreventive agents.

  15. Does Addition of NO2 to Carbon-Centered Radicals Yield RONO or RNO2? An Investigation Using Distonic Radical Ions (United States)

    Kirk, Benjamin B.; Trevitt, Adam J.; Blanksby, Stephen J.


    Nitrogen dioxide is used as a "radical scavenger" to probe the position of carbon-centered radicals within complex radical ions in the gas phase. As with analogous neutral radical reactions, this addition results in formation of an [M + NO2]+ adduct, but the structural identity of this species remains ambiguous. Specifically, the question remains: do such adducts have a nitro- (RNO2) or nitrosoxy- (RONO) moiety, or are both isomers present in the adduct population? In order to elucidate the products of such reactions, we have prepared and isolated three distonic phenyl radical cations and observed their reactions with nitrogen dioxide in the gas phase by ion-trap mass spectrometry. In each case, stabilized [M + NO2]+ adduct ions are observed and isolated. The structure of these adducts is probed by collision-induced dissociation and ultraviolet photodissociation action spectroscopy and a comparison made to the analogous spectra of authentic nitro- and nitrosoxy-benzenes. We demonstrate unequivocally that for the phenyl radical cations studied here, all stabilized [M + NO2]+ adducts are exclusively nitrobenzenes. Electronic structure calculations support these mass spectrometric observations and suggest that, under low-pressure conditions, the nitrosoxy-isomer is unlikely to be isolated from the reaction of an alkyl or aryl radical with NO2. The combined experimental and theoretical results lead to the prediction that stabilization of the nitrosoxy-isomer will only be possible for systems wherein the energy required for dissociation of the RO-NO bond (or other low energy fragmentation channels) rises close to, or above, the energy of the separated reactants.

  16. Phosphine-free conversion of alcohols into alkyl thiocyanates using trichloroisocyanuric acid/NH4SCN

    Institute of Scientific and Technical Information of China (English)

    Roya Azadi; Babak Mokhtari; Mohamad-Ali Makaremi


    A convenient and efficient phosphine-free procedure for the one-pot conversion of primary,secondary and tertiary alcohols into the corresponding alkyl thiocyanates or alkyl isothiocyanates is described using trichloroisocyanuric acid/NH4SCN.

  17. Immobilization of lipases on alkyl silane modified magnetic nanoparticles: effect of alkyl chain length on enzyme activity.

    Directory of Open Access Journals (Sweden)

    Jiqian Wang

    Full Text Available BACKGROUND: Biocatalytic processes often require a full recycling of biocatalysts to optimize economic benefits and minimize waste disposal. Immobilization of biocatalysts onto particulate carriers has been widely explored as an option to meet these requirements. However, surface properties often affect the amount of biocatalysts immobilized, their bioactivity and stability, hampering their wide applications. The aim of this work is to explore how immobilization of lipases onto magnetite nanoparticles affects their biocatalytic performance under carefully controlled surface modification. METHODOLOGY/PRINCIPAL FINDINGS: Magnetite nanoparticles, prepared through a co-precipitation method, were coated with alkyl silanes of different alkyl chain lengths to modulate their surface hydrophobicity. Candida rugosa lipase was then directly immobilized onto the modified nanoparticles through hydrophobic interaction. Enzyme activity was assessed by catalytic hydrolysis of p-nitrophenyl acetate. The activity of immobilized lipases was found to increase with increasing chain length of the alkyl silane. Furthermore, the catalytic activities of lipases immobilized on trimethoxyl octadecyl silane (C18 modified Fe(3O(4 were a factor of 2 or more than the values reported from other surface immobilized systems. After 7 recycles, the activities of the lipases immobilized on C18 modified nanoparticles retained 65%, indicating significant enhancement of stability as well through hydrophobic interaction. Lipase immobilized magnetic nanoparticles facilitated easy separation and recycling with high activity retaining. CONCLUSIONS/SIGNIFICANCE: The activity of immobilized lipases increased with increasing alkyl chain length of the alkyl trimethoxy silanes used in the surface modification of magnetite nanoparticles. Lipase stability was also improved through hydrophobic interaction. Alkyl silane modified magnetite nanoparticles are thus highly attractive carriers for

  18. Free radicals and male reproduction. (United States)

    Agarwal, Ashok; Allamaneni, Shyam S R


    Male factor accounts for almost 50% cases of infertility. The exact mechanism of sperm dysfunction is not known in many cases. Extensive research in the last decade has led to the identification of free radicals (reactive oxygen species) as mediators of sperm dysfunction in both specific diagnoses and idiopathic cases of male infertility. Elevated levels of reactive oxygen species are seen in up to 30-80% of men with male infertility. The role of free radicals has been studied extensively in the process of human reproduction. We know now that a certain level of free radicals is necessary for normal sperm function, whereas an excessive level of free radicals can cause detrimental effect on sperm function and subsequent fertilisation and offspring health. Oxidative stress develops when there is an imbalance between generation of free radicals and scavenging capacity of anti-oxidants in reproductive tract. Oxidative stress has been shown to affect both standard semen parameters and fertilising capacity. In addition, high levels of free radicals have been associated with lack of or poor fertility outcome after natural conception or assisted reproduction. Diagnostic techniques to quantify free radicals in infertile patients can assist physicians treating patients with infertility to plan for proper treatment strategies. In vivo anti-oxidants can be used against oxidative stress in male reproductive tract. Supplementation of in vitro anti-oxidants can help prevent the oxidative stress during sperm preparation techniques in assisted reproduction.

  19. Thermochemistry and Kinetic Analysis of the Unimolecular Oxiranyl Radical Dissociation Reaction: A Theoretical Study. (United States)

    Wang, Heng; Bozzelli, Joseph W


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

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

    Directory of Open Access Journals (Sweden)

    Donatella Della Porta


    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.

  1. Silver-Catalyzed Decarboxylative Radical Azidation of Aliphatic Carboxylic Acids in Aqueous Solution. (United States)

    Liu, Chao; Wang, Xiaoqing; Li, Zhaodong; Cui, Lei; Li, Chaozhong


    We report herein an efficient and general method for the decarboxylative azidation of aliphatic carboxylic acids. Thus, with AgNO3 as the catalyst and K2S2O8 as the oxidant, the reactions of various aliphatic carboxylic acids with tosyl azide or pyridine-3-sulfonyl azide in aqueous CH3CN solution afforded the corresponding alkyl azides under mild conditions. A broad substrate scope and wide functional group compatibility were observed. A radical mechanism is proposed for this site-specific azidation.

  2. 40 CFR 721.3900 - Alkyl polyethylene glycol phosphate, potassium salt. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl polyethylene glycol phosphate... Specific Chemical Substances § 721.3900 Alkyl polyethylene glycol phosphate, potassium salt. (a) Chemical... as alkyl polyethylene glycol phosphate, potassium salt (P-90-481), is subject to reporting under...

  3. 40 CFR 721.5380 - Mixed alkyl phenolic novolak resin (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixed alkyl phenolic novolak resin... Specific Chemical Substances § 721.5380 Mixed alkyl phenolic novolak resin (generic). (a) Chemical... as mixed alkyl phenolic novolak resin (PMN P-98-718) is subject to reporting under this section...

  4. 40 CFR 721.6475 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl polycarboxylic acids, esters... Significant New Uses for Specific Chemical Substances § 721.6475 Alkyl polycarboxylic acids, esters with... chemical substances identified generically as alkyl polycarboxylic acids, esters with ethoxylated...

  5. Laboratory studies of nitrate radical chemistry - application to atmospheric processes

    Energy Technology Data Exchange (ETDEWEB)

    Noremsaune, Ingse


    This thesis studies atmospheric chemistry and tries in particular to fill gaps in the data base of atmospheric reactions. It studies the nitrate radical reactions with chloroethenes and with but-2-yne (2-butyne). The mechanisms and rate coefficients for the NO{sub 3}-initiated degradation of the chloroethenes and 2-butyne were investigated by means of the static reaction chamber and the fast flow-discharge technique. The reactions between the nitrate radical and the chloroethenes were studied at atmospheric pressure in a reaction chamber with synthetic air as bath gas. FTIR (Fourier Transform InfraRed spectroscopy) spectroscopy was used to follow the reactions and to identify the products. Products were observed for the reactions with (E)-1,2-dichloroethene and tetrachloroethene, although the absorption bands are weak. The alkyl peroxynitrate and nitrate compounds form very strong and characteristic absorption bands. The rate coefficients for the reactions between NO{sub 3} and the chloroethenes were investigated at room temperature by three different methods. The results are given in tables. 132 refs., 44 figs., 21 tabs.

  6. Role of methyl radicals in the growth of PAHs. (United States)

    Shukla, Bikau; Miyoshi, Akira; Koshi, Mitsuo


    The role of methyl radicals in the networking of sp(2) carbons has been explored through kinetic analysis of mass spectra of the gas-phase products of the pyrolysis of toluene and toluene/acetone mixtures. Pyrolytic reactions were performed in a flow tube reactor at temperatures of 1140-1320 K and a constant total pressure of 10.38 Torr with a residence time of 0.585 s. On addition of acetone, methyl substituted products and their derivatives were enhanced. Mass peaks were observed in several sequences at an interval of 14 mass units; these ions correspond to methyl substituted products formed as a result of hydrogen abstraction (-H) followed by methyl radical addition (+CH(3)). Each major peak was usually preceded by a peak at two mass units lower, which was likely produced through dehydrogenation/dehydrocyclization (-H(2)) of methyl substituted products. Detected species include a large number of alkyl, cyclotetrafused (CT), cyclopentafused (CP) mono-, di-, and polycyclic aromatic hydrocarbons (PAHs) along with primary PAHs. The analysis showed that MAC (methyl addition/cyclization) has a unique capacity to induce the sequential growth of hexagonal networks of sp(2) carbons from all fusing sites of a PAH. Moreover, MAC was found capable of answering an important question in PAH growth, which is expansion of the CT --> CP --> hexagonal network for which other reported mechanisms are inefficient.

  7. Synthesis and Performance of a Biomimetic Indicator for Alkylating Agents. (United States)

    Provencher, Philip A; Love, Jennifer A


    4-(4-Nitrobenzyl)pyridine (NBP) is a colorimetric indicator compound for many types of carcinogenic alkylating agents. Because of the similar reactivity of NBP and guanine in DNA, NBP serves as a DNA model. NBP assays are used in the toxicological screening of pharmaceutical compounds, detection of chemical warfare agents, environmental hygiene technology, preliminary toxicology tests, mutagenicity of medicinal compounds, and other chemical analyses. Nevertheless, the use of NBP as a DNA model suffers from the compound's low water solubility, its lack of reactive oxygen sites, and dissimilar steric encumbrance compared to DNA. We report herein the design and synthesis of NBP derivatives that address some of these issues. These derivatives have been tested in solution and found to be superior in the colorimetric assay of the alkylating anticancer drug cyclophosphamide. The derivatives have also been integrated into a polymeric silica material which changes color upon the exposure to dangerous alkylating agents, such as iodomethane vapor, without the need for an exogenous base. This material modernizes the NBP assay from a time-consuming laboratory analysis to a real-time solid state sensor, which requires neither solvent nor additional reagents and can detect both gas- and solution-phase alkylating agents.

  8. Ionic liquid containing hydroxamate and N-alkyl sulfamate ions

    Energy Technology Data Exchange (ETDEWEB)

    Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan


    Embodiments of the invention are related to ionic liquids and more specifically to ionic liquids used in electrochemical metal-air cells in which the ionic liquid includes a cation and an anion selected from hydroxamate and/or N-alkyl sulfamate anions.

  9. Ruthenium-Catalyzed Alkylation of Oxindole with Alcohols

    DEFF Research Database (Denmark)

    Jensen, Thomas; Madsen, Robert


    An atom-economical and solvent-free catalytic procedure for the mono-3-alkylation of oxindole with alcohols is described. The reaction is mediated by the in situ generated catalyst from RuCl3 center dot xH(2)O and PPh3 in the presence of sodium hydroxide, The reactions proceed in good to excellent...

  10. Students' Understanding of Alkyl Halide Reactions in Undergraduate Organic Chemistry (United States)

    Cruz-Ramirez de Arellano, Daniel


    Organic chemistry is an essential subject for many undergraduate students completing degrees in science, engineering, and pre-professional programs. However, students often struggle with the concepts and skills required to successfully solve organic chemistry exercises. Since alkyl halides are traditionally the first functional group that is…

  11. Synthesis of Hydroxytyrosyl Alkyl Ethers from Olive Oil Waste Waters

    Directory of Open Access Journals (Sweden)

    Juan Fernández-Bolaños


    Full Text Available The preparation of a new type of derivatives of the naturally occurring antioxidant hydroxytyrosol is reported. Hydroxytyrosyl alkyl ethers were obtained in high yield by a three-step procedure starting from hydroxytyrosol isolated from olive oil waste waters. Preliminary results obtained by the Rancimat method have shown that these derivatives retain the high protective capacity of free hydroxytyrosol.

  12. On the Boiling Points of the Alkyl Halides. (United States)

    Correia, John


    Discusses the variety of explanations in organic chemistry textbooks of a physical property of organic compounds. Focuses on those concepts explaining attractive forces between molecules. Concludes that induction interactions play a major role in alkyl halides and other polar organic molecules and should be given wider exposure in chemistry texts.…

  13. Effect of alkyl substitutions on self-assembly

    Institute of Scientific and Technical Information of China (English)


    The self-assemblies of 4-hexadecyloxybenzoic acid and 3,4,5-trihexadecyloxybenzoic acid have been studied by using scanning tunneling microscopy (STM). The well-ordered assemblies with different arrangement have been investigated. The structural change is attributed to the different number of substituted alkyl chains on periphery.

  14. Research progress in ionic liquids catalyzed isobutane/butene alkylation

    Institute of Scientific and Technical Information of China (English)

    Panxue Gan; Shengwei Tang


    The complicated reaction mechanism and the character of competitive reactions lead to a stringent requirement for the catalyst of C4 alkylation process. Due to their unique properties, ionic liquids (ILs) are thought to be new potential acid catalysts for C4 alkylation. An analysis of the regular and modified chloroaluminate ILs, novel Brønsted ILs and composite ILs used in isobutane/butene alkylation shows that the use of either ILs or ILs coupled with mineral acid as homogeneous catalysts can help to greatly adjust the acid strength. By modifying the struc-tural parameters of the cations and anions of the ILs, the solubility of the reactants could also be adjusted, which in turn displays a positive effect on improving the activity of ILs. Immobilization of ILs is an effective way to mod-ulate the surface adsorption/desorption properties and acid strength distribution of the solid acid catalysts. Such a process has a tremendous potential to reduce the deactivation of catalyst and enhance the activity of the solid acid catalyst. The development of novel acid catalysts for C4 alkylation is a comprehensive consideration of acid strength and its distribution, interfacial properties and transport characteristics.


    Directory of Open Access Journals (Sweden)

    Yu. P. Sernyak


    Full Text Available Objective: to evaluate the impact of dissection of the dorsal venous complex without pre-ligation, suturing, or coagulation during radical prostatectomy (RPE in patients with localized prostate cancer (PC on the quality of surgery and the function of urinary retention.Subjects and methods. The data of 42 patients who had undergone posterior and anterior anatomical repair and vesicourethral anastomosis using a V-lock suture after prostatectomy were analyzed. All the patients were divided into 2 groups. Group 1 consisted of 22 patients in whom the dorsal venous complex was closed using a 3-0 vicryl suture before urethral dissection. Group 2 included 20 patients in whom the urethra was dissected without suturing the venous complex.Results. In group 1, complete urinary retention after catheter removal was noted in 9 (40.9 % and 15 (68 % patients within 24 hours and after 3 months, respectively. Following 12 months, two (9 % patients were observed to have partial mild urinary incontinence (as many as 2 pads per day. Group 2 patients showed complete urinary retention in 17 (85 % cases on the first day after catheter removal; all the patients retained urine 3 months later.Conclusion. In patients with localized PC, dissection of the dorsal venous complex without presuturing during laparoscopic RPE exerts a considerable impact on the preservation of urinary retention, namely 45% more of the patients reported complete urinary retention in early periods and 10 % more did this in later periods. At the same time, there was no statistically significant increase in intraoperative blood loss (p > 0.05, the number of positive edges, or biochemical recurrences.


    Directory of Open Access Journals (Sweden)

    Yu. P. Sernyak


    Full Text Available Objective: to evaluate the impact of dissection of the dorsal venous complex without pre-ligation, suturing, or coagulation during radical prostatectomy (RPE in patients with localized prostate cancer (PC on the quality of surgery and the function of urinary retention.Subjects and methods. The data of 42 patients who had undergone posterior and anterior anatomical repair and vesicourethral anastomosis using a V-lock suture after prostatectomy were analyzed. All the patients were divided into 2 groups. Group 1 consisted of 22 patients in whom the dorsal venous complex was closed using a 3-0 vicryl suture before urethral dissection. Group 2 included 20 patients in whom the urethra was dissected without suturing the venous complex.Results. In group 1, complete urinary retention after catheter removal was noted in 9 (40.9 % and 15 (68 % patients within 24 hours and after 3 months, respectively. Following 12 months, two (9 % patients were observed to have partial mild urinary incontinence (as many as 2 pads per day. Group 2 patients showed complete urinary retention in 17 (85 % cases on the first day after catheter removal; all the patients retained urine 3 months later.Conclusion. In patients with localized PC, dissection of the dorsal venous complex without presuturing during laparoscopic RPE exerts a considerable impact on the preservation of urinary retention, namely 45% more of the patients reported complete urinary retention in early periods and 10 % more did this in later periods. At the same time, there was no statistically significant increase in intraoperative blood loss (p > 0.05, the number of positive edges, or biochemical recurrences.

  17. Electron and hydrogen self-exchange of free radicals of sterically hindered tertiary aliphatic amines investigated by photo-CIDNP

    Directory of Open Access Journals (Sweden)

    Martin Goez


    Full Text Available The photoreactions of diazabicyclo[2,2,2]octane (DABCO and triisopropylamine (TIPA with the sensitizers anthraquinone (AQ and xanthone (XA or benzophenone (BP were investigated by time-resolved photo-CIDNP (photochemically induced dynamic nuclear polarization experiments. By varying the radical-pair concentration, it was ensured that these measurements respond only to self-exchange reactions of the free amine-derived radicals (radical cations DH•+ or α-amino alkyl radicals D• with the parent amine DH; the acid–base equilibrium between DH•+ and D• also plays no role. Although the sensitizer does not at all participate in the observed processes, it has a pronounced influence on the CIDNP kinetics because the reaction occurs through successive radical pairs. With AQ, the polarizations stem from the initially formed radical-ion pairs, and escaping DH•+ then undergoes electron self-exchange with DH. In the reaction sensitized with XA (or BP, the polarizations arise in a secondary pair of neutral radicals that is rapidly produced by in-cage proton transfer, and the CIDNP kinetics are due to hydrogen self-exchange between escaping D• and DH. For TIPA, the activation parameters of both self-exchange reactions were determined. Outer-sphere reorganization energies obtained with the Marcus theory gave very good agreement between experimental and calculated values of ∆G‡298.

  18. Antioxidant balance and free radical generation in vitamin e-deficient mice after dermal exposure to cumene hydroperoxide. (United States)

    Shvedova, A A; Kisin, E R; Murray, A R; Kommineni, C; Castranova, V; Mason, R P; Kadiiska, M B; Gunther, M R


    Organic peroxides are widely used in the chemical industry as initiators of oxidation for the production of polymers and fiber-reinforced plastics, in the manufacture of polyester resin coatings, and pharmaceuticals. Free radical production is considered to be one of the key factors contributing to skin tumor promotion by organic peroxides. In vitro experiments have demonstrated metal-catalyzed formation of alkoxyl, alkyl, and aryl radicals in keratinocytes incubated with cumene hydroperoxide. The present study investigated in vivo free radical generation in lipid extracts of mouse skin exposed to cumene hydroperoxide. The electron spin resonance (ESR) spin-trapping technique was used to detect the formation of alpha-phenyl-N-tert-butylnitrone (PBN) radical adducts, following intradermal injection of 180 mg/kg PBN. It was found that 30 min after topical exposure, cumene hydroperoxide (12 mmol/kg) induced free radical generation in the skin of female Balb/c mice kept for 10 weeks on vitamin E-deficient diets. In contrast, hardly discernible radical adducts were detected when cumene hydroperoxide was applied to the skin of mice fed a vitamin E-sufficient diet. Importantly, total antioxidant reserve and levels of GSH, ascorbate, and vitamin E decreased 34%, 46.5%. 27%, and 98%, respectively, after mice were kept for 10 weeks on vitamin E-deficient diet. PBN adducts detected by ESR in vitamin E-deficient mice provide direct evidence for in vivo free radical generation in the skin after exposure to cumene hydroperoxide.

  19. Penile rehabilitation after radical prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Ohl, Dana A; Ralph, David;


    The pathophysiology of erectile dysfunction after radical prostatectomy (RP) is believed to include neuropraxia, which leads to temporarily reduced oxygenation and subsequent structural changes in penile tissue. This results in veno-occlusive dysfunction, therefore, penile rehabilitation programm...

  20. Redox Properties of Free Radicals. (United States)

    Neta, P.


    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)

  1. Synthesis, properties and drug potential of the photosensitive alkyl- and alkylsiloxy-ligated silicon phthalocyanine Pc 227. (United States)

    Li, Jun; Yang, Yang; Zhang, Ping; Sounik, James R; Kenney, Malcolm E


    The photosensitive, alkyl- and alkylsiloxy-ligated silicon phthalocyanine, SiPc[(CH2)3SH][OSi(CH3)2(CH2)3N(CH3)2], Pc 227, has been prepared and characterized. This phthalocyanine yields the experimental photodynamic therapy (PDT) drug Pc 4, SiPc[OH][OSi(CH3)2(CH2)3N(CH3)2], when irradiated with red light. To provide an understanding of the process by which Pc 227 and other alkyl-alkylsiloxysilicon phthalocyanines such as Pc 227 are photolyzed, bond dissociation energy, natural bond orbital (NBO) charge distribution, spin density distribution, nucleus-independent chemical shift (NICS), and electron localization function (ELF) calculations have been carried out on two models related to it. These show that the lowest energy pathway for the photolysis of Pc 227 is a homolysis involving a phthalocyanine π radical having a low SiPc-C bond dissociation energy. The promise of the results of this study for synthetic chemistry and drug development is discussed.

  2. Addition of ester enolates to N-alkyl-2-fluoropyridinium salts: total synthesis of (+/-)-20-deoxycamptothecin and (+)-camptothecin. (United States)

    Bennasar, M-Lluïsa; Zulaica, Ester; Juan, Cecília; Alonso, Yolanda; Bosch, Joan


    Several 4-substituted dihydropyridones or 2-pyridones have been prepared by nucleophilic addition of alpha-(methylsulfanyl)ester enolates to N-alkyl-2-fluoropyridinium salts, followed by acid hydrolysis or oxidation with concomitant hydrolysis, of the intermediate 2-fluoro-1,4-dihydropyridine adducts, respectively. Addition of the enolate derived from isopropyl alpha-(methylsulfanyl)butyrate to N-(quinolylmethyl)-2-fluoropyridinium triflate 21 followed by DDQ treatment gave pyridone 29, from which (+/-)-20-deoxycamptothecin (31), a known precursor of camptothecin, was synthesized by a radical cyclization-desulfurization, with subsequent elaboration of the lactone E ring by chemoselective reduction. A similar sequence starting from the enolate of a chiral 2-hydroxybutyric acid derivative (33) provides access to natural (+)-camptothecin (37).


    NARCIS (Netherlands)



    Fusion of vesicles formed from synthetic, asymmetric (i.e mixed-chain) sodium di-n-alkyl phosphates (1-6) has been studied with a resonance energy transfer assay for lipid mixing and with transmission electron microscopy. Fusion was induced by Ca2+ ions above the Lalpha --> Lbeta phase transition te

  4. Levels and pattern of alkyl nitrates, multifunctional alkyl nitrates, and halocarbons in the air over the Atlantic Ocean (United States)

    Fischer, Ralf G.; Kastler, Jürgen; Ballschmiter, Karlheinz


    The Albatross Campaign was a research cruise of the German research vessel RV Polarstern (cruise ANT XFV/1) in October and November 1996 across the Atlantic Ocean. The cruise started in Bremerhaven, Germany, reached the polar region at 67°N, followed the 30°W meridian longitude, crossed the equatorial region, and ended at 50°S at Punta Quilla, Argentina. A second cruise leg closer to the African continent started from Capetown, South Africa, passed the Canary Island, and ended through the English Channel at Bremerhaven, Germany, in May/June 1998. Measurements of atmospheric levels of C1-C13 alkyl mononitrates, 24 alkyl dinitrates (C3-C6), 19 hydroxy alkyl nitrates (C2-C6), and benzyl nitrate, as well as the halocarbons tetrachloroethene, hexachloroethane, and bromoform are presented in this work. The halocarbons are used to assess the origin of the air parcels analyzed. Levels and patterns of multifunctional alkyl nitrates in the marine air are described here for the first time. The air masses include polluted air from the northern Europe, as well as highly degraded air masses of the South Atlantic trade wind region that represent global baseline levels. Two independent analytical methods were used in combination to cover the whole range of organic nitrates. First, the low-volume adsorptive enrichment of organic traces on Tenax, followed by thermodesorption cold trap HRGC-ECD and thermodesorption cold trap HRGC-(EI)MSD was used. Second, high-volume adsorptive enrichment of organic traces on silica gel was applied followed by solvent desorption, NP-HPLC group separation, and HRGC-(EI)-MSD. Short-chain alkyl nitrates (C4-C6) showed mixing ratios in the range of 0.2-2.5 parts per trillion by volume (pptv), with a local minimum for the tropical regions and significantly lower ratios for the Southern Hemisphere. The mixing ratio of the sum of 36 long-chain alkyl mononitrates (C7-C13) ranged from 0.02-0.43 pptv, the mixing ratio of the sum of 23 alkyl dinitrates (C3-C

  5. Formation and decay of the peroxy radicals in the oxidation process of Glyoxal, Methylglyoxal and Hydroxyacetone in aqueous solution (United States)

    Schaefer, Thomas; Weller, Christian; Herrmann, Hartmut


    Volatile organic compounds (VOCs) are emitted into the atmosphere in large amounts from biogenic and anthropogenic sources. For example, the semivolatile carbonyl compounds glyoxal and methylglyoxal will be produced in the oxidation process of isoprene, while hydroxyacetone can be formed by the combustion of biomass. Additionally, these semivolatile carbonyl compounds might be important for the formation of secondary organic aerosol (SOA) by partitioning between gas- and liquid phase of pre-existing particles. In the gas phase as well as in the aqueous phase (cloud droplets, fog, rain and deliquescent particles) these compounds can be further oxidized, e.g., by radicals (OH and NO3) leading to peroxy radical and then to substitued organics. There are still uncertainties concerning the oxidation pathways of glyoxal, after H-atom abstraction by, e.g., OH radicals, via alkyl radical to the peroxy radical under addition of molecular oxygen. One concept[1] claims that for dilute solutions ( 1 mM the formation of the peroxy radicals is a minor reaction pathway because of a lower rate constant of k = 1 × 106 M-1 s-1 estimated after Guzman et al., 2006[3]. The difference in the rate constants of the oxygen addition is of about three orders of magnitude and thus leads to different oxidation products and yields in the aqueous solution. Laboratory studies of glyoxal oxidation under varying oxygen concentrations have been performed in order to investigate the importance of the peroxy radical formation and alkyl radical recombination in more detail. The formation and the decay of the formed glyoxyl radicals and glyoxyl peroxy radicals were studied in low and high concentrated oxygen solutions using a laser photolysis long path absorption setup (LP-LPA). Additionally, the Tdependent decay of the peroxy radicals formed in the oxidation of methyglyoxal and hydroxyacetone was also studied using the same experiment. 1 Buxton, G. V., Malone, T. N. und Salmon, G. A., J. Chem. Soc

  6. Inhibitory Activities of Alkyl Syringates and Related Compounds on Aflatoxin Production

    Directory of Open Access Journals (Sweden)

    Tomohiro Furukawa


    Full Text Available Inhibitors of aflatoxin production of aflatoxigenic fungi are useful for preventing aflatoxin contamination in crops. As methyl syringate weakly inhibits aflatoxin production, aflatoxin production inhibitory activities of additional alkyl syringates with alkyl chains from ethyl to octyl were examined. Inhibitory activity toward aflatoxin production of Aspergillus flavus became stronger as the length of the alkyl chains on the esters became longer. Pentyl, hexyl, heptyl, and octyl syringates showed strong activity at 0.05 mM. Heptyl and octyl parabens, and octyl gallate also inhibited aflatoxin production as strongly as octyl syringate. Alkyl parabens and alkyl gallates inhibit the complex II activity of the mitochondrial respiration chain; thus, whether alkyl syringates inhibit complex II activity was examined. Inhibitory activities of alkyl syringates toward complex II also became stronger as the length of the alkyl chains increased. The complex II inhibitory activity of octyl syringate was comparable to that of octyl paraben and octyl gallate. These results suggest that alkyl syringates, alkyl parabens, and alkyl gallates, including commonly used food additives, are useful for aflatoxin control.

  7. Inhibitory Activities of Alkyl Syringates and Related Compounds on Aflatoxin Production (United States)

    Furukawa, Tomohiro; Iimura, Kurin; Kimura, Taichi; Yamamoto, Toshiyoshi; Sakuda, Shohei


    Inhibitors of aflatoxin production of aflatoxigenic fungi are useful for preventing aflatoxin contamination in crops. As methyl syringate weakly inhibits aflatoxin production, aflatoxin production inhibitory activities of additional alkyl syringates with alkyl chains from ethyl to octyl were examined. Inhibitory activity toward aflatoxin production of Aspergillus flavus became stronger as the length of the alkyl chains on the esters became longer. Pentyl, hexyl, heptyl, and octyl syringates showed strong activity at 0.05 mM. Heptyl and octyl parabens, and octyl gallate also inhibited aflatoxin production as strongly as octyl syringate. Alkyl parabens and alkyl gallates inhibit the complex II activity of the mitochondrial respiration chain; thus, whether alkyl syringates inhibit complex II activity was examined. Inhibitory activities of alkyl syringates toward complex II also became stronger as the length of the alkyl chains increased. The complex II inhibitory activity of octyl syringate was comparable to that of octyl paraben and octyl gallate. These results suggest that alkyl syringates, alkyl parabens, and alkyl gallates, including commonly used food additives, are useful for aflatoxin control. PMID:27338472

  8. Characterization by EPR of radicals in HDPE, PA6 and HDPE/PA6 blend irradiated with gamma rays

    Energy Technology Data Exchange (ETDEWEB)

    Silva, P. [Centro de Fisica, Instituto Venezolano de Investigacion Cientifica IVIC, Carretera Panamericana Km. 11, A.P. 21827, Caracas 1020-A (Venezuela); Albano, C.; Lovera, D. [Centro de Quimica, IVIC (Venezuela); Perera, R. [Departamento de Mecanica, Universidad Simon Bolivar, Caracas (Venezuela)


    Using electron paramagnetic resonance (EPR), we studied the tree radical formation in high-density Polyethylene (HDPE), polyamide (PA6) and HDPE/PA6 (80/20)blend, irradiated with integral doses (D), 0 < D < 1000 KGy, with a dose rate of irradiation in air of 6.6 KGy/h. Typical spectra indicative of the formation of allyl, alkyl and poly enyl radicals were obtained. A decay in the total number of spins per gram (C/g), when the samples are aged by a period of time of 30 days, was found, which is typical of a recombination of radicals with their environment. Additionally, a different order fit for the C/g as a function of D was obtained, which is indicative of the complex behavior of the kinetics of the decomposition. (Author)

  9. Antioxidative Effect of Schiff Bases with o-Hydroxybenzylidene Groupon Free Radical Induced Hemolysis of Human Red Blood Cell

    Institute of Scientific and Technical Information of China (English)


    The hemolysis of human red blood cells was initiated by a water-soluble free radical initiator, 2,2′-azobis-(2-amidinopropane hydrochloride)(AAPH), at 37 ℃ in phosphate buffered saline(pH=7.4). The respective addition of 1-[N-(o-hydroxybenzylidene)amino]tetradecane(TDCA), 1,2-di[N-(o-hydroxybenzylidene)amino]cyclohexane(DACH), 4-[N-(o-hydroxybenzylidene)amino]benzoic acid(PABA), 4-nitro[N-(o-hydroxybenzylidene)]aniline(APNA) or N-(o-hydroxybenzylidene)aniline(APA) can all prolong the inhibition period of hemolysis, indicating that the above Schiff bases play an antioxidative role in free radical induced hemolysis. It can be concluded that Schiff base with an alkyl group or a conjugated system in the molecule protect red blood cells against free radical induced hemolysis efficiently. This information may be useful for antioxidant drug design.

  10. Peroxy radical partitioning during the AMMA radical intercomparison exercise

    Directory of Open Access Journals (Sweden)

    M. D. Andrés-Hernández


    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.

  11. 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


    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

  12. Radical formation by heavy metals

    Energy Technology Data Exchange (ETDEWEB)

    Beuter, W.


