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Sample records for stabilized radical tempo

  1. Improved radical stability of viologen anolytes in aqueous organic redox flow batteries.

    Science.gov (United States)

    Hu, Bo; Tang, Yijie; Luo, Jian; Grove, Grant; Guo, Yisong; Liu, T Leo

    2018-05-09

    A high voltage (1.38 V) total organic aqueous redox flow battery is reported using 1,1'-bis[3-(trimethylammonio)propyl]-4,4'-bipyridinium tetrachloride ((NPr)2V) as an anolyte and 4-trimethylammonium-TEMPO chloride (NMe-TEMPO) as a catholyte. The exceptional radical stability of [(NPr)2V]+˙ enabled the flow battery in achieving 97.48% capacity retention for 500 cycles and a power density of 128.2 mW cm-2.

  2. The effects of metronomic pendular adjustment versus tap-tempo input on the stability and accuracy of tempo perception.

    Science.gov (United States)

    Brodsky, Warren

    2005-06-01

    This study explores tempo stability and accuracy while comparing two subject-response modes: the traditional metronomic pendular adjustment task versus tap-tempo input. Experiment 1 questioned if a single correct tempo measurement consistently emerges from repeated listenings, and if subject-response mode affects tempo stability and accuracy. Experiment 2 assessed incremental improvement between two repeated sessions, and questioned the incidence of self-pacing or congruent effects of potential delays on tempo responses. While single-session studies have shown that listeners find some tempos more enjoyable, can notice discrete differences in pace, and can remember rhythmic speed over prolonged periods of time, the current study employs a multiple-session format focusing on two diametrically opposed subject-response modes. The findings show that tempo responses by listeners without formal music training were consistent across listening sessions, and that responses from tap-tempo input were significantly more stable and accurate than responses from metronomic pendular adjustment tasks.

  3. Pentacene appended to a TEMPO stable free radical: the effect of magnetic exchange coupling on photoexcited pentacene.

    Science.gov (United States)

    Chernick, Erin T; Casillas, Rubén; Zirzlmeier, Johannes; Gardner, Daniel M; Gruber, Marco; Kropp, Henning; Meyer, Karsten; Wasielewski, Michael R; Guldi, Dirk M; Tykwinski, Rik R

    2015-01-21

    Understanding the fundamental spin dynamics of photoexcited pentacene derivatives is important in order to maximize their potential for optoelectronic applications. Herein, we report on the synthesis of two pentacene derivatives that are functionalized with the [(2,2,6,6-tetramethylpiperidin-1-yl)oxy] (TEMPO) stable free radical. The presence of TEMPO does not quench the pentacene singlet excited state, but does quench the photoexcited triplet excited state as a function of TEMPO-to-pentacene distance. Time-resolved electron paramagnetic resonance experiments confirm that triplet quenching is accompanied by electron spin polarization transfer from the pentacene excited state to the TEMPO doublet state in the weak coupling regime.

  4. TEMPO addition into pre-irradiated fluoropolymers and living-radical graft polymerization of styrene for preparation of polymer electrolyte membranes

    Energy Technology Data Exchange (ETDEWEB)

    Sawada, Shin-ichi, E-mail: sawada.shinnichi@jaea.go.j [Conducting Polymer Materials Research Group, Quantum Beam Science Directorate, Japan Atomic Energy Agency (JAEA), 1233 Watanuki, Takasaki, Gunma 370-1292 (Japan); Department of Nuclear Engineering and Management, Graduate School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Suzuki, Akihiro; Terai, Takayuki [Department of Nuclear Engineering and Management, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Maekawa, Yasunari, E-mail: maekawa.yasunari@jaea.go.j [Conducting Polymer Materials Research Group, Quantum Beam Science Directorate, Japan Atomic Energy Agency (JAEA), 1233 Watanuki, Takasaki, Gunma 370-1292 (Japan)

    2010-04-15

    We prepared proton exchange membranes (PEMs) by 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO)-mediated living-radical graft polymerization (LRGP) of styrene into fluoropolymer films and subsequent sulfonation. Poly(vinylidene fluoride) (PVDF) and poly(ethylene-co-tetrafluoroethylene) (ETFE) films were first irradiated and then treated with TEMPO solutions in various solvents. TEMPO addition was confirmed by the test of styrene grafting into TEMPO-treated films at 60 deg. C, at which the LRGP never proceeds. This test enabled us to differentiate the LRGP from the conventional graft polymerization. In order to gain a deep insight about TEMPO-addition reaction, the TEMPO-penetration behavior into the base polymer films was examined by a permeation experiment and computer simulation. Xylene and dioxane were appropriate solvents for the complete introduction of TEMPO into PVDF and ETFE films, respectively. Then, the LRGP of styrene was performed based on the fully TEMPO-capped films at 125 deg. C with various solvents. By using an alcoholic solvent, the degree of grafting was enhanced and it reached a maximum of 38%. This grafted film was sulfonated to prepare a PEM showing an ion exchange capacity of 2.2 meq/g and proton conductivity of 1.6x10{sup -1} S/cm.

  5. Bromine isotopic signature facilitates de novo sequencing of peptides in free-radical-initiated peptide sequencing (FRIPS) mass spectrometry.

    Science.gov (United States)

    Nam, Jungjoo; Kwon, Hyuksu; Jang, Inae; Jeon, Aeran; Moon, Jingyu; Lee, Sun Young; Kang, Dukjin; Han, Sang Yun; Moon, Bongjin; Oh, Han Bin

    2015-02-01

    We recently showed that free-radical-initiated peptide sequencing mass spectrometry (FRIPS MS) assisted by the remarkable thermochemical stability of (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO) is another attractive radical-driven peptide fragmentation MS tool. Facile homolytic cleavage of the bond between the benzylic carbon and the oxygen of the TEMPO moiety in o-TEMPO-Bz-C(O)-peptide and the high reactivity of the benzylic radical species generated in •Bz-C(O)-peptide are key elements leading to extensive radical-driven peptide backbone fragmentation. In the present study, we demonstrate that the incorporation of bromine into the benzene ring, i.e. o-TEMPO-Bz(Br)-C(O)-peptide, allows unambiguous distinction of the N-terminal peptide fragments from the C-terminal fragments through the unique bromine doublet isotopic signature. Furthermore, bromine substitution does not alter the overall radical-driven peptide backbone dissociation pathways of o-TEMPO-Bz-C(O)-peptide. From a practical perspective, the presence of the bromine isotopic signature in the N-terminal peptide fragments in TEMPO-assisted FRIPS MS represents a useful and cost-effective opportunity for de novo peptide sequencing. Copyright © 2015 John Wiley & Sons, Ltd.

  6. Cut-off effect of radical TEMPO derivatives in olive oil-in-water emulsions.

    Science.gov (United States)

    Lopez de Arbina, Amaia; Rezende, Marcos Caroli; Aliaga, Carolina

    2017-06-01

    Three oil-in-water emulsions were prepared from mixtures of olive oil and Tween 20 in water. The effectiveness of a series of radical 2,2,6,6-tetramethylpiperidinoxyl (TEMPO) derivatives of variable lipophilicity in reactions with antioxidant Trolox, and as pyrene-fluorescence quenchers, was compared in the three emulsions. A "cut-off" effect was observed for the pyrene quenching by the probes, but not for their reaction with Trolox. The results were rationalized in terms of the amphiphobic nature of the probes, and the different locations of probe, pyrene and Trolox in the three-phase microheterogeneous systems. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Synthesis and properties of novel TEMPO-contained polypyrrole derivatives as the cathode material of organic radical battery

    International Nuclear Information System (INIS)

    Xu, Lihuan; Yang, Fang; Su, Chang; Ji, Lvlv; Zhang, Cheng

    2014-01-01

    Two 2,2,6,6-tetramethylpiperidinyl-N-oxy (TEMPO) contained polypyrrole (PPy) derivatives with the different side-chain length were synthesized by esterification of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radial with pyrrole butyric acid and pyrrole caproic acid. Then the homopolymers of 4-(3-(Pyrrol-1-yl)butyryloxy)-2,2,6,6-tetramethylpiperidin-1-yloxy (PPy-B-TEMPO) and 4-(3-(Pyrrol-1-yl)hexanoyloxy)-2,2,6,6-tetramethylpiperidin-1-yloxy (PPy-C-TEMPO) were prepared by chemical oxidative polymerization. The structure, morphology, electrochemical properties of prepared polymers were characterized by fourier transform infrared spectroscopy (FTIR), ultraviolet visible spectroscopy (UV-vis), scanning electron microscopy (SEM), cyclic voltammograms (CV) and electrochemical impedance spectra (EIS), respectively. Also, the charge-discharge properties of the prepared polymers were studied by galvanostatic charge-discharge testing. The results demonstrated that the as-synthesized nitroxide radical polymers showed a reversible two-electron redox reaction process in the potential limits of 2.5–3.0 V and 3.4–3.8 V vs Li/Li + , respectively. Under our experimental conditions, PPy only presented the discharge capacity of 16.5 mAh·g −1 at 20 mA·g −1 between 2.5 and 4.2 V, while PPy-B-TEMPO with the short side-chain linked to TEMPO groups exhibited an initial discharge capacity of up to 86.5 mAh·g −1 with two well-defined plateaus. Furthermore, the PPy-C-TEMPO with the longer linking side-chain even displayed a discharge capacity of 115 mAh·g −1 . These superior electrochemical performances were ascribed to the flexible linking side-chain and the introduction of stable conductive PPy main chain, which benefits the improvement of charge carrier transportation in the aggregated polymer bulk

  8. Effect of TEMPO-oxidization and rapid cooling on thermo-structural properties of nanocellulose.

    Science.gov (United States)

    Mhd Haniffa, Mhd Abd Cader; Ching, Yern Chee; Chuah, Cheng Hock; Yong Ching, Kuan; Nazri, Nik; Abdullah, Luqman Chuah; Nai-Shang, Liou

    2017-10-01

    Recently, surface functionality and thermal property of the green nanomaterials have received wide attention in numerous applications. In this study, microcrystalline cellulose (MCC) was used to prepare the nanocrystalline celluloses (NCCs) using acid hydrolysis method. The NCCs was treated with TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxy radical]-oxidation to prepare TEMPO-oxidized NCCs. Cellulose nanofibrils (CNFs) also prepared from MCC using TEMPO-oxidation. The effects of rapid cooling and chemical treatments on the thermo-structural property studies of the prepared nanocelluloses were investigated through FTIR, thermogravimetric analysis-derivative thermogravimetric (TGA-DTG), and XRD. A posteriori knowledge of the FTIR and TGA-DTG analysis revealed that the rapid cooling treatment enhanced the hydrogen bond energy and thermal stability of the TEMPO-oxidized NCC compared to other nanocelluloses. XRD analysis exhibits the effect of rapid cooling on pseudo 2 I helical conformation. This was the first investigation performed on the effect of rapid cooling on structural properties of the nanocellulose. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Characterization of TEMPO-oxidized bacterial cellulose; Caracterizacao de celulose bacteriana tempo-oxidada

    Energy Technology Data Exchange (ETDEWEB)

    Nascimento, Eligenes S.; Pereira, Andre L.S.; Lima, Helder L.; Barroso, Maria K. de A., E-mail: eligenessampaio@hotmail.com [Universidade Federal Ceara (UFC), Fortaleza, CE (Brazil); Barros, Matheus de O. [Instituto Federal do Ceara (IFCE), Fortaleza, CE (Brazil); Morais, Joao P.S. [Embrapa Algodao, Campina Grande, PB (Brazil); Borges, Maria de F.; Rosa, Morsyleide de F. [Embrapa Agroindustria Tropical, Fortaleza, CE (Brazil)

    2015-07-01

    The aim of this study was to characterize the TEMPO-oxidized bacterial cellulose, as a preliminary research for further application in nanocomposites. Bacterial cellulose (BC) was selectively oxidized at C-6 carbon by TEMPO radical. Oxidized bacterial cellulose (BCOX) was characterized by TGA, FTIR, XRD, and zeta potential. BCOX suspension was stable at pH 7.0, presented a crystallinity index of 83%, in spite of 92% of BC, because of decrease in the free hydroxyl number. FTIR spectra showed characteristic BC bands and, in addition, band of carboxylic group, proving the oxidation. BCOX DTG showed, in addition to characteristic BC thermal events, a maximum degradation peak at 233 °C, related to sodium anhydro-glucuronate groups formed during the cellulose oxidation. Thus, BC can be TEMPO-oxidized without great loss in its structure and properties. (author)

  10. catalysed selective oxidation of benzyl alcohols using TEMPO and ...