    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.

  13. Prenyl sulfates as alkylating reagents for mercapto amino acids. (United States)

    Maltsev, Sergey; Sizova, Olga; Utkina, Natalia; Shibaev, Vladimir; Chojnacki, Tadeusz; Jankowski, Wieslaw; Swiezewska, Ewa


    A new methodology for prenylation of thiol compounds has been developed. The approach is based on the use of prenyl sulfates as new reagents for S-prenylation of benzenethiol and cysteamine in aqueous systems. The C(10)-prenols geraniol and nerol that differ in the configuration (E or Z, correspondingly) of the alpha-isoprene unit were efficiently O-sulfated in the presence of a pyridine-SO(3') complex. The obtained geranyl and neryl sulfates were tested as alkylating agents. These compounds were chosen to reveal the influence of the alpha-isoprene unit configuration on their alkylation (prenylation) ability. S-Geranyl cysteine was prepared to demonstrate the applicability of this method for prenylation of peptides containing mercapto amino acids.

  14. Safety Assessment of Alkyl Esters as Used in Cosmetics. (United States)

    Fiume, Monice M; Heldreth, Bart A; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan


    The Cosmetic Ingredient Review Expert Panel (Panel) assessed the safety of 237 alkyl esters for use in cosmetics. The alkyl esters included in this assessment have a variety of reported functions in cosmetics, with skin-conditioning agent being the most common function. The Panel reviewed available animal and clinical data in making its determination of safety on these ingredients, and where there were data gaps, similarity in structure, properties, functions, and uses of these ingredients allowed for extrapolation of the available toxicological data to assess the safety of the entire group. The Panel concluded that these ingredients are safe in cosmetic formulations in the present practices of use and concentration when formulated to be nonirritating.

  15. Molecular simulation of alkyl monolayers on the Si(111)surface

    Institute of Scientific and Technical Information of China (English)

    YUAN; Shiling; (苑世领); CAI; Zhengting; (蔡政亭); XIAO; Li; (肖莉); XU; Guiying; (徐桂英); LIU; Yongjun; (刘永军)


    The structure of twelve-carbon monolayers on the H-terminated Si(111) surface is investigated by molecular simulation method. The best substitution percent on Si(111) surface obtained via molecular mechanics calculation is equal to 50%, and the (8×8) simulated cell can be used to depict the structure of alkyl monolayer on Si surface. After two-dimensional cell containing alkyl chains and four-layer Si(111) crystal at the substitution 50% is constructed, the densely packed and well-ordered monolayer on Si(111) surface can be shown through energy minimization in the suitable-size simulation cell. These simulation results are in good agreement with the experiments. These conclusions show that molecular simulation can provide otherwise inaccessible mesoscopic information at the molecular level, and can be considered as an adjunct to experiments.

  16. Isolation of a Cyclic (Alkyl)(amino)germylene. (United States)

    Wang, Liliang; Lim, Yi Shan; Li, Yongxin; Ganguly, Rakesh; Kinjo, Rei


    A 1,4-addition of a dichlorogermylene dioxane complex with α,β-unsaturated imine 1 gave a dichlorogermane derivative 2 bearing a GeC₃N five-membered ring skeleton. By reducing 2 with KC₈, cyclic (alkyl)(amino)germylene 3 was synthesized and fully characterized. Germylene 3 readily reacted with TEMPO, N₂O and S₈, producing the 1:2 adduct 4, the oxo-bridged dimer 5 and the sulfido-bridged dimer 6, respectively.

  17. Neurobehavioral teratogenicity of perfluorinated alkyls in an avian model


    Pinkas, Adi; Slotkin, Theodore A.; Brick-Turin, Yael; Van der Zee, Eddy A.; Yanai, Joseph


    Perfluorinated alkyls are widely-used agents that accumulate in ecosystems and organisms because of their slow rate of degradation. There is increasing concern that these agents may be developmental neurotoxicants and the present study was designed to develop an avian model for the neurobehavioral teratogenicity of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Fertilized chicken eggs were injected with 5 or 10 mg/kg of either compound on incubation day 0. On the day of h...

  18. New potential of the reductive alkylation of amines (United States)

    Gusak, K. N.; Ignatovich, Zh V.; Koroleva, E. V.


    Available data on the reductive alkylation of amines with carbonyl compounds — a key method for the preparation of secondary and tertiary amines — are described systematically. The review provides information on the relevant reducing agents and catalysts and on the use of chiral catalysts in stereo- and enantiocontrolled reactions of amine synthesis. The effect of the reactant and catalyst structures on the reaction rates and chemo- and stereo(enantio)selectivity is considered. The bibliography includes 156 references.

  19. Epistemological barriers to radical behaviorism. (United States)

    O'Donohue, W T; Callaghan, G M; Ruckstuhl, L E


    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.

  20. Epistemological barriers to radical behaviorism (United States)

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


    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

  1. Alkylation of Benzene with Propylene Catalyzed by Ionic Liquids

    Institute of Scientific and Technical Information of China (English)

    Sun Xuewen; Zhao Suoqi


    The alkylation of benzene with propylene catalyzed by ionic liquids to obtain cumene was investigated. Propylene conversion and cumene selectivity under mild reaction conditions were improved greatly after the ionic liquid was modified with HCl. Under the conditions of 20 oC, 0.1MPa, 5 min of reaction time, and a molar ratio of benzene to propylene of 10:1, propylene conversion increased from 83.6% to 100%, and cumene selectivity increased from 90.86% to 98.47%. In addition, it was found that the reaction could be carried out in two different stages so as to obtain a better result. At the first stage, the key reaction was alkylation and a higher propylene conversion was obtained at a lower temperature;At the second stage, the key reaction was transalkylation and a higher temperature was used to improve cumene selectivity. The reaction temperature, pressure and the amount of catalyst used in this work were lower than those used in traditional alkylation processes.

  2. Chemotherapy-induced pulmonary hypertension: role of alkylating agents. (United States)

    Ranchoux, Benoît; Günther, Sven; Quarck, Rozenn; Chaumais, Marie-Camille; Dorfmüller, Peter; Antigny, Fabrice; Dumas, Sébastien J; Raymond, Nicolas; Lau, Edmund; Savale, Laurent; Jaïs, Xavier; Sitbon, Olivier; Simonneau, Gérald; Stenmark, Kurt; Cohen-Kaminsky, Sylvia; Humbert, Marc; Montani, David; Perros, Frédéric


    Pulmonary veno-occlusive disease (PVOD) is an uncommon form of pulmonary hypertension (PH) characterized by progressive obstruction of small pulmonary veins and a dismal prognosis. Limited case series have reported a possible association between different chemotherapeutic agents and PVOD. We evaluated the relationship between chemotherapeutic agents and PVOD. Cases of chemotherapy-induced PVOD from the French PH network and literature were reviewed. Consequences of chemotherapy exposure on the pulmonary vasculature and hemodynamics were investigated in three different animal models (mouse, rat, and rabbit). Thirty-seven cases of chemotherapy-associated PVOD were identified in the French PH network and systematic literature analysis. Exposure to alkylating agents was observed in 83.8% of cases, mostly represented by cyclophosphamide (43.2%). In three different animal models, cyclophosphamide was able to induce PH on the basis of hemodynamic, morphological, and biological parameters. In these models, histopathological assessment confirmed significant pulmonary venous involvement highly suggestive of PVOD. Together, clinical data and animal models demonstrated a plausible cause-effect relationship between alkylating agents and PVOD. Clinicians should be aware of this uncommon, but severe, pulmonary vascular complication of alkylating agents.

  3. Synthesis and Antioxidant Activity of Hydroxytyrosol Alkyl-Carbonate Derivatives. (United States)

    Fernandez-Pastor, Ignacio; Fernandez-Hernandez, Antonia; Rivas, Francisco; Martinez, Antonio; Garcia-Granados, Andres; Parra, Andres


    Three procedures have been investigated for the isolation of tyrosol (1) and hydroxytyrosol (2) from a phenolic extract obtained from the solid residue of olive milling. These three methods, which facilitated the recovery of these phenols, were chemical or enzymatic acetylation, benzylation, and carbomethoxylation, and subsequent carbonylation or acetonation reactions. Several new lipophilic alkyl-carbonate derivatives of hydroxytyrosol have been synthesized, coupling the primary hydroxy group of this phenol, through a carbonate linker, using alcohols with different chain lengths. The antioxidant properties of these lipophilic derivatives have been evaluated by different methods and compared with free hydroxytyrosol (2) and also with the well-known antioxidants BHT and α-tocopherol. Three methods were used for the determination of this antioxidant activity: FRAP and ABTS assays, to test the antioxidant power in hydrophilic media, and the Rancimat test, to evaluate the antioxidant capacity in a lipophilic matrix. These new alkyl-carbonate derivatives of hydroxytyrosol enhanced the antioxidant activity of this natural phenol, with their antioxidant properties also being higher than those of the commercial antioxidants BHT and α-tocopherol. There was no clear influence of the side-chain length on the antioxidant properties of the alkyl-carbonate derivatives of 2, although the best results were achieved mainly by the compounds with a longer chain on the primary hydroxy group of this natural phenolic substance.

  4. Polycyclic aromatic acids are primary metabolites of alkyl-PAHs - a case study with Nereis diversicolor

    DEFF Research Database (Denmark)

    Malmquist, Linus Mattias Valdemar; Selck, Henriette; Jørgensen, Kåre Bredeli;


    Although concentrations of alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) in oil-contaminated sediments are higher than those of unsubstituted PAHs, only little attention has been given to metabolism and ecotoxicity of alkyl-PAHs. In this study we demonstrated that metabolism of alkyl-PA...... that carboxylic acid metabolites of alkyl-PAHs have the potential of constituting a new class of contaminants in marine waters that needs attention in relation to ecological risk assessments....

  5. A physicochemical examination of the free radical scavenging activity of Trolox: mechanism, kinetics and influence of the environment. (United States)

    Alberto, Marta E; Russo, Nino; Grand, Andre; Galano, Annia


    The free radical scavenging activity of Trolox was studied for aqueous and lipid environments using the Density Functional Theory. Several reaction mechanisms and free radicals of different chemical nature have been included in this study, as well as the influence of the pH. Trolox was found to be a powerful ˙OH and alkoxy scavenger, regardless of the conditions under which the reaction takes place. It was also found to be very efficient as a peroxy radical scavenger in aqueous solution, while its protective effects against this particular kind of free radicals are significantly reduced in lipid solution. Four reaction mechanisms were found to significantly contribute to the ˙OH scavenging activity of Trolox in aqueous solution: hydrogen transfer (HT), radical adduct formation (RAF), single electron transfer (SET), and sequential proton loss electron transfer (SPLET), while in lipid media two of them are relevant: HT and RAF. The ˙OCH3, ˙OOH, and ˙OOCHCH2 scavenging processes are predicted to take place almost exclusively by HT from the phenolic OH group in lipid media, and in aqueous solution at pH < 11, while at higher pH values the SPLET mechanism is proposed as the main one. This is also the case for other non-halogenated alkyl or alkenyl peroxy (and alkoxy) radicals. The agreement with the available experimental data supports the reliability of the presented calculations.

  6. Radical democratic politics and feminism

    Directory of Open Access Journals (Sweden)

    Martínez Labrin, Soledad


    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

  7. Vaginal radical trachelectomy: an update. (United States)

    Plante, Marie


    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.

  8. Generation of free radicals from lipid hydroperoxides by Ni2+ in the presence of oligopeptides. (United States)

    Shi, X; Dalal, N S; Kasprzak, K S


    The generation of free radicals from lipid hydroperoxides by Ni2+ in the presence of several oligopeptides was investigated by electron spin resonance (ESR) utilizing 5,5-dimethyl-1-pyrroline N-oxide (DMPO) as a spin trap. Incubation of Ni2+ with cumene hydroperoxide or t-butyl hydroperoxide did not generate any detectable free radical. In the presence of glycylglycylhistidine (GlyGlyHis), however, Ni2+ generated cumene peroxyl (ROO.) radical from cumene hydroperoxide, with the free radical generation reaching its saturation level within about 3 min. The reaction was first order with respect to both cumene hydroperoxide and Ni2+. Similar results were obtained using t-butyl hydroperoxide, but the yield of t-butyl peroxyl radical generation was about 7-fold lower. Other histidine-containing oligopeptides such as beta-alanyl-L-histidine (carnosine), gamma-aminobutyryl-L-histidine (homocarnosine), and beta-alanyl-3-methyl-L-histidine (anserine) caused the generation of both cumene alkyl (R.) and cumene alkoxyl (RO.) radicals in the reaction of Ni2+ with cumene hydroperoxide. Similar results were obtained using t-butyl hydroperoxide. Glutathione also caused generation of R. and RO. radicals in the reaction of Ni2+ with cumene hydroperoxide but the yield was approximately 25-fold greater than that produced by the histidine-containing peptides, except GlyGlyHis. The ratio of DMPO/R. and DMPO/RO. produced with glutathione and cumene hydroperoxide was approximately 3:1. Essentially the same results were obtained using t-butyl hydroperoxide except that the ratio of DMPO/R. to DMPO/RO. was approximately 1:1. The free radical generation from cumene hydroperoxide reached its saturation level almost instantaneously while in the case of t-butyl hydroperoxide, the saturation level was reached in about 3 min. In the presence of oxidized glutathione, the Ni2+/cumene hydroperoxide system caused DMPO/.OH generation from DMPO without forming free hydroxyl radical. Since glutathione

  9. Remediation of polluted soils contaminated with Linear Alkyl Benzenes using Fenton's reagent

    Directory of Open Access Journals (Sweden)

    Douglas do Nascimento Silva


    Full Text Available Linear Alkyl Benzenes (LABs are used as insulating oil for electric cables. When it happens a spill, LABs they are basically sorbed in the soil, because, these compounds have high hidrophobicity and low vapor pressure. The conventional methods of treatment of soils are not efficient. The Fenton's reaction (reaction between a solution of iron II and hydrogen peroxide it generates hydroxyl radicals, not selective, and capable of oxidize a great variety of organic compounds. A study was conducted to evaluate the viability of use of the Fenton's reagents to promote the remediation of polluted soils with Linear Alkyl Benzenes. A column was especially projected for these experiments, packed with a sandy and other soil loamy. The pH of the soil was not altered. The obtained results demonstrated the technical viability of the process of injection of the Fenton's reagents for the treatment of polluted areas with LABs.Os Linear Alquilbenzenos (LABs são usados como fluido refrigerante de cabos elétricos. Quando ocorre um vazamento, os LABs ficam basicamente adsorvidos no solo, pois, são compostos bastante hidrofóbicos e com baixa pressão de vapor. Os métodos convencionais de tratamento de solos não são eficientes. A reação de Fenton (solução de ferro II e peróxido de hidrogênio gera radicais hidroxila, não seletivos, e capazes de oxidar uma grande variedade de compostos orgânicos, chegando a mineralização dos mesmos. Neste trabalho foi estudada a viabilidade de utilização dos reagentes de Fenton para promover a remediação de solos contaminados com LABs. Utilizou-se uma coluna especialmente projetada para estes experimentos, empacotada com um solo arenoso e outro argiloso. O pH do solo não foi alterado. Os resultados obtidos demonstram a viabilidade técnica do processo de injeção dos reagentes de Fenton para o tratamento de áreas contaminadas com LABs.

  10. Radical Innovation and Network Evolution

    NARCIS (Netherlands)

    S.M.W. Phlippen (Sandra); M. Riccaboni


    textabstractThis paper examines how a radical technological innovation affects alliance formation of firms and subsequent network structures. We use longitudinal data of interfirm R&D collaborations in the biopharmaceutical industry in which a new technological regime is established. Our findings su

  11. Wild radical square zero algebras

    Institute of Scientific and Technical Information of China (English)


    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.

  12. Is Radical Innovation Management Misunderstood?

    DEFF Research Database (Denmark)

    Kristiansen, Jimmi Normann; Gertsen, Frank


    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...

  13. Exploring the Theories of Radicalization

    Directory of Open Access Journals (Sweden)

    Maskaliūnaitė Asta


    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.

  14. Radical review of NHS funding. (United States)


    The Government is to carry out a radical review of the way the NHS is funded, Prime Minister Margaret Thatcher confirmed last week. And she hinted that she herself would be taking a leading role in drawing up proposals for reform.

  15. Detecting Social Polarization and Radicalization

    DEFF Research Database (Denmark)

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


    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...

  16. Students' Ideas and Radical Constructivism (United States)

    Sánchez Gómez, Pedro J.


    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…

  17. A quantitative approach to the free radical interaction between alpha-tocopherol or ascorbate and flavonoids. (United States)

    Fujisawa, Seiichiro; Ishihara, Mariko; Atsumi, Toshiko; Kadoma, Yoshinori


    Despite numerous previous studies, the mechanism of the free radical interaction between alpha-tocopherol (VE), or ascorbate and flavonoids, as coantioxidants remains unclear. The synergistic antioxidant effects of VE or L-ascorbyl 2,6-dibutyrate (ASDB, an ascorbate derivative) with the flavonoids (-)-epicatechin (EC), (-)-epigallocatechin (EGC), (-)-epicatechin gallate (ECG) and (-)-epigallocatechin gallate (EGCG) and methyl gallate (MG), were investigated by the induction period method in the polymerization of methyl methacrylate (MMA), initiated by thermal decomposition of 2,2'-azobis(isobutyronitrile) (an alkyl radical, R *), under nearly anaerobic conditions. For VE, a synergistic antioxidant effect was observed with MG, EC, EGC and ECG, whereas this activity was decreased by the addition of EGCG. For ASDB, a synergistic antioxidant effect was observed with EGC and ECG, whereas this activity was decreased by the addition of EGCG or MG. A synergistic antioxidant effect (regeneration of VE) appears to be feasible even though the BDE (phenolic O-H bond dissociation entropy) of the coantioxidants is significantly higher than that of VE. The driving force for the regeneration process may be the removal of the semiquinone radical from the flavonoids MG, EC, EGC and ECG by the VE radical. In the ASDB/flavonoid mixture, flavonoid radicals are scavenged by ASDB. The partial regeneration of flavonoids by ASDB may follow a similar recycling mechanism to that of the well-known VE/ascorbate mixture. The free radical interaction between EGCG and VE or ASDB decreased the antioxidant effect. Such enhancement of prooxidation in EGCG/VE or EGCG/ASDB mixtures oxidized by R * may increase their cytotoxic effects.

  18. A facile and convenient method for synthesis of alkyl thiocyanates under homogeneous phase transfer catalyst conditions

    Institute of Scientific and Technical Information of China (English)

    Ali Reza Kiasat; Rashid Badri; Soheil Sayyahi


    A simple and environmentally friendly method is described for the efficient conversion of alkyl halide to alkyl thiocyanate using tetrabutylammonium bromide (TBAB) as a phase transfer catalyst.The reactions occur in water and furnish the corresponding alkyl thiocyanate in high yields.No evidence for the formation of isothiocyanates as by-product of the reaction was observed and the products were obtained in pure form without further purification.

  19. Highly enantio- and diastereoselective allylic alkylation of Morita-Baylis-Hillman carbonates with allyl ketones

    KAUST Repository

    Tong, Guanghu


    The asymmetric allylic alkylation of Morita-Baylis-Hillman (MBH) carbonates with allyl ketones has been developed. The α-regioselective alkylation adducts, containing a hexa-1,5-diene framework with important synthetic value, were achieved in up to 83% yield, >99% ee, and 50:1 dr by using a commercially available Cinchona alkaloid as the catalyst. From the allylic alkylation adduct, a cyclohexene bearing two adjacent chiral centers was readily prepared. © 2013 American Chemical Society.

  20. A Versatile Approach for the Asymmetric Synthesis of 3-Alkyl-isoindolin-1-ones

    Institute of Scientific and Technical Information of China (English)

    CHEN,Ming-De(陈明德); HE,Ming-Zhu(贺明珠); HUANG,Li-Qiang(黄利强); RUAN, Yuan-Ping( 阮源萍 ); HUANG, Pei-Qiang (黄培强)


    A flexxible approach to(R)-3-alkyl-isoindolin-1-ones and (R)-3-aryl-isoindolin-1-ones via a diastereoselective-alkylation is described. Present method is versatile in scope, allowing the easy introduction of various C-3 substituents by Grignard addition to phthalimide derived from (R)-phenylglycinol.3-Alkyl-3-hydroxy-isoindolin-1-ones can also be obtained in the first step of the present method.

  1. Reaction between protein radicals and other biomolecules

    DEFF Research Database (Denmark)

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


    oil-in-water emulsion resulted in additional formation of lipid hydroperoxides and conjugated dienes. The results clearly show that protein radicals have to be considered as dynamic species during oxidative processes in biological systems and that protein radicals should not be considered as end-products......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....... 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...

  2. Methods of producing alkylated hydrocarbons from an in situ heat treatment process liquid (United States)

    Roes, Augustinus Wilhelmus Maria; Mo, Weijian; Muylle, Michel Serge Marie; Mandema, Remco Hugo; Nair, Vijay


    A method for producing alkylated hydrocarbons is disclosed. Formation fluid is produced from a subsurface in situ heat treatment process. The formation fluid is separated to produce a liquid stream and a first gas stream. The first gas stream includes olefins. The liquid stream is fractionated to produce at least a second gas stream including hydrocarbons having a carbon number of at least 3. The first gas stream and the second gas stream are introduced into an alkylation unit to produce alkylated hydrocarbons. At least a portion of the olefins in the first gas stream enhance alkylation.

  3. Ab initio study of the influence of resonance stabilization on intramolecular ring closure reactions of hydrocarbon radicals. (United States)

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


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

  4. Oxygen free radicals in rheumatoid arthritis

    NARCIS (Netherlands)

    P. Biemond (Pieter)


    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

  5. Differential alkylation-based redox proteomics - Lessons learnt

    DEFF Research Database (Denmark)

    Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina


    is a critical evaluation of differential alkylation-based strategies for the analysis of S-nitrosylation and S-sulfenylation. The aim is to assess the current status and to provide insights for future directions in the dynamically evolving field of redox proteomics. To achieve that we collected 35 original......, including the amount of starting material required for analysis. The results of this meta-analysis are the core of this review, complemented by issues related to biological models and sample preparation in redox proteomics, including conditions for free thiol blocking and labelling of target cysteine...

  6. Synthesis and cytotoxic activity of some derivatives of alkyl piperidine. (United States)

    Jahan, Sarwat; Akhtar, Shamim; Saify, Zafar Saied; Mushtaq, Nousheen; Sial, Ali Akbar; Kamil, Arfa; Arif, Muhammed


    Synthesis of novel phenacyl derivatives of alkyl piperidine as cytotoxic agents via simple and single step reaction procedure is going to be reported here. Twelve new compounds were successfully synthesized in moderate yield and in solid form. Their synthesis was confirmed by TLC, melting point, CHN analysis and through different spectral studies such as UV, IR, Mass and proton NMR. The advantages of this synthetic route are simple operation, mild reaction conditions and good yields. These newly synthesized derivatives were extensively explored for their cytotoxicity by brine shrimp lethality assay.

  7. Alkyl polyglycoside-sorbitan ester formulations for improved oil recovery

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Y.; Iglauer, S.; Shuler, P.; Tang, Y. [Power Environmental Energy Research Institute (PEERI), Covina, CA (United States); Goddard, W.A. III [California Inst. of Technology, Pasadena, CA (US). Div. of Chemistry and Chemical Engineering, Materials and Process Simulation Center (MSC)


    We measured interfacial tensions (IFT) of aqueous alkyl polyglucoside (APG) systems formulated with sorbitan ester-type cosurfactants against n-octane. The study focused on low to ultra-low IFT systems which are relevant for enhanced oil recovery (EOR). In addition, we measured equilibrium adsorption concentrations of these surfactants and cosurfactants onto kaolinite clay, commonly found in oil reservoirs. We present one surfactant EOR laboratory flood experiment with one selected APG-sorbitan ester formulation with which we recovered 94% of initial oil in place (IOIP). (orig.)

  8. 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: [Department of Radiology, University of California at San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0610 (United States)


    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.

  9. Highly durable photochromic radical complexes having no steric protections of radicals. (United States)

    Kobayashi, Yoichi; Mishima, Yasuhiro; Mutoh, Katsuya; Abe, Jiro


    Steric protection groups are usually necessary for stable radicals. However, here, we developed novel photochromic radical complexes which generate sterically unprotected imidazolyl and phenoxyl radicals upon UV light irradiation based on the phenoxyl-imidazolyl radical complex (PIC) framework. These photochromic compounds show excellent durability against repeated irradiation of intense nanosecond laser pulses even in polar protic solvents, such as ethanol.

  10. Evaluation of anti-herpetic and antioxidant activities, and cytotoxic and genotoxic effects of synthetic alkyl-esters of gallic acid. (United States)

    Savi, Luciane A; Leal, Paulo C; Vieira, Tiago O; Rosso, Rober; Nunes, Ricardo J; Yunes, Rosendo A; Creczynski-Pasa, Tânia B; Barardi, Célia R M; Simões, Cláudia M O


    The n-alkyl esters of gallic acid (CAS 13857-8) have a diverse range of uses as antioxidants in food, cosmetics and pharmaceutical industries. Pharmaceutical studies performed with these compounds have found that they have many therapeutic potentialities including anti-cancer, antiviral and antimicrobial properties. However, more interest has been devoted to their antioxidant activity due to the ability to scavenge and reduce reactive oxygen species (ROS) formation. In this study, gallic acid and 14 different alkyl gallates were tested. The cytotoxicity and anti-herpetic (HSV-1, KOS and 29-R strains) activity were studied by using the MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) colorimetric assay and the cell viability by using the Trypan blue dye exclusion method. The genotoxicity was studied by the Comet assay and the antioxidant activity by using the DPPH (1,1-diphenyl-2-picrylhydrazyl) radical scavenging and microsomal lipid peroxidation-inhibiting activities. The results showed that all the tested compounds have anti-herpetic activity at non cytotoxic concentrations with selectivity indices (SI = CC50/EC50) varying from 0.89 to 18.34, depending on the used HSV-1 strain. It was observed that all tested alkyl gallates showed some degree of genotoxicity, at the tested concentrations, except cetyl gallate, at 256.60 micromol/L (p <0.05, t-Student test), probably induced by ROS released by infected cells and/or by the alkyl gallates that were not antioxidants, at the tested concentrations, in which they demonstrated anti-herpetic activity. The hydroxyl groups can induce DNA damage due interactions with some metal ions, which are naturally present in the culture medium supplemented with fetal bovine serum, probably explaining the genotoxicity detected. However, the obtained results showed considerable antioxidant activity at smaller concentrations, when compared to quercetin which is considered as a reference drug due to its already described

  11. Geoscientists and the Radical Middle (United States)

    Tinker, S. W.


    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.

  12. Use of high-performance liquid chromatography to detect hydroxyl and superoxide radicals generated from mitomycin C. (United States)

    Pritsos, C A; Constantinides, P P; Tritton, T R; Heimbrook, D C; Sartorelli, A C


    Distinguishing between short-lived reactive oxygen species like hydroxyl and superoxide radicals is difficult; the most successful approaches employ electron spin resonance (ESR) spin-trapping techniques. Using the spin trap 5,5-dimethyl-l-pyrroline N-oxide (DMPO) to selectively trap various radicals in the presence and absence of ethanol, an HPLC system which is capable of separating the hydroxyl- and superoxide-generated DMPO adduct species has been developed. The radical-generated DMPO adducts were measured with an electrochemical detector attached to the HPLC system and confirmed by spin-trapping techniques. The HPLC separation was carried out on an ODS reverse-phase column with a pH 5.1 buffered 8.5% acetonitrile mobile phase. The advantage of the HPLC system described is that it permits the separation and detection of hydroxyl and superoxide radicals without requiring ESR instrumentation. The antineoplastic bioreductive alkylating agent mitomycin C, when activated by NADPH-cytochrome c reductase, was shown to generate both hydroxyl and superoxide radicals.

  13. The role of structural effects on the reactions of alkoxyl radicals with trialkyl and triaryl phosphites. A time-resolved kinetic study. (United States)

    Bietti, Massimo; Calcagni, Alessandra; Salamone, Michela


    A time-resolved kinetic study on the reactions of alkoxyl radicals with trialkyl and triaryl phosphites ((RO)(3)P: R = Me, Et, i-Pr, t-Bu; (ArO)(3)P: Ar = C(6)H(5), 2,4-(t-Bu)(2)C(6)H(3)) has been carried out. In the (RO)(3)P series, the alkoxyl radicals (cumyloxyl (CumO(*)) and benzyloxyl (BnO(*))) undergo addition to the phosphorus center with formation of intermediate tetraalkoxyphosphoranyl radicals (R'OP(*)(OR)(3): R = Me, Et, i-Pr, t-Bu; R' = Bn, Cum). The addition rate constants are influenced by steric effects, decreasing on going from R = Me to R = t-Bu and from BnO(*) to CumO(*). Rate constants for beta-scission of the phosphoranyl radicals R'OP(*)(OR)(3) have also been determined, increasing, for a given alkyl group R, in the order R' = tert-butyl < R' = benzyl < R' = cumyl and, for a given R' group, on going from R = Me to R = i-Pr. This behavior has been explained in terms of the relative stability of the radicals formed after beta-scission, suggesting moreover that steric effects play in this case a minor role. CumO(*) reacts with triaryl phosphites (ArO)(3)P to give phenoxyl radicals, with rate constants that are influenced to a limited extent by substitution of the aromatic rings. The radical scavenging ability of these substrates is briefly discussed.

  14. The isobutylene-isobutane alkylation process in liquid HF revisited. (United States)

    Esteves, P M; Araújo, C L; Horta, B A C; Alvarez, L J; Zicovich-Wilson, C M; Ramírez-Solís, A


    Details on the mechanism of HF catalyzed isobutylene-isobutane alkylation were investigated. On the basis of available experimental data and high-level quantum chemical calculations, a detailed reaction mechanism is proposed taking into account solvation effects of the medium. On the basis of our computational results, we explain why the density of the liquid media and stirring rates are the most important parameters to achieve maximum yield of alkylate, in agreement with experimental findings. The ab initio Car-Parrinello molecular dynamics calculations show that isobutylene is irreversibly protonated in the liquid HF medium at higher densities, leading to the ion pair formation, which is shown to be a minimum on the potential energy surface after optimization using periodic boundary conditions. The HF medium solvates preferentially the fluoride anion, which is found as solvated [FHF](-) or solvated F(-.)(HF)(3). On the other hand, the tert-butyl cation is weakly solvated, where the closest HF molecules appear at a distance of about 2.9 Angstrom with the fluorine termination of an HF chain.


    Directory of Open Access Journals (Sweden)

    Zeynep Kaya


    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.

  16. Oxidative stress, free radicals and protein peroxides. (United States)

    Gebicki, Janusz M


    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.

  17. Sedentary aging increases resting and exercise-induced intramuscular free radical formation. (United States)

    Bailey, Damian M; McEneny, Jane; Mathieu-Costello, Odile; Henry, Robert R; James, Philip E; McCord, Joe M; Pietri, Sylvia; Young, Ian S; Richardson, Russell S


    Mitochondrial free radical formation has been implicated as a potential mechanism underlying degenerative senescence, although human data are lacking. Therefore, the present study was designed to examine if resting and exercise-induced intramuscular free radical-mediated lipid peroxidation is indeed increased across the spectrum of sedentary aging. Biopsies were obtained from the vastus lateralis in six young (26 + or - 6 yr) and six aged (71 + or - 6 yr) sedentary males at rest and after maximal knee extensor exercise. Aged tissue exhibited greater (P < 0.05 vs. the young group) electron paramagnetic resonance signal intensity of the mitochondrial ubisemiquinone radical both at rest (+138 + or - 62%) and during exercise (+143 + or - 40%), and this was further complemented by a greater increase in alpha-phenyl-tert-butylnitrone adducts identified as a combination of lipid-derived alkoxyl-alkyl radicals (+295 + or - 96% and +298 + or - 120%). Lipid hydroperoxides were also elevated at rest (0.190 + or - 0.169 vs. 0.148 + or - 0.071 nmol/mg total protein) and during exercise (0.567 + or - 0.259 vs. 0.320 + or - 0.263 nmol/mg total protein) despite a more marked depletion of ascorbate and uptake of alpha/beta-carotene, retinol, and lycopene (P < 0.05 vs. the young group). The impact of senescence was especially apparent when oxidative stress biomarkers were expressed relative to the age-related decline in mitochondrial volume density and absolute power output at maximal exercise. In conclusion, these findings confirm that intramuscular free radical-mediated lipid peroxidation is elevated at rest and during acute exercise in aged humans.

  18. Synthesis of alkylated deoxyno irimycin and 1,5-dideoxy-1,5-iminoxylitol analogues:

    DEFF Research Database (Denmark)

    Szczepina, M.G.; Johnston, B.D; Yuan, Y.


    The syntheses of N-alkylated deoxynojirimycin and 1,5-dideoxy-1,5-iminoxylitol derivatives having either a D- or an L-erythritol-3-sulfate functionalized N-substituent are reported. The alkylating agent used was a cyclic sulfate derivative, whereby selective attack of the nitrogen atom at the lea...