    Indian Academy of Sciences (India)

    A general scheme for the oxidation of benzyl alcohols catalyzed by silica functionalized copper (II) has been designed. TEMPO, a free radical, assists this oxidation that was initiated by molecular oxygen which converts it to a primary oxidant. This catalytic combination i.e. SiO2 -Cu(II) in presence of TEMPO and oxygen ...

  11. Relative stability of radicals derived from artemisinin: A semiempirical and DFT study

    Science.gov (United States)

    Arantes, C.; de Araujo, M. T.; Taranto, A. G.; de M. Carneiro, J. W.

    The semiempirical AM1 and PM3 methods, as well as the density functional (DFT/B3LYP) approach using the 6-31g(d) basis set, were employed to calculate the relative stability of intermediate radicals derived from artemisinin, a sesquiterpene lactone having an endoperoxide bridge that is essential for its antimalarial activity. The compounds studied have their nonperoxidic oxygen atom of the trioxane ring and/or the carbonyl group replaced by a CH2 unit. Relative stabilities were calculated by means of isodesmic equations using artemisinin as reference. It was found that replacement of oxygen atoms decreases the relative stability of the anionic radical intermediates. In contrast, for compounds with inverted stereochemistry the intermediate radicals were found to be more stable than those with the artemisinin-like stereochemistry. These relative stabilities may modulate the antimalarial potency. Radicals centered on carbon are always more stable than the corresponding radicals centered on oxygen.

  12. Dissociation Behavior of a TEMPO-Active Ester Cross-Linker for Peptide Structure Analysis by Free Radical Initiated Peptide Sequencing (FRIPS) in Negative ESI-MS.

    Science.gov (United States)

    Hage, Christoph; Ihling, Christian H; Götze, Michael; Schäfer, Mathias; Sinz, Andrea

    2017-01-01

    We have synthesized a homobifunctional amine-reactive cross-linking reagent, containing a TEMPO (2,2,6,6-tetramethylpiperidine-1-oxy) and a benzyl group (Bz), termed TEMPO-Bz-linker, to derive three-dimensional structural information of proteins. The aim for designing this novel cross-linker was to facilitate the mass spectrometric analysis of cross-linked products by free radical initiated peptide sequencing (FRIPS). In an initial study, we had investigated the fragmentation behavior of TEMPO-Bz-derivatized peptides upon collision activation in (+)-electrospray ionization collision-induced dissociation tandem mass spectrometry (ESI-CID-MS/MS) experiments. In addition to the homolytic NO-C bond cleavage FRIPS pathway delivering the desired odd-electron product ions, an alternative heterolytic NO-C bond cleavage, resulting in even-electron product ions mechanism was found to be relevant. The latter fragmentation route clearly depends on the protonation of the TEMPO-Bz-moiety itself, which motivated us to conduct (-)-ESI-MS, CID-MS/MS, and MS 3 experiments of TEMPO-Bz-cross-linked peptides to further clarify the fragmentation behavior of TEMPO-Bz-peptide molecular ions. We show that the TEMPO-Bz-linker is highly beneficial for conducting FRIPS in negative ionization mode as the desired homolytic cleavage of the NO-C bond is the major fragmentation pathway. Based on characteristic fragments, the isomeric amino acids leucine and isoleucine could be discriminated. Interestingly, we observed pronounced amino acid side chain losses in cross-linked peptides if the cross-linked peptides contain a high number of acidic amino acids. Graphical Abstract ᅟ.

  13. Characterization of TEMPO-oxidized bacterial cellulose

    International Nuclear Information System (INIS)

    Nascimento, Eligenes S.; Pereira, Andre L.S.; Lima, Helder L.; Barroso, Maria K. de A.; Barros, Matheus de O.; Morais, Joao P.S.; Borges, Maria de F.; Rosa, Morsyleide de F.

    2015-01-01

    The aim of this study was to characterize the TEMPO-oxidized bacterial cellulose, as a preliminary research for further application in nanocomposites. Bacterial cellulose (BC) was selectively oxidized at C-6 carbon by TEMPO radical. Oxidized bacterial cellulose (BCOX) was characterized by TGA, FTIR, XRD, and zeta potential. BCOX suspension was stable at pH 7.0, presented a crystallinity index of 83%, in spite of 92% of BC, because of decrease in the free hydroxyl number. FTIR spectra showed characteristic BC bands and, in addition, band of carboxylic group, proving the oxidation. BCOX DTG showed, in addition to characteristic BC thermal events, a maximum degradation peak at 233 °C, related to sodium anhydro-glucuronate groups formed during the cellulose oxidation. Thus, BC can be TEMPO-oxidized without great loss in its structure and properties. (author)

  14. Energize Electrochemical Double Layer Capacitor by Introducing an Ambipolar Organic Redox Radical in Electrolyte.

    Science.gov (United States)

    Wang, Yonggang; Hu, Lintong; Zhang, Yue; Shi, Chao; Guo, Kai; Zhai, Tianyou; Li, Huiqiao

    2018-05-24

    Carbon based electrochemical double layer capacitors (EDLCs) generally exhibit high power and long life, but low energy density/capacitance. Pore/morphology optimization and pseudocapacitive materials modification of carbon materials have been used to improve electrode capacitance, but leading to the consumption of tap density, conductivity and stability. Introducing soluble redox mediators into electrolyte is a promising alternative to improve the capacitance of electrode. However, it is difficult to find one redox mediator that can provide additional capacitance for both positive and negative electrodes simultaneously. Here, an ambipolar organic radical, 2, 2, 6, 6-tetramethylpiperidinyloxyl (TEMPO) is first introduced to the electrolyte, which can substantially contribute additional pseudocapacitance by oxidation at the positive electrode and reduction at the negative electrode simultaneously. The EDLC with TEMPO mediator delivers an energy density as high as 51 Wh kg-1, 2.4 times of the capacitor without TEMPO, and a long cycle stability over 4000 cycles. The achieved results potentially point a new way to improve the energy density of EDLCs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Transparent bionanocomposite films based on chitosan and TEMPO-oxidized cellulose nanofibers with enhanced mechanical and barrier properties.

    Science.gov (United States)

    Soni, Bhawna; Hassan, El Barbary; Schilling, M Wes; Mahmoud, Barakat

    2016-10-20

    The development of biobased active films for use in food packaging is increasing due to low cost, environmental appeal, renewability and availability. The objective of this research was to develop an effective and complete green approach for the production of bionanocomposite films with enhanced mechanical and barrier properties. This was accomplished by incorporating TEMPO-oxidized cellulose nanofibers (2,2,6,6-tetramethylpiperidine-1-oxyl radical) into a chitosan matrix. An aqueous suspension of chitosan (100-75wt%), sorbitol (25wt%) and TEMPO-oxidized cellulose nanofibers (TEMPO-CNFs, 0-25wt%) were cast in an oven at 40°C for 2-4days. Films were preconditioned at 25°C and 50% RH for characterization. The surface morphology of the films was revealed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The thermal properties and crystal structure of the films were evaluated by thermogravimetric analysis (TGA-DTG) and X-ray diffraction (XRD). Incorporation of TEMPO-CNFs enhanced the mechanical strength of the films due to the high aspect ratio (3-20nm width, and 10-100nm length) of TEMPO-CNFs and strong interactions with the chitosan matrix. Oxygen and water vapor transmission rates for films that are prepared with chitosan and TEMPO-CNFs (15-25wt%) were significantly reduced. Furthermore, these bionanocomposite films had good thermal stability. Use of TEMPO-CNFs in this method makes it possible to produce bionanocomposite films that are flexible, transparent, and thus have potential in food packaging applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Quantifying TEMPO Redox Polymer Charge Transport toward the Organic Radical Battery.

    Science.gov (United States)

    Karlsson, Christoffer; Suga, Takeo; Nishide, Hiroyuki

    2017-03-29

    To design new and better organic active battery materials in a rational fashion, fundamental parameters of the charge transport must be studied. Herein we report on the electronic conductivity by electron diffusion in a TEMPO-containing redox polymer, and the reorganization energy of the TEMPO self-exchange in an organic solvent is determined for the first time. The electronic conductivity was 8.5 μS/cm at E 0 and corresponded to a redox hopping mechanism. The apparent electron diffusion coefficient was 1.9 × 10 -9 cm 2 /s at room temperature, and at short times the ion diffusion was limiting with a diffusion coefficient of 6.5 × 10 -10 cm 2 /s. The reorganization energy was determined to be 1.01 eV, indicating a rather polar chemical environment for the TEMPO groups. The implications for the usage of this type of materials in organic energy storage are discussed. As conductivity through 10 μm was demonstrated, we show that, if sufficient swellability can be ensured, charge can be transported through several micrometer thick layers in a battery electrode without any conducting additive.

  17. Structural, thermal and photo-physical data of azo-aromatic TEMPO derivatives before and after their grafting to polyolefins

    Directory of Open Access Journals (Sweden)

    Francesca Cicogna

    2016-03-01

    Full Text Available The data reported in this paper are complementary to the characterization of 4-(phenylazo-benzoyl-2,2,6,6-tetramethylpiperidine-1-oxyl radical (AzO-TEMPO and of the 4-(2-thienylazo-benzoyl-2,2,6,6-tetramethylpiperidine-1-oxyl radical (ThiO-TEMPO before and after their grafting to two polyethylene matrices (a copolymer ethylene/α-olefin (co-EO and a high density polyethylene (HDPE. Particularly the data reported in this paper confirm the structure (FT-IR analysis, the thermal (TGA and EPR and the photo-physical (UV–vis properties of the RO-TEMPO derivatives before and after their grafting. Herein, the FT-IR spectrum and TGA thermogram of ThiO-TEMPO were compared with those of AzO-TEMPO. Moreover, the superimposition of UV–vis spectra collected during the irradiation under 366 or 254 nm emitting lamp of AzO-TEMPO and ThiO-TEMPO in acetonitrile solution are reported. Finally, a complete DSC characterization of the functionalized POs is shown.DOI of original article: 〈http://dx.doi.org/10.1016/j.polymer.2015.11.018〉 [1

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

    Science.gov (United States)

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

    2010-11-01

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

  19. Thermosetting polymer for dynamic nuclear polarization: Solidification of an epoxy resin mixture including TEMPO

    Energy Technology Data Exchange (ETDEWEB)

    Noda, Yohei, E-mail: noda.yohei@jaea.go.jp [Quantum Beam Science Centre, Sector of Nuclear Science Research, Japan Atomic Energy Agency, Shirakata-Shirane, Tokai, Ibaraki 319-1195 (Japan); Kumada, Takayuki [Quantum Beam Science Centre, Sector of Nuclear Science Research, Kansai Photon Science Institute, Japan Atomic Energy Agency, Kizugawa, Kyoto 619-0215 (Japan); Yamaguchi, Daisuke; Shamoto, Shin-ichi [Quantum Beam Science Centre, Sector of Nuclear Science Research, Japan Atomic Energy Agency, Shirakata-Shirane, Tokai, Ibaraki 319-1195 (Japan)

    2015-03-11

    We investigated the dynamic nuclear polarization (DNP) of typical thermosetting polymers (two-component type epoxy resins; Araldite{sup ®} Standard or Araldite{sup ®} Rapid) doped with a (2,2,6,6-tetramethylpiperidine-1-yl)oxy (TEMPO) radical. The doping process was developed by carefully considering the decomposition of TEMPO during the solidification of the epoxy resin. The TEMPO electron spin in each two-component paste decayed slowly, which was favorable for our study. Furthermore, despite the dissolved TEMPO, the mixture of the two-component paste successfully solidified. With the resulting TEMPO-doped epoxy-resin samples, DNP experiments at 1.2 K and 3.35 T indicated a magnitude of a proton-spin polarization up to 39%. This polarization is similar to that (35%) obtained for TEMPO-doped polystyrene (PS), which is often used as a standard sample for DNP. To combine this solidification of TEMPO-including mixture with a resin-casting technique enables a creation of polymeric target materials with a precise and complex structure.

  20. Structure and properties of tempo-oxidized cotton fibers

    Directory of Open Access Journals (Sweden)

    Milanovic Jovana

    2012-01-01

    Full Text Available In this paper, the influence of the catalytic oxidation using water soluble and stable nitroxyl radical 2,2´,6,6´-tetramethylpiperidine-1-oxyl (TEMPO on structure and properties of cotton fibers was studied. In particular, the selective TEMPO-mediated oxidation has become very interesting way for introduction of functional groups into cellulose fibers with the aim to obtain oxycellulose fibers with specific properties. Unmodified and modified fibers were characterized in terms of weight loss values, introduced functional groups and crystallinity index. Also, oxidized fibers were characterized in terms of the sorption, morphological, and physico-mechanical properties. The TEMPO-oxidized cotton fibers show a minimum increase of fineness (from 1.32 to 1.28 dtex and increase of crystallinity index (up to 91.9%, while the tensile strength of fibers decreases (up to 10.82 cN/tex. By the TEMPO-mediated oxidation of cotton fibers significant amount of carboxyl groups (up to 0.795 mmol/g cell can be introduced into cellulose fibers. Introduced hydrophilic carboxyl groups increases the sorption properties of oxidized fibers, that can be used directly or for further chemical modification.

  1. Correlation between inter-spin interaction and molecular dynamics of organic radicals in organic 1D nanochannels

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, Hirokazu [Department of Chemistry, College of Humanities and Sciences, Nihon University 3-25-40, Sakura-jo-sui, Setagaya-ku, Tokyo, 156-8550 (Japan)

    2015-12-31

    One-dimensional (1D) molecular chains of 4-substituted-2,2,6,6-tetramethyl-1-piperidinyloxyl (4-X-TEMPO) radicals were constructed in the crystalline 1D nanochannels of 2,4,6-tris(4-chlorophenoxy)-1,3,5-triazine (CLPOT) used as a template. The ESR spectra of CLPOT inclusion compounds (ICs) using 4-X-TEMPO were examined on the basis of spectral simulation using EasySpin program package for simulating and fitting ESR spectra. The ESR spectra of [(CLPOT){sub 2}-(TEMPO){sub 1.0}] IC were isotropic in the total range of temperatures. The peak-to-peak line width (ΔB{sub pp}) became monotonically narrower from 2.8 to 1.3 mT with increase in temperature in the range of 4.2–298 K. The effect of the rotational diffusion motion of TEMPO radicals in the CLPOT nanochannels for the inter-spin interaction of the [(CLPOT){sub 2}-(TEMPO){sub 1.0}] IC was found to be smaller than the case of [(TPP){sub 2}−(TEMPO){sub 1.0}] IC (TPP = tris(o-phenylenedioxy)cyclotriphosphazene) reported in our previous study. The ΔB{sub pp} of the [(CLPOT){sub 2}-(TEMPO){sub 1.0}] IC in the whole range of temperatures was much narrower than the estimation to be based on the Van Vleck’s formula for the second moment of the rigid lattice model where the electron spin can be considered as fixed; 11 mT of Gaussian line-width component. This suggests the possibility of exchange narrowing in the 1D organic-radical chains of the [(CLPOT){sub 2}-(TEMPO){sub 1.0}] IC. On the other hand, the ESR spectra of [(CLPOT){sub 2}-(MeO-TEMPO){sub 0.41}] IC (MeO-TEMPO = 4-methoxy-TEMPO) were reproduced by a superposition of major broad isotropic adsorption line and minor temperature-dependent modulated triplet component. This suggests that the IC has the part of 1D organic-radical chains and MeO-TEMPO molecules isolated in the CLPOT nanochannels.

  2. Cellulose Nanocomposites by Melt Compounding of TEMPO-Treated Wood Fibers in Thermoplastic Starch Matrix

    Directory of Open Access Journals (Sweden)

    Aline Cobut

    2014-04-01

    Full Text Available To facilitate melt compounding of cellulose nanofibrils (CNF based composites, wood pulp fibers were subjected to a chemical treatment whereby the fibers were oxidized using 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO. This treatment introduced negatively charged carboxylate groups to the fibers. TEMPO-treated fibers (TempoF were added to a mixture of amylopectin starch, glycerol, and water. Granules were prepared from this mixture and processed into CNF composites by extrusion. TempoF were easier to process into composites as compared with non-treated pulp fibers (PF. SEM revealed partial disintegration of TempoF during melt processing. Consequently, TempoF gave composites with much better mechanical properties than those of conventional composites prepared from pulp fibers and TPS. Particularly, at 20 wt% TempoF content in the composite, the modulus and strength were much improved. Such a continuous melt processing route, as an alternative to laboratory solvent casting techniques, may promote large-scale production of CNF-based composites as an environmentally friendly alternative to synthetic plastics/composites.

  3. Investigation of the Mechanism of Electron Capture and Electron Transfer Dissociation of Peptides with a Covalently Attached Free Radical Hydrogen Atom Scavenger.

    Science.gov (United States)

    Sohn, Chang Ho; Yin, Sheng; Peng, Ivory; Loo, Joseph A; Beauchamp, J L

    2015-11-15

    The mechanisms of electron capture and electron transfer dissociation (ECD and ETD) are investigated by covalently attaching a free-radical hydrogen atom scavenger to a peptide. The 2,2,6,6-tetramethylpiperidin-l-oxyl (TEMPO) radical was chosen as the scavenger due to its high hydrogen atom affinity (ca. 280 kJ/mol) and low electron affinity (ca. 0.45 ev), and was derivatized to the model peptide, FQX TEMPO EEQQQTEDELQDK. The X TEMPO residue represents a cysteinyl residue derivatized with an acetamido-TEMPO group. The acetamide group without TEMPO was also examined as a control. The gas phase proton affinity (882 kJ/mol) of TEMPO is similar to backbone amide carbonyls (889 kJ/mol), minimizing perturbation to internal solvation and sites of protonation of the derivatized peptides. Collision induced dissociation (CID) of the TEMPO tagged peptide dication generated stable odd-electron b and y type ions without indication of any TEMPO radical induced fragmentation initiated by hydrogen abstraction. The type and abundance of fragment ions observed in the CID spectra of the TEMPO and acetamide tagged peptides are very similar. However, ECD of the TEMPO labeled peptide dication yielded no backbone cleavage. We propose that a labile hydrogen atom in the charge reduced radical ions is scavenged by the TEMPO radical moiety, resulting in inhibition of N-C α backbone cleavage processes. Supplemental activation after electron attachment (ETcaD) and CID of the charge-reduced precursor ion generated by electron transfer of the TEMPO tagged peptide dication produced a series of b + H (b H ) and y + H (y H ) ions along with some c ions having suppressed intensities, consistent with stable O-H bond formation at the TEMPO group. In summary, the results indicate that ECD and ETD backbone cleavage processes are inhibited by scavenging of a labile hydrogen atom by the localized TEMPO radical moiety. This observation supports the conjecture that ECD and ETD processes involve long

  4. Reactions of nitroxide radicals in aqueous solutions exposed to non-thermal plasma: limitations of spin trapping of the plasma induced species

    Science.gov (United States)

    Gorbanev, Yury; Stehling, Nicola; O'Connell, Deborah; Chechik, Victor

    2016-10-01

    Low temperature (‘cold’) atmospheric pressure plasmas have gained much attention in recent years due to their biomedical effects achieved through the interactions of plasma-induced species with the biological substrate. Monitoring of the radical species in an aqueous biological milieu is usually performed via electron paramagnetic resonance (EPR) spectroscopy using various nitrone spin traps, which form persistent radical adducts with the short-lived radicals. However, the stability of these nitroxide radical adducts in the plasma-specific environment is not well known. In this work, chemical transformations of nitroxide radicals in aqueous solutions using a model nitroxide 4-oxo-TEMPO were studied using EPR and LC-MS. The kinetics of the nitroxide decay when the solution was exposed to plasma were assessed, and the reactive pathways proposed. The use of different scavengers enabled identification of the types of reactive species which cause the decay, indicating the predominant nitroxide group reduction in oxygen-free plasmas. The 2H adduct of the PBN spin trap (PBN-D) was shown to decay similarly to the model molecule 4-oxo-TEMPO. The decay of the spin adducts in plasma-treated solutions must be considered to avoid rendering the spin trapping results unreliable. In particular, the selectivity of the decay indicated the limitations of the PTIO/PTI nitroxide system in the detection of nitric oxide.

  5. Oxidation and Free Radical Decay in Vitamin E-stabilized, Radiation Cross-linked UHMWPE

    International Nuclear Information System (INIS)

    Oral, E.

    2006-01-01

    A novel a-tocopherol (vitamin E, α-T)-stabilized, cross-linked ultra-high molecular weight polyethylene (UHMWPE) (αTPE) was developed for total joint arthroplasty as a bearing surface with low wear and improved mechanical properties. Accelerated aging showed α-T protects irradiated UHMWPE against oxidation. However, accelerated aging may not truly reflect in vivo and shelf oxidation. We used real-time aging to monitor the evolution of oxidation and free radical signals of α-T to determine the mechanism of oxidative stability. UHMWPE blocks (30x30x10 mm) were machined and γ-irradiated (85 kGy) in argon. The blocks were doped in α-T for 5 hours at 120 degree and homogenized for 64 hours at 120 degree in argon, packaged in vacuum and γ-sterilized (25 kGy). Samples were aged in air at room temperature, in air at 40 degree and in water at 40 degree. Measurements were at 1, 2, 3, 4 and 7 months. Sections cut from the aged blocks (150μm) were boiled in hexane overnight to extract free species and evaluated by FTIR. Oxidation indices were calculated by taking the area under the carbonyl peak and normalizing it to a skeletal peak. ESR was used to determine the content and type of free radicals. Control was 100-kGy irradiated, unstabilized UHMWPE. αTPE showed a small amount of oxidation, which stabilized after 2 months. This indicated that the decay of the hydroperoxides formed by the reaction of the residual free radicals with oxygen was exhausted by α-T due to its ability to scavenge free radicals. In contrast, control UHMWPE continued to oxidize because the residual free radicals likely continued to form hydroperoxides and additional free radicals, furthering the oxidation reactions. There was a shift in the free radical signature of both αTPE and control from the sextet alkyl/allyl radicals to a sharp singlet during aging. Most likely, trapped free radicals move along the crystal stems until they react with another free radical or until they reach the crystal

  6. Nitroxide-mediated controlled radical polymerisation: towards control of molar mass Controlled Radical Polymerisation

    NARCIS (Netherlands)

    Bon, S.A.F.; Bergman, F.A.C.; Es, van J.J.G.S.; Klumperman, B.; German, A.L.; Matyjaszewski, K.

    1998-01-01

    The mechanism of the TEMPO-mediated controlled radical polymerization of styrene in bulk is discussed. It is shown that the isotropic correlation time (tc) of a nitroxide can be used as a measure of the diffusive rate coefficient of trapping (ketD). A general empirical relationship for the density

  7. Comparison of fluorescence-based techniques for the quantification of particle-induced hydroxyl radicals

    Directory of Open Access Journals (Sweden)

    Cohn Corey A

    2008-02-01

    Full Text Available Abstract Background Reactive oxygen species including hydroxyl radicals can cause oxidative stress and mutations. Inhaled particulate matter can trigger formation of hydroxyl radicals, which have been implicated as one of the causes of particulate-induced lung disease. The extreme reactivity of hydroxyl radicals presents challenges to their detection and quantification. Here, three fluorescein derivatives [aminophenyl fluorescamine (APF, amplex ultrared, and dichlorofluorescein (DCFH] and two radical species, proxyl fluorescamine and tempo-9-ac have been compared for their usefulness to measure hydroxyl radicals generated in two different systems: a solution containing ferrous iron and a suspension of pyrite particles. Results APF, amplex ultrared, and DCFH react similarly to the presence of hydroxyl radicals. Proxyl fluorescamine and tempo-9-ac do not react with hydroxyl radicals directly, which reduces their sensitivity. Since both DCFH and amplex ultrared will react with reactive oxygen species other than hydroxyl radicals and another highly reactive species, peroxynitite, they lack specificity. Conclusion The most useful probe evaluated here for hydroxyl radicals formed from cell-free particle suspensions is APF due to its sensitivity and selectivity.