  19. Synthesis of 2-substituted tryptophans via a C3- to C2-alkyl migration

    Directory of Open Access Journals (Sweden)

    Michele Mari


    Full Text Available The reaction of 3-substituted indoles with dehydroalanine (Dha derivatives under Lewis acid-mediated conditions has been investigated. The formation of 2-substituted tryptophans is proposed to occur through a selective alkylative dearomatization–cyclization followed by C3- to C2-alkyl migration and rearomatization.

  20. The Retention Behaviors of Benzene and Its Alkyl Homologues in Microemulsion Electrokinetic Chromatography

    Institute of Scientific and Technical Information of China (English)


    The retention behaviors of benzene and its alkyl homologues in microemulsion electrokinetic chromatography were investigated in both anionic and cationic surfactant MEEKC systems. The effects of the composition of microemulsion on retention time and selectivity were studied. A good linear relationship was obtained between log k' and the carbon number of alkyl chain.

  1. Liposomes containing alkylated methotrexate analogues for phospholipase A(2) mediated tumor targeted drug delivery

    DEFF Research Database (Denmark)

    Kaasgaard, Thomas; Andresen, Thomas Lars; Jensen, Simon Skøde;


    to the alpha-carboxylic acid. The cytotoxicity of the gamma-alkylated compound towards KATO III (IC50 = 55 nM) and HT-29 (IC50 = 400 nM) cell lines, Was unaffected by the alkylation, whereas the additional benzyl group on the alpha-carboxyl group made the Compound nontoxic. The gamma-derivative with promising...

  2. A new procedure for N1-alkylation of imidazolidin-4-ones and its NMR characterization (United States)

    Vale, Nuno; Figueiredo, Patrícia


    N1-unsubstituted imidazolidin-4-ones of primaquine (PQ) can be stabilized by N1-alkylation under basic conditions. Here we report the development, with our conditions, of peptidomimetic derivatives of PQ with L-amino acid and alkyl derivatives. The new derivatives represent potential new therapeutics for use against protozoan parasites, through enzymatic protection of aminopeptidases.

  3. Catalytic Alkylation of 2-Methylfuran with Formalin Using Supported Acidic Ionic Liquids

    DEFF Research Database (Denmark)

    Li, Hu; Shunmugavel, Saravanamurugan; Yang, Song;


    Biphasic alkylation of 2-methylfuran (2-MF) with formalin was carried out with a series of SBA-15 supported acidic ionic liquid catalysts (acidic SILCs) under mild reaction conditions. Acidic SILC with sulfonic acid groups (SO3H) and long alkyl chains was observed to have higher catalytic activity...

  4. The asymmetric alkylation of dimethylhydrazones; intermolecular chirality transfer using sparteine as chiral ligand. (United States)

    McSweeney, Christina M; Foley, Vera M; McGlacken, Gerard P


    The asymmetric alkylation of ketones represents a fundamental transformation in organic chemistry. Chiral auxiliaries have been used almost exclusively for this transformation. Herein we describe a strategy for the generation of enantiomerically enriched α-alkylated ketones up to an er of 83 : 17, using a chiral ligand protocol.

  5. Sources and proxy potential of long chain alkyl diols in lacustrine environments.

    NARCIS (Netherlands)

    Rampen, Sebastiaan W.; Datema, Mariska; Rodrigo-Gámiz, M.; Schouten, Stefan; Reichart, Gert-Jan; Sinninghe Damste, Jaap S.


    Long chain 1,13- and 1,15-alkyl diols form the base of a number of recently proposed proxies used for climate reconstruction. However, the sources of these lipids and environmental controls on their distribution are still poorly constrained. We have analyzed the long chain alkyl diol (LCD) compositi

  6. Sources and proxy potential of long chain alkyl diols in lacustrine environments

    NARCIS (Netherlands)

    Rampen, S.; Datema, M.; Rodrigo-Gámiz, M.; Schouten, S.; Reichart, G.-J.; Sinninghe Damsté, J.S.


    Long chain 1,13- and 1,15-alkyl diols form the base of a number of recently proposed proxies used for climate reconstruction. However, the sources of these lipids and environmental controls on their distribution are still poorly constrained. We have analyzed the long chain alkyl diol (LCD) compositi

  7. Effects of alkyl side chains on properties of aliphatic amino acids probed using quantum chemical calculations. (United States)

    Ganesan, Aravindhan; Wang, Feng; Brunger, Michael; Prince, Kevin


    Effects of alkyl side chains (R-) on the electronic structural properties of aliphatic amino acids are investigated using quantum mechanical approaches. The carbon (C 1s) binding energy spectra of the aliphatic amino acids are derived from the C 1s spectrum of glycine (the parent spectrum) by the addition of spectral peaks, depending on the alkyl side chains, appearing in the lower energy region IP aliphatic amino acids owing to perturbations depending on the size and structure of the alkyl chains. The pattern of the N 1s and O 1s spectra in glycine is retained in the spectra of the other amino acids with small shifts to lower energy, again depending on the alkyl side chain. The Hirshfeld charge analyses confirm the observations. The alkyl effects on the valence binding energy spectra of the amino acids are concentrated in the middle valence energy region of 12-16 eV, and hence this energy region of 12-16 eV is considered as the `fingerprint' of the alkyl side chains. Selected valence orbitals, either inside or outside of the alkyl fingerprint region, are presented using both density distributions and orbital momentum distributions, in order to understand the chemical bonding of the amino acids. It is also observed that the HOMO-LUMO energy gaps of the aliphatic amino acids are reduced with the growth of the alkyl side chain.

  8. Glycidol-carbohydrate hybrids: a new family of DNA alkylating agents. (United States)

    Toshima, Kazunobu; Okuno, Yukiko; Matsumura, Shuichi


    Novel and chiral glycidol-carbohydrate hybrids possessing an epoxy group as a DNA alkylating moiety were designed and synthesized. These artificial hybrids selectively alkylated DNA at the N-7 sites of the guanines and cleaved DNA without any additives. The binding ability of the glycidol was significantly enhanced by the attachment of the carbohydrate.

  9. Modification with alkyl chains and the influence on thermal and mechanical properties of aromatic hyperbranched polyesters

    NARCIS (Netherlands)

    Schmaljohann, Dirk; Häußler, Liane; Pötschke, Petra; Voit, Brigitte I.; Loontjens, Ton J.A.


    All-aromatic hyperbranched polyesters with hydroxy endgroups were functionalized with aliphatic n-alkyl carboxylic acids. The length of the n-alkyl chain as well as the degree of modification were varied and the resulting, partially amphiphilic polymers were characterized by differential scanning ca

  10. Vibrational state distribution and relaxation of vinoxy radicals (United States)

    Su, Hongmei; Bersohn, Richard


    The vinoxy radical ṡCH2CHO is a product of the reaction of O(3P) atoms with terminal alkenes and can also be made by photodissociation of an alkyl vinyl ether. In either case it is formed in a vibrationally excited state. The nascent radical displays a rich electronic spectrum to the red of its X→B band origin consisting of bands originating from vibrationally excited states. Some transitions, true "hot bands," terminate on the vibrationless B state; others, sequence bands, terminate on vibrationally excited B states. The spectra become unobservably weak at a certain energy. The difference between that energy and the energy of the band origin is roughly the maximum vibrational energy in the radical. This is 5600 cm-1 for the vinoxy produced by photodissociation of ethyl vinyl ether at 193 nm and 3200 cm-1 for the product of the reaction of O(3P) with ethylene, propene, 1-butene, and 1-pentene. There is a remarkable cooling of the vibrations as the hydrocarbon chain lengthens. The average vibrational energy of the vinoxy product of the reaction O(3P) with ethylene, propene, 1-butene, and 1-pentene is 2100, 1800, 1570, and 1180 cm-1, respectively. This cooling implies that the reaction complex lives long enough for internal vibrational relaxation to occur. The average vibrational energy in the reaction-produced vinoxy is small, which implies that there is considerable kinetic energy. The time dependence of the intensity of the hot bands measures the relaxation rates of different energies, some of which are the energies of a single vibrational state. The ground-state population increases monotonically to an asymptote. The population of most states grows with time and then decays. The growth is due to a cascading from upper states. The populations of the highest energy states decay monotonically; the still higher energy states are almost unpopulated. These results prove that the relaxation proceeds stepwise. The magnitude of the step, ˜200-300 cm-1, can be

  11. 40 CFR 721.10145 - Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino... (United States)


    ... alcohol, halogenated alkane, substituted epoxide, and amino compound (generic). 721.10145 Section 721... Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino compound... identified generically as modified reaction products of alkyl alcohol, halogenated alkane,...

  12. GABA receptor antagonists and insecticides: common structural features of 4-alkyl-1-phenylpyrazoles and 4-alkyl-1-phenyltrioxabicyclooctanes. (United States)

    Sammelson, Robert E; Caboni, Pierluigi; Durkin, Kathleen A; Casida, John E


    Fipronil [5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfinylpyrazole] is one of the most important insecticides. Structure-activity studies described here reveal that fipronil retains its very high binding potency at the human beta3 and house fly gamma-aminobutyric acid (GABA) receptors and toxicity to house flies on replacing the pyrazole trifluoromethylsulfinyl moiety with tert-butyl or isopropyl and the phenyl trifluoromethyl substituent with ethynyl, trifluoromethoxy, bromo or chloro. Among the compounds studied, those with other alkyl groups at the 4-position of the pyrazole, as well as phenyl substitution without one or both of the 2,6-dichloro groups, are less effective. 5-Amino-4-tert-butyl-3-cyano-1-(2,6-dichloro-4-ethynylphenyl)pyrazole is highly effective and almost isosteric with 4-tert-butyl-3-cyano-1-(4-ethynylphenyl)-2,6,7-trioxabicyclo[2.2.2]octane (the most potent 4-alkyl-1-phenyltrioxabicyclooctane) as a noncompetitive GABA antagonist and insecticide. These findings are interpreted as three binding subsites in the GABA receptor: a hydrophobic site undergoing steric interaction with the tert-butyl or equivalent group; a hydrogen bonding site to pyrazole N-2; a pi bonding site to the face of the phenyl moiety; with supplemental enhancement by the 3-cyano and 4-ethynyl substituents.

  13. Sulfated Alkyl Glucopyranans with Potent Antiviral Activity Synthesized by Ring-Opening Copolymerization of Anhydroglucose and Alkyl Anhydroglucose Monomers

    Directory of Open Access Journals (Sweden)

    Shiming Bai


    Full Text Available Sulfated glucopyranans having long alkyl groups were prepared by the ring-opening copolymerization of benzylated 1,6-anhydroglucopyranose with 3-O-octadecyl 1,6-anhydro-β-d-glucopyranose monomers, and subsequent deprotection and sulfation. Water-soluble sulfated glucopyranans with 2.8 and 4.7 mol% of 3-O-octadecyl group and lower molecular weights of M-n = 2.5 × 103–5.1 × 103 have potent anti-HIV activity at 0.05–1.25 μg/mL, even though sulfated polysaccharides with molecular weights below M-n = 6 × 103 had low anti-HIV activity. The interaction with poly-l-lysine as a model compound of proteins was analyzed by SPR, DSL, and zeta potential, indicating that the sulfated 3-O-octadecyl glucopyranans had high association and low dissociation rate constants, and the particle size increased after addition of poly-l-lysine. The anti-HIV activity was induced by electrostatic interaction between sulfate groups and amino groups of poly-l-lysine and by the synergistic effect of the hydrophobic long alkyl chain and hydrophilic sulfated group.

  14. Alkylating ability of carbohydrate oxetanes: Practical synthesis of bolaform skeleton derivative

    Directory of Open Access Journals (Sweden)

    Hadžić Pavle A.


    Full Text Available Alkylating ability of oxetane ring in carbohydrate structure was investigated and flexible method for bolaform amphiplile skeleton construction with xylose as polar heads is proposed. The method is based on oxetane ring opening in easily accessible 3,5-anhydro-1,2-O-cyclohexylidenexylofuranose (1. One step nitrogen alkylation in terminal diamines with 1 gave basic cationic bolaform skeleton with xylose as potential polar heads and deliberately chosen length of non polar spacer. Under similar experimental conditions, but with appropriate molar ratio of alkylating agent, alkylation reaction provide for selective monoalkylation of diamines. Successful alkylation in xanthine series (theophylline was also achieved with 1, giving a new 5-deoxy-5-(7´-theophyllineamino-α-D-xylofuranose derivative.

  15. Alkylation damage in DNA and RNA--repair mechanisms and medical significance

    DEFF Research Database (Denmark)

    Drabløs, Finn; Feyzi, Emadoldin; Aas, Per Arne


    Alkylation lesions in DNA and RNA result from endogenous compounds, environmental agents and alkylating drugs. Simple methylating agents, e.g. methylnitrosourea, tobacco-specific nitrosamines and drugs like temozolomide or streptozotocin, form adducts at N- and O-atoms in DNA bases. These lesions...... are mainly repaired by direct base repair, base excision repair, and to some extent by nucleotide excision repair (NER). The identified carcinogenicity of O(6)-methylguanine (O(6)-meG) is largely caused by its miscoding properties. Mutations from this lesion are prevented by O(6)-alkylG-DNA alkyltransferase......, inactivation of the MMR system in an AGT-defective background causes resistance to the killing effects of O(6)-alkylating agents, but not to the mutagenic effect. Bifunctional alkylating agents, such as chlorambucil or carmustine (BCNU), are commonly used anti-cancer drugs. DNA lesions caused by these agents...

  16. An EPR study of the radical addition to 3-nitropentan-2-one as an archetype of α-carbonylnitroalkanes. (United States)

    Campredon, Mylène; Alberti, Angelo


    Carbon, silicon, germanium, tin and lead-centered radicals were reacted with 3-nitropentan-2-one and 3-nitropentan-2-ol inside the cavity of an electron paramagnetic resonance spectrometer. In all cases, selective addition to the nitrogroup was observed with detection of the corresponding oxynitroxide radicals. In the case of the carbonyl substrate, alkyl acyl nitroxides were also detected because of α-photocleavage. The oxynitroxides decayed with a first order kinetics via fragmentation of the carbon-nitrogen bond (denitration). Unexpectedly, the activation parameters were fairly similar to those previously reported for the corresponding tert-butyl oxynitroxides and almost independent from the presence of a carbonyl or a hydroxyl group on the carbon adjacent to the one bearing the nitrogroup.

  17. Reaction between radicals and N-alkoxyamines As coordinated cleavage with fragmentation (United States)

    Denisov, E. T.; Shestakov, A. F.


    Quantum chemical calculations of the enthalpy and activation energy of two reactions with MeO{2/⊙} attacking the CH- and CH2-groups of 2,2,6,6-tetramethylpiperidineoxy-2'-butane are performed. It is shown that the cleavage of hydrogen atoms is accompanied by coordinated breaking of N-O-bonds in the former case and C-O-bonds in the latter. Based on the obtained results, a new scheme is proposed for the cyclic mechanism behind the cleavage of chains on nitroxyl radicals in oxidizing hydrocarbons and polymers that agrees with experimental data. At the center of this cyclic mechanism lies the fast exothermic reaction between peroxyl radicals and N-alkoxyamine with the cleavage of H atoms and the coordinated fragmentation of molecules. Using the model of intersecting parabolas, an algorithm for calculating the enthalpies, activation energies, and rate constants of these reactions with the participation of alkyl, alkoxy, aminyl, peroxyl, phenoxyl, thiyl, and hydroxyl radicals is proposed.

  18. Unimolecular HO2 Loss from Peroxy Radicals Formed in Autoxidation Is Unlikely under Atmospheric Conditions. (United States)

    Hyttinen, Noora; Knap, Hasse C; Rissanen, Matti P; Jørgensen, Solvejg; Kjaergaard, Henrik G; Kurtén, Theo


    A concerted HO2 loss reaction from a peroxy radical (RO2), formed from the addition of O2 to an alkyl radical, has been proposed as a mechanism to form closed-shell products in the atmospheric oxidation of organic molecules. We investigate this reaction computationally with four progressively oxidized radicals. Potential energy surfaces of the O2 addition and HO2 loss reactions were calculated at ROHF-RCCSD(T)-F12a/VDZ-F12//ωB97xD/aug-cc-pVTZ level of theory and the master equation solver for multienergy well reactions (MESMER) was used to calculate Bartis-Widom phenomenological rate coefficients. The rate coefficients were also compared with the unimolecular rate coefficients of the HO2 loss reaction calculated with transition state theory at atmospheric temperature and pressure. On the basis of our calculations, the unimolecular concerted HO2 loss is unlikely to be a major pathway in the formation of highly oxidized closed-shell molecules in the atmosphere.

  19. Online radicalization: the net or the netizen?

    Directory of Open Access Journals (Sweden)

    Femi Richard Omotoyinbo


    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

  20. Radical polymerization of styrene controlled by half-sandwich Mo(III)/Mo(IV) couples: all basic mechanisms are possible. (United States)

    Le Grognec, E; Claverie, J; Poli, R


    Density functional calculations of bond dissociation energies (BDEs) have been used as a guide to the choice of metal system suitable for controlling styrene polymerization by either the stable free radical polymerization (SFRP) or the atom transfer radical polymerization (ATRP) mechanism. In accord with the theoretical prediction, CpMo(eta(4)-C(4)H(6))(CH(2)SiMe(3))(2), 2, is not capable of yielding SFRP of styrene. Still in accord with theoretical prediction, CpMo(eta(4)-C(4)H(6))Cl(2), 1, CpMo(PMe(3))(2)Cl(2), 3, and CpMo(dppe)Cl(2) (dppe = 1,2-bis(diphenylphosphino)ethane), 4, yield controlled styrene polymerization by the SFRP mechanism in the presence of 2,2'-azobisisobutyronitrile (AIBN). This arises from the generation of a putative Mo(IV) alkyl species from the AIBN-generated radical addition to the Mo(III) compound. The controlled nature of the polymerizations is indicated by linear M(n) progression with the conversion in all cases and moderate polydispersity indices (PDIs). Controlled polymerization of styrene is also given by compounds 3 and 4 in combination with alkyl bromides. These complexes then operate by the ATRP mechanism, again in accord with the theoretical predictions. Controlled character is revealed by linear increase of M(n) versus conversion, low PDIs, a stop-and-go experiment, and (1)H NMR and MALDI-TOF analyses of the polymer end groups. The same controlled polymerization is given by a "reverse" ATRP experiment, starting from AIBN and CpMo(PMe(3))(2)Cl(2)Br, 5. On the other hand, when compound 1 or 2 is used in combination with an alkyl bromide (as for an ATRP experiment), the isolated polystyrene shows by M(n), (1)H NMR, and MALDI-TOF analyses that catalytic chain transfer (CCT) radical polymerization takes place in this case. Kinetics simulations underscore the conditions regulating the radical polymerization mechanism and the living character of the polymerization. The complexes herein described are ineffective at controlling the

  1. Remembering Dutch-Moluccan radicalism

    DEFF Research Database (Denmark)

    Marselis, Randi Lorenz


    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......, as well as in user-generated comments in an online discussion. The television film represented an inclusive memory culture that made room for the difficult memories of all parties involved, including the radicalised, young hijackers. Based on a multidimensional model of mass media reception, the analysis...

  2. Radical conservatism and Danish imperialism

    DEFF Research Database (Denmark)


    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...

  3. Laser spectroscopy of hydrocarbon radicals

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  4. Aromatic-radical oxidation chemistry

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  5. Radical constructivism: Between realism and solipsism (United States)

    Martínez-Delgado, Alberto


    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.

  6. 40 CFR 721.3830 - Formaldehyde, reaction products with an alkylated phenol and an aliphatic amine (generic). (United States)


    ... an alkylated phenol and an aliphatic amine (generic). 721.3830 Section 721.3830 Protection of... products with an alkylated phenol and an aliphatic amine (generic). (a) Chemical substance and significant..., reaction products with an alkylated phenol and an aliphatic amine (PMN P-99-0531) is subject to...

  7. 75 FR 50926 - 2-propenoic acid, 2-methyl-, C12-16-alkyl esters, telomers with 1-dodecanethiol, polyethylene... (United States)


    ... AGENCY 40 CFR Part 180 2-propenoic acid, 2-methyl-, C12-16-alkyl esters, telomers with 1-dodecanethiol... tolerance for residues of 2-propenoic acid, 2-methyl-, C12-16- alkyl esters, telomers with 1-dodecanethiol... residues of 2-propenoic acid, 2-methyl-, C12-16-alkyl esters, telomers with 1-dodecanethiol,...

  8. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl polycarboxylic acids, esters... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols,...

  9. 40 CFR 721.6100 - Phosphoric acid, C6-12-alkyl esters, compounds with 2-(dibutylamino) ethanol. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Phosphoric acid, C6-12-alkyl esters... Significant New Uses for Specific Chemical Substances § 721.6100 Phosphoric acid, C6-12-alkyl esters... reporting. (1) The chemical substances identified as phosphoric acid, C6-12-alkyl esters, compounds with...

  10. Quantitative structure–activity relationships for chronic toxicity of alkyl-chrysenes and alkyl-benz[a]anthracenes to Japanese medaka embryos (Oryzias latipes)

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Hongkang [Department of Biology, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Morandi, Garrett D. [School of Environmental Studies, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Brown, R. Stephen [School of Environmental Studies, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Department of Chemistry, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Snieckus, Victor; Rantanen, Toni [Department of Chemistry, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Jørgensen, Kåre B. [Department of Mathematics and Natural Sciences, University of Stavanger, 4036 Stavanger (Norway); Hodson, Peter V., E-mail: [Department of Biology, Queen' s University, Kingston, Ontario K7L3N6 (Canada); School of Environmental Studies, Queen' s University, Kingston, Ontario K7L3N6 (Canada)


    Highlights: • Medaka embryos were exposed to alkyl chrysenes and benzo[a]anthracenes (BAA). • Concentrations were kept constant by partition controlled delivery. • Chrysene was not toxic within solubility limits, in contrast to BAA. • Alkylation increased the toxicity of chrysene and BAA. • Toxicity was related to hydrophobicity and to specific modes of action. - Abstract: Alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) are a class of compounds found at significant concentrations in crude oils, and likely the main constituents responsible for the chronic toxicity of oil to fish. Alkyl substituents at different locations on the aromatic rings change the size and shape of PAH molecules, which results in different interactions with tissue receptors and different severities of toxicity. The present study is the first to report the toxicity of several alkylated derivatives of chrysene and benz[a]anthracene to the embryos of Japanese medaka (Oryzias latipes) using the partition controlled delivery (PCD) method of exposure. The PCD method maintained the desired exposure concentrations by equilibrium partitioning of hydrophobic test compounds from polydimethylsiloxane (PDMS) films. Test concentrations declined by only 13% over a period of 17 days. Based on the prevalence of signs of blue sac disease (BSD), as expressed by median effective concentrations (EC50s), benz[a]anthracene (B[a]A) was more toxic than chrysene. Alkylation generally increased toxicity, except at position 2 of B[a]A. Alkyl-PAHs substituted in the middle region had a lower EC50 than those substituted at the distal region. Except for B[a]A and 7-methylbenz[a]anthracene (7-MB), estimated EC50 values were higher than their solubility limits, which resulted in limited toxicity within the range of test concentrations. The regression between log EC50s and log K{sub ow} values provided a rough estimation of structure–activity relationships for alkyl-PAHs, but K{sub ow} alone did not provide

  11. Breastfeeding as an Exposure Pathway for Perfluorinated Alkylates

    DEFF Research Database (Denmark)

    Mogensen, Ulla B; Grandjean, Philippe; Nielsen, Flemming


    Perfluorinated alkylate substances (PFASs) are widely used and have resulted in human exposures worldwide. PFASs occur in breast milk, and the duration of breastfeeding is associated with serum-PFAS concentrations in children. To determine the time-dependent impact of this exposure pathway, we...... examined the serum concentrations of five major PFASs in a Faroese birth cohort at birth, and at ages 11, 18, and 60 months. Information about the children's breastfeeding history was obtained from the mothers. The trajectory of serum-PFAS concentrations during months with and without breastfeeding...... increases during partial breast-feeding. In contrast to this main pattern, perfluorohexanesulfonate was not affected by breast-feeding. After cessation of breastfeeding, all serum concentrations decreased. This finding supports the evidence of breastfeeding being an important exposure pathway to some PFASs...

  12. Separation of Scintillation and Cherenkov Lights in Linear Alkyl Benzene

    CERN Document Server

    Li, Mohan; Yeh, Minfang; Wang, Zhe; Chen, Shaomin


    To separate scintillation and Cherenkov lights in water-based liquid scintillator detectors is a desired feature for future neutrino and proton decay researches. Linear alkyl benzene (LAB) is one important ingredient of a water-based liquid scintillator being developed. In this paper we observed a good separation of scintillation and Cherenkov lights in an LAB sample. The rising and decay times of the scintillation light of the LAB were measured to be $(7.7\\pm3.0)\\ \\rm{ns}$ and $(36.6\\pm2.4)\\ \\rm{ns}$, respectively, while the full width [-3$\\sigma$, 3$\\sigma$] of the Cherenkov light was 12 ns dominated by the time resolution of our photomultiplier tubes. The light yield of the scintillation was measured to be $(1.01\\pm0.12)\\times10^3\\ \\rm{photons}/\\rm{MeV}$.

  13. Branched alkyl alcohol propoxylated sulfate surfactants for improved oil recovery

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Y.; Iglauer, S.; Shuler, P.; Tang, Y. [California Institute of Technology, Covina, CA (US). Power, Environmental and Energy Research (PEER) Center; Goddard, W.A. III [California Institute of Technology, Pasadena, CA (United States). Materials and Process Simulation Center


    This investigation considers branched alkyl alcohol propoxylated sulfate surfactants as candidates for chemical enhanced oil recovery (EOR) applications. Results show that these anionic surfactants may be preferred candidates for EOR as they can be effective at creating low interfacial tension (IFT) at dilute concentrations, without requiring an alkaline agent or cosurfactant. In addition, some of the formulations exhibit a low IFT at high salinity, and hence may be suitable for use in more saline reservoirs. Adsorption tests onto kaolinite clay indicate that the loss of these surfactants can be comparable to or greater than other types of anionic surfactants. Surfactant performance was evaluated in oil recovery core flood tests. Selected formulations recovered 35-50% waterflood residual oil even with dilute 0.2 wt% surfactant concentrations from Berea sandstone cores. (orig.)

  14. Monolayer structures of alkyl aldehydes: Odd-membered homologues

    Energy Technology Data Exchange (ETDEWEB)

    Phillips, T.K. [BP Institute, Department of Chemistry, University of Cambridge, Cambridge (United Kingdom); Clarke, S.M., E-mail: [BP Institute, Department of Chemistry, University of Cambridge, Cambridge (United Kingdom); Bhinde, T. [BP Institute, Department of Chemistry, University of Cambridge, Cambridge (United Kingdom); Castro, M.A.; Millan, C. [Instituto Ciencia de los Materiales de Sevilla, Departamento de Quimica Inorganica (CSIC-Universidad de Sevilla) (Spain); Medina, S. [Centro de Investigacion, Tecnologia e Innovacion de la Universidad de Sevilla (CITIUS), Sevilla (Spain)


    Crystalline monolayers of three aldehydes with an odd number of carbon atoms in the alkyl chain (C{sub 7}, C{sub 9} and C{sub 11}) at low coverages are observed by a combination of X-ray and neutron diffraction. Analysis of the diffraction data is discussed and possible monolayer crystal structures are proposed; although unique structures could not be ascertained for all molecules. We conclude that the structures are flat on the surface, with the molecules lying in the plane of the layer. The C{sub 11} homologue is determined to have a plane group of either p2, pgb or pgg, and for the C{sub 7} homologue the p2 plane group is preferred.

  15. Enhanced performance of alkylated graphene reinforced polybutylene succinate nanocomposite (United States)

    Abidin, A. S. Zainal; Yusoh, K.; Jamari, S. S.; Abdullah, A. H.; Ismail, Z.


    Polybutylene succinate (PBS) was being grafted with octadecylamine-functionalized graphene oxide (GO-ODA) to produce novel PBS/GO-ODA nanocomposites by solution blending technique. Alkylated graphene oxide has superhydrophobic surface thus improved the affinity of the filler with low polar polymer such as PBS. The structure and compatibility of the filler and nanocomposites were being characterized using Fourier transform infrared spectroscopy (FTIR), Universal tensile machine (UTM) and thermogravimetric analysis (TGA). Enhancement of tensile strength and Young's modulus by 30% and 165% respectively was achieved with cooperation of 0.5% GO-ODA loading. The functionalization of GO-ODA in PBS matrix leads to the improvement in the nanocomposites properties.

  16. Molecular and Electronic Structure of n-Alkyl Cyanobiphenyl Nematogens

    Energy Technology Data Exchange (ETDEWEB)

    Risser, Steven M.(TEXAS A and M UNIVERSITY); Ferris, Kim F.(BATTELLE (PACIFIC NW LAB))


    First principle electronic structure calculations (ab-initio and density functional) were performed on a series of substituted cyanobiphenyls to examine the structural and electronic properties as a function of the alkyl tail length and changes in torsion angle about the central bond connecting the rings. We find good agreement between our results and previous electronic structure studies for the optimized torsion angle between phenyls in the cyanobiphenyls, and changes in dipole moment for the cyanobiphenyls. We also find the torsion angle and rotational barriers in cyanobiphenyls to be similar to that in simple biphenyl. However, we find large discrepancies with the recent density functional calculations that reported a much smaller torsion angle in the syanobiphenyls.

  17. Fridel-Crafts alkylation of iodine catalyed by ultrasound assisted

    Directory of Open Access Journals (Sweden)

    Manoel G. de Oliveira


    Full Text Available Triarymethanes (TRAMs are used as antitubercular agents, antitumor or antiviral.1 Was weighed 2 mmol of (1a, 1 mmol of (2a, 10 mol% of I2 in 5 mL of CH2Cl2, the reaction was brought to ultrasound bath (SONIC MODEL LS-4, 7D of 44 kH and 150 W (Scheme 1.The product was purified on silica gel-60, eluting mixture 8:2 of (Hexano:Ethyl acetate. Under these conditions 65% of the product (3a was obtained. The compound was characterized by third m.p. 161ºC (161-162ºC.1 The Fridel-Crafts alkylation catalyzed by I2 bath ultrasound occurs at short reaction time requiring less energy expenditure compared to the method of agitation. It is intended to increase the study of various aromatic compounds (1, different aldehydes (2 and vary the use of solvents.

  18. EPR spin trapping of protein radicals

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan; Hawkins, Clare Louise


    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...... tumbling radicals are often broad and relatively poor in distinctive features, a number of techniques have been developed that allow a wealth of information to be obtained about the nature, site, and reactions of such radicals. This article summarizes recent developments in this area and reviews selected...

  19. Radical Reactions and Its Synthetic Application

    Institute of Scientific and Technical Information of China (English)

    Takeaki Naito


    @@ 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.

  20. Measurements of NMHCs, Halocarbons, and Light Alkyl Nitrates During TOPSE (United States)

    Blake, N. J.; Blake, D. R.; Sive, B. C.; Sive, B. C.; Katzenstein, A. S.; Meinardi, S.; Wingenter, O. W.; Wingenter, O. W.; Ridley, B. A.


    Nonmethane hydrocarbons (NMHCs), halocarbons, and alkyl nitrates were measured in nearly 2500 whole air samples collected aboard the National Center for Atmospheric Research (NCAR) C-130 aircraft as part of the Tropospheric Ozone Production about the Spring Equinox (TOPSE) campaign. Thirty-eight flights were made during seven deployments at mid- to high-latitudes over Arctic North America flying from Boulder, Colorado (40° N) as far north as 85° N. The deployments were flown over a four-month period from early February to mid-May. The TOPSE campaign was designed to observe the chemical and dynamical evolution of tropospheric chemical composition at northern mid-latitudes, and to investigate the significance of volatile organic carbon (VOC) species to the spring-time ozone maximum. For the region to the north of 50° N, total C2-C9 NMHC mixing ratios gradually decreased from their wintertime maximum of nearly 10 ppbC to about 4 ppbC in May at a rate of approximately 1.7 ppbC/month. By comparison, ozone increased by about 15 ppbv over the same period ( ~4.4 ppb/month). The rate of decay of the speciated NMHCs was dependent on their individual OH lifetimes. Total light (C1-C4) alkyl nitrates decreased from about 25 pptv to about 10 pptv and represented approximately10% or less of NOY. The strong latitude gradients, with highest levels north of 50° N were associated with the earliest deployments. By May, the latitudinal NMHC gradients had all but disappeared. Similarly, negative NMHC gradients with altitude were strongest early in the campaign. We identified several interesting episodes of long-range transport of both polluted and clean marine air masses into the sampling region, in addition to regions of very low NMHC levels associated with boundary layer ozone depletion events.

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

    Directory of Open Access Journals (Sweden)

    Bahir ahmad


    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.

  2. Serendipitous Findings While Researching Oxygen Free Radicals


    Floyd, Robert A.


    This review is based on the honor of receiving the Discovery Award from the Society of Free Radical Biology and Medicine. The review is reflective and presents our thinking which led to experiments that yielded novel observations. Critical questioning of our understanding of oxygen free radicals in biomedical problems led us to use and develop more direct and extremely sensitive methods. This included nitrone free radical spin-trapping and HPLC-electrochemical detection. This technology led t...

  3. Bioinspired terpene synthesis: a radical approach. (United States)

    Justicia, José; Álvarez de Cienfuegos, Luis; Campaña, Araceli G; Miguel, Delia; Jakoby, Verena; Gansäuer, Andreas; Cuerva, Juan M


    This tutorial review highlights the development of radical-based bioinspired synthesis of terpenes from the initial proposal to the development of modern catalytic methods for performing such processes. The power of the radical approach is demonstrated by the straightforward syntheses of many natural products from readily available starting materials. The efficiency of these processes nicely complements the described cationic polyolefin cyclisations and even suggests that modern radical methods provide means to improve upon nature's synthetic pathways.

  4. Superspecial radical%超特殊根

    Institute of Scientific and Technical Information of China (English)



    定义了超特殊根,即由无零因子的绝对半素环类所确定的上根,并证明了它是一个特殊根。%The superspecial radical is defined, it is the upper radical, determined by the rings class consisted without divisors of zero and absolutely semiprings. And it is a special radical.

  5. Neurotoxins: Free Radical Mechanisms and Melatonin Protection



    Toxins that pass through the blood-brain barrier put neurons and glia in peril. The damage inflicted is usually a consequence of the ability of these toxic agents to induce free radical generation within cells but especially at the level of the mitochondria. The elevated production of oxygen and nitrogen-based radicals and related non-radical products leads to the oxidation of essential macromolecules including lipids, proteins and DNA. The resultant damage is referred to as oxidative and nit...

  6. Radical-free biology of oxidative stress



    Free radical-induced macromolecular damage has been studied extensively as a mechanism of oxidative stress, but large-scale intervention trials with free radical scavenging antioxidant supplements show little benefit in humans. The present review summarizes data supporting a complementary hypothesis for oxidative stress in disease that can occur without free radicals. This hypothesis, which is termed the “redox hypothesis,” is that oxidative stress occurs as a consequence of disruption of thi...

  7. Photodynamically generated bovine serum albumin radicals

    DEFF Research Database (Denmark)

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


    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...... of proteases. The generation of protein-derived radicals also results in an enhancement of photobleaching of the porphyrin, suggesting that protein radical generation is linked to porphyrin photooxidation....

  8. Synthesis and characterization of functional copolymer/organo-silicate nanoarchitectures through interlamellar complex-radical (coterpolymerization

    Directory of Open Access Journals (Sweden)


    Full Text Available The functional copolymers, having a combination of rigid/flexible linkages and an ability of complex-formation with interlayered surface of organo-silicate, and their nanocomposites have been synthesized by interlamellar complex-radical (coterpolymerization of intercalated monomer complexes of maleic anhydride (MA and itaconic acid (IA with dimethyl dodecylamine surface modified montmorillonite (organo-MMT (MA…DMDA-MMT and IA…DMDA-MMT n-butyl methacrylate (BMA and/or BMA/styrene monomer mixtures. The results of nanocomposite structure–composition– property relationship studies indicate that interlamellar complex-formation between anhydride/acid units and surface alkyl amine and rigid/flexible linkage balance in polymer chains are important factors providing the effective intercalation/ exfoliation of the polymer chains into the silicate galleries, the formation of nanostructural hybrids with higher thermal stability, dynamic mechanical behaviour and well dispersed morphology.

  9. Formation of free radicals during phacoemulsification. (United States)

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


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

  10. Near-Ring Radicals and Class Pairs

    Institute of Scientific and Technical Information of China (English)

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


    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.

  11. Aag DNA glycosylase promotes alkylation-induced tissue damage mediated by Parp1.

    Directory of Open Access Journals (Sweden)

    Jennifer A Calvo


    Full Text Available Alkylating agents comprise a major class of front-line cancer chemotherapeutic compounds, and while these agents effectively kill tumor cells, they also damage healthy tissues. Although base excision repair (BER is essential in repairing DNA alkylation damage, under certain conditions, initiation of BER can be detrimental. Here we illustrate that the alkyladenine DNA glycosylase (AAG mediates alkylation-induced tissue damage and whole-animal lethality following exposure to alkylating agents. Aag-dependent tissue damage, as observed in cerebellar granule cells, splenocytes, thymocytes, bone marrow cells, pancreatic β-cells, and retinal photoreceptor cells, was detected in wild-type mice, exacerbated in Aag transgenic mice, and completely suppressed in Aag⁻/⁻ mice. Additional genetic experiments dissected the effects of modulating both BER and Parp1 on alkylation sensitivity in mice and determined that Aag acts upstream of Parp1 in alkylation-induced tissue damage; in fact, cytotoxicity in WT and Aag transgenic mice was abrogated in the absence of Parp1. These results provide in vivo evidence that Aag-initiated BER may play a critical role in determining the side-effects of alkylating agent chemotherapies and that Parp1 plays a crucial role in Aag-mediated tissue damage.

  12. Kinetic study of the anaerobic biodegradation of alkyl polyglucosides and the influence of their structural parameters. (United States)

    Ríos, Francisco; Fernández-Arteaga, Alejandro; Lechuga, Manuela; Jurado, Encarnación; Fernández-Serrano, Mercedes


    This paper reports a study of the anaerobic biodegradation of non-ionic surfactants alkyl polyglucosides applying the method by measurement of the biogas production in digested sludge. Three alkyl polyglucosides with different length alkyl chain and degree of polymerization of the glucose units were tested. The influence of their structural parameters was evaluated, and the characteristics parameters of the anaerobic biodegradation were determined. Results show that alkyl polyglucosides, at the standard initial concentration of 100 mgC L(-1), are not completely biodegradable in anaerobic conditions because they inhibit the biogas production. The alkyl polyglucoside having the shortest alkyl chain showed the fastest biodegradability and reached the higher percentage of final mineralization. The anaerobic process was well adjusted to a pseudo first-order equation using the carbon produced as gas during the test; also, kinetics parameters and a global rate constant for all the involved metabolic process were determined. This modeling is helpful to evaluate the biodegradation or the persistence of alkyl polyglucosides under anaerobic conditions in the environment and in the wastewater treatment.

  13. a First-Principles Model of Fermi Resonance in the Alkyl CH Stretch Region: Application to Hydronaphthalenes, Indanes, and Cyclohexane (United States)

    Sibert, Edwin; Kidwell, Nathanael; Zwier, Timothy S.


    The infrared (IR) spectroscopy of the alkyl CH stretch region (2750-3000 cm-1) of a series of bicyclic hydrocarbons and free radicals has been studied under supersonic expansion cooling in the gas phase, and compared with a theoretical model that describes the local mode stretch-bend Fermi resonance interactions. The double resonance method of fluorescence-dip infrared (FDIR) spectroscopy was used on the stable molecules 1,2-dihydronaphthalene, 1,4-dihydronaphthalene, tetralin, indene, and indane using the S_0-S_1 origin transition as a monitor of transitions. Resonant ion-dip infrared (RIDIR) spectra were recorded for the trihydronaphthyl (THN) and inden-2-yl methyl (I2M) radicals. The previously developed model Hamiltonian [J. Chem. Phys. 138 064308 (2013)] incorporates cubic stretch-bend coupling with parameters obtained from density functional theory methods. Full dimensional calculations are compared to reduced dimensional Hamiltonian results in which anharmonic CH streches and CH_2 scissor modes are Fermi coupled. Excellent agreement between theoretical results is found. Scale factors of select terms in the reduced dimensional Hamiltonian, obtained by fitting the theoretical Hamiltonian predictions to the experimental spectra, are found to be similar to previous work. The resulting Hamiltonian predicts successfully all the major spectral features considered in this study. A simplified model is introduced in which the CH_2 groups are decoupled. This model enables the assignment of many of the spectral features. The model results are extended to describe the CH stretch spectrum of the chair and twist-boat conformers of cyclohexane. The chair conformer is used to illustrate the shortcomings of the CH_2 coupling model.

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

    Institute of Scientific and Technical Information of China (English)


    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.

  15. Separation and identification of DMPO adducts of oxygen-centered radicals formed from organic hydroperoxides by HPLC-ESR, ESI-MS and MS/MS. (United States)

    Guo, Qiong; Qian, Steven Y; Mason, Ronald P


    Many electron spin resonance (ESR) spectra of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) radical adducts from the reaction of organic hydroperoxides with heme proteins or Fe(2+) were assigned to the adducts of DMPO with peroxyl, alkoxyl, and alkyl radicals. In particular, the controversial assignment of DMPO/peroxyl radical adducts was based on the close similarity of their ESR spectra to that of the DMPO/superoxide radical adduct in conjunction with their insensitivity to superoxide dismutase, which distinguishes the peroxyl adducts from the DMPO/superoxide adduct. Although recent reports assigned the spectra suggested to be DMPO/peroxyl radical adducts to the DMPO/methoxyl adduct based on independent synthesis of the adduct and/or (17)O-labeling, (17)O-labeling is extremely expensive, and both of these assignments were still based on hyperfine coupling constants, which have not been confirmed by independent techniques. In this study, we have used online high performance liquid chromatography (HPLC or LC)/ESR, electrospray ionization-mass spectrometry (ESI-MS) and tandem mass spectrometry (MS/MS) to separate and directly characterize DMPO oxygen-centered radical adducts formed from the reaction of Fe(2+) with t-butyl or cumene hydroperoxide. In each reaction system, two DMPO oxygen-centered radical adducts were separated and detected by online LC/ESR. The first DMPO radical adduct from both systems showed identical chromatographic retention times (t(R) = 9.6 min) and hyperfine coupling constants (a(N) = 14.51 G, a(H)(beta) = 10.71 G, and a(H)(gamma) = 1.32 G). The ESI-MS and MS/MS spectra demonstrated that this radical was the DMPO/methoxyl radical adduct, not the peroxyl radical adduct as was thought at one time, although its ESR spectrum is nearly identical to that of the DMPO/superoxide radical adduct. Similarly, based on their MS/MS spectra, we verified that the second adducts (a(N) = 14.86 G and a(H)(beta) = 16.06 G in the reaction system containing t

  16. Students' Ideas and Radical Constructivism (United States)

    Sánchez Gómez, Pedro J.


    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.

  17. Iron and iron derived radicals

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  18. Photoionisation of the tropyl radical

    Directory of Open Access Journals (Sweden)

    Kathrin H. Fischer


    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.

  19. Alkyl propoxy ethoxylate "graded" surfactants: micelle formation and structure in aqueous solutions. (United States)

    Sarkar, Biswajit; Alexandridis, Paschalis


    The self-assembly of alkyl propoxy ethoxylate surfactants in aqueous solutions has been investigated with a focus on the (i) thermodynamics of micellization (critical micellization concentration; free energy, enthalpy, and entropy of micellization) and (ii) structure of the micelles (overall shape and size; local environment in the micelle core and corona) as affected by the surfactant composition (variation of degree of ethoxylation). The various results are compared to those for alkyl ethoxylate and poly(ethylene oxide)-b-poly(propylene oxide) amphiphiles with the aim to elucidate the role of the middle, propoxy, block in the novel alkyl propoxy ethoxylate surfactants which exhibit a "graded" hydrophobic-hydrophilic character.

  20. Quantitative Structure—Activity Relationships in the Lithium and Sodium Affinities of n—Alkyl Fluorides

    Institute of Scientific and Technical Information of China (English)

    KeChunZHANG; JianMiaoFAN; 等


    B3L YP/6-31+g(d,p)method was used to calculate the lithium and sodium affinities of n-alkyl fluoride. These affinities were found to obey the Holmes relationship, i.e.they correlate linearly with the quotient n/(n+1), where n is the number of carbon atoms in the alkyl chain. From the correlation the limiting values of lithium and sodium affinities for very long alkyl chain were predicted to be-153.3kJ/mol and -108.4kJ/mol,respectively.

  1. Enzymatic production of alkyl esters through alcoholysis: A critical evaluation of lipases and alcohols

    DEFF Research Database (Denmark)

    Li, Deng; Xu, Xuebing; Gudmundur G, Haraldsson


    This paper focuses on a detailed evaluation of commercially available immobilized lipases and simple monohydric alcohols for the production of alkyl esters from sunflower oil by enzymatic alcoholysis. Six lipases were tested with seven alcohols, including straight and branched-chain primary...... yield of FA alkyl esters, with yields well over 90% for methanol, absolute ethanol, and 1-propanol. Overall, 96% ethanol was the preferred alcohol for all lipases except Novozym 435, and ethanolysis reactions reached the maximal conversion efficiency. Increasing the water content in the system resulted...... commercial immobilized lipases are highly efficient and promising for the production of alkyl esters, offering high reaction yields and a simple operation process....

  2. Quantitative Structure-Activity Relationships in the Lithium and Sodium Affinities of n-Alkyl Fluorides

    Institute of Scientific and Technical Information of China (English)


    B3LYP/6-31+g (d, p) method was used to calculate the lithium and sodium affinities of n-alkyl fluoride. These affinities were found to obey the Holmes relationship, i.e. they correlate linearly with the quotient n/(n+1), where n is the number of carbon atoms in the alkyl chain. From the correlation the limiting values of lithium and sodium affinities for very long alkyl chain were predicted to be -153.3 kJ/mol and -108.4 kJ/mol, respectively.

  3. A mild and efficient procedure for the synthesis of ethers from various alkyl halides

    Directory of Open Access Journals (Sweden)

    Mosstafa Kazemi


    Full Text Available A simple, mild and practical procedure has been developed for the synthesis of symmetrical and unsymmetrical ethers by using DMSO, TBAI in the presence of K2CO3. We extended the utility of Potassium carbonate as an efficient base for the preparation of ethers. A wide range of alkyl aryl and dialkyl ethers are synthezied from treatment of aliphatic alcohols and phenols with various alkyl halides in the prescence of efficient base Potassium carbonate. Secondary alkyl halides were easily converted to corresponding ethers in releatively good yields . This is a mild, simple and practical procedure for the preparation of ethers in high yields and suitable times under mild condition.

  4. Ultrasonic Relaxation Study of 1-Alkyl-3-methylimidazolium-Based Room-Temperature Ionic Liquids: Probing the Role of Alkyl Chain Length in the Cation. (United States)

    Zorębski, Michał; Zorębski, Edward; Dzida, Marzena; Skowronek, Justyna; Jężak, Sylwia; Goodrich, Peter; Jacquemin, Johan


    Ultrasound absorption spectra of four 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides were determined as a function of the alkyl chain length on the cation from 1-propyl to 1-hexyl from 293.15 to 323.15 K at ambient pressure. Herein, the ultrasound absorption measurements were carried out using a standard pulse technique within a frequency range from 10 to 300 MHz. Additionally, the speed of sound, density, and viscosity have been measured. The presence of strong dissipative processes during the ultrasound wave propagation was found experimentally, i.e., relaxation processes in the megahertz range were observed for all compounds over the whole temperature range. The relaxation spectra (both relaxation amplitude and relaxation frequency) were shown to be dependent on the alkyl side chain length of the 1-alkyl-3-methylimidazolium ring. In most cases, a single-Debye model described the absorption spectra very well. However, a comparison of the determined spectra with the spectra of a few other imidazolium-based ionic liquids reported in the literature (in part recalculated in this work) shows that the complexity of the spectra increases rapidly with the elongation of the alkyl chain length on the cation. This complexity indicates that both the volume viscosity and the shear viscosity are involved in relaxation processes even in relatively low frequency ranges. As a consequence, the sound velocity dispersion is present at relatively low megahertz frequencies.

  5. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations. (United States)

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim A


    Alkylations of chiral or achiral Ni(II) complexes of glycine Schiff bases constitute a landmark in the development of practical methodology for asymmetric synthesis of α-amino acids. Straightforward, easy preparation as well as high reactivity of these Ni(II) complexes render them ready available and inexpensive glycine equivalents for preparing a wide variety of α-amino acids, in particular on a relatively large scale. In the case of Ni(II) complexes containing benzylproline moiety as a chiral auxiliary, their alkylation proceeds with high thermodynamically controlled diastereoselectivity. Similar type of Ni(II) complexes derived from alanine can also be used for alkylation providing convenient access to quaternary, α,α-disubstituted α-amino acids. Achiral type of Ni(II) complexes can be prepared from picolinic acid or via recently developed modular approach using simple secondary or primary amines. These Ni(II) complexes can be easily mono/bis-alkylated under homogeneous or phase-transfer catalysis conditions. Origin of diastereo-/enantioselectivity in the alkylations reactions, aspects of practicality, generality and limitations of this methodology is critically discussed.

  6. Synthesis and anti-TMV activity of novel N-(3-alkyl-1H-pyrazol-4-yl)-3-alkyl-4-substituted- 1H-pyrazole-5-carboxamides

    Institute of Scientific and Technical Information of China (English)

    Da Qiang Zhang; Gao Fei Xu; Zhi Jin Fan; Dao Quan Wang; Xin Ling Yang; De Kai Yuan


    In oraer to investigate the biological activity of novel bis-pyrazole compounds,a series of N-(3-alkyl-5-(N-methylcarbamyl)-1H-pyrazol-4-yl)-3-alkyl-4-substituted-1H-pyrazole-5-carboxamides were designed and synthesized with ethyl 3-alkyl-1H-pyrazole-5-carboxylate 1 as starting materials.N-Methyl-3-alkyl-4-amino-1H-pyrazole-5-carboxamides 6 were obtained from 1 via 5 steps.3-Alkyl-4-substitued-1H-pyrazole-5-carboxyl chlorides 4a,4b,11a,11b,11c or 12 were also obtained from 1 via several steps.Target compounds 7a-7g were obtained after the reaction of 6 with the above 1H-pyrazole-5-carboxyl chlorides.Preliminary bioassay showed some compounds possessing good inactivation effect against TMV (tobacco mosaic virus).Compound 7a showed higher activity superior to ningnanmycin at a concentration of 5.0 × 10-4 g/mL and equal acdvity at 1.0 × 10-4 g/nL; 7b and 7c showed equal activity to virazole both at concentrations of 5.0 × 10-4 g/mL and 1.0 × 10-4 g/mL.

  7. Current approaches to improve the anticancer chemotherapy with alkylating agents: state of the problem in world and Ukraine.

    Directory of Open Access Journals (Sweden)

    Iatsyshyna A. P.


    Full Text Available Alkylating agents are frequently used in many established anticancer chemotherapies. They alkylate the genomic DNA at various sites. Alkylation of the guanine at the O6-position is cytotoxic, it has the strongest mutagenic potential, as well as can cause the tumor development. Alkyl groups at the O6-position of guanine are removed by the DNA repair enzyme O6-methylguanine-DNA methyltransferase (MGMT. The effectiveness of alkylating chemotherapy is limited by MGMT in cancer cells and adverse toxic side effects in normal cells. Different approaches consisting in the modulation of the MGMT expression and activity are under development now to improve the cancer chemotherapy. They include two main directions, in particular, the increase in chemosensitivity of cancer cells to alkylating drugs and the protection of normal cells from the toxic side effects of chemotherapy. This review is focused on current attempts to improve the alkylating chemotherapy of malignant tumours worldwide and state of the issue in Ukraine

  8. Hydroxyl radical reaction with trans-resveratrol: initial carbon radical adduct formation followed by rearrangement to phenoxyl radical. (United States)

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


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

  9. Radical Behaviorism and Buddhism: Complementarities and Conflicts (United States)

    Diller, James W.; Lattal, Kennon A.


    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…

  10. 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.


    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

  11. Moment matrices, border bases and radical computation

    NARCIS (Netherlands)

    Mourrain, B.; Lasserre, J.B.; Laurent, M.; Rostalski, P.; Trebuchet, P.


    In this paper, we describe new methods to compute the radical (resp. real radical) of an ideal, assuming it complex (resp. real) variety is nte. The aim is to combine approaches for solving a system of polynomial equations with dual methods which involve moment matrices and semi-denite programming.

  12. Moment matrices, border bases and radical computation

    NARCIS (Netherlands)

    Mourrain, B.; Lasserre, J.B.; Laurent, M.; Rostalski, P.; Trebuchet, P.


    In this paper, we describe new methods to compute the radical (resp. real radical) of an ideal, assuming it complex (resp. real) variety is nte. The aim is to combine approaches for solving a system of polynomial equations with dual methods which involve moment matrices and semi-denite programming.

  13. Organic chemistry: A radical step forward (United States)

    Zhang, Wenhao; Li, Ang


    Free radicals are notorious for unselective coupling reactions; however, the coupling of free radicals generated from acyl tellurides has now been shown to form C-C bonds with remarkable fidelity, which enables easy one-step assembly of densely oxygenated natural product motifs.

  14. Radical-Local Teaching and Learning

    DEFF Research Database (Denmark)

    Hedegaard, Mariane; Chaiklin, Seth

    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...

  15. Victimology: A Consideration of the Radical Critique. (United States)

    Friedrichs, David O.


    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)

  16. Localization versus delocalization in diamine radical cations

    DEFF Research Database (Denmark)

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


    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...

  17. Free Radical Mechanisms in Autoxidation Processes. (United States)

    Simic, Michael G.


    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)

  18. Place of Schauta's radical vaginal hysterectomy. (United States)

    Roy, Michel; Plante, Marie


    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.

  19. Alkyl chain length dependence of the field-effect mobility in novel anthracene derivatives. (United States)

    Back, Jang Yeol; An, Tae Kyu; Cheon, Ye Rim; Cha, Hyojung; Jang, Jaeyoung; Kim, Yebyeol; Baek, Yonghwa; Chung, Dae Sung; Kwon, Soon-Ki; Park, Chan Eon; Kim, Yun-Hi


    We report six asymmetric alkylated anthracene-based molecules with different alkyl side chain lengths for use in organic field-effect transistors (OFETs). Alkyl side chains can potentially improve the solubility and processability of anthracene derivatives. The crystallinity and charge mobility of the anthracene derivatives may be improved by optimizing the side chain length. The highest field-effect mobility of the devices prepared here was 0.55 cm(2)/(V s), for 2-(p-pentylphenylethynyl)anthracene (PPEA). The moderate side chain length appeared to be optimal for promoting self-organization among asymmetric anthracene derivatives in OFETs, and was certainly better than the short or long alkyl side chain lengths, as confirmed by X-ray diffraction measurements.

  20. Metal salts of alkyl catechol dithiophosphoric acids and oil compositions containing the salts

    Energy Technology Data Exchange (ETDEWEB)

    Yamaguchi, E.S.; Liston, T.V.


    Metal salts of alkyl catechol esters of dithiophosphoric acid suitable as additives in oil compositions are disclosed in this patent. Oil compositions containing the salts of such esters show improved extreme pressure/anti-wear and anit-oxidant properties.

  1. Deprotonation of C-alkyl groups of cationic N-heterocyclic ligands. (United States)

    Cabeza, Javier A; García-Álvarez, Pablo; Pérez-Carreño, Enrique; Pruneda, Vanessa


    The C-alkyl groups of C-alkylpyrazinium-derived ligands have been selectively deprotonated by K[N(SiMe(3))(2)], through charge-controlled processes, to give neutral products that contain C-alkylidenepyrazine-derived ligands.

  2. Photochemical alkylation of inorganic selenium in the presence of low molecular weight organic acids. (United States)

    Guo, Xuming; Sturgeon, Ralph E; Mester, Zoltán; Gardner, Graeme J


    Using a flow-through photochemical reactor and a low pressure mercury lamp as a UV source, alkyl selenium species are formed from inorganic selenium(IV) in the presence of low molecular weight organic acids (LMW acids). The volatile alkyl Se species were cryogenically trapped and identified by GC-MS and GC-ICP-MS. In the presence of formic, acetic, propionic and malonic acids, inorganic selenium(IV) is converted by UV irradiation to volatile selenium hydride and carbonyl, dimethylselenide and diethylselenide, respectively. Se(IV) was successfully removed from contaminated agricultural drainage waters (California, U.S.A.) using a batch photoreactor system Se. Photochemical alkylation may thus offer a promising means of converting toxic selenium salts, present in contaminated water, to less toxic dimethylselenide. The LMW acids and photochemical alkylation process may also be key to understanding the source of atmospheric selenium and are likely involved in its mobility in the natural anaerobic environment.


    Multispectral techniques (gas chromatography combined with low and high resolution electron-impact mass spectrometry, low and high resolution chemical ionization mass spectrometry, and Fourier transform infrared mass spectroscopy) were used to identify 13 alkyl and chloralkyl pho...

  4. Electrochemical and thermal grafting of alkyl grignard reagents onto (100) silicon surfaces. (United States)

    Vegunta, Sri Sai S; Ngunjiri, Johnpeter N; Flake, John C


    Passivation of (100) silicon surfaces using alkyl Grignard reagents is explored via electrochemical and thermal grafting methods. The electrochemical behavior of silicon in methyl or ethyl Grignard reagents in tetrahydrofuran is investigated using cyclic voltammetry. Surface morphology and chemistry are investigated using atomic force microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS). Results show that electrochemical pathways provide an efficient and more uniform passivation method relative to thermal methods, and XPS results demonstrate that electrografted terminations are effective at limiting native oxide formation for more than 55 days in ambient conditions. A two-electron per silicon mechanism is proposed for electrografting a single (1:1) alkyl group per (100) silicon atom. The mechanism includes oxidation of two Grignard species and subsequent hydrogen abstraction and alkylation reaction resulting in a covalent attachment of alkyl groups with silicon.

  5. A General Two-Step Procedure for the N-Alkylation of Selenoamides

    Institute of Scientific and Technical Information of China (English)

    ZHAO,Hua-Rong(赵华绒); YU,Qing-Sen(俞庆森)


    Selenoamides are prepared via N-alkylated in a two-step procedure: Benzotriazole, aldehyde and primary selenoamide reacted together to yield an adduct which was then reduced to the N-substituted selenoamide by NaBH4.

  6. Alkyl chain length impacts the antioxidative effect of lipophilized ferulic acid in fish oil enriched milk

    DEFF Research Database (Denmark)

    Sørensen, Ann-Dorit Moltke; Lyneborg, Karina Sieron; Villeneuve, Pierre


    Lipophilization of phenolics by esterification with fatty alcohols may alter their localization in an emulsion and thereby their antioxidant efficacy. In this study, synthesized unbranched alkyl ferulates were evaluated as antioxidants in fish oil enriched milk. Lipid oxidation was determined...

  7. Transesterified tyrosol and hydroxytyrosol alkyl esters from cuphea oil – antioxidant behavior in Liposomes (United States)

    Tyrosol and hydroxytyrosol are the antioxidant molecules abundantly found in olive oil. Transesterification of tyrosol and hydroxytyrosol with cuphea oil results in medium chain alkyl esters with antioxidant properties. Membrane partitioning, antioxidant capacity, and membrane location of these nove...

  8. A one-pot synthesis of functionalized azadienes from 2-hydroxypyridine, activated acetylenes and alkyl isocyanides

    Directory of Open Access Journals (Sweden)

    Elnaz Ghasemi


    Full Text Available A one-pot synthesis of dialkyl 2-[(alkylimino(2-oxopyridin-1(2H-ylmethyl]but-2-enedioate from alkyl isocyanides, dialkyl acetylenedicarboxylates, and 2-hydroxypyridine, in good yields, is described.

  9. A one-pot synthesis of functionalized azadienes from 2-hydroxypyridine, activated acetylenes and alkyl isocyanides


    Elnaz Ghasemi; Issa Yavar


    A one-pot synthesis of dialkyl 2-[(alkylimino)(2-oxopyridin-1(2H)-yl)methyl]but-2-enedioate from alkyl isocyanides, dialkyl acetylenedicarboxylates, and 2-hydroxypyridine, in good yields, is described.

  10. Pilot study of radical hysterectomy versus radical trachelectomy on sexual distress. (United States)

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


    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.

  11. Characterization of two alkyl hydroperoxide reductase C homologs alkyl hydroperoxide reductase C_H1 and alkyl hydroperoxide reductase C_H2 in Bacillus subtilis

    Institute of Scientific and Technical Information of China (English)

    Mee-Kyung; Cha; Yoo-Jeen; Bae; Kyu-Jeong; Kim; Byung-Joon; Park; Il-Han; Kim


    AIM: To identify alkyl hydroperoxide reductase subunit C(AhpC) homologs in Bacillus subtilis(B. subtilis) and to characterize their structural and biochemical properties. AhpC is responsible for the detoxification of reactive oxygen species in bacteria.METHODS: Two AhpC homologs(AhpC_H1 and AhpC_H2) were identified by searching the B. subtilis database; these were then cloned and expressed in Escherichia coli. AhpC mutants carrying substitutions of catalytically important Cys residues(C37S, C47 S, C166 S, C37/47 S, C37/166 S, C47/166 S, and C37/47/166 S for AhpC_H1; C52 S, C169 S, and C52/169 S for AhpC_H2) were obtained by site-directed mutagenesis and purified, and their structure-function relationship was analyzed. The B. subtilis ahp C genes were disrupted by the short flanking homology method, and the phenotypes of the resulting AhpC-deficient bacteria were examined.RESULTS: Comparative characterization of AhpC homologs indicates that AhpC_H1 contains an extra C37, which forms a disulfide bond with the peroxidatic C47, and behaves like an atypical 2-Cys AhpC, while AhpC_H2 functions like a typical 2-Cys AhpC. Tryptic digestion analysis demonstrated the presence of intramolecular Cys37-Cys47 linkage, which could be reduced by thioredoxin, resulting in the association of the dimer into higher-molecular-mass complexes. Peroxidase activity analysis of Cys→Ser mutants indicated that three Cys residues were involved in the catalysis. AhpC_H1 was resistant to inactivation by peroxide substrates, but had lower activity at physiological H2O2 concentrations compared to AhpC_H2, suggesting that in B. subtilis, the enzymes may be physiologically functional at different substrate concentrations. The exposure to organic peroxides induced AhpC_H1 expression, while AhpC_H1-deficient mutants exhibited growth retardation in the stationary phase, suggesting the role of AhpC_H1 as an antioxidant scavenger of lipid hydroperoxides and a stress-response factor in B. subtilis

  12. Lubricating oil compositions containing overbased calcium sulfonates and metal salts of alkyl catechol dithiophosphoric acid

    Energy Technology Data Exchange (ETDEWEB)

    Yamaguchi, E.S.; Cerrito, E.; Liston, T.V.


    This patent describes a lubricating oil composition containing an overbased calcium hydrocarbyl sulfonate. The improvement wherein the lubricating oil composition additionally comprises an effective amount to reduce wear of a metal salt of an alkyl catechol dithiophosphoric acid ester of the formula: wherein R is alkyl containing 10 to 18 carbon atoms, or mixtures thereof, M is an alkali or alkaline earth metal or transition metal and n corresponds to the valence of the metal M.

  13. Alkylating ability of carbohydrate oxetanes: Practical synthesis of bolaform skeleton derivative



    Alkylating ability of oxetane ring in carbohydrate structure was investigated and flexible method for bolaform amphiplile skeleton construction with xylose as polar heads is proposed. The method is based on oxetane ring opening in easily accessible 3,5-anhydro-1,2-O-cyclohexylidenexylofuranose (1). One step nitrogen alkylation in terminal diamines with 1 gave basic cationic bolaform skeleton with xylose as potential polar heads and deliberately chosen lengt...

  14. Tilting and Tumbling in Transmembrane Anion Carriers: Activity Tuning through n‐Alkyl Substitution


    Edwards, Sophie J.; Marques, Igor; Dias, Christopher M.; Tromans, Robert A.; Lees, Nicholas R; Félix, Vítor; Valkenier, Hennie; Davis, Anthony P


    Abstract Anion transport by synthetic carriers (anionophores) holds promise for medical applications, especially the treatment of cystic fibrosis. Among the factors which determine carrier activity, the size and disposition of alkyl groups is proving remarkably important. Herein we describe a series of dithioureidodecalin anionophores, in which alkyl substituents on one face are varied from C0 to C10 in two‐carbon steps. Activities increase then decrease as the chain length grows, peaking qui...

  15. Alkyl polyglycoside/1-naphthol formulations. A case study of surfactant enhanced oil recovery

    Energy Technology Data Exchange (ETDEWEB)

    Iglauer, Stefan; Wu, Yongfu; Shuler, Patrick; Tang, Yongchun [California Institute of Technology, Covina, CA (United States). Div. of Chemistry and Chemical Engineering; Goddard, William A. III [California Institute of Technology, Pasadena, CA (United States). Div. of Chemistry and Chemical Engineering


    We present a case study of surfactant enhanced oil recovery using Alkyl polyglucoside/1-naphthol formulations. Alkyl polyglucosides are a green, non-toxic and renewable surfactant class synthesized out of agricultural raw materials. We measured interfacial tensions versus n-octane and viscosities of these formulations and conducted one coreflood enhanced oil recovery (EOR) experiment where we recovered 82.6 % of initial oil in place demonstrating that these formulations are efficient EOR agents. (orig.)