  8. Characterization of TEMPO-oxidized bacterial cellulose scaffolds for tissue engineering applications

    International Nuclear Information System (INIS)

    Luo, Honglin; Xiong, Guangyao; Hu, Da; Ren, Kaijing; Yao, Fanglian; Zhu, Yong; Gao, Chuan; Wan, Yizao

    2013-01-01

    Introduction of active groups on the surface of bacterial cellulose (BC) nanofibers is one of the promising routes of tailoring the performance of BC scaffolds for tissue engineering. This paper reported the introduction of aldehyde groups to BC nanofibers by 2,2,6,6-tetramethylpyperidine-1-oxy radical (TEMPO)-mediated oxidation and evaluation of the potential of the TEMPO-oxidized BC as tissue engineering scaffolds. Periodate oxidation was also conducted for comparison. Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) analyses were carried out to determine the existence of aldehyde groups on BC nanofibers and the crystallinity. In addition, properties relevant to scaffold applications such as morphology, fiber diameter, mechanical properties, and in vitro degradation were characterized. The results indicated that periodate oxidation could introduce free aldehyde to BC nanofibers and the free aldehyde groups on the TEMPO-oxidized BC tended to transfer to acetal groups. It was also found that the advantageous 3D structure of BC scaffolds remained unchanged and that no significant changes in morphology, fiber diameter, tensile structure and in vitro degradation were found after TEMPO-mediated oxidation while significant differences were observed upon periodate oxidation. The present study revealed that TEMPO-oxidation could impart BC scaffolds with new functions while did not degrade their intrinsic advantages. - Highlights: • TEMPO-mediated oxidation on BC scaffold for tissue engineering use was conducted. • TEMPO-mediated oxidation did not degrade the intrinsic advantages of BC scaffold. • TEMPO-mediated oxidation could impart BC scaffold with new functional groups. • Feasibility of TEMPO-oxidized BC as tissue engineering scaffold was confirmed

  9. Scope and limitations of the TEMPO/EPR method for singlet oxygen detection: the misleading role of electron transfer.

    Science.gov (United States)

    Nardi, Giacomo; Manet, Ilse; Monti, Sandra; Miranda, Miguel A; Lhiaubet-Vallet, Virginie

    2014-12-01

    For many biological and biomedical studies, it is essential to detect the production of (1)O2 and quantify its production yield. Among the available methods, detection of the characteristic 1270-nm phosphorescence of singlet oxygen by time-resolved near-infrared (TRNIR) emission constitutes the most direct and unambiguous approach. An alternative indirect method is electron paramagnetic resonance (EPR) in combination with a singlet oxygen probe. This is based on the detection of the TEMPO free radical formed after oxidation of TEMP (2,2,6,6-tetramethylpiperidine) by singlet oxygen. Although the TEMPO/EPR method has been widely employed, it can produce misleading data. This is demonstrated by the present study, in which the quantum yields of singlet oxygen formation obtained by TRNIR emission and by the TEMPO/EPR method are compared for a set of well-known photosensitizers. The results reveal that the TEMPO/EPR method leads to significant overestimation of singlet oxygen yield when the singlet or triplet excited state of the photosensitizer is efficiently quenched by TEMP, acting as electron donor. In such case, generation of the TEMP(+) radical cation, followed by deprotonation and reaction with molecular oxygen, gives rise to an EPR-detectable TEMPO signal that is not associated with singlet oxygen production. This knowledge is essential for an appropriate and error-free application of the TEMPO/EPR method in chemical, biological, and medical studies. Copyright © 2014 Elsevier Inc. All rights reserved.

  10. Thermal stability of radiation-induced free radicals in γ-irradiated l-alanine single crystals

    International Nuclear Information System (INIS)

    Maltar-Strmecki, N.; Rakvin, B.

    2005-01-01

    Decay of the radiation-induced stable free radicals in l-alanine single crystals and powders at the temperatures from 379 to 476K was examined by electron paramagnetic resonance. For single crystals, the calculated activation energy of the radical decay is 104.3±1.7kJ/mol (i.e. 12 538+/-202K) and the frequency factor lnν 0 is 24.1±0.4min -1 . The lifetime of the radical in single crystals at 296K is 162 years. The results confirm the long-term stability of the radicals, but the decay was found to be faster in large crystals than in powders

  11. Preparation of polystyrene-poly(ethylene glycol) diblock copolymer by "living" free radical polymerization

    DEFF Research Database (Denmark)

    Chen, Xianyi; Gao, Bo; Kops, Jørgen

    1998-01-01

    terminated with a TEMPO unit (MPEG-TEMPO), which was further used to prepare the diblock copolymer PS-b-PEG by 'living' free radical polymerisation of styrene. The product was purified and identified by H-1 n.m.r. and GPC. However, large amounts of homopolystyrene was also formed by simultaneous thermal...

  12. Esterified dendritic TAM radicals with very high stability and enhanced oxygen sensitivity.

    Science.gov (United States)

    Song, Yuguang; Liu, Yangping; Hemann, Craig; Villamena, Frederick A; Zweier, Jay L

    2013-02-15

    In this work, we have developed a new class of dendritic TAM radicals (TG, TdG, and dTdG) through a convergent method based on the TAM core CT-03 or its deuterated analogue dCT-03 and trifurcated Newkome-type monomer. Among these radicals, dTdG exhibits the best EPR properties with sharpest EPR singlet and highest O(2) sensitivity due to deuteration of both the ester linker groups and the TAM core CT-03. Like the previous dendritic TAM radicals, these new compounds also show extremely high stability toward various reactive species owing to the dendritic encapsulation. The highly charged nature of these molecules resulting from nine carboxylate groups prevents concentration-dependent EPR line broadening at physiological pH. Furthermore, we demonstrate that these TAM radicals can be easily derivatized (e.g., PEGylation) at the nine carboxylate groups and the resulting PEGylated analogue dTdG-PEG completely inhibits the albumin binding, thereby enhancing suitability for in vivo applications. These new dendritic TAM radicals show great potential for in vivo EPR oximetric applications and provide insights on approaches to develop improved and targeted EPR oximetric probes for biomedical applications.

  13. Nitroxyl free radicals formed from hindered amine light stabilizers under 60Co γ-ray irradiation

    International Nuclear Information System (INIS)

    Wang Huiliang; Chen Wenxiu

    2006-01-01

    Nitroxyl free radicals formed from several low molecular weight (LMW) hindered amine light stabilizers (HALS) under 60 Co γ-ray irradiation was studied with electron spin resonance (ESR) spectroscopy. All the HALSs irradiated in air formed nitroxyl free radicals under irradiation in air. For most of the HALSs, concentration of the nitroxyl free radicals increased linearly and quickly with absorbed dose in 0-10 kGy range, but increased slowly, or even kept constant, with doses of greater than 10 kGy. Concentration of nitroxyl free radicals formed from LMW HALS was usually higher than high molecular weight HALS. Tetramethyl HALS was easier to form nitroxyl free radicals than pentamethyl HLAS. Concentration of nitroxyl free radicals formed from the samples irradiated in oxygen was about two times higher than that the samples irradiated in air. Mechanisms of the nitroxyl free radical formation from the γ-ray irradiated HALSs were was discussed. (authors)

  14. Effects of Tempo, Musical Experience, and Listening Modes on Tempo Modulation Perception.

    Science.gov (United States)

    Sheldon, Deborah A.

    1994-01-01

    Reports on the effects of tempo direction, listening mode, and level of musical experience on speed and accuracy in tempo change among 160 music majors and nonmajors. Finds that music majors more accurately detected tempo changes than did nonmajors. (CFR)

  15. Engineering a horseradish peroxidase C stable to radical attacks by mutating multiple radical coupling sites.

    Science.gov (United States)

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

    2015-04-01

    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. © 2014 Wiley Periodicals, Inc.

  16. Tactus ≠ Tempo: Some Dissociations Between Attentional Focus, Motor Behavior, and Tempo Judgment

    Directory of Open Access Journals (Sweden)

    Justin London

    2011-08-01

    Full Text Available Three experiments explored the relationships between surface rhythmic activity, tactus or beat rate, attentional focus, sensorimotor synchronization (tapping, and tempo perception. All involved a rhythmic standard followed by a comparison; the experimental task was a judgment of “slower, same, or faster.” In Experiment 1 participants simply judged relative speed; they focused on the beat level in Experiment 2, and they tapped along as they made their judgments in Experiment 3. In all three experiments judgments were highly accurate (89-97% correct, relative to beat-level inter-onset interval when the standard-comparison involved the same pattern/same tempo, and performed similarly for the same pattern at different tempos (80-83% correct. Performance degraded significantly in other contexts, especially for different patterns at the same tempo. A main effect for pattern (two levels: same vs. different and a pattern x tempo interaction were observed in all three experiments; a main effect for tempo (collapsed to two levels: same vs. different occurred only in Experiment 1. Analysis of a subset of the experimental conditions indicated that surface activity was of greater salience than the beat level in some contexts. Tapping along (Experiment 3 did not improve overall performance any more than simply focusing on the tactus level (Experiment 2, and a possible biasing effect of tapping rate on tempo judgment was observed. Thus there is an apparent dissociation between tactus rate, attentional focus, tapping behavior and tempo judgment. This suggests that our perception of musical speed or tempo is more than simple apprehension of the tactus rate.

  17. Utilização do TEMPO (N-oxil-2,2,6,6-tetrametilpiperidina na oxidação de álcoois primários e secundários The use of TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl for the oxidation of primary and secondary alcohols

    Directory of Open Access Journals (Sweden)

    Marcus Vinícius Nora de Souza

    2004-04-01

    Full Text Available The oxidation of alcohols to obtain ketones, aldehydes or carboxylic acids is a fundamental transformation in organic synthesis and many reagents are known for these conversions. However, there is still a demand for mild and selective reagents for the oxidation of alcohols in the presence of other functional groups. As an alternative, the nitroxyl radical TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl has been demonstrated to be a useful reagent for the transformation of alcohols. The oxidation of alcohols using TEMPO is often efficient, fast, selective, made in mild conditions and can tolerate sensitive functional groups. In this article we report different methodologies using TEMPO in the oxidation of alcohols.

  18. Tempo cambiamento invarianza

    CERN Document Server

    Toraldo di Francia, Giuliano

    1994-01-01

    Il tempo e la grammatica. Tra soggettivo e oggettivo. La scoperta dell'intersoggettivo. Qual è il tempo vero? Gl'invarianti. Le leggi classiche del mondo fisico. La probabilità, personaggio centrale. Irreversibilità, complessità, caos. Il tempo relativo. La storia. Si tratta di temi e riflessioni che riguardano le scienze dure della natura. "Quelle scienze, scrive l'autore, come spero di riuscire ad argomentare nelle pagine che seguono, oggi non sono più così separate e lontane dalle scienze storiche come furono in passato. Ci fu in quelle lezioni un problema di scelta: che cosa è essenziale offrire alla meditazione di chi intende dedicarsi alla ricerca e allo studio degli eventi storici".

  19. Ser do tempo em Bergson

    OpenAIRE

    Coelho, Jonas Gonçalves

    2004-01-01

    O artigo apresenta a concepção bergsoniana de duração. Pretende-se mostrar que, segundo Bergson, o tempo dos filósofos e cientistas é um tempo fictício, um esquema espacial que oculta a natureza do tempo real, o qual não pode ser separado dos acontecimentos físicos e psicológicos. Para Bergson, o tempo real é sucessão, continuidade, mudança, memória e criação. We considered Bergson's duration concept. We intended to show that, according to Bergson, the time of philosophers and scientists i...

  20. One-Step Cationic Grafting of 4-Hydroxy-TEMPO and its Application in a Hybrid Redox Flow Battery with a Crosslinked PBI Membrane.

    Science.gov (United States)

    Chang, Zhenjun; Henkensmeier, Dirk; Chen, Ruiyong

    2017-08-24

    By using a one-step epoxide ring-opening reaction between 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-hydroxy-TEMPO) and glycidyltrimethylammonium cation (GTMA + ), we synthesized a cation-grafted TEMPO (g + -TEMPO) and studied its electrochemical performance against a Zn 2+ /Zn anode in a hybrid redox flow battery. To conduct Cl - counter anions, a crosslinked methylated polybenzimidazole (PBI) membrane was prepared and placed between the catholyte and anolyte. Compared to 4-hydroxy-TEMPO, the positively charged g + - TEMPO exhibits enhanced reaction kinetics. Moreover, flow battery tests with g + -TEMPO show improved Coulombic, voltage, and energy efficiencies and cycling stability over 140 cycles. Crossover of active species through the membrane was not detected. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Intramolecular transformation of thiyl radicals to α-aminoalkyl radicals: 'ab initio' calculations on homocystein

    International Nuclear Information System (INIS)

    Chhun, S.; Berges, J.; Bleton, V.; Abedinzadeh, Z.