  16. Research on the Sizing Performance of Starch Grafted Poly-hydroxy Alkyl-acid Esters

    Institute of Scientific and Technical Information of China (English)

    GUO La-mei; GUO Liang-hong


    Starch grafted poly-hydroxy alkyl-acid esters were prepared via graft polymerization. Different characteristics of grafted starches were tested such as viscosity, viscosity stability, adhesion as well as properties of sized yams. Sizing performance was analyzed from the aspect of physical and chemical reactions between polymer molecules. It shows that starch grafted poly-hydroxy alkyl-acid esters have excellent sizing performance and could absolutely be used as sizes for polyester-cotton yarns.

  17. Nickel-catalyzed cross-electrophile coupling of 2-chloropyridines with alkyl bromides. (United States)

    Everson, Daniel A; Buonomo, Joseph A; Weix, Daniel J


    The synthesis of 2-alkylated pyridines by the nickel-catalyzed cross-coupling of two different electrophiles, 2-chloropyridines with alkyl bromides, is described. Compared to our previously published conditions for aryl halides, this method uses the different, more rigid bathophenanthroline ligand and is conducted at high concentration in DMF solvent. The method displays promising functional group compatibility and the conditions are orthogonal to the Stille coupling.

  18. Asymmetric Intramolecular Alkylation of Chiral Aromatic Imines via Catalytic C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Watzke, Anja; Wilson, Rebecca; O' Malley, Steven; Bergman, Robert; Ellman, Jonathan


    The asymmetric intramolecular alkylation of chiral aromatic aldimines, in which differentially substituted alkenes are tethered meta to the imine, was investigated. High enantioselectivities were obtained for imines prepared from aminoindane derivatives, which function as directing groups for the rhodium-catalyzed C-H bond activation. Initial demonstration of catalytic asymmetric intramolecular alkylation also was achieved by employing a sterically hindered achiral imine substrate and catalytic amounts of a chiral amine.

  19. Dependence of micelle size and shape on detergent alkyl chain length and head group.

    Directory of Open Access Journals (Sweden)

    Ryan C Oliver

    Full Text Available Micelle-forming detergents provide an amphipathic environment that can mimic lipid bilayers and are important tools for solubilizing membrane proteins for functional and structural investigations in vitro. However, the formation of a soluble protein-detergent complex (PDC currently relies on empirical screening of detergents, and a stable and functional PDC is often not obtained. To provide a foundation for systematic comparisons between the properties of the detergent micelle and the resulting PDC, a comprehensive set of detergents commonly used for membrane protein studies are systematically investigated. Using small-angle X-ray scattering (SAXS, micelle shapes and sizes are determined for phosphocholines with 10, 12, and 14 alkyl carbons, glucosides with 8, 9, and 10 alkyl carbons, maltosides with 8, 10, and 12 alkyl carbons, and lysophosphatidyl glycerols with 14 and 16 alkyl carbons. The SAXS profiles are well described by two-component ellipsoid models, with an electron rich outer shell corresponding to the detergent head groups and a less electron dense hydrophobic core composed of the alkyl chains. The minor axis of the elliptical micelle core from these models is constrained by the length of the alkyl chain, and increases by 1.2-1.5 Å per carbon addition to the alkyl chain. The major elliptical axis also increases with chain length; however, the ellipticity remains approximately constant for each detergent series. In addition, the aggregation number of these detergents increases by ∼16 monomers per micelle for each alkyl carbon added. The data provide a comprehensive view of the determinants of micelle shape and size and provide a baseline for correlating micelle properties with protein-detergent interactions.

  20. Activated-sludge nitrification in the presence of linear and branched-chain alkyl benzene sulfonates. (United States)

    Baillod, C R; Boyle, W C


    The effects of biodegradable linear alkyl benzene sulfonate and branched-chain alkyl benzene sulfonate detergents on activated-sludge nitrification were investigated by administering a synthetic waste containing up to 23 mg of each detergent per liter to eight bench-scale, batch, activated-sludge units. It was found that both detergents tended to promote complete oxidation of ammonia to nitrate, whereas control units produced approximately equal amounts of nitrite and nitrate. Various hypotheses are offered to explain the phenomenon.

  1. The formation of [M-H]+ ions in N-alkyl-substituted thieno[3,4-c]-pyrrole-4,6-dione derivatives during atmospheric pressure photoionization mass spectrometry

    KAUST Repository

    Sioud, Salim


    RESULTS [M-H]+ ions were observed under APPI conditions. The type of dopant and the length of the alkyl chain affected the formation of these ions. MS/MS fragmentation of [M-H]+ and [M + H]+ ions exhibited completely different patterns. Theoretical calculations revealed that the loss of hydrogen molecules from the [M + H]+ ions is the most favourable condition under which to form [M-H]+ ions.CONCLUSIONS [M-H]+ ions were detected in all the TPD derivatives studied here under the special experimental conditions during APPI, using a halogenated benzene dopant, and TPD containing substituted N-alkyl side chains with a minimum of four carbon atoms. Density functional theory calculations showed that for [M-H]+ ions to be formed under these conditions, the loss of hydrogen molecules from the [M + H]+ ions is proposed to be necessary.RATIONALE The formation of ions during atmospheric pressure photoionization (APPI) mass spectrometry in the positive mode usually provides radical cations and/or protonated species. Intriguingly, during the analysis of some N-alkyl-substituted thieno[3,4-c]pyrrole-4,6-dione (TPD) derivatives synthesized in our laboratory, unusual [M-H]+ ion peaks were observed. In this work we investigate the formation of [M-H]+ ions observed under APPI conditions.METHODS Multiple experimental parameters, including the type of ionization source, the composition of the solvent, the type of dopant, the infusion flow rate, and the length of the alkyl side chain were investigated to determine their effects on the formation of [M-H]+ ions. In addition, a comparison study of the gas-phase tandem mass spectrometric (MS/MS) fragmentation of [M + H]+ vs [M-H]+ ions and computational approaches were used.

  2. Role of clay as catalyst in Friedel–Craft alkylation

    Indian Academy of Sciences (India)

    Tanushree Choudhury; Nirendra M Misra


    Solid acids have become increasingly important for many liquid-phase industrial reactions these days. Montmorillonite clays (2:1 clay mineral) have been used as efficient solid acid catalysts for a number of organic and liquid phase reactions and offer several advantages over classic acids. Tailor made catalysts can be prepared from clays by suitably adjusting their acidity and surface area by acid activation. In the present work, preparation, characterization and performance of Pt (II) clays, Cu (II) clays, acid clay, and sol–gel hybrids of Cu (II) clays as solid catalysts in a test Friedel–Craft alkylation reaction of benzyl chloride with toluene using differential scanning calorimeter (DSC) are reported. Product formation has been analysed by FTIR spectroscopy. The main objective of this work is to show how clay as a solid catalyst affects reaction rates and activation energies. Acidity and dispersion of solid catalysts are twomain factors which govern a catalysis reaction. Kinetic parameter analysis and XRD studies confirm that acid Pt (II) clay and Pt (II) clay dispersed by natural dispersants aremore effective catalysts. In contrast to the reactions using AlCl3, the experimental conditions are non-polluting and the final work up does not require any aqueous treatment.

  3. Alkyl CH Stretch Vibrations as a Probe of Conformational Preferences (United States)

    Sibert, Edwin L. Sibert, Iii; Buchanan, Evan G.; Zwier, Timothy S.


    Theoretical IR spectra of 1,2-diphenoxyethane (C_6H_5-O-CH_2-CH_2-O-C_6H_5 DPOE) and 1,2-diphenylethane (C_6H_5-CH_2-CH_2-C_6H_5 DPE) are presented and compared to results of single-conformation spectroscopy of jet cooled molecules. The theoretical transition energies and intensites are obtained from a model based on a local mode Hamiltonian that includes all local cubic stretch-bend couplings that are then projected onto the normal modes. The model parameters are obtained from density functional theory methods. Full dimensional calculations are compared to those of reduced dimensions that include anharmonic CH streches Fermi coupled to scissor modes. Excellent agreement is found. Scale factors of select terms in the reduced dimensional Hamiltonian are determined by fitting the theoretical Hamiltonian to the anti DPE spectrum. Using the same scaling, Hamiltonians for other conformers of the above molecules are generated and used to predict structures by comparing to experimentally determined spectra in the alkyl CH stretch region. The level patterns in the resulting spectra are elucidated in terms of the model parameters. The model results are extended to interpret the spectra of more complicated macrocycles containing multiple -CH_2CH_2- ethano bridges such as the dibenzo-15-crown-5 ether and 2,2,2-paracyclophane.

  4. Fatty acid alkyl esters: perspectives for production of alternative biofuels. (United States)

    Röttig, Annika; Wenning, Leonie; Bröker, Daniel; Steinbüchel, Alexander


    The global economy heads for a severe energy crisis: whereas the energy demand is going to rise, easily accessible sources of crude oil are expected to be depleted in only 10-20 years. Since a serious decline of oil supply and an associated collapse of the economy might be reality very soon, alternative energies and also biofuels that replace fossil fuels must be established. In addition, these alternatives should not further impair the environment and climate. About 90% of the biofuel market is currently captured by bioethanol and biodiesel. Biodiesel is composed of fatty acid alkyl esters (FAAE) and can be synthesized by chemical, enzymatic, or in vivo catalysis mainly from renewable resources. Biodiesel is already established as it is compatible with the existing fuel infrastructure, non-toxic, and has superior combustion characteristics than fossil diesel; and in 2008, the global production was 12.2 million tons. The biotechnological production of FAAE from low cost and abundant feedstocks like biomass will enable an appreciable substitution of petroleum diesel. To overcome high costs for immobilized enzymes, the in vivo synthesis of FAAE using bacteria represents a promising approach. This article points to the potential of different FAAE as alternative biofuels, e.g., by comparing their fuel properties. In addition to conventional production processes, this review presents natural and genetically engineered biological systems capable of in vivo FAAE synthesis.

  5. Regioselective synthesis of C3 alkylated and arylated benzothiophenes (United States)

    Shrives, Harry J.; Fernández-Salas, José A.; Hedtke, Christin; Pulis, Alexander P.; Procter, David J.


    Benzothiophenes are heterocyclic constituents of important molecules relevant to society, including those with the potential to meet modern medical challenges. The construction of molecules would be vastly more efficient if carbon-hydrogen bonds, found in all organic molecules, can be directly converted into carbon-carbon bonds. In the case of elaborating benzothiophenes, functionalization of carbon-hydrogen bonds at carbon-number 3 (C3) is markedly more demanding than at C2 due to issues of regioselectivity (C3 versus C2), and the requirement of high temperatures, precious metals and the installation of superfluous directing groups. Herein, we demonstrate that synthetically unexplored but readily accessible benzothiophene S-oxides serve as novel precursors for C3-functionalized benzothiophenes. Employing an interrupted Pummerer reaction to capture and then deliver phenol and silane coupling partners, we have discovered a directing group-free method that delivers C3-arylated and -alkylated benzothiophenes with complete regioselectivity, under metal-free and mild conditions.

  6. Electrophilic Metal Alkyl Chemistry in New Ligand Environments

    Energy Technology Data Exchange (ETDEWEB)

    Jordan, Richard F. [University of Chicago


    The goals of this project were to design new electrophilic metal alkyl complexes and to exploit these systems in fundamental studies of olefin polymerization and other important and new catalytic reactions. A key target reaction is insertion copolymerization of olefins and polar CH2=CHX vinyl monomers such as vinyl halides and vinyl ethers. During the period covered by this report we (i) investigated the properties of ortho-alkoxy-arylphosphine ligands in Ni-based olefin polymerization catalysts, (ii) studied the synthesis of double-end-capped polyethylene using group 4 metal catalysts that contain tris-pyrazolylborate ligands, (iii) explored the ethylene insertion reactivity of group 4 metal tris-pyrazolyl-borate complexes, (iv) showed that (α-diimine)PdMe{sup +} species undergo multiple insertion of silyl vinyl ethers, (v) synthesized and explored the reactivity of base-free Ni benzyl complexes that contain ortho-phosphino-arene sulfonate ligands, (vi) established the mechanism of the reaction of vinyl chloride with (α-diimine)PdMe{sup +} catalysts, (vii) explored the role of cationic polymerization and insertion chemistry in the reactions of vinyl ethers with (α-diimine)PdMe{sup +} species, (viii) discovered a new class of self-assembled tetranuclear Pd catalysts that produce high molecular weight linear polyethylene and copolymerize ethylene and vinyl fluoride, and (ix) developed model systems that enabled investigation of cis-trans isomerization of {phosphine-sulfonate}Pd(II) complexes.

  7. Bifunctional alkyl nitrates - trace constituents of the atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Kastler, J. [Department of Analytical and Environmental Chemistry, University of Ulm (Germany); Ballschmiter, K. [Center of Technology Assessment in Baden-Wuerttemberg, Stuttgart (Germany)


    Mono- and multifunctional esters of nitric acid (alkyl nitrates or organonitrates) form very complex mixtures of organic trace constituents in air. An analytical method was developed which combines selectivity in separation and detection in order to simplify this complexity in analytical terms. Mononitrates, dinitrates, keto nitrates, hydroxy nitrates of alkanes and alkenes, respecitvely, and bifunctional terpene nitrates were synthesized as reference substances. A specially developed new HPLC stationary phase (organonitrate phase) allows a group separation of mono-, di-, and hydroxy nitrates. After the HPLC preseparation the single components were finally separated by capillary HRGC-ECD and HRGC-MSD on polar and non-polar stationary phases. Mass spectrometric detection in the selected-ion-mode using the highly selective NO{sub 2}{sup +} fragment (m/z = 46 amu) led to very good selectivities for the nitric acid ester moiety. The analysis of a 100 m{sup 3} ambient air sample using this new analytical protocol allowed the identification of seven hydroxy nitrates and 24 dinitrates ranging from C2 to C7, 22 of them for the first time ever. (orig.) With 3 figs., 3 tabs., 20 refs.

  8. Synthesis and Antiangiogenic Activity of N-Alkylated Levamisole Derivatives (United States)

    Sylvest, Lene; Friis, Tina; Staerk, Dan; Jørgensen, Flemming Steen; Olsen, Christian A.; Houen, Gunnar


    Inhibition of angiogenesis is a promising addition to current cancer treatment strategies. Neutralization of vascular endothelial growth factor by monoclonal antibodies is clinically effective but may cause side effects due to thrombosis. Low molecular weight angiogenesis inhibitors are currently less effective than antibody treatment and are also associated with serious side effects. The discovery of new chemotypes with efficient antiangiogenic activity is therefore of pertinent interest. (S)-Levamisole hydrochloride, an anthelminthic drug approved for human use and with a known clinical profile, was recently shown to be an inhibitor of angiogenesis in vitro and exhibited tumor growth inhibition in mice. Here we describe the synthesis and in vitro evaluation of a series of N-alkylated analogues of levamisole with the aim of characterizing structure–activity relationships with regard to inhibition of angiogenesis. N-Methyllevamisole and p-bromolevamisole proved more effective than the parent compound, (S)-levamisole hydrochloride, with respect to inhibition of angiogenesis and induction of undifferentiated cluster morphology in human umbilical vein endothelial cells grown in co-culture with normal human dermal fibroblasts. Interestingly, the cluster morphology caused by N-methyllevamisole was different than the clusters observed for levamisole, and a third “cord-like” morphology resembling that of the known drug suramin was observed for an aniline-containing derivative. New chemotypes exhibiting antiangiogenic effects in vitro are thus described, and further investigation of their underlying mechanism of action is warranted. PMID:23024819

  9. Synthesis and antiangiogenic activity of N-alkylated levamisole derivatives.

    Directory of Open Access Journals (Sweden)

    Anders N Hansen

    Full Text Available Inhibition of angiogenesis is a promising addition to current cancer treatment strategies. Neutralization of vascular endothelial growth factor by monoclonal antibodies is clinically effective but may cause side effects due to thrombosis. Low molecular weight angiogenesis inhibitors are currently less effective than antibody treatment and are also associated with serious side effects. The discovery of new chemotypes with efficient antiangiogenic activity is therefore of pertinent interest. (S-levamisole hydrochloride, an anthelminthic drug approved for human use and with a known clinical profile, was recently shown to be an inhibitor of angiogenesis in vitro and exhibited tumor growth inhibition in mice. Here we describe the synthesis and in vitro evaluation of a series of N-alkylated analogues of levamisole with the aim of characterizing structure-activity relationships with regard to inhibition of angiogenesis. N-methyllevamisole and p-bromolevamisole proved more effective than the parent compound, (S-levamisole hydrochloride, with respect to inhibition of angiogenesis and induction of undifferentiated cluster morphology in human umbilical vein endothelial cells grown in co-culture with normal human dermal fibroblasts. Interestingly, the cluster morphology caused by N-methyllevamisole was different than the clusters observed for levamisole, and a third "cord-like" morphology resembling that of the known drug suramin was observed for an aniline-containing derivative. New chemotypes exhibiting antiangiogenic effects in vitro are thus described, and further investigation of their underlying mechanism of action is warranted.

  10. Glassy crystalline state and water sorption of alkyl maltosides. (United States)

    Kocherbitov, Vitaly; Söderman, Olle


    A differential scanning calorimetric and sorption calorimetric study of two alkyl maltosides, C8G2 and C10G2, was performed. In the dry state, C8G2 and C10G2 do not form solid crystals but undergo a glass transition upon temperature change. The glass is partly ordered and has the same lamellar structure as the liquid crystals formed by the two maltosides. To reflect the presence of the glass transition and the structure, the terms "glassy crystals" and "glassy liquid crystals" can be used. A mechanism of the relaxation of the glassy crystals based on the results of small-angle X-ray scattering experiments is proposed. Experiments on water sorption showed that the glassy crystals turn into lyotropic liquid crystals upon sorption of water at constant temperature. This isothermal glass transition can be characterized by water content and change of partial molar enthalpy of mixing of water. A method to calculate the phase diagram liquid crystals-glassy liquid crystals is proposed.

  11. Middle-phase microemulsions of green surfactant alkyl polyglucosides

    Institute of Scientific and Technical Information of China (English)

    CHAI; Jinling; (柴金岭); LI; Ganzuo; (李干佐); ZHANG; Gaoyong; (张高勇); LOU; Anjing; ZHANG; Jian; (张剑); ZHANG; Yue; (张越)


    The microemulsion behavior in the quaternary system alkyl polyglucoside (C8G1.46 , C10G1.54)/1-butanol/cyclohexane/water has been studied at 40℃ with the alcohol concentration scanning and the fishlike phase diagram methods. Increasing δat a constant γ causes a phase inversion from an oil-in-water microemulsion in contact with excess oil (Winsor I or 2 ) to a water-in-oil microemulsion in contact with excess water (Winsor Ⅲ or ) via a middle-phase microemulsionin contact with excess oil and water (Winsor Ⅲ or 3). By using the simple mass balance equation and the HLB plane equation, the mass fraction of 1-butanol in the interfacial layer, S s2, the monomeric solubilities of APG and 1-butanol, S1 and S2, in the oil phase, and the mass fractions of APG and 1-butanol in the interfacial layer (C1 and C2 ) have been calculated, respectively. The effects of different alcohols, aqueous media and oils on the phase behavior and the composition of the interfacial layer are also investigated. It is found that the alcohols with longer hydrocarbon chain, oil molecules with smaller molecular volume and the addition of inorganic salt can increase the solubilization of the microemulsions .

  12. Polymer-hybridized liposomes anchored with alkyl grafted poly(asparagine). (United States)

    Park, Sung-Il; Lee, Eun-Ok; Kim, Jin Woong; Kim, Youn Joon; Han, Sang Hoon; Kim, Jong-Duk


    Polymer-hybridized liposomes (PHLs) of saturated lecithin were formed by association of poly(asparagines) grafted with alkyl chains (PAsn-g-Cn). The thermal, physical, and surface properties of the polymer-hybridized liposomes were examined with varying polymer concentration, alkyl chain length (C(8), C(12), C(18), C(22)), and degree of substitution (DS) in the polymer. The inclusion of the polymer raised the membrane fluidity of liposomes. By the incorporation of small amount of polymer, the membrane rigidity of liposomes dropped sharply and then increased close to the original level as the polymer concentrations increased in the cases of PAsn-g-C(18) and PAsn-g-C(22). Also, the membrane rigidity and stability of PHLs increased with alkyl chain length at the same polymer concentration. The surface charge of PHL associated with PAsn-g-C(22) was changed by DS of alkyl chains. The polymer bearing long alkyl chains (C(12), C(18), C(22)) formed PHLs well at low polymer concentration and the number of disk-shaped polymer-lipid mixed micelles increased with polymer concentration. The anchored polymers induced shifts in gel-to-liquid crystal transition temperature (Tc) of the vesicles and Tc varied with polymer concentration, alkyl chain length, and DS of the polymer.

  13. Physico-chemical properties and toxicity of alkylated polycyclic aromatic hydrocarbons. (United States)

    Kang, Hyun-Joong; Lee, So-Young; Kwon, Jung-Hwan


    Crude oil and refined petroleum products contain many polycyclic and heterocyclic aromatic hydrocarbons, in particular, alkylated PAHs. Although alkylated PAHs are found in significantly higher quantities than their corresponding unsubstituted PAHs, the most studies on the physico-chemical properties and toxicities of these compounds have been conducted on unsubstituted PAHs. In this study, we measured crucial physico-chemical properties (i.e., water solubility, partition coefficients between polydimethylsiloxane and water (KPDMSw), and partition coefficient between liposomes and water (Klipw)) of selected alkylated PAHs, and evaluated their toxicity using the luminescence inhibition of Aliivibrio fischeri and growth inhibition of Raphidocelis subcapitata. In general, the logarithms of these properties for alkylated PAHs showed good linear correlations with log Kow, as did those for unsubstituted PAHs. Changes in molecular symmetry on the introduction of alkyl groups on aromatic ring structure significantly altered water solubility. The inhibition of bacterial luminescence and algal growth by alkylated PAHs can be explained well by the baseline toxicity hypothesis, and good linear relationships between log Kow or log Klipw and log (1/EC50) were found.


    Directory of Open Access Journals (Sweden)

    I. V. Chernyshev


    Full Text Available Background. Radical prostatectomy (RPE is today the gold standard treatment option for locally advanced prostate cancer (PC. These operations are performed both openly and using video-assisted endosurgery. Since 2009, the Research Institute of Urology has been made 70 extraperitoneoscopic RPEs (ERPE.Objective: to assess the complications of ERPE with the validated Clavien complication scale.Materials and methods. The authors retrospectively analyzed the case histories of 70 patients with locally advanced PC who had undergone ERPE. The complications were allocated to 3 groups: intraoperative, early (within 1 month and late (over 1 month postoperative ones. All found complications were stratified using Clavien classification scale.Results. The total number of ERPE complications accounted for 35.7%. The most common complications, such as anastomotic incompetence and blood loss that required hemotransfusion, were 9.8 and 11.3%, respectively. Rectal damage was intraoperatively found in 2 cases. Obturator nerve damage was also recognized intraoperatively and did not result in the occurrence of neurological symptoms. The severest complication (Clavien scale grade V was pulmonary embolism causing death.Conclusion. Postoperative complications of ERPE were observed in a small percentage of the patients and posed no serious threat to their life. The analysis of the complications of ERPE suggests that this treatment for locally advanced PC is a current safe and low-traumatic method.


    Directory of Open Access Journals (Sweden)

    I. V. Chernyshev


    Full Text Available Background. Radical prostatectomy (RPE is today the gold standard treatment option for locally advanced prostate cancer (PC. These operations are performed both openly and using video-assisted endosurgery. Since 2009, the Research Institute of Urology has been made 70 extraperitoneoscopic RPEs (ERPE.Objective: to assess the complications of ERPE with the validated Clavien complication scale.Materials and methods. The authors retrospectively analyzed the case histories of 70 patients with locally advanced PC who had undergone ERPE. The complications were allocated to 3 groups: intraoperative, early (within 1 month and late (over 1 month postoperative ones. All found complications were stratified using Clavien classification scale.Results. The total number of ERPE complications accounted for 35.7%. The most common complications, such as anastomotic incompetence and blood loss that required hemotransfusion, were 9.8 and 11.3%, respectively. Rectal damage was intraoperatively found in 2 cases. Obturator nerve damage was also recognized intraoperatively and did not result in the occurrence of neurological symptoms. The severest complication (Clavien scale grade V was pulmonary embolism causing death.Conclusion. Postoperative complications of ERPE were observed in a small percentage of the patients and posed no serious threat to their life. The analysis of the complications of ERPE suggests that this treatment for locally advanced PC is a current safe and low-traumatic method.

  16. Involvement of free radicals in breast cancer. (United States)

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


    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. However, both reactive species may contribute to improve the outcomes of radiotherapy in cancer patients. Besides, high levels of reactive oxygen species may be indicators of genotoxic damage in non-irradiated normal tissues. The purpose of this article is to review recent research on free radicals and carcinogenesis in order to understand the pathways that contribute to tumor malignancy. This review outlines the involvement of free radicals in relevant cellular events, including their effects on genetic instability through (growth factors and tumor suppressor genes, their enhancement of mitogenic signals, and their participation in cell remodeling, proliferation, senescence, apoptosis, and autophagy processes; the possible relationship between free radicals and inflammation is also explored. This knowledge is crucial for evaluating the relevance of free radicals as therapeutic targets in cancer.

  17. Engineering a horseradish peroxidase C stable to radical attacks by mutating multiple radical coupling sites. (United States)

    Kim, Su Jin; Joo, Jeong Chan; Song, Bong Keun; Yoo, Young Je; Kim, Yong Hwan


    Peroxidases have great potential as industrial biocatalysts. In particular, the oxidative polymerization of phenolic compounds catalyzed by peroxidases has been extensively examined because of the advantage of this method over other conventional chemical methods. However, the industrial application of peroxidases is often limited because of their rapid inactivation by phenoxyl radicals during oxidative polymerization. In this work, we report a novel protein engineering approach to improve the radical stability of horseradish peroxidase isozyme C (HRPC). Phenylalanine residues that are vulnerable to modification by the phenoxyl radicals were identified using mass spectrometry analysis. UV-Vis and CD spectra showed that radical coupling did not change the secondary structure or the active site of HRPC. Four phenylalanine (Phe) residues (F68, F142, F143, and F179) were each mutated to alanine residues to generate single mutants to examine the role of these sites in radical coupling. Despite marginal improvement of radical stability, each single mutant still exhibited rapid radical inactivation. To further reduce inactivation by radical coupling, the four substitution mutations were combined in F68A/F142A/F143A/F179A. This mutant demonstrated dramatic enhancement of radical stability by retaining 41% of its initial activity compared to the wild-type, which was completely inactivated. Structure and sequence alignment revealed that radical-vulnerable Phe residues of HPRC are conserved in homologous peroxidases, which showed the same rapid inactivation tendency as HRPC. Based on our site-directed mutagenesis and biochemical characterization, we have shown that engineering radical-vulnerable residues to eliminate multiple radical coupling can be a good strategy to improve the stability of peroxidases against radical attack.

  18. Radical pancreaticoduodenectomy for benign disease.

    LENUS (Irish Health Repository)

    Kavanagh, D O


    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

  19. Effect of the alkyl chain length on the rotational dynamics of nonpolar and dipolar solutes in a series of N-alkyl-N-methylmorpholinium ionic liquids. (United States)

    Khara, Dinesh Chandra; Kumar, Jaini Praveen; Mondal, Navendu; Samanta, Anunay


    Rotational dynamics of two dipolar solutes, 4-aminophthalimide (AP) and 6-propionyl-2-dimethylaminonaphthalene (PRODAN), and a nonpolar solute, anthracene, have been studied in N-alkyl-N-methylmorpholinium (alkyl = ethyl, butyl, hexyl, and octyl) bis(trifluoromethansulfonyl)imide (Tf2N) ionic liquids as a function of temperature and excitation wavelength to probe the microheterogeneous nature of these ionic liquids, which are recently reported to be more structured than the imidazolium ionic liquids (Khara and Samanta, J. Phys. Chem. B2012, 116, 13430-13438). Analysis of the measured rotational time constants of the solutes in terms of the Stokes-Einstein-Debye (SED) hydrodynamic theory reveals that with increase in the alkyl chain length attached to the cationic component of the ionic liquids, AP shows stick to superstick behavior, PRODAN rotation lies between stick and slip boundary conditions, whereas anthracene exhibits slip to sub slip behavior. The contrasting rotational dynamics of these probe molecules is a reflection of their location in distinct environments of the ionic liquids thus demonstrating the heterogeneity of these ionic liquids. The microheterogeneity of these media, in particular, those with the long alkyl chain, is further evidence from the excitation wavelength dependence study of the rotational diffusion of the dipolar probe molecules.

  20. Coating Platinum Nanoparticles with Methyl Radicals: Effects on Properties and Catalytic Implications. (United States)

    Bar-Ziv, Ronen; Zilbermann, Israel; Shandalov, Michael; Shevchenko, Vladimir; Meyerstein, Dan


    It was recently reported that the reaction of methyl radicals with Pt(0) nanoparticles (NPs), prepared by the reduction of Pt(SO4)2 with NaBH4, is fast and yields as the major product stable (Pt(0)-NPs)-(CH3)n and as side products, in low yields, C2H6, C2H4, and some oligomers. We decided to study the effect of this coating on the properties of the Pt(0)-NPs. The results show that the coating can cover up to 75% of the surface Pt(0) atoms. The rate constant of the reaction, k((.)CH3+Pt(0)-NPs), decreases with the increase in the surface coverage, leading to competing reaction paths in the solution, which gradually become dominant, affecting the composition of the products. The methyl coating also affects the zeta potential, the UV spectra, and the electrocatalytic reduction of water in the presence of the NPs. Thus, the results suggest that binding alkyl radicals to Pt(0) surfaces might poison the NPs catalytic activity. When the Pt(0)-NPs are prepared by the reduction of a different precursor salt, PtCl6(2-), nearly no C2 H4 and oligomers are formed and the methyl coating covers a larger percentage of the surface Pt(0) atoms. The difference is attributed to the morphology of the Pt(0)-NPs: those prepared from Pt(SO4)2 are twinned nanocrystals, whereas those prepared from PtCl6(2-) consist mostly of single crystals. Thus, the results indicate that the side products, or most of them at least, are formed on the twinned Pt(0) nanocrystal edges created between (111) facets. In addition, the results show that Pt(0)-NPs react very differently compared with other noble metals, for example, Au(0) and Ag(0); this difference is attributed in part to the difference in the bond strength, (M(0)-NP)-CH3, and should be considered in heterogeneous catalytic processes involving alkyl radicals as intermediates.

  1. Psychopathology according to behaviorism: a radical restatement. (United States)

    Pérez-Alvarez, Marino


    This article is a radical restatement of the predominant psychopathology, which is characterized by nosological systems and by its approach towards a neurobiological conception of the so-called mental disorders. The "radical" sense of this restatement is that of radical behaviorism itself. As readers will recall, "radical" applied to behaviorism means total (not ignoring anything that interests psychology), pragmatic (referring to the practical sense of knowledge), and it also derives from the Latin word for "root" (and thus implies change beginning at a system's roots or getting to the root of things, in this case, of psychological disorders). Based on this, I introduce the Aristotelian distinction of material and form, which, besides being behaviorist avant la lettre, is used here as a critical instrument to unmask the hoax of psychopathology as it is presented. The implications of this restatement are discussed, some of them already prepared for clinical practice.

  2. Radicals involved in photoallergen/protein interactions

    Energy Technology Data Exchange (ETDEWEB)

    Delahanty, J.N.; Evans, J.C.; Rowlands, C.C.; Barratt, M.D.; Pendlington, R.U. (University College, Cardiff (England))


    Aqueous solutions (pH = 8) of both 3,3'-dimethyl and 4,4'-dimethyl substituted analogues of the photoallergen fentichlor (bis(2-hydroxy-5-chlorophenyl)sulphide) produced stable semiquinone radicals when irradiated with u.v. light (greater than 310 nm). These radicals have been characterised using electron spin resonance techniques: the results confirm the assignment of hyperfine coupling constants for the parent fentichlor radical. The binding of fentichlor to HSA was found to be partly oxygen dependent demonstrating a role for semiquinone type radicals in the binding mechanism. The stoichiometry and specificity of the binding of the dimethyl analogues to soluble proteins were found to be similar to that of fentichlor itself.

  3. Magnetic Trapping of Cold Methyl Radicals

    CERN Document Server

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


    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.

  4. Neo-liberal Governing of 'Radicals'

    DEFF Research Database (Denmark)

    Lindekilde, Lasse


    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 ...

  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


    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. Fast beam studies of free radical photodissociation

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  7. Optimal pain management for radical prostatectomy surgery

    DEFF Research Database (Denmark)

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


    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......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....

  8. Radicalization and the Use of Social Media

    Directory of Open Access Journals (Sweden)

    Robin Thompson


    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.

  9. Hydroxyl radical generation by red tide algae. (United States)

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


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

  10. Catalytic Radical Domino Reactions in Organic Synthesis (United States)

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


    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

  11. Moment matrices, border bases and radical computation


    Mourrain, B.; J. B. Lasserre; Laurent, Monique; Rostalski, P.; Trebuchet, Philippe


    In this paper, we describe new methods to compute the radical (resp. real radical) of an ideal, assuming it complex (resp. real) variety is nte. The aim is to combine approaches for solving a system of polynomial equations with dual methods which involve moment matrices and semi-denite programming. While the border basis algorithms of [17] are ecient and numerically stable for computing complex roots, algorithms based on moment matrices [12] allow the incorporation of additional polynomials, ...

  12. Free Radical Mechanisms of Xenobiotic Mammalian Cytotoxicities (United States)


    frequent mechanism of xenobiotic liver toxicity is biotransformation by cytochrome P,5o- enzymes to toxic free radical intermediates. The primary objective...vascular cells was to incubate the cells with both the spin trapping agent methyl nitroso propane ( MNP ) and IRP chemicals to determine if free radical...gave a reasonably strong MNP -adduct signal. Figure 1 gives the MNP adduct signal for carbon tetrachloride and trichloroethylene, as well as that for

  13. Isobutane/2-butene alkylation over potential heterogeneous catalysts in a slurry reactor

    Energy Technology Data Exchange (ETDEWEB)

    Roervik, T.


    The trend towards more effective use of fossil fuels and reduced environmental pollution represents a major task of improvement within the refinery processes. The highly isomerized and high octane paraffins produced from isobutane and light olefins by alkylation fulfill all the requirements for reformulated gasoline. This doctoral thesis discusses new catalyst systems because of their potential in alkylation. A slurry reactor apparatus for solid-acid catalysed isobutane/butene alkylation was developed and used to investigate the performance of various heterogeneous catalysts. The selected materials were mainly zeolite types with faujasite structures. The samples were characterized by various methods before alkylation. In general, the order of decreasing catalyst activity after 3 h of reaction at 80{sup o}C was found to be: H-EMT >> H-FAU, dealuminated H-FAU >> NS.500, TA-Y, CeY-98 > Nafion-H. The order of decreasing alkylate selectivity of the catalysts was: H-EMT >> dealuminated H-FAU > H-FAU >> Nafion-H > CeY-98 > TA-Y > H-SAPO-37, NS.500. H-EMT was the most promising system for further development, also because of the very low formation of the undesirable isooctenes and a high selectivity towards isooctanes among the alkylates. A high density of accessible strong acid sites was found to be essential for a high alkylation activity and selectivity. Open structure, like hexagonal faujasite, was advantageous. The distribution of trimethylpentanes formed in zeolites was ascribed to pore restrictions as a major factor. The effect of operating conditions on catalyst performance was investigated statistically, and a high dilution of butene in the slurry reactor was found to be very important. 153 refs., 40 figs., 12 tabs.

  14. 40 CFR 721.3130 - Sulfuric acid, mono-C9-11-alkyl esters, sodium salts. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Sulfuric acid, mono-C9-11-alkyl esters... Specific Chemical Substances § 721.3130 Sulfuric acid, mono-C9-11-alkyl esters, sodium salts. (a) Chemical... acid, mono-C9-11-alkyl esters, sodium salts (PMN P-01-149; CAS No. 84501-49-5) is subject to...

  15. A Scalable Protocol for the Regioselective Alkylation of 2-Methylcyclohexane-1,3-dione with Unactivated sp3 Electrophiles (United States)

    Sharpe, Robert J.; Portillo, Maribel; Vélez, Robert A.


    A method for the C-selective alkylation of 2-methylcyclohexane-1,3-dione with unactivated sp3 electrophiles is accomplished via alkylation and subsequent deprotection of the derived ketodimethyl hydrazones. The present method provides a high-yielding entry to dialkyl cycloalkanones that cannot be accessed via direct alkylation of 2-methylcyclohexane-1,3-dione. The title reaction may be useful in the scalable preparation of terpene and steroidal building blocks in the arena of natural product synthesis. PMID:26525231

  16. Inactivation of Bacillus atrophaeus by OH radicals (United States)

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


    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.

  17. Oxygen radicals, inflammation, and tissue injury. (United States)

    Ward, P A; Warren, J S; Johnson, K J


    Inflammatory reactions often result in the activation and recruitment of phagocytic cells (e.g., neutrophils and/or tissue macrophages) whose products result in injury to the tissue. In killing of endothelial cells by activated neutrophils as well as in lung injury produced by either activated neutrophils or activated macrophages there is evidence that H2O2 and iron play a role. HO. may be a key oxygen product related to the process of injury. Endothelial cells in some vascular compartments may be susceptible to neutrophil mediated injury in a manner that is independent of oxygen radicals. On the basis of in vitro observations, a synergy exits between platelets and neutrophils, resulting in enhanced oxygen radical formation by the latter. Finally, the cytokines, interleukin 1 and tumor necrosis factor, released from macrophages have both direct stimulatory effects on oxygen radical formation in neutrophils and can "prime" macrophages for enhanced oxygen radical responses to other agonists. Cytokines may also alter endothelial cells rendering them more susceptible to oxygen radical mediated injury by neutrophils. This suggests a complex network of interactions between phagocytic cells and peptide mediators, the result of which is acute, oxygen radical mediated tissue injury.

  18. Free radicals in biology. Volume III

    Energy Technology Data Exchange (ETDEWEB)

    Pryor, W.A. (ed.)


    This volume covers topics ranging from radiation chemistry to biochemistry, biology, and medicine. This volume attempts to bridge the gap between chemical investigations and the medical applications and implications of free radical reactions. Chapter 1 provides a general introduction to the technique of radiation chemistry, the thermodynamics and kinetic factors that need be considered, the use of pulse radiolysis and flow techniques, and the application of these methods to free radicals of biological interest. Chapter 3 discusses the mechanisms of carbon tetrachloride toxicity. Chapter 4 reviews the morphological, histochemical, biochemical, and chemical nature of lipofuscin pigments. This chapter brings together the evidence that lipofuscin pigments arise from free radical pathology and that the formation of these pigments proves the presence of lipid peroxidation in vivo. Chapter 5 reviews the evidence for production of free (i.e., scavengeable) radicals from the reactions of selected enzymes with their substrates. Chapter 6 discusses one of the systems in which free radical damage is clearly important in vivo, both for man and animal, the damage caused to skin by sunlight. The evidence that free radical reactions can contribute to carcinogenesis dates from the earliest observations that ionizing radiation often produces higher incidences of tumors. A current working hypothesis is that chemical toxins cause damage to DNA and that the repair of this damge may incorporate viral genetic information into the host cell's chromosomes, producing cell transformation and cancer. The mechanism whereby chemical carcinogens become bound to DNA to produce point defects is discussed in Chapter 7.

  19. Radical Scavenging Effects of Different Veronica species

    Directory of Open Access Journals (Sweden)

    Ummuhan Şebnem Harput


    Full Text Available It is well known that the excessive production of reactive oxygen species is hazardous for living organisms and damages major cellular constituents such as DNA, lipid and protein. To find new products reducing free radical damage is very important researches in recent pharmaceutical investigations. Considering this information, fourteen Veronica species are decided to research in the view point of their antioxidant capacity and the chemical content. Water extracts of the plants were tested for their radical scavenging activity against 2,2-diphenyl-1-picryl hydrazyl (DPPH, superoxide (SO and nitric oxide (NO radicals spectroscopically. Dose dependent radical scavenging activity was observed and the results were found to be comparable to that of ascorbic acid, quercetin and BHA which are known antioxidative compounds. In addition, gallic acid equivalent total phenolic contents of the plants were also determined using Folin-Ciocalteau reagent. The most significant scavenging activity was found for V. chamaedrys against SO radical (IC50 113.40 μg/ml and V. officinalis against DPPH and NO radicals (IC50 40.93 μg/ml, 570.33 μg/ml, respectively .

  20. Radioprotective thermally generated free-radical dextrins

    Institute of Scientific and Technical Information of China (English)



    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.

  1. Radicalization and Radical Catalysis of Biomass Sugars: Insights from First-principles Studies (United States)

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


    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.

  2. Degradation of various alkyl ethers by alkyl ether-degrading Actinobacteria isolated from activated sludge of a mixed wastewater treatment. (United States)

    Kim, Yong-Hak; Cha, Chang-Jun; Engesser, Karl-Heinrich; Kim, Sang-Jong


    Various substrate specificity groups of alkyl ether (AE)-degrading Actinobacteria coexisted in activated sewage sludge of a mixed wastewater treatment. There were substrate niche overlaps including diethyl ether between linear AE- and cyclic AE-degrading strains and phenetole between monoalkoxybenzene- and linear AE-degrading strains. Representatives of each group showed different substrate specificities and degradation pathways for the preferred substrates. Determining the rates of initial reactions and the initial metabolite(s) from whole cell biotransformation helped us to get information about the degradation pathways. Rhodococcus sp. strain DEE5311 and Rhodococcus rhodochrous strain 117 both were able to degrade anisole and phenetole through aromatic 2-monooxygenation to form 2-alkoxyphenols. In contrast, diethyl ether-oxidizing strain DEE5311 capable of degrading a broad range of linear AE, dibenzyl ether and monoalkoxybenzenes initially transformed anisole and phenetole to phenol via direct O-dealkylation. Compared to this, cyclic AE-degrading Rhodococcus sp. strain THF100 preferred tetrahydrofuran (265 ± 35 nmol min(-1)mg(-1) protein) to diethyl ether (diethoxybenzene-degrading Rhodococcus sp. strain DEOB100 and Gordonia sp. strain DEOB200 transformed 1,3-/1,4-dialkoxybenzenes to 3-/4-alkoxyphenols by similar manners in the order of rates (nmol min(-1) mg(-1) protein): 1,4-diethoxybenzene (11.1 vs. 3.9)>1,4-dimethoxybenzene (1.6 vs. 2.6)>1,3-dimethoxybenzene (0.6 vs. 0.6). This study suggests that the AE-degrading Actinobacteria can orchestrate various substrate specificity responses to the degradation of various categories of AE pollutants in activated sludge communities.

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

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


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

  4. Kinetics of toluene alkylation with methanol catalyzed by pure and hybridized HZSM-5 catalysts

    KAUST Repository

    Alabi, Wahab


    A kinetic study of toluene alkylation with methanol was performed over pure HZSM-5, mordenite/ZSM-5 (hybrid of mordenite and HZSM-5), and ZM13 (composite mixture of HZSM-5 and MCM-41 at pH 13). Experimental runs were conducted using a batch fluidized bed reactor at temperatures of 300, 350 and 400 °C and reaction times of 3, 5, 7, 10, 13, 15 and 20. s. The rate of toluene methylation and toluene disproportionation were studied on the three catalysts (toluene alkylation is usually accompanied by toluene disproportionation on acid catalyst). Based on the results obtained, a simplified power law kinetic model consisting of three reactions was developed to estimate the activation energies of toluene methylation and disproportionation simultaneously. Coke formation on catalysts was accounted for using both reaction time and reactant conversion decay functions. All parameters were estimated based on quasi-steady state approximation. Estimated kinetic parameters were in good agreement with experimental results. The order of alkylation ability of the catalysts was found to be ZM13 > HZSM-5 > mordenite/ZSM-5, while the reverse is for toluene disproportionation (mordenite/ZSM-5 > HZSM-5 > ZM13). Thus, alkylation of toluene is most favorable on ZM13 due to combined effect of mesoporosity induced through its synthetic route and acid content. Toluene/MeOH molar ratio of 1:1 was most suitable for toluene alkylation reaction. © 2012 Elsevier B.V.

  5. Retention behavior of alkyl-substituted polycyclic aromatic sulfur heterocycles in reversed-phase liquid chromatography. (United States)

    Wilson, Walter B; Sander, Lane C; de Alda, Miren Lopez; Lee, Milton L; Wise, Stephen A


    Retention indices for 79 alkyl-substituted polycyclic aromatic sulfur heterocycles (PASHs) were determined by using reversed-phase liquid chromatography (LC) on a monomeric and polymeric octadecylsilane (C18) stationary phase. Molecular shape parameters [length, breadth, thickness (T), and length-to-breadth ratio (L/B)] were calculated for all the compounds studied. Based on separations of isomeric methylated polycyclic aromatic hydrocarbons on polymeric C18 phases, alkyl-substituted PASHs are expected to elute based on increasing L/B ratios. However, the correlation coefficients had a wide range of values from r=0.43 to r=0.93. Several structural features besides L/B ratios were identified to play an important role in the separation mechanism of PASHs on polymeric C18 phases. First, the location of the sulfur atom in a bay-like-region results in alkylated-PASHs being more retentive than non-bay-like-region alkylated-PASHs, and they elute later than expected based on L/B value. Second, the placement of the alkyl group in the k region of the structure resulted in a later elution than predicted by L/B. Third, highly nonplanar methyl-PASHs (i.e., 1-Me and 11-MeBbN12T) elute prior to the parent PASH (BbN12T).

  6. Neurotoxicity induced by alkyl nitrites: Impairment in learning/memory and motor coordination. (United States)

    Cha, Hye Jin; Kim, Yun Ji; Jeon, Seo Young; Kim, Young-Hoon; Shin, Jisoon; Yun, Jaesuk; Han, Kyoungmoon; Park, Hye-Kyung; Kim, Hyung Soo


    Although alkyl nitrites are used as recreational drugs, there is only little research data regarding their effects on the central nervous system including their neurotoxicity. This study investigated the neurotoxicity of three representative alkyl nitrites (isobutyl nitrite, isoamyl nitrite, and butyl nitrite), and whether it affected learning/memory function and motor coordination in rodents. Morris water maze test was performed in mice after administrating the mice with varying doses of the substances in two different injection schedules of memory acquisition and memory retention. A rota-rod test was then performed in rats. All tested alkyl nitrites lowered the rodents' capacity for learning and memory, as assessed by both the acquisition and retention tests. The results of the rota-rod test showed that isobutyl nitrite in particular impaired motor coordination in chronically treated rats. The mice chronically injected with isoamyl nitrite also showed impaired function, while butyl nitrite had no significant effect. The results of the water maze test suggest that alkyl nitrites may impair learning and memory. Additionally, isoamyl nitrite affected the rodents' motor coordination ability. Collectively, our findings suggest that alkyl nitrites may induce neurotoxicity, especially on the aspect of learning and memory function.


    Directory of Open Access Journals (Sweden)



    Full Text Available Present investigation is focused on systematic and detailed characterization of alkyl phosphonium intercalated montmorillonite (MMT. The objective of the work is to provide a better understanding of the specific changes in properties of the hybrid material with changes in structure of incoming organic cations. In the present work, Na-MMT was intercalated with phosphonium salts of two different cationic head compositions namely alkyl triphenyl and alkyl tributyl groups. Length of alkyl chain was also varied. Resultant organic-inorganic hybrids were characterized by X-ray diffraction (XRD, Transmission electron microscopy (TEM, Thermogravimetry (TG and Fourier transformed infrared spectroscopy (FTIR. Effective volume occupied by the cationic heads influenced interlayer arrangements. Intercalated MMT with two different cationic heads behaved differently in relation to thermal decomposition patterns. Possible explanation was given based on hybridization of bonds. Van der Waals attachment of alkyl chains influenced the interlayer stacking and organic loading. Attempts were made to correlate the changes in properties of intercalated MMT with the structural aspects of incoming organic cations.

  8. Alkyl caffeates improve the antioxidant activity, antitumor property and oxidation stability of edible oil.

    Directory of Open Access Journals (Sweden)

    Jun Wang

    Full Text Available Caffeic acid (CA is distributed widely in nature and possesses strong antioxidant activity. However, CA has lower solubility in non-polar media, which limits its application in fat-soluble food. To increase the lipophilicity of natural antioxidant CA, a series of alkyl caffeates were synthesized and their antioxidant and antitumor activities were investigated. The antioxidant parameters, including the induction period, acid value and unsaturated fatty acid content, of the alkyl caffeates in edible oil were firstly investigated. The results indicated that alkyl caffeates had a lower DPPH IC₅₀ (14-23 µM compared to CA, dibutyl hydroxy toluene (BHT and Vitamin C (24-51 µM, and significantly inhibited four human cancer cells (SW620, SW480, SGC7901 and HepG2 with inhibition ratio of 71.4-78.0% by a MTT assay. With regard to the induction period and acid value assays, methyl and butyl caffeates had higher abilities than BHT to restrain the oxidation process and improve the stability of edible oil. The addition of ethyl caffeate to oil allowed maintenance of a higher unsaturated fatty acid methyl ester content (68.53% at high temperatures. Overall, the alkyl caffeats with short chain length (n<5 assessed better oxidative stability than those with long chain length. To date, this is the first report to the correlations among the antioxidant activity, anticancer activity and oxidative stability of alkyl caffeates.

  9. V-shaped crystalline structures of di-n-alkyl esters of phosphoric acid. (United States)

    Thünemann, Andreas F; Kurth, Dirk G; Beinhoff, Matthias; Bienert, Ralf; Schulz, Burkhard


    We prepared crystals of di-n-alkyl esters of phosphoric acid with chain lengths of n = 10, 12, 14, 16, and 18. These were characterized by single-crystal X-ray analysis and differential scanning calorimetry (DSC). It was found that the alkyl chains are in an extended all-trans conformation and aligned close to perpendicular, forming V-shaped molecules. This is in strong contrast to the typical arrangement of the alkyl chains of phospholipids where the two alkyl chains are arranged parallel in the same direction (e.g., tuning fork configuration in bilayers). Additionally, it was found that the arrangement of the V-shaped molecules of the di-n-alkyl esters in neighboring stacks of the lamellar crystals is antiparallel for short chain lengths (n = 10 and 12) and parallel for the longer (n = 14 and 16). DSC reveals that the melting of the crystals increases systematically with increasing chain lengths from 48 to 82 degrees C. The contribution of each methylene group to the melting enthalpy (70-133 kJ/mol) is independent of the chain length (3.9 kJ per mol CH2).

  10. Theoretical study on the reaction mechanism of (CH3)3CO(.) radical with NO

    Institute of Scientific and Technical Information of China (English)

    ZHAO; Hongmei; LIU; Kun; SUN; Chengke; LI; Zonghe


    [1]Sun, Z., Zheng, S. J., Wang, J. et al., First experimental observation on different ionic states of the tert-butoxy [(CH3)3CO' ] radical, Chem. Eur. J., 2001, 7(14): 2995-2999.[2]Wang, J., Sun, Z., Zhu, X. J. et al., First experimental observation on different ionic states of the CH3CH2O radical: a HeI photoelectron spectrum of the ethoxy CH3CH2O radical, Chem. Phys. Lett.,2001, 340: 98-102.[3]Zhu, X. J., Ge, M. F., Wang, J. et al., First experimental observation on different ionic states of both methylthio (CH3S') and methoxy (CH3O') radicals, Angew. Chem. Int. Ed., 2000, 39(11):1940-1943.[4]Ramond, T. M., Davico, G. E., Schwartz, R. L. et al., Vibronic structure of alkoxy radicals via photoelectron spectroscopy, J.Chem. Phys., 1999, 112: 1158-1169.[5]Blitz, M., Pilling, M. J., Robertson, S. H. et al., Direct studies on the decomposition of the tert-butoxy radical and its reaction with NO, Phys. Chem. Chem. Phys., 1999, 1: 73-80.[6]Lee, Y. Y., Wann, G., Lee, Y. P., Vibronic analysis of the A → X laser-induced fluorescence of jet-cooled methoxy (CH3O) radical,J. Chem. Phys., 1993, 99: 9465-9471.[7]Wiberg, K. B., Structures and charge distributions in alkoxide ions, J. Am. Chem. Soc., 1990, 112: 3379-3385.[8]Janousek, B. K., Zimmerman, A. H., Reed, K. J. et al., Electron photodetachment from aliphatic molecular anions, gas-phase electron affinities of methoxyl, tert-butoxyl, and neopentoxyl radicals, J. Am. Chem. Soc., 1978, 100: 6142-6148.[9]Griller, D., Ingold, K. U., Persistent carbon-centered radicals,Acc. Chem. Res., 1976, 9: 13-19.[10]Haire, D. L., Janzen, E. G., Synthesis and spin trapping kinetics of new alkyl substituted cyclic nitrones, Can. J. Chem., 1982, 60:1514-1522.[11]Walling, C., Kurkov, V. P., Positive halogen compounds, XV. Kinetics of the chlorination of Hydrocarbons by t-butyl hypochlorite,J. Am. Chem. Soc., 1967, 89: 4895-4901.[12]Becke, A. D., Density-functional thermochemistry, Ⅲ. The

  11. In vivo and in vitro estrogen bioactivities of alkyl parabens. (United States)

    Lemini, Cristina; Jaimez, Ruth; Avila, María Estela; Franco, Yanira; Larrea, Fernando; Lemus, Ana Elena


    The alkyl esters of p-hydroxybenzoic acid known as parabens (Pbens) are used as preservatives in food, pharmaceutical and cosmetic formulations. They have been reported as estrogenic. Here, we present evidence for the in vivo and in vitro bioactivities and receptor binding affinities of methylparaben (MePben), ethylparaben (EtPben), propylparaben (PrPben), and butylparaben (BuPben) compared with those of estradiol (E2). Estrogenicity was studied using the uterotrophic assay in immature (Im) and adult ovariectomized (Ovx) CD1 mice, and in immature female Wistar rats (IW). Animals were subcutaneously (sc) treated for three consecutive days with different molar equivalent doses ranging from 3.62 to 1086 micromol/kg body weight of Pbens, E2 (0.036 micromol/kg), or vehicle. Pbens increased uterine weight in Im and Ovx animals and their relative uterotrophic effect to E2 (100) (RUEE2) were from 34 to 91. The relative uterotrophic potencies related to E2 (100) (RUPE2) of these compounds were from 0.003 to 0.007. The E2 ED50 for CD1 animals able to increase the uterine weight was 7 microg/kg (0.9-55 confidence limits); and that of Pbens ranged from 18 to 74 mg/kg. In IW rats, the ED50 were from 33 to 338 mg/kg. All Pbens, except MePb, competed with [3H]E2 for the estrogen receptor binding sites. The uterotrophic effects of Pbens in Im mice have a positive correlation with the side-chain length of the ester group of these compounds. The E2 and Pbens relative binding affinities (RBA) and Ki values correlated to their estrogenic activity. The NOELs values for Pbens uterotrophic activity in Im were from 0.6 to 6.5 mg/kg per day; and Ovx from 6 to 55 mg/kg. The NOELs IW ranged from 16.5 to 70 mg/kg indicating that Im were more susceptible than Ovx and IW to these effects. The data shown here confirm the estrogenicity of Pbens.

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

    NARCIS (Netherlands)

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


    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

  13. Environmentally persistent free radicals (EPFRs)-2. Are free hydroxyl radicals generated in aqueous solutions? (United States)

    Khachatryan, Lavrent; Dellinger, Barry


    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 samples, (2) a strong correlation between the concentration of DMPO-OH adducts and EPFRs per gram of particles, and (3) a slow, constant growth of DMPO-OH concentration over a period of days in solution containing 50 μg/mL EPFRs particles + DMPO (150 mM) + reagent balanced by 200 μL phosphate buffered (pH = 7.4) saline. However, failure to form secondary radicals using standard scavengers, such as ethanol, dimethylsulfoxide, sodium formate, and sodium azide, suggests free hydroxyl radicals may not have been generated in solution. This suggests surface-bound, rather than free, hydroxyl radicals were generated by a surface catalyzed-redox cycle involving both the EPFRs and Cu(II)O. Toxicological studies clearly indicate these bound free radicals promote various types of cardiovascular and pulmonary disease normally attributed to unbound free radicals; however, the exact chemical mechanism deserves further study in light of the implication of formation of bound, rather than free, hydroxyl radicals.

  14. Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions (United States)

    Carraher, Jack McCaslin

    leads to the dissociation of H2O2 from Cr(III), while in the H+-independent reaction, CraqOOH2+ is transformed to Cr(V). Both scavengers rapidly remove Cr(V) and simplify both the kinetics and products by impeding formation of Cr(IV, V, VI). Syntheses, Reactivity, and Thermodynamic Considerations LRhR2+. Macrocyclic rhodium(II) complexes LRh(H 2O)2+ (L = L1= cyclam and L2 = meso-Me6-cyclam) react with alkyl hydroperoxides R(CH3)2COOH to generate the corresponding rhodium(III) alkyls LRh(H2O)R2+ (R = CH3, C2 H5, PhCH2). Methyl and benzyl complexes can also be prepared by bimolecular group transfer from alkyl cobaloximes (dmgX) 2(H2O)CoR (where R = CH3, CH2Ph and dmgX is either dimethylglyoxime or a BF2-capped derivative of dmg) to LRh(H2O)2+. When R = C2H5, C3H7 or C4H9, the mechanism changes from group transfer to hydrogen atom abstraction from the coordinated alkyl and produces LRh(H2O)H2+ and an a-olefin. The new LRh(H2O)R2+ complexes were characterized by solution NMR and by crystal structure analysis. They exhibit great stability in aqueous solution at room temperature, but undergo efficient Rh-C bond cleavage upon photolysis. 'Green' Model for Decarboxylation of Biomass Derived Acids via Photolysis of in situ formed Metal-Carboxylate Complexes. Photolysis of aqueous solutions containing propionic acid and Fe 3+ aq in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe2+. Photolysis in the presence of O2 yields catalytic amounts of hydrocarbon products. When halide ions are present during photolysis; nearly quantitative yields of ethyl halides are produced via extraction of a halide atom from FeX2+ by ethyl radical. The rate constants for ethyl radical reactions with FeCl2+ (k = 4.0 (+/- 0.5) x 106 M-1s-1) and with FeBr 2+ (k = 3.0 (+/- 0.5) x 107 M-1s -1) were determined via competition reactions. Irradiation of solutions containing aqueous Cu2+ salts and linear carboxylic acids yield alpha

  15. Thermal properties of alkyl-substituted 3,3'-bis(dipyrrolylmethene) dihydrobromides

    Energy Technology Data Exchange (ETDEWEB)

    Guseva, G.B., E-mail: [Institute of Solution Chemistry, Russian Academy of Sciences, 1 Akademicheskaya Street, 153045 Ivanovo (Russian Federation); Dudina, N.A.; Vyugin, E.V. Antina A.I.; Berezin, M.B.; Yutanova, S.L. [Institute of Solution Chemistry, Russian Academy of Sciences, 1 Akademicheskaya Street, 153045 Ivanovo (Russian Federation)


    Highlights: {yields} The thermodestruction of 3,3'-bis(dipyrromethene) dihydrobromides was performed. {yields} The dissociation stage of the salts with removal of HBr molecules are not observed. {yields} An increase of alkylation causes an increase of the salts thermal stability. {yields} The thermal stability a increase in argon as compared with air. - Abstract: 3,3'-Bis(dipyrrolylmethene) dihydrobromides (H{sub 2}L.2HBr) with various types of alkylation have been synthesized. The compounds were characterized by recording of their proton NMR-, IR- and electronic absorption spectra. The thermal destruction of the compounds was studied thermogravimetrically. An increase in the degree of alkylation causes an increase of the salts thermal stability in air and argon.


    Institute of Scientific and Technical Information of China (English)

    Mei-fang Liu; Yu-lan Chen; Bo Zhu; Yang Han; Wei-guo Huang; Chun Du; Zhi-shan Bo


    Two kinds of polyfluorenes bearing two lateral pyrene terminated alkyl chains and two alkyl chains per repeating unit were synthesized by Suzuki polycondensation and used to disperse single-walled carbon nanotubes (SWCNT) in organic solvents.Stable polymer-SWCNT complex can be formed via the multivalent π-π stacking interaction of the lateral pyrene functional groups and the polyfluorene backbone with the outer surface of carbon nanotubes; meanwhile the lateral alkyl chains can impart good solubility to the complex.As expected,polyfluorenes bearing lateral pyrene functional groups and octyl chains exhibited much higher carbon nanotube solubility in common organic solvents than the corresponding polyfluorenes beating only octyl chains.Photophysical studies indicated that the formation of polymer-SWCNT complex can effectively quench the fluorescence ofpolyfluorenes.

  17. Studies on Properties of Tetra-p-nitro-tetra-O-alkyl-calix [4] arenes

    Institute of Scientific and Technical Information of China (English)

    LU,Guo-Yuan; SONG,Wei; LIU,Min-Hua; LIU,Fang; JIN,Chuan-Min


    This paper reports the properties of the novel tetra- p-nitro- te tra-O-alkyl-calix[4]arenes (alkyl= n-C4H9, 1; n-C8H17, 2; n-C12H25, 3; n-C16H33, 4). X-ray crystallographic analysis and 1H NMR revealed that they exist as pinched-cone confor mation in crystal or cone conformation in soiution. EFISH ex periments at 1064 nm in CHCl3 indicated that tetra-p-nitro-te- tra-O-butyl-calix[4]arene (1) has higher hyperpolarizability βz values than the corresponding reference compound p-nitro phenyl butyl ether, without red shift of the charge transfer band. Compounds 2, 3 and 4 with longer alkyl chains can form monolayer at the air/water.

  18. An electron density analysis of the proximity effect in linear alkyl diethers (United States)

    Vila, Antonio; Mosquera, Ricardo A.


    Atomic and bond properties within the atoms in molecules (AIM) approach have been computed for a series of 52 alkyl diethers of formula CH 3(CH 2) nO(CH 2) lO(CH 2) mCH 3 on HF/6-31++G**//HF/6-31G* electron distributions. The results indicate that the mutual influence of oxygen atoms is negligible when they are separated by more than three methylene groups, and that 13 different approximate transferable oxygen atoms can be considered in alkyl diethers. The regression analysis indicates that the atomic population, and remaining non-energetic properties of the different transferable oxygens for l>3 agree within the statistical error with those for the corresponding alkyl monoethers.

  19. Comparative embryotoxicity of phenanthrene and alkyl-phenanthrene to marine medaka (Oryzias melastigma). (United States)

    Mu, Jingli; Wang, Juying; Jin, Fei; Wang, Xinhong; Hong, Huasheng


    Alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) are the predominant form of PAHs in oil, comprising 85-95% of total PAHs. However, little attention has been paid to these chemicals in ecological risk assessment of marine oil spill. A comparative study of the toxic effects of phenanthrene and retene (7-isopropyl-1-methylphenanthrene, an alkyl-phenanthrene) on the early life stage of marine medaka (Oryzias melastigma) was conducted. Results showed that retene was significantly more toxic than phenanthrene, and marine medaka could be more sensitive to retene than some freshwater fishes. Retene had a higher excretion rate than phenanthrene during the larvae stage. Both of compounds resulted in developmental malformation of marine medaka embryos, with phenanthrene affecting on peripheral vascular system and yolk sac, while retene affecting on cardiac tissues. The toxicity of phenanthrene might be mainly related to its anesthetic effects, and that of retene might be related to the CYP1A-mediated toxicity of its metabolites.

  20. Effect of Magnetite Nano Particles on p-n-Alkyl Benzoic Acid Mesogens

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    S. Sreehari Sastry


    Full Text Available The magnetite (Fe3O4 nanoparticles (0.5 wt% of size less than 20 nm doped in p-n-alkyl benzoic acids where n varies from heptyl (7 to nonyl (9 are prepared and the presence of Fe+3 is confirmed through UV-Visible spectrophotometer. Textural and phase transition temperature studies are carried out using polarizing optical microscopy on pure and nano doped p-n-alkyl benzoic acids. These results are further confirmed by DSC at a scan rate of 5ºC/min and dielectric studies. Dielectric studies are carried out, in which the variation of dielectric constant, loss and the conductivity are analyzed with respect to temperatures and frequencies. Increment of relaxation times for nano doped heptyl and nonyl benzoic acids are observed which implies that the dielectric nature is strengthened for the nano doped mesogens. The preference of nano doped p-n-alkyl benzoic acids is discussed.

  1. Poly(vinyl chloride-grafted multi-walled carbon nanotubes via Friedel-Crafts alkylation

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    Full Text Available A novel approach was developed for the surface modification of the multi-walled carbon nanotubes (MWCNTs with high percentage of grafting (PG% by the grafting of polymer via the Friedel-Crafts alkylation. The graft reaction conditions, such as the amount of catalyst added, the reaction temperature, and the reaction time were optimized for the Friedel-Crafts alkylation of the MWCNTs with poly(vinyl chloride (PVC with anhydrous aluminum chloride (AlCl3 as catalyst in chloroform (CHCl3. The Fourier Transform Infrared (FT-IR, Raman, and thermogravimetric (TGA analysis showed that PVC had been successfully grafted onto MWCNTs both at the ends and on the sidewalls by the proposed Friedel-Crafts alkylation. The PVC grafted MWCNTs (PVC-MWCNTs could be dispersed well in organic solvent and the dispersion was more stable.

  2. Modeling Radicalization Phenomena in Heterogeneous Populations (United States)


    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

  3. 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.