    2000-01-01

    One-electron oxidation of thiols by oxidizing radicals leads to the formation of thiyl radical and carbon-centered radicals. It has been shown experimentally that in the absence of oxygen, the thiyl radicals derived from certain thiols of biological interest such as glutathion, cysteine and homocysteine decay rapidly by intramolecular rearrangement reactions into the carbon-centered radical. In the present work we have investigated theoretically the structure and the stability of thiyl and carbon-centered radicals of homocysteine in order to check the possibility of this rearrangement. (author)

  2. Ser do tempo em Bergson

    OpenAIRE

    Coelho,Jonas Gonçalves

    2004-01-01

    O artigo apresenta a concepção bergsoniana de duração. Pretende-se mostrar que, segundo Bergson, o tempo dos filósofos e cientistas é um tempo fictício, um esquema espacial que oculta a natureza do tempo real, o qual não pode ser separado dos acontecimentos físicos e psicológicos. Para Bergson, o tempo real é sucessão, continuidade, mudança, memória e criação. El presente artículo trata de la concepción bergsoniana de duración. Pretendemos mostrar que, según Bergson, el tiempo de los filós...

  3. Synthesis and electron paramagnetic resonance study of a nitroxide free radical covalently bonded on aminopropyl-silica gel

    International Nuclear Information System (INIS)

    Tudose, Madalina; Constantinescu, Titus; Balaban, Alexandru T.; Ionita, Petre

    2008-01-01

    A solid spin-labeled material was obtained starting from 2-chloro-3,5-dinitro-N-(4-(2,2,6,6-tetramethyl-piperidine-1-oxyl) -benzamide) and aminopropyl-silica gel. Stability tests showed that even after several months the spin-labeled material had the same properties as immediately after synthesis. EPR properties of the TEMPO-derivatized silica were studied as a function of solvent polarity and temperature. Rotational correlation times were calculated from EPR spectra and correlated with solvent characteristics and temperature. Polar solvents induce a fast motion of the spin-label, clearly seen in the EPR spectra by the apparition of the well-known TEMPO radical triplet. The solid spin-labeled (dry) sample showed a high interspin interaction, which can be disrupted not only by different (liquid) solvents, but also by absorption of different solids, like cyclodextrins, dendrimers or polyethyleneglycols. Also, changes induced by the temperature were studied in the case of toluene wet sample. From 150 to 370 K, the spectrum is changing from a slow motion spectrum type to a fast motion regime. The preparative procedures to obtain the spin-labeled silica as well as some of its parameters are described

  4. Synthesis and electron paramagnetic resonance study of a nitroxide free radical covalently bonded on aminopropyl-silica gel

    Energy Technology Data Exchange (ETDEWEB)

    Tudose, Madalina; Constantinescu, Titus [Institute of Physical Chemistry, Spl. Independentei 202, 060021 Bucharest (Romania); Balaban, Alexandru T. [Texas A and M University at Galveston, Marine Sciences Department, Galveston, TX 77551 (United States); Ionita, Petre [Institute of Physical Chemistry, Spl. Independentei 202, 060021 Bucharest (Romania)], E-mail: pionita@icf.ro

    2008-01-30

    A solid spin-labeled material was obtained starting from 2-chloro-3,5-dinitro-N-(4-(2,2,6,6-tetramethyl-piperidine-1-oxyl) -benzamide) and aminopropyl-silica gel. Stability tests showed that even after several months the spin-labeled material had the same properties as immediately after synthesis. EPR properties of the TEMPO-derivatized silica were studied as a function of solvent polarity and temperature. Rotational correlation times were calculated from EPR spectra and correlated with solvent characteristics and temperature. Polar solvents induce a fast motion of the spin-label, clearly seen in the EPR spectra by the apparition of the well-known TEMPO radical triplet. The solid spin-labeled (dry) sample showed a high interspin interaction, which can be disrupted not only by different (liquid) solvents, but also by absorption of different solids, like cyclodextrins, dendrimers or polyethyleneglycols. Also, changes induced by the temperature were studied in the case of toluene wet sample. From 150 to 370 K, the spectrum is changing from a slow motion spectrum type to a fast motion regime. The preparative procedures to obtain the spin-labeled silica as well as some of its parameters are described.

  5. Tempo curves considered harmful

    NARCIS (Netherlands)

    Desain, P.; Honing, H.

    1993-01-01

    In the literature of musicology, computer music research and the psychology of music, timing or tempo measurements are mostly presented in the form of continuous curves. The notion of these tempo curves is dangerous, despite its widespread use, because it lulls its users into the false impression

  6. Konvergensi di Ruang Redaksi pada Kelompok Media Tempo

    Directory of Open Access Journals (Sweden)

    Wahyudi Marhaen Pratopo

    2018-03-01

    Full Text Available This study seeks to reveal the implementation of convergence in the newsroom with case study of Tempo Group. This research uses qualitative approach and case study method. This study reveals that Tempo began to implement newroom convergence after publishing Kora Tempo in 2001. The effort toward newsroom convergence was realized by forming Tempo Newsroom which is meant as a news control center. After passing a series of trials and policy changes, the Tempo Group finally adopted full editorial convergence since 2012. In the application of this editorial convergence, Tempo chose the Newsroom 3.0 model, a newsroom management system that brings together news gathering and news processing to provide news needs for some outlet: tempo.co, Koran Tempo, and Tempo Magazine.

  7. Diasteromeric Effect on the Homolysis of the C–ON Bond in Alkoxyamines: A DFT Investigation of 1,3-Diphenylbutyl-TEMPO

    Directory of Open Access Journals (Sweden)

    Valérie Roubaud

    2010-09-01

    Full Text Available The rate constants kd of the homolysis of the C–ON bond in styryl dyads TEMPO-based alkoxyamines have recently been published (Li et al. Macromolecules 2006, 39, 9201. The diastereoisomers exhibited different values which were higher than for the unimer TEMPO-styryl alkoxyamine 1. At a first glance, the localization of the steric strain was not obvious. To decipher this problem, diastereoisomer models 2 (RR/SS and 3 (RS/SR, as well as the released alkyl radicals, were calculated at the B3LYP/6-31G(d level. It was revealed that the increase in kd from 1 to 3 was due to the compression (buttressing effect of the reactive center by the second styryl moiety. The difference in kd for the diastereoisomer was clearly an activation entropy effect DS≠ because the alkyl fragment of the RS/SR diastereoismer exhibited the same conformation as the released radical whereas the conformation for the RR/SS diastereoisomer was quite different and thus required the rotation of several bonds to reach the correct TS, which cost DS≠, and thus lowers kd.

  8. Protein capped nanosilver free radical oxidation: role of biomolecule capping on nanoparticle colloidal stability and protein oxidation.

    Science.gov (United States)

    Ahumada, Manuel; Bohne, Cornelia; Oake, Jessy; Alarcon, Emilio I

    2018-05-03

    We studied the effect of human serum albumin protein capped spherical nanosilver on the nanoparticle stability upon peroxyl radical oxidation. The nanoparticle-protein composite is less prone to oxidation compared to the individual components. However, higher concentrations of hydrogen peroxide were formed in the nanoparticle-protein system.

  9. Tropospheric Emissions: Monitoring of Pollution (TEMPO)

    Science.gov (United States)

    Chance, Kelly; Liu, Xiong; Suleiman, Raid M.; Flittner, David E.; Al-Saadi, Jassim; Janz, Scott J.

    2014-06-01

    TEMPO, selected by NASA as the first Earth Venture Instrument, will measure atmospheric pollution for greater North America from space using ultraviolet and visible spectroscopy. TEMPO measures from Mexico City to the Canadian oil sands, and from the Atlantic to the Pacific, hourly and at high spatial resolution. TEMPO provides a tropospheric measurement suite that includes the key elements of tropospheric air pollution chemistry. Measurements are from geostationary (GEO) orbit, to capture the inherent high variability in the diurnal cycle of emissions and chemistry. The small product spatial footprint resolves pollution sources at sub-urban scale. Together, this temporal and spatial resolution improves emission inventories, monitors population exposure, and enables effective emission-control strategies. TEMPO takes advantage of a GEO host spacecraft to provide a modest-cost mission that measures the spectra required to retrieve O3, NO2, SO2, H2CO, C2H2O2, H2O, aerosols, cloud parameters, and UVB radiation. TEMPO thus measures the major elements, directly or by proxy, in the tropospheric O3 chemistry cycle. Multi-spectral observations provide sensitivity to O3 in the lowermost troposphere, reducing uncertainty in air quality predictions by 50 %. TEMPO quantifies and tracks the evolution of aerosol loading. It provides near-real-time air quality products that will be made widely, publicly available. TEMPO makes the first tropospheric trace gas measurements from GEO, by building on the heritage of five spectrometers flown in low-earth-orbit (LEO). These LEO instruments measure the needed spectra, although at coarse spatial and temporal resolutions, to the precisions required for TEMPO and use retrieval algorithms developed for them by TEMPO Science Team members and currently running in operational environments. This makes TEMPO an innovative use of a well-proven technique, able to produce a revolutionary data set. TEMPO provides much of the atmospheric measurement

  10. The Effect of Melodic Activity, Tempo Change, and Audible Beat on Tempo Perception of Elementary School Students.

    Science.gov (United States)

    Kuhn, Terry Lee; Booth, Gregory D.

    1988-01-01

    Investigated the influence of melodic activity (ornamented and plain) on students' perception of tempo. Third, fifth, and sixth graders indicated whether the tempo of the second example in each paired comparison item was faster, slower, or stayed the same. Suggests that tempo perception lessons be preceded by instruction on melodic activity and…

  11. I misteri del tempo l'universo dopo Einstein

    CERN Document Server

    Davies, Paul

    1996-01-01

    Quando fu esattamente l'inizio del tempo? Il viaggio nel tempo è realtà o fantasia? Sono possibili gli esperimenti con il tempo? Questo importante saggio indaga sull'enigma del tempo, un tema affascinante da sempre al centro delle speculazioni scientifiche e religiose.

  12. Algebraic and radical potential fields. Stability domains in coordinate and parametric space

    Science.gov (United States)

    Uteshev, Alexei Yu.

    2018-05-01

    A dynamical system d X/d t = F(X; A) is treated where F(X; A) is a polynomial (or some general type of radical contained) function in the vectors of state variables X ∈ ℝn and parameters A ∈ ℝm. We are looking for stability domains in both spaces, i.e. (a) domain ℙ ⊂ ℝm such that for any parameter vector specialization A ∈ ℙ, there exists a stable equilibrium for the dynamical system, and (b) domain 𝕊 ⊂ ℝn such that any point X* ∈ 𝕊 could be made a stable equilibrium by a suitable specialization of the parameter vector A.

  13. Spontaneous Entrainment of Running Cadence to Music Tempo.

    Science.gov (United States)

    Van Dyck, Edith; Moens, Bart; Buhmann, Jeska; Demey, Michiel; Coorevits, Esther; Dalla Bella, Simone; Leman, Marc

    Since accumulating evidence suggests that step rate is strongly associated with running-related injuries, it is important for runners to exercise at an appropriate running cadence. As music tempo has been shown to be capable of impacting exercise performance of repetitive endurance activities, it might also serve as a means to (re)shape running cadence. The aim of this study was to validate the impact of music tempo on running cadence. Sixteen recreational runners ran four laps of 200 m (i.e. 800 m in total); this task was repeated 11 times with a short break in between each four-lap sequence. During the first lap of a sequence, participants ran at a self-paced tempo without musical accompaniment. Running cadence of the first lap was registered, and during the second lap, music with a tempo matching the assessed cadence was played. In the final two laps, the music tempo was either increased/decreased by 3.00, 2.50, 2.00, 1.50, or 1.00 % or was kept stable. This range was chosen since the aim of this study was to test spontaneous entrainment (an average person can distinguish tempo variations of about 4 %). Each participant performed all conditions. Imperceptible shifts in musical tempi in proportion to the runner's self-paced running tempo significantly influenced running cadence ( p  tempo conditions and adaptation in running cadence ( p  effect of condition on the level of entrainment was revealed ( p  effects of music tempo on running cadence can only be obtained up to a certain level of tempo modification. Finally, significantly higher levels of tempo entrainment were found for female participants compared to their male counterparts ( p  music tempo could serve as an unprompted means to impact running cadence. As increases in step rate may prove beneficial in the prevention and treatment of common running-related injuries, this finding could be especially relevant for treatment purposes, such as exercise prescription and gait retraining. Music tempo

  14. Formation of stable radicals during perfluoroalkane radiolysis

    International Nuclear Information System (INIS)

    Allayarov, S.R.; Demidov, S.V.; Kiryukhin, D.P.; Mikhajlov, A.I.; Barkalov, I.M.