  4. S - and N-alkylating agents diminish the fluorescence of fluorescent dye-stained DNA. (United States)

    Giesche, Robert; John, Harald; Kehe, Kai; Schmidt, Annette; Popp, Tanja; Balzuweit, Frank; Thiermann, Horst; Gudermann, Thomas; Steinritz, Dirk


    Sulfur mustard (SM), a chemical warfare agent, causes DNA alkylation, which is believed to be the main cause of its toxicity. SM DNA adducts are commonly used to verify exposure to this vesicant. However, the required analytical state-of-the-art mass-spectrometry methods are complex, use delicate instruments, are not mobile, and require laboratory infrastructure that is most likely not available in conflict zones. Attempts have thus been made to develop rapid detection methods that can be used in the field. The analysis of SM DNA adducts (HETE-G) by immunodetection is a convenient and suitable method. For a diagnostic assessment, HETE-G levels must be determined in relation to the total DNA in the sample. Total DNA can be easily visualized by the use of fluorescent DNA dyes. This study examines whether SM and related compounds affect total DNA staining, an issue that has not been investigated before. After pure DNA was extracted from human keratinocytes (HaCaT cells), DNA was exposed to different S- and N-alkylating agents. Our experiments revealed a significant, dose-dependent decrease in the fluorescence signal of fluorescent dye-stained DNA after exposure to alkylating agents. After mass spectrometry and additional fluorescence measurements ruled out covalent modifications of ethidium bromide (EthBr) by SM, we assumed that DNA crosslinks caused DNA condensation and thereby impaired access of the fluorescent dyes to the DNA. DNA digestion by restriction enzymes restored fluorescence, a fact that strengthened our hypothesis. However, monofunctional agents, which are unable to crosslink DNA, also decreased the fluorescence signal. In subsequent experiments, we demonstrated that protons produced during DNA alkylation caused a pH decrease that was found responsible for the reduction in fluorescence. The use of an appropriate buffer system eliminated the adverse effect of alkylating agents on DNA staining with fluorescent dyes. An appropriate buffer system is thus

  5. Synthesis and pharmacology of N-alkylated derivatives of the excitotoxin ibotenic acid

    DEFF Research Database (Denmark)

    Madsen, U; Dumpis, M A; Bräuner-Osborne, Hans


    Three amino-alkylated derivatives of the naturally occurring excitatory amino acid (EAA) receptor agonist ibotenic acid (Ibo) have been synthesized and tested pharmacologically. N-Methyl-Ibo (1a) and N-ethyl-Ibo (1b) were shown to be agonists at NMDA receptors (EC50 = 140 and 320 microM, respecti......Three amino-alkylated derivatives of the naturally occurring excitatory amino acid (EAA) receptor agonist ibotenic acid (Ibo) have been synthesized and tested pharmacologically. N-Methyl-Ibo (1a) and N-ethyl-Ibo (1b) were shown to be agonists at NMDA receptors (EC50 = 140 and 320 micro...

  6. A study on synthesis and oxidation mechanism of mono-alkyl phosphate

    Institute of Scientific and Technical Information of China (English)


    Oxidation of white phosphorus by peroxides to produce mono-alkyl phosphate in the alcoholic solution has been studied under non-and catalytic conditions. In this paper,the mechanism of the oxidation process was analyzed. The content of mono-alkyl phosphate in the product is affected by different types of alcoholic solution and peroxide solvent. The result shows the availability of the following order for the activity of the peroxide solvent and alcoholic solutions-tert-butyl hydroperoxide>(di) benzoyl perox...

  7. Alkylation mechanism of benzene with 1-dodecene catalyzed by Et3NHCl-AlCl3

    Institute of Scientific and Technical Information of China (English)


    The isotope exchange method was employed to investigate the catalytic mechanism of ionic liquid in alkylation of benzenes with olefins.It is proposed that alkylation was induced by the Lewis acid AlCl3 which attracted π electrons of 1-dodecene to shift toward 1-carbon,thus forming a carbonium ion.The carbonium ion further reacted with benzenes to form a complex.Due to unstabilit of the complex,a deuterated ring proton was transferred into an electronegative 1-carbon of the side chain to substitute for the AlCl3,accordingly 2-phenyldodecane was generated.

  8. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

    KAUST Repository

    Stoltz, Brian


    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

  9. Ab initio research on DNA base alkylation by the β-position metabolite of methylethylnitrosamine

    Institute of Scientific and Technical Information of China (English)

    ZHAO Lijiao; ZHONG Rugang; YUAN Xiaolong; CUI Yasong; DAI Qianhuan


    Ab initio calculation is carried out to study the different supposed mechanisms of DNA base alkylation by β-sulphate-nitrosamines at RHF/6-31G(d) and MP2/6-31G(d)levels. Full geometric structure optimization is done for all reactants, intermediates, products and transition states. The activation energy and IRC are obtained. The results show that the anchimeric assistant effect promotes the alkylation of DNA base by β-sulphate-nitrosamines. Solvent calculation is carried out with Onsager model of SCRF method at the same level. The results indicate that the activation energy is decreased obviously in water.

  10. Neighbor-directed histidine N(τ) alkylation. A route to imidazolium-containing phosphopeptide macrocycles

    Energy Technology Data Exchange (ETDEWEB)

    Qian, Wen-Jian [National Cancer Inst., Frederick, MD (United States); Park, Jung-Eun [National Cancer Inst., Bethesda, MD (United States); Grant, Robert [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lai, Christopher C. [National Cancer Inst., Frederick, MD (United States); Kelley, James A. [National Cancer Inst., Frederick, MD (United States); Yaffe, Michael B. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lee, Kyung S. [National Cancer Inst., Bethesda, MD (United States); Burke, Terrence R. [National Cancer Inst., Frederick, MD (United States)


    Our recently discovered, selective, on-resin route to N(τ)-alkylated imidazolium-containing histidine residues affords new strategies for peptide mimetic design. In this, we demonstrate the use of this chemistry to prepare a series of macrocyclic phosphopeptides, in which imidazolium groups serve as ring-forming junctions. These cationic moieties subsequently serve to charge-mask the phosphoamino acid group that directed their formation. Furthermore, neighbor-directed histidine N(τ)-alkylation opens the door to new families of phosphopeptidomimetics for use in a range of chemical biology contexts.

  11. Surface Structures Formed by a Copper(II Complex of Alkyl-Derivatized Indigo

    Directory of Open Access Journals (Sweden)

    Akinori Honda


    Full Text Available Assembled structures of dyes have great influence on their coloring function. For example, metal ions added in the dyeing process are known to prevent fading of color. Thus, we have investigated the influence of an addition of copper(II ion on the surface structure of alkyl-derivatized indigo. Scanning tunneling microscope (STM analysis revealed that the copper(II complexes of indigo formed orderly lamellar structures on a HOPG substrate. These lamellar structures of the complexes are found to be more stable than those of alkyl-derivatized indigos alone. Furthermore, 2D chirality was observed.

  12. Synthesis of triated N1`-alkyl derivatives of the delta opioid receptor ligand naltrindole

    Energy Technology Data Exchange (ETDEWEB)

    Lever, J.R.; Johnson, S.M. [Johns Hopkins Univ. School of Hygiene and Public Health, Environmental Health Sciences Dept., Baltimore, MD (United States)


    Tritiated N1`-methyl and N1`-ethyl analogues of naltrindole (NTI) have been synthesized for evaluation as radioligands for studies of delta opioid receptors. The two N1`-alkyl-5`,7`-dibromoNTI precursors for radiolabeling were prepared by base-promoted alkylation of 2,4-dibromophenylhydrazine with either iodomethane or iodoethane followed by condensation with naltrexone using the Fischer indole synthesis. Catalytic debromotritiation followed by HPLC purification afforded [{sup 3}H]MeNTI (17.3 Ci/mmol) and [{sup 3}H]EtNTI (22.5 Ci/mmol) with high chemical and radiochemical purities ({>=} 99.8%). (author).

  13. Palladium catalysed asymmetric alkylation of benzophenone Schiff base glycine esters in ionic liquids

    Indian Academy of Sciences (India)

    Dae Hyun Kim; Jin Kyu Im; Dae Won Kim; Minserk Cheong; Hoon Sik Kim; Deb Kumar Mukherjee


    Asymmetric alkyl substitution of various benzophenone Schiff base substrates under biphasic conditions proceeded using optically active Palladium(II) complexes. The corresponding products were obtained in high yields but with moderate enantiomeric excess (ee). Addition of specific ionic liquids to the reaction medium enhanced reactivity and selectivity for phase transfer catalytic (PTC) glycine alkylation. It has been found that there is an anionic influence of the ionic liquids that modify the steric environment around the enolate ion. A computer-assisted molecular design of enantioselective phase-transfer catalysis with the palladium complex and the ionic liquid has been done.

  14. Effects of alkyl chain positioning on conjugated polymer microstructure and field-effect mobilities

    KAUST Repository

    Schroeder, Bob C.


    Solubilizing alkyl chains play a crucial role in the design of semiconducting polymers because they define the materials solubility and processability as well as both the crystallinity and solid-state microstructure. In this paper, we present a scarcely explored design approach by attaching the alkyl side chains on one side (cis-) or on both sides (trans-) of the conjugated backbone. We further investigate the effects of this structural modification on the solid-state properties of the polymers and on the charge-carrier mobilities in organic thin-film transistors. Copyright © Materials Research Society 2015

  15. Efficient SN2 fluorination of primary and secondary alkyl bromides by copper(I) fluoride complexes

    KAUST Repository

    Liu, Yanpin


    Copper(I) fluoride complexes ligated by phenanthroline derivatives have been synthesized and structurally characterized by X-ray crystallography. These complexes adopt as either ionic or neutral forms in the solid state, depending on the steric bulkiness of the substituent groups on the phenanthroline ligands. These complexes react with primary and secondary alkyl bromides to produce the corresponding alkyl fluorides in modest to good yields. This new method is compatible with a variety of important functional groups such as ether, thioether, amide, nitrile, methoxyl, hydroxyl, ketone, ester, and heterocycle moieties. © 2013 American Chemical Society.

  16. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates. (United States)

    McDougal, Nolan T; Virgil, Scott C; Stoltz, Brian M


    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

  17. Catalytic Enantioselective Electrophilic Aminations of Acyclic α-Alkyl β-Carbonyl Nucleophilies. (United States)

    Liu, Xiaofeng; Sun, Bingfeng; Deng, Li


    Highly enantioselective aminations of acyclic α-alkyl β-keto thioesters and trifluoroethyl α-methyl α-cyanoacetate (12) with as low as 0.05 mol % of a bifunctional cinchona alkaloid catalyst were established. This ability to afford highly enantioselectivity for the amination of α-alkyl β-carbonyl compounds renders the 6'-OH cinchona alkaloid-catalyzed amination applicable for the enantioselective synthesis of acyclic chiral compounds bearing N-substituted quaternary stereocenters. The synthetic application of this reaction is illustrated in a concise asymmetric synthesis of α-methylserine, a key intermediate previously utilized in the total synthesis of a small molecule immunomodulator, conagenin.

  18. Studies on Phase Behavior of Alkyl Polyglucoside Based on Microemulsions with Modified Fishlike Phase Diagram

    Institute of Scientific and Technical Information of China (English)

    Jin Ling CHAI; Gan Zuo LI; Zhao Yu DIAO; Gao Yong ZHANG


    The three-phase behavior in the quaternary system of an alkyl (C8/10- or C12/14-) polyglucoside / 1-butanol / n-octane / water has been studied at 40 ℃ with the modified fishlike phase diagram, which is presented by us for the first time. The mass fraction of 1-butanol in the hydrophile-lipophile balanced interfacial layer, AS, the coordinates of the start point B and the end point E of the phase diagram, and the solubilities of alkyl polyglucoside and 1-butanol in n-octane phase were calculated. The solubilization of the microemulsion was also discussed.

  19. Intramolecular effects on the kinetics of unimolecular reactions of β-HOROO˙ and HOQ˙OOH radicals. (United States)

    Lizardo-Huerta, J C; Sirjean, B; Bounaceur, R; Fournet, R


    A theoretical study describing the influence of intramolecular effects on the energy barriers and rate constants of unimolecular reactions involving β-HOROO˙ and HOQ˙OOH radicals is proposed. The reactions considered are HO2˙ elimination, the Waddington mechanism, H-shift, cyclic ether formation and β-scission. All the calculations are performed at the CBS-QB3 level of theory along with canonical transition state theory and statistical thermodynamics, including a specific treatment of hindered rotors. Several structural parameters are investigated, such as the location of the hydroxyl function in the cyclic transition states or the substitution of H atoms by alkyl groups on carbon atoms involved in the reaction coordinate. It is shown that these molecular systems involve numerous transition states, especially for reactions such as 1,5 or 1,6 H-shift, and that, a priori simplification is not possible. It is also shown that the position of the -OH group in the transition state can largely modify both the barrier heights and the rate constants. However, opposite trends can be observed depending on the competition between energetic and entropic effects. Similar observations are made when H atoms are replaced by methyl or alkyl groups. These results can largely be explained by intramolecular effects such as hydrogen bonds, stabilization effects (from -OH or -CH3 groups), steric influences and by the coupling between them. The last point renders the classic establishment of the structure-reactivity relationship challenging.

  20. High-Power-Density Organic Radical Batteries. (United States)

    Friebe, Christian; Schubert, Ulrich S


    Batteries that are based on organic radical compounds possess superior charging times and discharging power capability in comparison to established electrochemical energy-storage technologies. They do not rely on metals and, hence, feature a favorable environmental impact. They furthermore offer the possibility of roll-to-roll processing through the use of different printing techniques, which enables the cost-efficient fabrication of mechanically flexible devices. In this review, organic radical batteries are presented with the focus on the hitherto developed materials and the key properties thereof, e.g., voltage, capacity, and cycle life. Furthermore, basic information, such as significant characteristics, housing approaches, and applied additives, are presented and discussed in the context of organic radical batteries.

  1. Exploring How Lead Users Develop Radical Innovation

    DEFF Research Database (Denmark)

    Lettl, Christopher; Hienerth, Christoph; Gemuenden, Hans Georg


    In this study, we explore how lead users develop radical innovations outside of manufacturing firms. We analyze the transition from a very early stage of activities to the ultimate commercialization of these innovations. The focus in this context is on the initiatives undertaken by lead users...... 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...

  2. Resveratrol products resulting by free radical attack (United States)

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


    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.

  3. 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:


    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.

  4. A Radically Configurable Six-State Compound

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, J.C.; Fahrenbach, Albert C.; Cao, Dennis; Dyar, Scott M.; Frasconi, M.; Giesener, M. A.; Benítez, D.; Tkatchouk, E.; Li, H.; Stern, Charlotte L.; Sarjeant, Amy A.; Hartlieb, K.J.; Liu, Z.; Carmieli, Raanan; Botros, Y.Y.; Wasielewski, M. R.; Goddard III, W.A.; Stoddart, J. Fraser


    Most organic radicals possess short lifetimes and quickly undergo dimerization or oxidation. Here, we report on the synthesis by radical templation of a class of air- and water-stable organic radicals, trapped within a homo[2]catenane composed of two rigid and fixed cyclobis(paraquat-p-phenylene) rings. The highly energetic octacationic homo[2]catenane, which is capable of accepting up to eight electrons, can be configured reversibly, both chemically and electrochemically, between each one of six experimentally accessible redox states (0, 2+, 4+, 6+, 7+, and 8+) from within the total of nine states evaluated by quantum mechanical methods. All six of the observable redox states have been identified by electrochemical techniques, three (4+, 6+, and 7+) have been characterized by x-ray crystallography, four (4+, 6+, 7+, and 8+) by electron paramagnetic resonance spectroscopy, one (7+) by superconducting quantum interference device magnetometry, and one (8+) by nuclear magnetic resonance spectroscopy.

  5. Free radicals, antioxidant defense systems, and schizophrenia. (United States)

    Wu, Jing Qin; Kosten, Thomas R; Zhang, Xiang Yang


    The etiopathogenic mechanisms of schizophrenia are to date unknown, although several hypotheses have been suggested. Accumulating evidence suggests that excessive free radical production or oxidative stress may be involved in the pathophysiology of schizophrenia as evidenced by increased production of reactive oxygen or decreased antioxidant protection in schizophrenic patients. This review aims to summarize the basic molecular mechanisms of free radical metabolism, the impaired antioxidant defense system and membrane pathology in schizophrenia, their interrelationships with the characteristic clinical symptoms and the implications for antipsychotic treatments. In schizophrenia, there is accumulating evidence of altered antioxidant enzyme activities and increased levels of lipid peroxidation, as well as altered levels of plasma antioxidants. Moreover, free radical-mediated abnormalities may contribute to specific aspects of schizophrenic symptomatology and complications of its treatment with antipsychotic drugs, as well as the development of tardive dyskinesia (TD). Finally, the potential therapeutic strategies implicated by the accumulating data on oxidative stress mechanisms for the treatment of schizophrenia are discussed.

  6. 40 CFR 721.6183 - Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow alkyl amines... (United States)


    ... - maleic anhydride polymer and hydrogenated tallow alkyl amines, sodium salts, compds. with ethanolamine... Substances § 721.6183 Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow... anhydride polymer and hydrogenated tallow alkyl amines, sodium salts, compds. with ethanolamine (PMN...

  7. Regiospecific oxidation of an alkyl group of aromatic amine to carbonyl group by DDQ in aq.medium

    Institute of Scientific and Technical Information of China (English)

    Madhav S. Mane; Ravi S. Balaskar; Sandip N. Gavade; Pramod N. Pabrekar; Murlidhar S. Shingare; Dhananjay V. Mane


    The regiospecific oxidation of alkyl group of both sterically hindered and unhindered aromatic amine to corresponding carbonyl compound was done in aq. medium by using DDQ. The optimized reaction protocol was found to be most simple, high yielding and novel method for oxidation of alkyl group of aromatic amine in to its carbonyl compound.

  8. Elementary reaction allyl radical with oxygen

    Institute of Scientific and Technical Information of China (English)

    DONG Feng; KONG Fanao


    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.

  9. Update on Robotic Laparoscopic Radical Prostatectomy

    Directory of Open Access Journals (Sweden)

    Garrett S. Matsunaga


    Full Text Available The da Vinci surgical robot has been shown to help shorten the learning curve for laparoscopic radical prostatectomy (LRP for both laparoscopically skilled and na surgeons[1,2]. This approach has shown equal or superior outcomes to conventional laparoscopic prostatectomy with regard to ease of learning, initial complication rates, conversion to open, blood loss, complications, continence, potency, and margin rates. Although the data are immature to compare oncologic and functional outcomes to open prostatectomy, preliminary data are promising.Herein, we review the technique and outcomes of robotic-assisted laparoscopic radical prostatectomy (RALP.

  10. Radical Islamism and Migrant Integration in Denmark

    DEFF Research Database (Denmark)

    Goli, Marco; Rezaei, Shahamak


    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...

  11. Resonance ionization detection of combustion radicals

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  12. Identification of isopropylbiphenyl, alkyl diphenylmethanes, diisopropylnaphthalene, linear alkyl benzenes and other polychlorinated biphenyl replacement compounds in effluents, sediments and fish in the Fox River System, Wisconsin (United States)

    Peterman, Paul H.; Delfino, Joseph J.


    Five polychlorinated biphenyl replacement dye solvents and a diluent present in carbonless copy paper were identified by gas chromatography/mass spectrometry in the following matrices: effluents from a de-inking–recycling paper mill and a municipal wastewater treatment plant receiving wastewaters from a carbonless copy paper manufacturing plant; sediments; and fish collected near both discharges in the Fox River System, Wisconsin. An isopropylbiphenyl dye solvent mixture included mono-, di- and triisopropylbiphenyls. Also identified were two dye solvent mixtures marketed under the trade name Santosol. Santosol 100 comprised ethyl-diphenylmethanes (DPMs), benzyl-ethyl-DPMs, and dibenzyl-ethyl-DPMs. Similarly, Santosol 150 comprised dimethyl-DPMs, benzyl-dimethyl-DPMs, and dibenzyl-dimethyl-DPMs. Diisopropylnaphthalenes, widely used as a dye solvent in Japan, were identified for the first time in the US environment. sec-Butylbiphenyls and di-sec-butylbiphenyls, likely constituents of a sec-butylbiphenyl dye solvent mixture, were tentatively identified. Linear alkyl benzenes (C10 to C13-LABs) constituted the Alkylate 215 diluent mixture. Although known to occur as minor constituents in linear alkyl sulfonate detergents, LAB residues have not been previously attributed to commercial use of LABs.

  13. Competing with the radical right. Distances between the European radical right and other parties on typical radical right issues

    NARCIS (Netherlands)

    Immerzeel, T.; Lubbers, M.; Coffe, H.R.


    The popularity of European Radical Right Populist parties (RRPs) has led to investigations into the distances between RRPs’ and other parties’ stances regarding immigration. This article adds to this literature by investigating the distance between RRPs and the other parties on a wider variety of ty

  14. Structural Characterization of N-Alkylated Twisted Amides: Consequences for Amide Bond Resonance and N-C Cleavage. (United States)

    Hu, Feng; Lalancette, Roger; Szostak, Michal


    Herein, we describe the first structural characterization of N-alkylated twisted amides prepared directly by N-alkylation of the corresponding non-planar lactams. This study provides the first experimental evidence that N-alkylation results in a dramatic increase of non-planarity around the amide N-C(O) bond. Moreover, we report a rare example of a molecular wire supported by the same amide C=O-Ag bonds. Reactivity studies demonstrate rapid nucleophilic addition to the N-C(O) moiety of N-alkylated amides, indicating the lack of n(N) to π*(C=O) conjugation. Most crucially, we demonstrate that N-alkylation activates the otherwise unreactive amide bond towards σ N-C cleavage by switchable coordination.

  15. Peroxy Radical Chemistry and Partitioning under a Ponderosa Pine Canopy (United States)

    Wolfe, G. M.; Cantrell, C. A.; Mauldin, L.; Kim, S.; Henry, S. B.; Boyle, E. S.; Karl, T.; Harley, P. C.; Turnipseed, A.; Zheng, W.; Flocke, F. M.; Apel, E. C.; Hornbrook, R. S.; Hall, S. R.; Ullmann, K.; Guenther, A. B.; DiGangi, J. P.; Kaser, L.; Schnitzhofer, R.; Hansel, A.; Graus, M.; Nakashima, Y.; Kajii, Y. J.; Keutsch, F. N.


    As the first intermediates in the OH-initiated oxidation of hydrocarbons, peroxy radicals are central to the photochemistry of the lower atmosphere. Peroxy radical abundance and partitioning controls relative rates of radical propagation and termination in low-NOx regimes, and the coupled cycling of these molecules lies at the heart of recently-highlighted deficiencies in traditional chemical mechanisms. Using observations of hydroperoxy (HO2) and total peroxy (HO2 + RO2) radicals acquired during the summer 2010 BEACHON-ROCs campaign, we explore the processes affecting radical-mediated chemistry within a rural Ponderosa pine forest in central Colorado. Steady-state and fully-coupled 0-D modeling studies are used to provide complementary perspectives on our understanding of the radical budget in this environment. Analysis will focus on the nature and impact of unidentified radical sources and sinks and on how the composition of the peroxy radical pool modulates radical regeneration.

  16. 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.

  17. Ultrafast synthesis of ultrahigh molar mass polymers by metal-catalyzed living radical polymerization of acrylates, methacrylates, and vinyl chloride mediated by SET at 25 degrees C. (United States)

    Percec, Virgil; Guliashvili, Tamaz; Ladislaw, Janine S; Wistrand, Anna; Stjerndahl, Anna; Sienkowska, Monika J; Monteiro, Michael J; Sahoo, Sangrama


    Conventional metal-catalyzed organic radical reactions and living radical polymerizations (LRP) performed in nonpolar solvents, including atom-transfer radical polymerization (ATRP), proceed by an inner-sphere electron-transfer mechanism. One catalytic system frequently used in these polymerizations is based on Cu(I)X species and N-containing ligands. Here, it is reported that polar solvents such as H(2)O, alcohols, dipolar aprotic solvents, ethylene and propylene carbonate, and ionic liquids instantaneously disproportionate Cu(I)X into Cu(0) and Cu(II)X(2) species in the presence of a diversity of N-containing ligands. This disproportionation facilitates an ultrafast LRP in which the free radicals are generated by the nascent and extremely reactive Cu(0) atomic species, while their deactivation is mediated by the nascent Cu(II)X(2) species. Both steps proceed by a low activation energy outer-sphere single-electron-transfer (SET) mechanism. The resulting SET-LRP process is activated by a catalytic amount of the electron-donor Cu(0), Cu(2)Se, Cu(2)Te, Cu(2)S, or Cu(2)O species, not by Cu(I)X. This process provides, at room temperature and below, an ultrafast synthesis of ultrahigh molecular weight polymers from functional monomers containing electron-withdrawing groups such as acrylates, methacrylates, and vinyl chloride, initiated with alkyl halides, sulfonyl halides, and N-halides.

  18. Binary functionalization of H:Si(111) surfaces by alkyl monolayers with different linker atoms enhances monolayer stability and packing. (United States)

    Arefi, Hadi H; Nolan, Michael; Fagas, Giorgos


    Alkyl monolayer modified Si forms a class of inorganic-organic hybrid materials with applications across many technologies such as thin-films, fuel/solar-cells and biosensors. Previous studies have shown that the linker atom, through which the monolayer binds to the Si substrate, and any tail group in the alkyl chain, can tune the monolayer stability and electronic properties. In this paper we study the H:Si(111) surface functionalized with binary SAMs: these are composed of alkyl chains that are linked to the surface by two different linker groups. Aiming to enhance SAM stability and increase coverage over singly functionalized Si, we examine with density functional theory simulations that incorporate vdW interactions, a range of linker groups which we denote as -X-(alkyl) with X = CH2, O(H), S(H) or NH(2) (alkyl = C6 and C12 chains). We show how the stability of the SAM can be enhanced by adsorbing alkyl chains with two different linkers, e.g. Si-[C, NH]-alkyl, through which the adsorption energy is increased compared to functionalization with the individual -X-alkyl chains. Our results show that it is possible to improve stability and optimum coverage of alkyl functionalized SAMs linked through a direct Si-C bond by incorporating alkyl chains linked to Si through a different linker group, while preserving the interface electronic structure that determines key electronic properties. This is important since any enhancement in stability and coverage to give more densely packed monolayers will result in fewer defects. We also show that the work function can be tuned within the interval of 3.65-4.94 eV (4.55 eV for bare H:Si(111)).

  19. 40 CFR 721.3025 - Fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (generic). (United States)


    ..., C12-18 alkyl esters (generic). 721.3025 Section 721.3025 Protection of Environment ENVIRONMENTAL... alkyl esters (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters...

  20. Radical Negativity: Music Education for Social Justice (United States)

    McLaren, Peter


    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…

  1. Serendipitous findings while researching oxygen free radicals. (United States)

    Floyd, Robert A


    This review is based on the honor of receiving the Discovery Award from the Society of Free Radical Biology and Medicine. The review is reflective and presents our thinking that led to experiments that yielded novel observations. Critical questioning of our understanding of oxygen free radicals in biomedical problems led us to use and develop more direct and extremely sensitive methods. This included nitrone free radical spin trapping and HPLC-electrochemical detection. This technology led to the pioneering use of salicylate to trap hydroxyl free radicals and show increased flux in ischemia/reperfused brain regions and also to first sensitively detect 8-hydroxyl-2-deoxyguanosine in oxidatively damaged DNA and help assess its role in cancer development. We demonstrated that methylene blue (MB) photoinduces formation of 8-hydroxyguanine in DNA and RNA and discovered that MB sensitively photoinactivates RNA viruses, including HIV and the West Nile virus. Studies in experimental stroke led us serendipitously to discover that alpha-phenyl-tert-butylnitrone (PBN) was neuroprotective if given after the stroke. This led to extensive commercial development of NXY-059, a PBN derivative, for the treatment of stroke. More recently we discovered that PBN nitrones have potent anti-cancer activity and are active in preventing hearing loss caused by acute acoustical trauma.

  2. Designed metalloprotein stabilizes a semiquinone radical (United States)

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


    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.

  3. Identity and Islamic Radicalization in Western Europe

    NARCIS (Netherlands)

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


    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

  4. Albert Einstein: Radical Pacifist and Democrat (United States)

    Jayaraman, T.

    We draw attention here to the radical political grounding of Einstein's pacifism. We also drescribe some less commonly known aspects of his commitment to civil liberties, particularly in the context of the anti-l hysteria and anti-racism current in the United States of the late 1940s and 1950s. We also examine briefly his views on socialism.

  5. Radical recombinations in acetylene-air flames

    NARCIS (Netherlands)

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


    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

  6. User involvement competence for radical innovation

    DEFF Research Database (Denmark)

    Lettl, Christopher


    -assisted navigation systems. The case study analysis reveals that firms who closely interact with specific users benefit significantly for their radical innovation work. These users have a high motivation toward new solutions, are open to new technologies, possess diverse competencies, and are embedded into a very...

  7. 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...

  8. Radical Change: Digital Age Literature and Learning. (United States)

    Dresang, Eliza T.; McClelland, Kathryn


    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…

  9. Customers as Partners in Radical Service Innovation

    DEFF Research Database (Denmark)

    Scupola, Ada; Nicolajsen, Hanne Westh


      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 invo...

  10. Free radicals in adolescent varicocele testis. (United States)

    Romeo, Carmelo; Santoro, Giuseppe


    We examine the relationship between the structure and function of the testis and the oxidative and nitrosative stress, determined by an excessive production of free radicals and/or decreased availability of antioxidant defenses, which occur in the testis of adolescents affected by varicocele. Moreover, the effects of surgical treatment on oxidative stress were provided. We conducted a PubMed and Medline search between 1980 and 2014 using "adolescent," "varicocele," "free radicals," "oxidative and nitrosative stress," "testis," and "seminiferous tubules" as keywords. Cross-references were checked in each of the studies, and relevant articles were retrieved. We conclude that increased concentration of free radicals, generated by conditions of hypoxia, hyperthermia, and hormonal dysfunction observed in adolescent affected by varicocele, can harm germ cells directly or indirectly by influencing nonspermatogenic cells and basal lamina. With regard to few available data in current literature, further clinical trials on the pre- and postoperative ROS and RNS levels together with morphological studies of the cellular component of the testis are fundamental for complete comprehension of the role played by free radicals in the pathogenesis of adolescent varicocele and could justify its pharmacological treatment with antioxidants.


    Methods for the determination of the anionic surfactant Dowfax 8390 are described. Dowfax is a complex mixture of various alkylated and sulfonated diphenyl oxides. The primary component of Dowfax is monoalkylated disulfonated diphenyl oxide (MADS). This work uses ion pairing chro...

  12. Effect of cotton pectin content and bioscouring on alkyl-dimethyl-benzyl-ammonium chloride adsorption (United States)

    Our previous research has shown both the rate and the total amount of alkyl-dimethyl-benzyl-ammonium chloride (ADBAC) exhausted from a bulk solution of ADBAC are significantly greater for greige cotton nonwovens than cotton nonwovens that have been both scoured and bleached. The presence of pectin ...

  13. Alkyl ether lipids, ion channels and lipid raft reorganization in cancer therapy. (United States)

    Jaffrès, Paul-Alain; Gajate, Consuelo; Bouchet, Ana Maria; Couthon-Gourvès, Hélène; Chantôme, Aurélie; Potier-Cartereau, Marie; Besson, Pierre; Bougnoux, Philippe; Mollinedo, Faustino; Vandier, Christophe


    Synthetic alkyl lipids, such as the ether lipids edelfosine (1-O-octadecyl-2-O-methyl-rac-glycero-3-phosphocholine) and ohmline (1-O-hexadecyl-2-O-methyl-rac-glycero-3-β-lactose), are forming a class of antitumor agents that target cell membranes to induce apoptosis and to decrease cell migration/invasion, leading to the inhibition of tumor and metastasis development. In this review, we present the structure-activity relationship of edelfosine and ohmline, and we point out differences and similarities between these two amphiphilic compounds. We also discuss the mechanisms of action of these synthetic alkyl ether lipids (involving, among other structures and molecules, membrane domains, Fas/CD95 death receptor signaling, and ion channels), and highlight a key role for lipid rafts in the underlying process. The reorganization of lipid raft membrane domains induced by these alkyl lipids affects the function of death receptors and ion channels, thus leading to apoptosis and/or inhibition of cancer cell migration. The possible therapeutic use of these alkyl lipids and the clinical perspectives for these lipids in prevention or/and treatment of tumor development and metastasis are also discussed.

  14. Electron beam induced electronic transport in alkyl amine-intercalated VOx nanotubes

    NARCIS (Netherlands)

    O'Dwyer, C.; Lavayen, V.; Clavijo-Cedeno, C.; Sotomayor Torres, C.M.


    The electron beam induced electronic transport in primary alkyl amine-intercalated V2O5 nanotubes is investigated where the organic amine molecules are employed as molecular conductive wires to an aminosilanized substrate surface and contacted to Au interdigitated electrode contacts. The results dem

  15. Ruthenium(II)-Catalyzed C-C Arylations and Alkylations: Decarbamoylative C-C Functionalizations. (United States)

    Moselage, Marc; Li, Jie; Kramm, Frederik; Ackermann, Lutz


    Ruthenium(II)biscarboxylate catalysis enabled selective C-C functionalizations by means of decarbamoylative C-C arylations. The versatility of the ruthenium(II) catalysis was reflected by widely applicable C-C arylations and C-C alkylations of aryl amides, as well as acids with modifiable pyrazoles, through facile organometallic C-C activation.