    1984-01-01

    Accumulation and stabilization kinetics of perfluoroalkyls during α-radiolysis ( 60 Co) of perfluoralkanes (PFA) in a wide temperature range for different PFA fractions differing in the average molecular weight, is investigated. It is noted that low temperature (PFA) radiolysis (77 K) is of a linear nature of accumulation of stabilized radicals up to doses of approximately 700 KGy. In the case of PFA radiolysis at 300 K radiation yields of stable radicals are somewhat lower than at 47 K and at doses of 200-300 KGy, their accumulation ceases. It is shown that kinetics of formation and accumulation of stable radicals does not depend on molecular mass and PFA fraction viscosity. Perfluoroalkyl stability is explained by intra molecular conformation spheric insulation of the free valency. Perfluoroalkyl stability in different PFA fractions in a wide time range in different media is investigated

  15. Memory for vocal tempo and pitch.

    Science.gov (United States)

    Boltz, Marilyn G

    2017-11-01

    Two experiments examined the ability to remember the vocal tempo and pitch of different individuals, and the way this information is encoded into the cognitive system. In both studies, participants engaged in an initial familiarisation phase while attending was systematically directed towards different aspects of speakers' voices. Afterwards, they received a tempo or pitch recognition task. Experiment 1 showed that tempo and pitch are both incidentally encoded into memory at levels comparable to intentional learning, and no performance deficit occurs with divided attending. Experiment 2 examined the ability to recognise pitch or tempo when the two dimensions co-varied and found that the presence of one influenced the other: performance was best when both dimensions were positively correlated with one another. As a set, these findings indicate that pitch and tempo are automatically processed in a holistic, integral fashion [Garner, W. R. (1974). The processing of information and structure. Potomac, MD: Erlbaum.] which has a number of cognitive implications.

  16. Stability of radicals in electron-irradiated fluoropolymer film for the preparation of graft copolymer fuel cell electrolyte membranes

    DEFF Research Database (Denmark)

    Larsen, Mikkel Juul; Ma, Yue; Qian, Huan

    This presentation concerns the stability of radicals generated in poly(ethylene-alt-tetra­fluoro­ethylene) (ETFE) film by electron irradiation prior to grafting of styrene onto this base material. It has been demonstrated that the grafting yield decreases as the storage time of the irradiated fil...

  17. Tempos históricos, tempos físicos, tempos epidemiológicos: prováveis contribuições de Fernand Braudel e Ilya Prigogine ao pensamento epidemiológico

    Directory of Open Access Journals (Sweden)

    Sevalho Gil

    1997-01-01

    Full Text Available O texto é uma abordagem acerca do tempo enquanto categoria científica para a epidemiologia. A partir do aforismo tempo-lugar-pessoa, o tempo é apontado como elemento pouco pensado pela epidemiologia, embora esteja presente em vários dos seus conceitos. No entanto, o tema tem sido objeto de reflexão importante na movimentação recente de várias disciplinas, tais como a história, a geografia, a biologia e a física, e deve por isto representar para a epidemiologia um ponto de vista interessante, tanto no que concerne ao diálogo interdisciplinar quanto ao estabelecimento de um olhar crítico voltado para a própria disciplina. Com o objetivo de argumentar a respeito destes aspectos, apresenta-se o tempo histórico de Fernand Braudel e o tempo físico de Ilya Prigogine, construções teóricas que serão comparadas com um provável tempo epidemiológico. Ao final, usando a questão das infecções emergentes como exemplo, faz-se considerações sobre a aparente inadequação epistemológica do tempo epidemiológico para reconhecer e lidar com os aspectos sociais e históricos envolvidos na complexidade do adoecer humano coletivo.

  18. Oncological outcomes of laparoscopic radical nephrectomy for renal cancer Resultados oncológicos da nefrectomia radical laparoscópica no tratamento do carcinoma renal

    Directory of Open Access Journals (Sweden)

    Jose R. Colombo Jr.

    2007-01-01

    prontuários, laudos de exames radiológicos e ligações telefônicas para pacientes e/ou familiares. O seguimento foi calculado desde a data da cirurgia até a última consulta médica ou data de falecimento. RESULTADOS: Todos os procedimentos laparoscópicos foram realizados sem conversão para a técnica aberta. O tamanho médio tumoral foi de 5.8 e. 6.2 cm (P=0.44, perda sanguínea estimada de 183 e. 461 mL (P=0.004, e tempo operatório de 2.8 e. 3.7 horas (P<0.001 , respectivamente para os grupos nefrectomia radical laparoscópica e nefrectomia radical aberta. O tempo de seguimento médio foi de 5 anos para o grupo nefrectomia radical laparoscópica e 6 anos para o grupo nefrectomia radical aberta. A sobrevida global após 5 anos foi de 81% e 79% (P=0.47, e a sobrevida específica para cancer foi de 90% e 92% (P=0.70, para os grupos nefrectomia radical laparoscópica e nefrectomia radical aberta respectivamente. CONCLUSÃO: A nefrectomia radical laparoscópica tem resultados oncológicos em 5 anos similares a técnica convencional aberta.

  19. Increase in salivary oxytocin and decrease in salivary cortisol after listening to relaxing slow-tempo and exciting fast-tempo music.

    Directory of Open Access Journals (Sweden)

    Yuuki Ooishi

    Full Text Available Relaxation and excitation are components of the effects of music listening. The tempo of music is often considered a critical factor when determining these effects: listening to slow-tempo and fast-tempo music elicits relaxation and excitation, respectively. However, the chemical bases that underlie these relaxation and excitation effects remain unclear. Since parasympathetic and sympathetic nerve activities are facilitated by oxytocin and glucocorticoid, respectively, we hypothesized that listening to relaxing slow-tempo and exciting fast-tempo music is accompanied by increases in the oxytocin and cortisol levels, respectively. We evaluated the change in the salivary oxytocin and cortisol levels of participants listening to slow-tempo and fast-tempo music sequences. We measured the heart rate (HR and calculated the heart rate variability (HRV to evaluate the strength of autonomic nerve activity. After listening to a music sequence, the participants rated their arousal and valence levels. We found that both the salivary oxytocin concentration and the high frequency component of the HRV (HF increased and the HR decreased when a slow-tempo music sequence was presented. The salivary cortisol level decreased and the low frequency of the HRV (LF to HF ratio (LF/HF increased when a fast-tempo music sequence was presented. The ratio of the change in the oxytocin level was correlated with the change in HF, LF/HF and HR, whereas that in the cortisol level did not show any correlation with indices of autonomic nerve activity. There was no correlation between the change in oxytocin level and self-reported emotions, while the change in cortisol level correlated with the arousal level. These findings suggest that listening to slow-tempo and fast-tempo music is accompanied by an increase in the oxytocin level and a decrease in the cortisol level, respectively, and imply that such music listening-related changes in oxytocin and cortisol are involved in

  20. Increase in salivary oxytocin and decrease in salivary cortisol after listening to relaxing slow-tempo and exciting fast-tempo music

    Science.gov (United States)

    Watanabe, Ken; Kawato, Suguru; Kashino, Makio

    2017-01-01

    Relaxation and excitation are components of the effects of music listening. The tempo of music is often considered a critical factor when determining these effects: listening to slow-tempo and fast-tempo music elicits relaxation and excitation, respectively. However, the chemical bases that underlie these relaxation and excitation effects remain unclear. Since parasympathetic and sympathetic nerve activities are facilitated by oxytocin and glucocorticoid, respectively, we hypothesized that listening to relaxing slow-tempo and exciting fast-tempo music is accompanied by increases in the oxytocin and cortisol levels, respectively. We evaluated the change in the salivary oxytocin and cortisol levels of participants listening to slow-tempo and fast-tempo music sequences. We measured the heart rate (HR) and calculated the heart rate variability (HRV) to evaluate the strength of autonomic nerve activity. After listening to a music sequence, the participants rated their arousal and valence levels. We found that both the salivary oxytocin concentration and the high frequency component of the HRV (HF) increased and the HR decreased when a slow-tempo music sequence was presented. The salivary cortisol level decreased and the low frequency of the HRV (LF) to HF ratio (LF/HF) increased when a fast-tempo music sequence was presented. The ratio of the change in the oxytocin level was correlated with the change in HF, LF/HF and HR, whereas that in the cortisol level did not show any correlation with indices of autonomic nerve activity. There was no correlation between the change in oxytocin level and self-reported emotions, while the change in cortisol level correlated with the arousal level. These findings suggest that listening to slow-tempo and fast-tempo music is accompanied by an increase in the oxytocin level and a decrease in the cortisol level, respectively, and imply that such music listening-related changes in oxytocin and cortisol are involved in physiological

  1. Increase in salivary oxytocin and decrease in salivary cortisol after listening to relaxing slow-tempo and exciting fast-tempo music.

    Science.gov (United States)

    Ooishi, Yuuki; Mukai, Hideo; Watanabe, Ken; Kawato, Suguru; Kashino, Makio

    2017-01-01

    Relaxation and excitation are components of the effects of music listening. The tempo of music is often considered a critical factor when determining these effects: listening to slow-tempo and fast-tempo music elicits relaxation and excitation, respectively. However, the chemical bases that underlie these relaxation and excitation effects remain unclear. Since parasympathetic and sympathetic nerve activities are facilitated by oxytocin and glucocorticoid, respectively, we hypothesized that listening to relaxing slow-tempo and exciting fast-tempo music is accompanied by increases in the oxytocin and cortisol levels, respectively. We evaluated the change in the salivary oxytocin and cortisol levels of participants listening to slow-tempo and fast-tempo music sequences. We measured the heart rate (HR) and calculated the heart rate variability (HRV) to evaluate the strength of autonomic nerve activity. After listening to a music sequence, the participants rated their arousal and valence levels. We found that both the salivary oxytocin concentration and the high frequency component of the HRV (HF) increased and the HR decreased when a slow-tempo music sequence was presented. The salivary cortisol level decreased and the low frequency of the HRV (LF) to HF ratio (LF/HF) increased when a fast-tempo music sequence was presented. The ratio of the change in the oxytocin level was correlated with the change in HF, LF/HF and HR, whereas that in the cortisol level did not show any correlation with indices of autonomic nerve activity. There was no correlation between the change in oxytocin level and self-reported emotions, while the change in cortisol level correlated with the arousal level. These findings suggest that listening to slow-tempo and fast-tempo music is accompanied by an increase in the oxytocin level and a decrease in the cortisol level, respectively, and imply that such music listening-related changes in oxytocin and cortisol are involved in physiological

  2. Tensão entre tempo social e tempo individual The tension between social time and individual time

    Directory of Open Access Journals (Sweden)

    Josué Pereira da Silva

    2009-01-01

    Full Text Available O artigo discute o tempo na obra de André Gorz, procurando a partir desse tema compreender sua concepção a respeito da relação entre indivíduo e sociedade. Para tanto, identifica e descreve suas três abordagens sobre o tempo: a primeira procura construir uma axiologia de valores baseada nas três dimensões temporais (passado, presente e futuro; a segunda discute a relação entre tempo e envelhecimento; e a terceira trata do tempo de trabalho. Após descrever cada uma dessas três abordagens sobre o tempo, o artigo conclui sugerindo que há uma tensão entre tempo social e tempo do indivíduo na teoria desse autor, tensão que decorre em boa medida de uma visão filosófica que concebe indivíduo e sociedade como entidades quase antagônicas.The article explores the theme of time in the work of André Gorz, using this motif as a basis for understanding his conception of the relationship between individual and society. This aim in mind, it identifies and describes his three approaches to time: the first seeks to construct an axiology of values based on the three temporal dimensions (past, present and future; the second examines the relationship between time and aging; and the third deals with the time of work. After describing each of these three approaches, the article concludes by identifying the tension between social time and individual time in the author's theory, a tension that largely arises from a philosophical viewpoint that conceives individual and society as almost antagonistic entities.