  16. Adsorption of alkyl-dimethyl-benzyl-ammonium chloride on differently pretreated nonwoven cotton substrate (United States)

    The adsorption of alkyl-dimethyl-benzyl-ammonium chloride (ADBAC), a cationic surfactant commonly employed as an antimicrobial agent, on greige, alkaline scoured, and bleached nonwoven cotton fabrics was investigated at varying surfactant concentrations and liquor ratios using UV-vis absorption spec...


    Ionic liquids as a clean catalyst for the alkylation of isobutane with 2-buteneKyesang Yoo, a Vasudevan V. Namboodiri,b Panagiotis G. Smirniotis,*a and Rajender S. Varma*b a Department of Chemical Engineering, University of Cincinnati, Cincinnati, OH 45221-0171, USA. ...

  18. Interplay between alkyl chain asymmetry and cholesterol addition in the rigid ion pair amphiphile bilayer systems (United States)

    Huang, Fong-yin; Chiu, Chi-cheng


    Ion pair amphiphile (IPA), a molecular complex composed of a pair of cationic and anionic surfactants, has been proposed as a novel phospholipid substitute. Controlling the physical stability of IPA vesicles is important for its application developments such as cosmetic and drug deliveries. To investigate the effects of IPA alkyl chain combinations and the cholesterol additive on the structural and mechanical properties of IPA vesicular bilayers, we conducted a series of molecular dynamics studies on the hexadecyltrimethylammonium-dodecylsulfate (HTMA-DS) and dodecyltrimethylammonium-hexadecylsulfate (DTMA-HS) IPA bilayers with cholesterol. We found that both IPA bilayers are in the gel phase at 298 K, consistent with experimental observations. Compared with the HTMA-DS system, the DTMA-HS bilayer has more disordered alkyl chains in the hydrophobic region. When adding cholesterol, it induces alkyl chain ordering around its rigid sterol ring. Yet, cholesterol increases the molecular areas for all species and disturbs the molecular packing near the hydrophilic region and the bilayer core. Cholesterol also promotes the alkyl chain mismatch between the IPA moieties, especially for the DTMA-HS bilayer. The combined effects lead to non-monotonically enhancement of the membrane mechanical moduli for both IPA-cholesterol systems. Furthermore, cholesterol can form H-bonds with the alkylsulfate and thus enhance the contribution of alkylsulfate to the overall mechanical moduli. Combined results provide valuable molecular insights into the roles of each IPA component and the cholesterol on modulating the IPA bilayer properties.


    NARCIS (Netherlands)



    Color tuning of luminescence via molecular engineering of the Active polymer is important for the commercial application of pi-conjugated polymers in photonic devices. The synthesis of a series of regiospecific alkylated polythiophenes is described. in which the effective conjugation length could be

  20. The acid free asymmetric intermolecular α-alkylation of aldehydes in fluorinated alcohols. (United States)

    Xiao, Jian; Zhao, Kai; Loh, Teck-Peng


    The acid free asymmetric intermolecular α-alkylation of aldehydes with alcohols has been discovered using trifluoroethanol as solvent. This unprecedented system affords the enantioenriched functionalized primary alcohols (after NaBH(4) reduction) in high yields and good to excellent enantioselectivities with wide substrate scope in the absence of any acid additive.

  1. New Route to Synthesize Surface Organometallic Complexes (SOMC): An Approach by Alkylating Halogenated Surface Organometallic Fragments

    KAUST Repository

    Hamieh, Ali Imad


    The aim of this thesis is to explore new simpler and efficient routes for the preparation of surface organometallic complexes (SOMC) for the transformation of small organic molecules to valuable products. The key element in this new route relies on surface alkylation of various halogenated surface coordination complexes or organometallic fragments (SOMF).

  2. Determinants of serum levels of perfluorinated alkyl acids in Danish pregnant women

    DEFF Research Database (Denmark)

    Bjerregaard-Olesen, Christian; Bach, Cathrine C; Long, Manhai


    Humans are exposed to perfluorinated alkyl acids (PFAAs) from food, drinking water, air, dust, and consumer products. PFAAs are persistent and bio-accumulative. In the present study, we aimed to establish how the serum levels of PFAAs differ according to age, pre-pregnancy body mass index (BMI...

  3. Long chain alkyl and alkenyl phenols from the roots of Ozoroa insignis

    Energy Technology Data Exchange (ETDEWEB)

    Yonghong Liu [Chinese Academy of Sciences, Guangzhou (China). Guangdong Key Lab. of Marine Materia Medica. South China Sea Institute of Oceanology; Abreu, Pedro J.M. [Universidade Nova de Lisboa, Caparica (Portugal). Dept. de Quimica. REQUIMTE


    Bioassay-guided fractionation of the ethanolic root extract of Ozoroa insignis, collected in Guinea-Bissau, led to the isolation of a 41-member library of alkyl and alkenylphenols, whose structures were determined by {sup 1}H and {sup 13}C NMR, and GCMS. Determination of double-bond positions in the side chains of alkenylphenols were established by methylthiolation-GCMS. (author)

  4. Memory effects in palladium-catalyzed allylic Alkylations of 2-cyclohexen-1-yl acetate

    DEFF Research Database (Denmark)

    Svensen, Nina; Fristrup, Peter; Tanner, David Ackland;


    The objective of this work was to characterize the enantiospecificity of the allylic alkylation of enantioenriched 2-cyclohexen-1-yl acetate with the enolate ion of dimethyl malonate catalyzed by unsymmetrical palladium catalysts. The precatalysts employed were (eta(3)-allyl)PdLCl, where L is a m...

  5. Determination of monounsaturated alkyl side chain 2-alkylcyclobutanones in irradiated foods

    NARCIS (Netherlands)

    Horvatovich, Péter; Miesch, Michel; Hasselmann, Claude; Delincée, Henry; Marchioni, Eric


    The 2-alkylcyclobutanones (2-ACBs) are formed from triglycerides by irradiation treatment and may be used as markers for this type of food processing. This paper describes a detection method for the analysis of monounsaturated alkyl side chain 2-ACBs, which is formed upon irradiation from monounsatu

  6. Mimicking cell membrane-like structures on alkylated silicon surfaces by peptide amphiphiles

    Energy Technology Data Exchange (ETDEWEB)

    Shamsi, Fahimeh, E-mail: [Biophysics and Bioengineering, School of Chemical and Biomolecular Engineering, University of Sydney, Sydney, NSW 2006 (Australia); Coster, Hans G.L. [Biophysics and Bioengineering, School of Chemical and Biomolecular Engineering, University of Sydney, Sydney, NSW 2006 (Australia)


    Highlights: {yields} Lipidated peptide amphiphiles were hydrophobically attached onto an alkylated surface. {yields} Morphology of nanofibres of the peptide amphiles depended on the acyl chain length. {yields} We show that extended 2D analogues of the nanofibre surface can be constructed. {yields} Peptide amphiphiles with shorter acyl chains formed more homogeneous layers. - Abstract: We present a new strategy for flexible attachment of peptide amphiphiles on functionalized silicon surfaces. This method involves the production of an alkylated surface on which a lipidated peptide can then be attached through hydrophobic interaction. We applied this to two derivatives of amphiphilic peptide molecules with the same amino acid sequence (A-A-A-A-G-G-G-E-R-G-D) but different in alkyl chain lengths (palmitic acid, undecanoic acid). The basis of this work was to develop substrates which are more biocompatible and bioactive. The ultra-thin peptide amphiphile films were characterized using electrical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (ATR-FTIR) spectroscopy. The results demonstrated that the length of the alkyl chain in the peptide amphiphile affects the packing and coverage of the peptides on the silicon surface.

  7. Alkyl-Functionalized Oxide-Free Silicon Nanoparticles: Synthesis and Optical Properties

    NARCIS (Netherlands)

    Rosso-Vasic, M.; Spruijt, E.; Lagen, van B.; Cola, de L.; Zuilhof, H.


    Highly monodisperse silicon nanoparticles (1.57 ± 0.21 nm) are synthesized with a covalently attached alkyl monolayer on a gram scale. Infrared spectroscopy shows that these silicon nanoparticles contain only a few oxygen atoms per nanoparticle. XPS spectra clearly show the presence of unoxidized Si

  8. Cytotoxic geranylated xanthones and O-alkylated derivatives of alpha-mangostin

    DEFF Research Database (Denmark)

    Ha, Ly Dieu; Hansen, Poul Erik; Vang, Ole;


    -O-alkylated α-mangostin derivatives were synthesized from α-mangostin. The structures of all compounds were assigned by spectroscopic methods (1D and 2D NMR and MS). Cytotoxicity of selected xanthones against MCF-7 and DLD-1 cell lines was examined. Evaluation of the structure–activity relationship showed...

  9. A General Two—Step Procedure for the N—Alkylation of Selenoamides

    Institute of Scientific and Technical Information of China (English)

    赵华绒; 俞庆森


    Selenoamides are prepared via N-alkylated in a two-step proce-dure:Benzotriazole,aldehyde and primary selenoamide reacted togeher to yield an adduct which was then reduced to the N-substituted selenoamide by NaBH4.

  10. Potential biological sources of long chain alkyl diols in a lacustrine system

    NARCIS (Netherlands)

    Villanueva, Laura; Besseling, Marc; Rodrigo-Gámiz, Marta; Rampen, Sebastiaan W.; Verschuren, Dirk; Sinninghe Damsté, Jaap S.


    Long chain alkyl diols (LCDs) have been detected in a range of marine and lacustrine environments, as well as in several algal cultures. However, the identity of the producers, their preferred ecological niche and seasonality are uncertain. We applied a gene-based approach to determine the identity

  11. Perfluorinated alkylated acids in groundwater and drinking water: Identification, origin and mobility

    NARCIS (Netherlands)

    C. Eschauzier; K.J. Raat; P.J. Stuyfzand; P. de Voogt


    Human exposure to perfluorinated alkylated acids (PFAA) occurs primarily via the dietary intake and drinking water can contribute significantly to the overall PFAA intake. Drinking water is produced from surface water and groundwater. Waste water treatment plants have been identified as the main sou

  12. Alkyl amine and vegetable oil mixture-a viable candidate for CO2 capture and utilization. (United States)

    Uma Maheswari, A; Palanivelu, K


    In this present work, the absorption of CO2 in alkyl amines and vegetable oil mixture has been evaluated. The results showed that the absorption is higher in alkyl amines and vegetable oil mixture compared with the aqueous alkyl amines. In addition to that, by employing the greener and non-toxic vegetable oil media, the CO2 gas has been captured as well as converted into value-added products, such as carbamates of ethylenediamine, diethylenetriamine, and triethylenetetramine. The carbamates have been isolated and characterized by Fourier transform infrared and (1)H and (13)C nuclear magnetic resonance spectroscopic techniques. The formation of these products in precipitate form has not been observed in the case of aqueous medium. Among the various alkyl amine and vegetable oil combinations, triethylenetetramine in coconut oil medium showed the maximum CO2 capture capacity of 72%. The coconut oil used for the process has been recovered, recycled, and reused for 3 cycles. Thus, this novel scheme seems to be a better alternative to conquer the drawback of aqueous amine-based CO2 capture as well as for the capture and utilization of the CO2 gas to gain the value-added products.

  13. The influence of acidity on zeolite H-BEA catalyzed isobutane/n-butene alkylation

    NARCIS (Netherlands)

    Nivarthy, Gautam S.; Seshan, K.; Lercher, Johannes A.


    The influence of the concentration of acid sites for isobutane/n-butene alkylation on zeolite BEA with varying degrees of Na+ ion exchange is reported. All catalysts studied showed complete n-butene conversion over a significant time-on-stream. Isooctanes were the dominating products over H-BEA, whi

  14. Enhancing alkylating agent resistance through ERCC2 gene transfection in human glioma cell line

    Institute of Scientific and Technical Information of China (English)

    CHEN Zhongping 陈忠平; ZHANG Junying 张俊英; Gérard MOHR


    Objective To confirm the enhancing effect of excision repair cross complementing rodent repair deficiency gene 2 (ERCC2) on alkylating agents resistance. Methods The authors constructed a pcDNA3-ERCC2 plasmid. The pcDNA3-ERCC2 was transfected into a selected ERCC2 negative human glioma cell line, SKMG-4, using liposome-mediated transfection. After G418 selection, a stable transfected cell line was obtained and tested for cytotoxicity of several alkylating agents. Results The stable transfectant was obtained and confirmed by RT-PCR as well as Western blot analysis to be strongly expressing ERCC2 at both mRNA and protein levels. The IC90 (μmol/L) of two alkylating agents, cisplatin and melphalan, increased from 1.0 to 1.75 (75%) and 5.6 to 9.0 (61%), respectively, compared with control cell line. Conclusion The present data provided evidences and confirmed the authors' previous results that ERCC2 contributes, at least partially, to alkylating agent resistance in human glioma cell line.

  15. Tungstosilicic Acid: An Efficient and Ecofriendly Catalyst for the Conversion of Alcohols to Alkyl Iodides

    Directory of Open Access Journals (Sweden)

    Masoud Mokhtary


    Full Text Available Treatment of a range of benzylic, allylic, and secondary aliphatic alcohols with potassium iodides in the presence of H4SiW12O40 affords the corresponding alkyl iodides in good to excellent yield with straightforward purification at room temperature in CH3CN.

  16. Hydrocarbon adsorption in an aqueous environment: A computational study of alkyls on Cu(111) (United States)

    Montemore, Matthew M.; Andreussi, Oliviero; Medlin, J. Will


    Hydrocarbon chains are important intermediates in various aqueous-phase surface processes, such as CO2 electroreduction, aqueous Fischer-Tropsch synthesis, and aqueous phase reforming of biomass-derived molecules. Further, the interaction between water and adsorbed hydrocarbons represents a difficult case for modern computational methods. Here, we explore various methods for calculating the energetics of this interaction within the framework of density functional theory and explore trade-offs between the use of low water coverages, molecular dynamics approaches, and minima hopping for identification of low energy structures. An effective methodology for simulating low temperature processes is provided by using a unit cell in which the vacuum space is filled with water, employing the minima hopping algorithm to search for low-lying minima, and including dispersion (van der Waals) interactions. Using this methodology, we show that a high coverage of adsorbed alkyls is destabilized by the presence of water, while a low coverage of alkyls is stabilized. Solvation has a small effect on the energetics of hydrocarbon chain growth, generally decreasing its favorability at low temperatures. We studied higher temperatures by running molecular dynamics simulations starting at the minima found by the minima hopping algorithm and found that increased temperatures facilitate chain growth. The self-consistent continuum solvation method effectively describes the alkyl-water interaction and is in general agreement with the explicit solvation results in most cases, but care should be taken at high alkyl coverage.

  17. Full-Scale Continuous Mini-Reactor Setup for Heterogeneous Grignard Alkylation of a Pharmaceutical Intermediate

    DEFF Research Database (Denmark)

    Pedersen, Michael Jønch; Holm, Thomas; Rahbek, Jesper P.


    A reactor setup consisting of two reactors in series has been implemented for a full-scale, heterogeneous Grignard alkylation. Solutions pass from a small filter reactor into a static mixer reactor with multiple side entries, thus combining continuous stirred tank reactor (CSTR) and plug flow rea...

  18. NMR study of 1,4-dihydropyridine derivatives endowed with long alkyl and functionalized chains

    Energy Technology Data Exchange (ETDEWEB)

    Suarez, Margarita; Salfran, Esperanza; Rodriguez, Hortensia; Coro, Julieta, E-mail: msuarez@fq.uh.c [Universidad de La Habana (Cuba). Facultad de Quimica. Lab. de Sintesis Organica; Molero, Dolores; Saez, Elena [Universidad Complutense, Madrid (Spain). CAI-RMN; Martinez-Alvarez, Roberto; Martin, Nazario [Universidad Complutense, Madrid (Spain). Facultad de Quimica. Dept. de Quimica Organica I


    The {sup 1}H , {sup 13}C and {sup 15}N NMR spectroscopic data for 1,4-dihydropyridine endowed with long alkyl and functionalized chain on C-3 and C-5, have been fully assigned by combination of one- and two dimensional experiments (DEPT, HMBC, HMQC, COSY, nOe). (author)

  19. Solvent effects in adsorption of alkyl thiols on gold structures: A molecular simulation study

    NARCIS (Netherlands)

    Pool, R.; Schapotschnikow, P.Z.; Vlugt, T.J.H.


    We carried out Monte Carlo simulations of gold nanocrystals (NCs) and (111) slabs covered with alkyl thiols, with and without explicit solvent (n-hexane), at T ) 300 K. Adsorption isotherms for propane- and octanethiol showed a phase behavior measured previously in experiments. Comparison of the ads

  20. Surprisingly Mild Enolate-Counterion-Free Pd(0)-Catalyzed Intramolecular Allylic Alkylations

    DEFF Research Database (Denmark)

    Madec, David; Prestat, Guillaume; Martini, Elisabetta;


    Palladium-catalyzed intramolecular allylic alkylations of unsaturated EWG-activated amides can take place under phase-transfer conditions or in the presence of a crown ether. These new reaction conditions are milder and higher yielding than those previously reported. A rationalization for such an...

  1. Carbon Dioxide Induced Alkene Extrusion from Bis(pentamethylcyclopentadienyl)titanium(III) Alkyls

    NARCIS (Netherlands)

    Luinstra, Gerrit A.; Teuben, Jan H.


    Reaction of titanium(III) alkyls, (η5-C5Me5)2TiR (R = Et or Prn), in toluene solution with CO2 proceeds at room temperature with formation of the titanium formate (η5-C5Me5)2TiO2CH, and the corresponding alkene (ethene or propene).

  2. In vitro susceptibilities in lymphocytes from mothers and cord blood to the monofunctional alkylating agent EMS

    DEFF Research Database (Denmark)

    Wyatt, N P; Falque-Gonzalez, C; Farrar, D;


    at the Bradford Royal Infirmary collected venous blood samples from mothers at the time of birth and venous cord blood post-delivery. Lymphocytes were isolated from both blood types and examined in the alkaline comet assay using the monofunctional alkylating agent ethyl methanesulphonate (EMS). There were...

  3. Experimental hydrophobicity parameters of perfluorinated alkylated substances from reversed-phase high performance liquid chromatography

    NARCIS (Netherlands)

    de Voogt, P.; Zurano, L.; Serné, P.; Haftka, J.J.H.


    Capacity factors of perfluorinated alkylated substances were obtained from isocratic reversed-phase high-performance liquid chromatography-mass spectrometry experiments at different organic modifier strengths of the mobile phase. The resulting capacity factor v. modifier strengths plots were extrapo


    NARCIS (Netherlands)



    Dialkylcarbodiimides in the presence of a Cu-I catalyst react cleanly with the hydroxyl group of N-methylated (1R,2S)-ephedrine and (1S,2S)-pseudoephedrine. These adducts react with nucleophiles like alkyl and aryl thiols as well as thioic acids and phthalimide to form the substitution products with

  5. Novel One-step Preparation of Functional Ionic Liquids Using Epoxides as Alkylation Reagents

    Institute of Scientific and Technical Information of China (English)

    MI Xue-Ling; LUO San-Zhong; HE Jia-Qi; CHENG Jin-Pei


    @@ Owing to their unique chemical and physical properties, ionic liquids (ILs) have received focus attention for application as solvent alternatives. ILs can be used in place of organic solvents in synthesis, catalysis, electrochem istry and liquid/liquid extractions. The commonly reported ILs have relied on pyridinium or imidazolium cations bearing simple alkyl groups.

  6. Influence of Backbone Fluorination in Regioregular Poly(3-alkyl-4-fluoro)thiophenes

    KAUST Repository

    Fei, Zhuping


    © 2015 American Chemical Society. We report two strategies toward the synthesis of 3-alkyl-4-fluorothiophenes containing straight (hexyl and octyl) and branched (2-ethylhexyl) alkyl groups. We demonstrate that treatment of the dibrominated monomer with 1 equiv of alkyl Grignard reagent leads to the formation of a single regioisomer as a result of the pronounced directing effect of the fluorine group. Polymerization of the resulting species affords highly regioregular poly(3-alkyl-4-fluoro)thiophenes. Comparison of their properties to those of the analogous non-fluorinated polymers shows that backbone fluorination leads to an increase in the polymer ionization potential without a significant change in optical band gap. Fluorination also results in an enhanced tendency to aggregate in solution, which is ascribed to a more co-planar backbone on the basis of Raman and DFT calculations. Average charge carrier mobilities in field-effect transistors are found to increase by up to a factor of 5 for the fluorinated polymers.

  7. Catalytic Enantioselective Alkylation of Benzaldehyde with Diethylzinc Using Chiral Nonracemic (Thio)-phosphoramidates

    NARCIS (Netherlands)

    Hulst, Ron; Heres, Hero; Fitzpatrick, Kevin; Peper, Nathalie C.M.W.; Kellogg, Richard M.


    Two chiral nonracemic γ-amino alcohols, ephedrine thiol and the corresponding (thio)-phosphoramidates have been examined as catalysts for the enantioselective alkylation of benzaldehyde by diethylzinc. Addition of titanium tetraisopropoxide increases the yield as well as the enantioselectivity; 1-ph

  8. Thermodynamic Interactions between Polystyrene and Long-Chain Poly(n-Alkyl Acrylates) Derived from Plant Oils. (United States)

    Wang, Shu; Robertson, Megan L


    Vegetable oils and their fatty acids are promising sources for the derivation of polymers. Long-chain poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) are readily derived from fatty acids through conversion of the carboxylic acid end-group to an acrylate or methacrylate group. The resulting polymers contain long alkyl side-chains with around 10-22 carbon atoms. Regardless of the monomer source, the presence of alkyl side-chains in poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) provides a convenient mechanism for tuning their physical properties. The development of structured multicomponent materials, including block copolymers and blends, containing poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) requires knowledge of the thermodynamic interactions governing their self-assembly, typically described by the Flory-Huggins interaction parameter χ. We have investigated the χ parameter between polystyrene and long-chain poly(n-alkyl acrylate) homopolymers and copolymers: specifically we have included poly(stearyl acrylate), poly(lauryl acrylate), and their random copolymers. Lauryl and stearyl acrylate were chosen as model alkyl acrylates derived from vegetable oils and have alkyl side-chain lengths of 12 and 18 carbon atoms, respectively. Polystyrene is included in this study as a model petroleum-sourced polymer, which has wide applicability in commercially relevant multicomponent polymeric materials. Two independent methods were employed to measure the χ parameter: cloud point measurements on binary blends and characterization of the order-disorder transition of triblock copolymers, which were in relatively good agreement with one another. The χ parameter was found to be independent of the alkyl side-chain length (n) for large values of n (i.e., n > 10). This behavior is in stark contrast to the n-dependence of the χ parameter predicted from solubility parameter theory. Our study complements prior work investigating the interactions between

  9. Radical scavenging activity of antioxidants evaluated by means of electrogenerated HO radical. (United States)

    Oliveira, Raquel; Geraldo, Dulce; Bento, Fátima


    A method is proposed and tested concerning the characterization of antioxidants by means of their reaction with electrogenerated HO radicals in galvanostatic assays with simultaneous O2 evolution, using a Pt anode fairly oxidized. The consumption of a set of species with antioxidant activity, ascorbic acid (AA), caffeic acid (CA), gallic acid (GA) and trolox (T), is described by a first order kinetics. The rate of the processes is limited by the kinetics of reaction with HO radicals and by the kinetics of charge transfer. Information regarding the scavenger activity of antioxidants is obtained by the relative value of the rate constant of the reaction between antioxidants and HO radicals, k(AO,HO)/k(O2). The number of HO radicals scavenged per molecule of antioxidant is also estimated and ranged from 260 (ascorbic acid) to 500 (gallic acid). The method is applied successfully in the characterization of the scavenger activity of ascorbic acid in a green-tea based beverage.

  10. Pressure effects on the radical-radical recombination reaction of photochromic bridged imidazole dimers. (United States)

    Mutoh, Katsuya; Abe, Jiro


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


    Institute of Scientific and Technical Information of China (English)

    Cheng-long Zhang; Yi-xian Wu; Xiao-yan Meng; Qiang Huang; Guan-ying Wu; Ri-wei Xu


    The highly reactive polyisobutylenes (PIBs) with 6t-double bonds (87.5 mol%) or tert-chloro (tert-Cl) groups (95 mol%) could be prepared via the cationic polymerization of isobutylene (IB) coinitiated by BF3 or TiCl4 respectively. The Friedel-Crafts alkylation of diphenylamine (DPA) with the highly reactive PIB with α-double bonds was further conducted under different conditions, such as at different alkylation temperature, in the mixed solvents of CH2Cl2/n-hexane with different solvent polarity and at DPA concentration ([DPA]). The resultant PIBs with sec-arylamino terminal groups were characterized by GPC with RI/UV dual detectors and 1H-NMR spectrum. The experimental results indicated that alkylation efficiency increased with increases in reaction temperature, solvent polarity and [DPA]. The 77 mol% of sec-arylamino terminated PIBs could be obtained in 10/90 (V/V) mixture of nHex/CH2Cl2 with [DPA]/[PIB] of 3.0 at 60℃ for 45 h. Moreover, the alkylation of DPA with highly reactive PIBs with mainly tert-CI terminal groups was also carried out in 10/90 (V/V) mixture of CH2/Cl2/nHex with [DPA]/[PIB] = 3.0 at 60℃ for 45 h, and almost monoalkylation with 100 mol% sec-arylamino terminal groups could be achieved. These results will help further explorations of the molecular engineering via combination of cationic polymerization with alkylation.

  12. The effect of the cation alkyl chain branching on mutual solubilities with water and toxicities (United States)

    Kurnia, Kiki A.; Sintra, Tânia E.; Neves, Catarina M. S. S.; Shimizu, Karina; Lopes, José N. Canongia; Gonçalves, Fernando; Ventura, Sónia P. M.; Freire, Mara G.; Santos, Luís M. N. B. F.; Coutinho, João A. P.


    The design of ionic liquids has been focused on the cation-anion combinations but other more subtle approaches can be used. In this work the effect of the branching of the cation alkyl chain on the design of ionic liquids (ILs) is evaluated. The mutual solubilities with water and toxicities of a series of bis(trifluoromethylsulfonyl)-based ILs, combined with imidazolium, pyridinium, pyrrolidinium, and piperidinium cations with linear or branched alkyl chains, are reported. The mutual solubility measurements were carried out in the temperature range from (288.15 to 323.15) K. From the obtained experimental data, the thermodynamic properties of the solution (in the water-rich phase) were determined and discussed. The COnductor like Screening MOdel for Real Solvents (COSMO-RS) was used to predict the liquid-liquid equilibrium. Furthermore, molecular dynamic simulations were also carried out aiming to get a deeper understanding of these fluids at the molecular level. The results show that the increase in the number of atoms at the cation ring (from five to six) leads to a decrease in the mutual solubilities with water while increasing their toxicity, and as expected from the well-established relationship between toxicities and hydrophobicities of ILs. The branching of the alkyl chain was observed to decrease the water solubility in ILs, while increasing the ILs solubility in water. The inability of COSMO-RS to correctly predict the effect of branching alkyl chains toward water solubility on them was confirmed using molecular dynamic simulations to be due to the formation of nano-segregated structures of the ILs that are not taken into account by the COSMO-RS model. In addition, the impact of branched alkyl chains on the toxicity is shown to be not trivial and to depend on the aromatic nature of the ILs. PMID:25119425

  13. Alkyl protocatechuates as novel urinary biomarkers of exposure to p-hydroxybenzoic acid esters (parabens). (United States)

    Wang, Lei; Kannan, Kurunthachalam


    Human exposure to p-hydroxybenzoic acid esters (parabens) is a concern, owing to adverse health effects of these compounds. Parabens are metabolized and eliminated from the human bodies within a few hours of exposure. In this study, for the first time, methyl- and ethyl-protocatechuates (OH-MeP and OH-EtP) and their parent compounds, methyl- (MeP) and ethyl-parabens (EtP), were determined in urine samples collected from U.S. children and adults. Alkyl protocatechuates were found in almost all urine samples, with median concentrations of 11.8 (OH-MeP) and 2.90ng/mL (OH-EtP) in adults, and 5.43 (OH-MeP) and 0.85ng/mL (OH-EtP) in children. In adults, the concentrations of urinary OH-MeP and OH-EtP were higher than the corresponding concentrations of MeP and EtP. Significant correlation between OH-MeP/OH-EtP and MeP/EtP was observed. This is the first report to document hydroxylation of parabens in humans, and to propose hydroxylated metabolites (i.e., alkyl protocatechuates) as alternative biomarkers of exposure to parabens in human biomonitoring studies. The rates of transformation of parabens between children and adults appeared to be different, as evidenced from the slopes of regression between alkyl protocatechuates and parabens. In addition to alkyl protocatechuates, hydroxybenzoic acid (4-HB) and 3,4-dihydroxybenzoic acid (3,4-DHB) were found at considerable levels in the urine samples. The occurrence of a significant proportion of alkyl protocatechuates and 3,4-DHB suggests the need for inclusion of these derivatives in accurate estimation of human exposure to parabens and in epidemiological studies that associate paraben exposure to health outcomes in populations.

  14. 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:


    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

  15. From N-vinylpyrrolidone anions to modified paraffin-like oligomers via double alkylation with 1,8-dibromooctane: access to covalent networks and oligomeric amines for dye attachment (United States)

    Obels, Daniela; Lievenbrück, Melanie


    Summary The double alkylation of N-vinylpyrrolidone (N-VP) with 1,8-dibromooctane yields paraffin-like oligomeric chains bearing polymerizable vinyl moieties. These oligomers were radically crosslinked in bulk with N-VP as co-monomer yielding swellable polymer disks. The vinylic side groups of the N-VP oligomers allow thiol–ene click reactions with 2-aminoethanethiol hydrochloride to obtain reactive amino-functionalized oligomers. Further modification of the free amino groups with 1,4-difluoro-9,10-anthraquinone (DFA) yields red-colored oligomeric anthraquinone dyes. The final reaction of DFA-substituted N-VP oligomers with Jeffamine® M 600 leads to blue-colored and branched oligomers with poly(ethylene glycol) side chains. PMID:27559389

  16. The Reaction Kinetics of Neutral Free Radicals and Radical Ions Studied by Laser Flash Photolysis


    Friedline, Robert Alan


    t-Butoxyl radical has been used as a chemical model for hydrogen abstractions in many enzymatic and biological systems. However, the question has arisen as to how well this reactive intermediate mimics these systems. In addressing this concern, absolute rate constants and Arrhenius parameters for hydrogen abstraction by t-butoxyl radical were measured for a broad class of substrates including amines, hydrocarbons, and alcohols using laser flash photolysis. Initially, no obvious reactivity ...

  17. Evaluation of the radical scavenging activity of a series of synthetic hydroxychalcones towards the DPPH radical

    Directory of Open Access Journals (Sweden)



    Full Text Available Sixteen hydroxychalcones were synthesized in sufficient purity by the Claisen–Schmidt condensation between appropriate acetophenones and aromatic aldehydes. All the compounds were evaluated for their ability to scavenge the stable free 2,2-diphenyl-1-picrylhydrazyl (DPPH radical. Important structure–activity relationships were observed that strongly contribute to the knowledge for the design of DPPH radical scavenging chalcones. Relevant theoretical parameters were computed in an attempt to understand and explain the obtained experimental results.

  18. Nature of the lowest excited states of neutral polyenyl radicals and polyene radical cations (United States)

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


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

  19. Radical surgery compared with intracavitary cesium followed by radical surgery in cervical carcinoma stage IB

    Energy Technology Data Exchange (ETDEWEB)

    Tinga, D.J.; Bouma, J.; Aalders, J.G. (Dept. of Obstetrics and Gynaecology, State Univ. Hospital, Groningen (Netherlands)); Hollema, H. (Dept. of Pathology, State Univ. Hospital, Groningen (Netherlands))


    Forty-nine patients aged {le} 45 years, with cervical carcinoma stage IB ({le} 3 cm) were treated with either primary radical surgery (n = 26), or intracavitary irradiation followed by radical surgery (n = 23). With primary surgery, ovarian function had been preserved in 15 of the 25 patients, who were alive and well. Seven of the primary surgery patients were irradiated postoperatively and 2 others with a central recurrence were cured by irradiation. One other patient, who was not irradiated postoperatively, had an intestinal metastasis and died of the disease. If any of the adverse prognostic factors (as reported in the literature) had been considered as an indication for postoperative irradiation, 17 patients instead of 7 would have been irradiated after primary radical surgery. In the comparable group of 23 patients treated by intracavitary irradiation and radical surgery (and in 4 cases postoperative irradiation as well) there was no recurrence. There was no significant statistical difference between the treatment results in the cesium + surgery group and those who underwent primary radical surgery. Young patients with early cervical carcinoma without prognostic indicators for postoperative irradiation can benefit from primary radical surgery, because their ovarian function can be preserved. (authors).

  20. Ovarian recurrence after radical trachelectomy for adenocarcinoma of the cervix. (United States)

    Piketty, Mathilde; Barranger, Emmanuel; Najat, Mourra; François, Paye; Daraï, Emile


    Radical trachelectomy is an effective fertility-sparing treatment for women with early-stage cervical cancer. We describe the first reported ovarian recurrence after radical trachelectomy for stage IB1 adenocarcinoma cervical cancer.