  3. Stability of cellulose radicals produced by radiation in spices as studied by the EPR spectroscopy

    International Nuclear Information System (INIS)

    Lehner, K.; Stachowicz, W.

    2003-01-01

    The results are presented of EPR measurements on the stability of cellulose radicals produced in 26 popular spices irradiated with a dose of 7 kGy of gamma rays. EPR measurements were done with the use of an EPR spectrometer EPR-10 MINI at X band (microwave radiation of frequency 9.5 GHz), produced by St. Petersburg Instruments Ltd. The aim of the work was to prove the applicability of the EPR method for the control of irradiation in the investigated spices. (author)

  4. Thermal- and pH-Dependent Size Variable Radical Nanoparticles and Its Water Proton Relaxivity for Metal-Free MRI Functional Contrast Agents.

    Science.gov (United States)

    Morishita, Kosuke; Murayama, Shuhei; Araki, Takeru; Aoki, Ichio; Karasawa, Satoru

    2016-09-16

    For development of the metal-free MRI contrast agents, we prepared the supra-molecular organic radical, TEMPO-UBD, carrying TEMPO radical, as well as the urea, alkyl group, and phenyl ring, which demonstrate self-assembly behaviors using noncovalent bonds in an aqueous solution. In addition, TEMPO-UBD has the tertiary amine and the oligoethylene glycol chains (OEGs) for the function of pH and thermal responsiveness. By dynamic light scattering and transmission electron microscopy imaging, the resulting self-assembly was seen to form the spherical nanoparticles 10-150 nm in size. On heating, interestingly, the nanoparticles showed a lower critical solution temperature (LCST) behavior having two-step variation. This double-LCST behavior is the first such example among the supra-molecules. To evaluate of the ability as MRI contrast agents, the values of proton ((1)H) longitudinal relaxivity (r1) were determined using MRI apparatus. In conditions below and above CAC at pH 7.0, the distinguishable r1 values were estimated to be 0.17 and 0.21 mM(-1) s(1), indicating the suppression of fast tumbling motion of TEMPO moiety in a nanoparticle. Furthermore, r1 values became larger in the order of pH 7.0 > 9.0 > 5.0. Those thermal and pH dependencies indicated the possibility of metal-fee MRI functional contrast agents in the future.

  5. Effects of Some Aspects of Rhythm on Tempo Perception.

    Science.gov (United States)

    Wang, Cecilia Chu

    1984-01-01

    Results indicated that significantly more time is needed to perceive tempo increase than tempo decrease, uneven rhythm then even rhythm, and melody alone than melody with accompaniment. Furthermore, significant interaction effects involving beat locations of tempo change suggest that differential groupings may be a factor in tempo discrimination.…

  6. Context effects on tempo and pleasantness judgments for Beatles songs.

    Science.gov (United States)

    Rashotte, Matthew A; Wedell, Douglas H

    2012-04-01

    Context effects on tempo and pleasantness judgments of different tempos were demonstrated in three experiments using Beatles songs. In Experiments 1 and 2, we explored how listening to versions of the same song that were played at different tempos affected tempo and pleasantness ratings. In both experiments, contrast effects were found on judgments of tempo, with target tempos rated faster when context tempos were slow than when they were fast. In both experiments, we also showed that the peak of the pleasantness rating function shifted toward the values of the context tempos, reflecting disordinal context effects on pleasantness relationships. Familiarity with the songs did not moderate these effects, and shifts in tempo ratings did not correlate with shifts in most pleasant target tempos when context was manipulated within subjects. In Experiment 3, we examined how manipulations of context tempos for one song affected judgments of the same song as compared with judgments of other more or less similar songs. For tempo ratings, contrast effects transferred to ratings of a similar song, but for pleasantness ratings, assimilative shifts of ideals were found only for the same song and not for similar songs. This pattern of results was supportive of independent bases for the two context effects.

  7. Relationship between exercise heart rate and music tempo preference.

    Science.gov (United States)

    Karageorghis, Costas I; Jones, Leighton; Low, Daniel C

    2006-06-01

    The present study examined the predicted positive and linear relationship (Iwanaga, 1995a, 1995b) between exercise heart rate and music tempo preference. Initially, 128 undergraduate students (M age = 20.0 years, SD = 0.9) were surveyed to establish their three favorite music artists. A separate experimental group of 29 undergraduates (M age = 20.3 years, SD = 1.2) selected the music of a single artist from the three highest-rated artists from the earlier survey. They reported their preference for slow, medium, and fast tempo selections from each artist for three treadmill walking conditions at 40%, 60%, and 75% maximal heart rate reserve. A mixed-model 3 x 3 x 2 (Exercise Intensity x Music Tempo x Gender) analysis of variance was used to analyze the data. Results indicated there was no three-way interaction for music preference. There was, however, a significant (p Music Tempo (partial eta2 = .09) and a significant (p effect for music tempo, with large differences evident between preference for medium versus slow tempo and fast versus slow tempo music at all exercise intensities (partial eta2 = .78). Participants reported a preference for both medium and fast tempo music at low and moderate exercise intensities and for fast tempo music at high intensity. Only partial support was found for the expected linear relationship between exercise intensity and music tempo preference.

  8. Modalization in the Political Column of Tempo Magazine

    OpenAIRE

    Rahmah, Maria Betti Sinaga and

    2017-01-01

    The study focuses on analyzing the use of modalization in the Political Column of Tempo Magazine. The objectives were to find out the type of modalization and to describe the use of modalization in the Political Column of Tempo magazine. The data were taken from Political Column of Tempo magazine published in June and July 2017. The source of data was Political Column in Tempo magazine. The data analysis applied descriptive qualitative research. There were 135 clauses which contained Modaliza...

  9. Automatic movie skimming with general tempo analysis

    Science.gov (United States)

    Lee, Shih-Hung; Yeh, Chia-Hung; Kuo, C. C. J.

    2003-11-01

    Story units are extracted by general tempo analysis including tempos analysis including tempos of audio and visual information in this research. Although many schemes have been proposed to successfully segment video data into shots using basic low-level features, how to group shots into meaningful units called story units is still a challenging problem. By focusing on a certain type of video such as sport or news, we can explore models with the specific application domain knowledge. For movie contents, many heuristic rules based on audiovisual clues have been proposed with limited success. We propose a method to extract story units using general tempo analysis. Experimental results are given to demonstrate the feasibility and efficiency of the proposed technique.

  10. Improvement of the thermal and thermo-oxidative stability of high-density polyethylene by free radical trapping of rare earth compound

    Energy Technology Data Exchange (ETDEWEB)

    Ran, Shiya; Zhao, Li; Han, Ligang [Laboratory of Polymer Materials and Engineering, Ningbo Institute of Technology, ZhejiangUniversity, Ningbo, 315100 (China); MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Institute of Polymer Composites, Zhejiang University, Hangzhou, 310027 (China); Guo, Zhenghong, E-mail: guozhenghong@nit.zju.edu.cn [Laboratory of Polymer Materials and Engineering, Ningbo Institute of Technology, ZhejiangUniversity, Ningbo, 315100 (China); Fang, Zhengping [Laboratory of Polymer Materials and Engineering, Ningbo Institute of Technology, ZhejiangUniversity, Ningbo, 315100 (China); MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Institute of Polymer Composites, Zhejiang University, Hangzhou, 310027 (China)

    2015-07-20

    Highlights: • Polyethylene filled with ytterbium trifluoromethanesulfonate was prepared. • A low Yb loading improved thermal stability of PE obviously by radical trapping. • Yb(OTf){sub 3} is expected to be an efficient thermal stabilizer for the polymer. - Abstract: A kind of rare earth compound, ytterbium trifluoromethanesulfonate (Yb(OTf){sub 3}), was introduced into high-density polyethylene (HDPE) by melt compounding to investigate the effect of Yb(OTf){sub 3} on the thermal and thermo-oxidative stability of HDPE. The results of thermogravimetric (TG) and differential scanning calorimetry (DSC) showed that the addition of Yb(OTf){sub 3} made the thermal degradation temperatures dramatically increased, the oxidative induction time (OIT) extended, and the enthalpy (ΔH{sub d}) reduced. Very low Yb(OTf){sub 3} loading (0.5 wt%) in HDPE could increase the onset degradation temperature in air from 334 to 407 °C, delay the OIT from 11.0 to 24.3 min, and decrease the ΔH{sub d} from 61.0 to 13.0 J/g remarkably. Electron spin resonance spectra (ESR), thermogravimetric analysis coupled to Fourier transform infrared spectroscopy (TGA-FTIR), rheological investigation and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) indicated that the free radicals-trapping ability of Yb(OTf){sub 3} was responsible for the improved thermal and thermo-oxidative stability.

  11. Fragmentation characteristics of the unstable [CH3 CO][radical sign] radicals generated by neutralization of [CH3CO]+ cations

    Science.gov (United States)

    Hop, C. E. C. A.; Holmes, J. L.

    1991-03-01

    The stability and fragmentation characteristics of [CH3 CO][radical sign] radicals, generated by vertical charge exchange between acetyl cations and permanent gases or metal vapours (He, Xe, NO, Cd, Na and K), were examined mass spectrometrically. Two dissociation reactions were observed, the losses of CH[radical sign]3 and H[radical sign]. The H[radical sign] loss reaction, the higher energy dissociation, became of greater importance as the exothermicity of the charge exchange was increased. Based on the analysis of the kinetic energy releases it was concluded that these decompositions arose from the population of two excited states of the [CH3 CO][radical sign] radical.

  12. On tempo tracking: Tempogram representation and Kalman filtering

    NARCIS (Netherlands)

    Cemgil, A.T.; Kappen, H.J.; Desain, P.W.M.; Honing, H.J.

    2001-01-01

    We formulate tempo tracking in a Bayesian framework where a tempo tracker is modeled as a stochastic dynamical system. The tempo is modeled as a hidden state variable of the system and is estimated by a Kalman filter. The Kalman filter operates on a Tempogram, a wavelet-like multiscale expansion of

  13. Tropospheric emissions: Monitoring of pollution (TEMPO)

    Science.gov (United States)

    Zoogman, P.; Liu, X.; Suleiman, R. M.; Pennington, W. F.; Flittner, D. E.; Al-Saadi, J. A.; Hilton, B. B.; Nicks, D. K.; Newchurch, M. J.; Carr, J. L.; Janz, S. J.; Andraschko, M. R.; Arola, A.; Baker, B. D.; Canova, B. P.; Chan Miller, C.; Cohen, R. C.; Davis, J. E.; Dussault, M. E.; Edwards, D. P.; Fishman, J.; Ghulam, A.; González Abad, G.; Grutter, M.; Herman, J. R.; Houck, J.; Jacob, D. J.; Joiner, J.; Kerridge, B. J.; Kim, J.; Krotkov, N. A.; Lamsal, L.; Li, C.; Lindfors, A.; Martin, R. V.; McElroy, C. T.; McLinden, C.; Natraj, V.; Neil, D. O.; Nowlan, C. R.; O`Sullivan, E. J.; Palmer, P. I.; Pierce, R. B.; Pippin, M. R.; Saiz-Lopez, A.; Spurr, R. J. D.; Szykman, J. J.; Torres, O.; Veefkind, J. P.; Veihelmann, B.; Wang, H.; Wang, J.; Chance, K.

    2017-01-01

    TEMPO was selected in 2012 by NASA as the first Earth Venture Instrument, for launch between 2018 and 2021. It will measure atmospheric pollution for greater North America from space using ultraviolet and visible spectroscopy. TEMPO observes from Mexico City, Cuba, and the Bahamas to the Canadian oil sands, and from the Atlantic to the Pacific, hourly and at high spatial resolution ( 2.1 km N/S×4.4 km E/W at 36.5°N, 100°W). TEMPO provides a tropospheric measurement suite that includes the key elements of tropospheric air pollution chemistry, as well as contributing to carbon cycle knowledge. Measurements are made hourly from geostationary (GEO) orbit, to capture the high variability present in the diurnal cycle of emissions and chemistry that are unobservable from current low-Earth orbit (LEO) satellites that measure once per day. The small product spatial footprint resolves pollution sources at sub-urban scale. Together, this temporal and spatial resolution improves emission inventories, monitors population exposure, and enables effective emission-control strategies. TEMPO takes advantage of a commercial GEO host spacecraft to provide a modest cost mission that measures the spectra required to retrieve ozone (O3), nitrogen dioxide (NO2), sulfur dioxide (SO2), formaldehyde (H2CO), glyoxal (C2H2O2), bromine monoxide (BrO), IO (iodine monoxide), water vapor, aerosols, cloud parameters, ultraviolet radiation, and foliage properties. TEMPO thus measures the major elements, directly or by proxy, in the tropospheric O3 chemistry cycle. Multi-spectral observations provide sensitivity to O3 in the lowermost troposphere, substantially reducing uncertainty in air quality predictions. TEMPO quantifies and tracks the evolution of aerosol loading. It provides these near-real-time air quality products that will be made publicly available. TEMPO will launch at a prime time to be the North American component of the global geostationary constellation of pollution monitoring

  14. Tropospheric Emissions: Monitoring of Pollution (TEMPO)

    Science.gov (United States)

    Zoogman, P.; Liu, X.; Suleiman, R. M.; Pennington, W. F.; Flittner, D. E.; Al-Saadi, J. A.; Hilton, B. B.; Nicks, D. K.; Newchurch, M. J.; Carr, J. L.; hide

    2016-01-01

    TEMPO (Tropospheric Emissions: Monitoring of Pollution) was selected in 2012 by NASA as the first Earth Venture Instrument, for launch between 2018 and 2021. It will measure atmospheric pollution for greater North America from space using ultraviolet and visible spectroscopy. TEMPO observes from Mexico City, Cuba, and the Bahamas to the Canadian oil sands, and from the Atlantic to the Pacific, hourly and at high spatial resolution (approximately 2.1 kilometers N/S by 4.4 kilometers E/W at 36.5 degrees N, 100 degrees W). TEMPO provides a tropospheric measurement suite that includes the key elements of tropospheric air pollution chemistry, as well as contributing to carbon cycle knowledge. Measurements are made hourly from geostationary (GEO) orbit, to capture the high variability present in the diurnal cycle of emissions and chemistry that are unobservable from current low-Earth orbit (LEO) satellites that measure once per day. The small product spatial footprint resolves pollution sources at sub-urban scale. Together, this temporal and spatial resolution improves emission inventories, monitors population exposure, and enables effective emission-control strategies. TEMPO takes advantage of a commercial GEO host spacecraft to provide a modest cost mission that measures the spectra required to retrieve ozone (O3), nitrogen dioxide (NO2), sulfur dioxide (SO2), formaldehyde (H2CO), glyoxal (C2H2O2), bromine monoxide (BrO), IO (iodine monoxide),water vapor, aerosols, cloud parameters, ultraviolet radiation, and foliage properties. TEMPO thus measures the major elements, directly or by proxy, in the tropospheric O3 chemistry cycle. Multi-spectral observations provide sensitivity to O3 in the lowermost troposphere, substantially reducing uncertainty in air quality predictions. TEMPO quantifies and tracks the evolution of aerosol loading. It provides these near-real-time air quality products that will be made publicly available. TEMPO will launch at a prime time to be the

  15. Nonhuman primates prefer slow tempos but dislike music overall.

    Science.gov (United States)

    McDermott, Josh; Hauser, Marc D

    2007-09-01

    Human adults generally find fast tempos more arousing than slow tempos, with tempo frequently manipulated in music to alter tension and emotion. We used a previously published method [McDermott, J., & Hauser, M. (2004). Are consonant intervals music to their ears? Spontaneous acoustic preferences in a nonhuman primate. Cognition, 94(2), B11-B21] to test cotton-top tamarins and common marmosets, two new-World primates, for their spontaneous responses to stimuli that varied systematically with respect to tempo. Across several experiments, we found that both tamarins and marmosets preferred slow tempos to fast. It is possible that the observed preferences were due to arousal, and that this effect is homologous to the human response to tempo. In other respects, however, these two monkey species showed striking differences compared to humans. Specifically, when presented with a choice between slow tempo musical stimuli, including lullabies, and silence, tamarins and marmosets preferred silence whereas humans, when similarly tested, preferred music. Thus despite the possibility of homologous mechanisms for tempo perception in human and nonhuman primates, there appear to be motivational ties to music that are uniquely human.

  16. Effect of Tempo on Pitch Perception.

    Science.gov (United States)

    Duke, Robert A.; And Others

    1988-01-01

    Presents a study which investigated the perception of music majors and nonmusic majors concerning their ability to discriminate the way in which altered musical excerpts differed in pitch or tempo (or both) from preceding presentations. Concludes that both groups responded similarly across conditions and replications, and that tempo changes were…

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

    Science.gov (United States)

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

    2016-06-21

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

  18. Radical chemistry of epigallocatechin gallate and its relevance to protein damage

    DEFF Research Database (Denmark)

    Hagerman, Ann E; Dean, Roger T; Davies, Michael Jonathan

    2003-01-01

    The radical chemistry of the plant polyphenolics epigallocatechin gallate (EGCG) and epigallocatechin (EGC) were investigated using electron paramagnetic resonance spectroscopy. Radical species formed spontaneously in aqueous solutions at low pH without external oxidant and were spin stabilized...... redox potentials of EGCG and EGC varied from 1000 mV at pH 3 to 400 mV at pH 8. The polyphenolics did not produce hydroxyl radicals unless reduced metal ions such as iron(II) were added to the system. Zinc(II)-stabilized EGCG radicals were more effective protein-precipitating agents than unoxidized EGCG...

  19. Increase in salivary oxytocin and decrease in salivary cortisol after listening to relaxing slow-tempo and exciting fast-tempo music

    OpenAIRE

    Ooishi, Yuuki; Mukai, Hideo; Watanabe, Ken; Kawato, Suguru; Kashino, Makio

    2017-01-01

    Relaxation and excitation are components of the effects of music listening. The tempo of music is often considered a critical factor when determining these effects: listening to slow-tempo and fast-tempo music elicits relaxation and excitation, respectively. However, the chemical bases that underlie these relaxation and excitation effects remain unclear. Since parasympathetic and sympathetic nerve activities are facilitated by oxytocin and glucocorticoid, respectively, we hypothesized that li...

  20. The Morphological Analysis Found in Tempo Magazine

    OpenAIRE

    Lubis, Khairunnisa

    2015-01-01

    A paper entitled “The Morphological Analysis Found in Tempo Magazine” discussed about affixation process that is one of field linguistics, Morphology. The data of this research is five articles in Tempo magazine 1405/September 23-29, 2013. The scope of this writing is to find some kinds of prefixes and suffixes are used in Tempo magazine and to find what the dominant affix is. The method of research applied is descriptive qualitative. After analyzing the data, there are 5 kinds of prefixes, n...

  1. Free radical scavenging and anti-oxidative activities of an ethanol-soluble pigment extract prepared from fermented Zijuan Pu-erh tea.

    Science.gov (United States)

    Fan, Jiang Ping; Fan, Chong; Dong, Wen Min; Gao, Bin; Yuan, Wei; Gong, Jia Shun

    2013-09-01

    An ethanol-soluble pigment extract was separated from fermented Zijuan Pu-erh tea. The compositions of the ethanol soluble pigment extract were analyzed by high-performance liquid chromatography-tandem mass spectroscopy (HPLC-MS/MS). The extract was prepared into a series of ethanol solutions and analyzed for free radical-scavenging activities (against two free radicals: 1,1-diphenyl-2-picrylhydrazyl (DPPH) and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO)) and in vitro anti-oxidative properties. Electron spin resonance spectroscopy showed that the peaks of DPPH and TEMPO decreased with increasing extract concentration, suggesting that the extract had excellent free radical-scavenging activities. In vitro cell culture suggested that, at 50-200 mg/L, the extract had no measurable effect on the viability of vascular endothelial cells (ECV340) but produced significant protective effects for cells that underwent oxidative injuries due to hydrogen peroxide (H₂O₂) treatment. Compared with the H₂O₂ treatment alone cells group, 200 mg/L of the extract increased the activity of superoxide dismutase (SOD) in cells by 397.3%, and decreased the concentration of malondialdehyde (MDA) and the activity of lactate acid dehydrogenase (LDH) by 47.8% and 69.6%, respectively. These results suggest that the extract has excellent free radical scavenging and anti-oxidative properties. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. Effect of interfibrillar PVA bridging on water stability and mechanical properties of TEMPO/NaClO2 oxidized cellulosic nanofibril films.

    Science.gov (United States)

    Hakalahti, Minna; Salminen, Arto; Seppälä, Jukka; Tammelin, Tekla; Hänninen, Tuomas

    2015-08-01

    TEMPO/NaClO2 oxidized cellulosic nanofibrils (TCNF) were covalently bonded with poly(vinyl alcohol) (PVA) to render water stable films. Pure TCNF films and TCNF-PVA films in dry state showed similar humidity dependent behavior in the elastic region. However, in wet films PVA had a significant effect on stability and mechanical characteristics of the films. When soaked in water, pure TCNF films exhibited strong swelling behavior and poor wet strength, whereas covalently bridged TCNF-PVA composite films remained intact and could easily be handled even after 24h of soaking. Wet tensile strength of the films was considerably enhanced with only 10 wt% PVA addition. At 25% PVA concentration wet tensile strengths were decreased and films were more yielding. This behavior is attributed to the ability of PVA to reinforce and plasticize TCNF-based films. The developed approach is a simple and straightforward method to produce TCNF films that are stable in wet conditions. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Implementation of Tropospheric Emissions: Monitoring of Pollution (TEMPO)

    Science.gov (United States)

    Chance, K.; Liu, X.; Suleiman, R. M.; Flittner, D. E.; Al-Saadi, J. A.; Janz, S. J.

    2014-12-01

    The updated status of TEMPO, as it proceeds from formulation phase into implementation phase is presented. TEMPO, the first NASA Earth Venture Instrument, will measure atmospheric pollution for greater North America from space using ultraviolet and visible spectroscopy. TEMPO measures from Mexico City to the Canadian oil sands, and from the Atlantic to the Pacific, hourly and at high spatial resolution. TEMPO provides a tropospheric measurement suite that includes the key elements of tropospheric air pollution chemistry. Measurements are from geostationary (GEO) orbit, to capture the inherent high variability in the diurnal cycle of emissions and chemistry. The small product spatial footprint resolves pollution sources at sub-urban scale. Together, this temporal and spatial resolution improves emission inventories, monitors population exposure, and enables effective emission-control strategies. TEMPO takes advantage of a GEO host spacecraft to provide a modest cost mission that measures the spectra required to retrieve O3, NO2, SO2, H2CO, C2H2O2, H2O, aerosols, cloud parameters, and UVB radiation. TEMPO thus measures the major elements, directly or by proxy, in the tropospheric O3 chemistry cycle. Multi-spectral observations provide sensitivity to O3 in the lowermost troposphere, reducing uncertainty in air quality predictions by 50%. TEMPO quantifies and tracks the evolution of aerosol loading. It provides near-real-time air quality products that will be made widely, publicly available. TEMPO provides much of the atmospheric measurement capability recommended for GEO-CAPE in the 2007 National Research Council Decadal Survey, Earth Science and Applications from Space: National Imperatives for the Next Decade and Beyond. GEO-CAPE is not planned for implementation this decade. However, instruments from Europe (Sentinel 4) and Asia (GEMS) will form parts of a global GEO constellation for pollution monitoring later this decade, with a major focus on intercontinental

  4. Diligencia de estudantes de graduação de tempo integral e tempo parcial

    OpenAIRE

    Eliel Unglaub

    2003-01-01

    Resumo: Este estudo teve por objetivo descrever, discutir e analisar a manifestação de diligência dos estudantes de graduação de Tempo integral e Tempo parcial, em suas múltiplas dimensões, tais como: Disciplina, Conformidade e Responsabilidade, Motivação, Devoção e Espiritualidade e Concentração e Assimilação, em cursos pré-selecionados da UNICAMP. Procurou-se descobrir em que medida outros fatores, tais como: sexo, estado civil, idade, trabalho, turno e renda familiar estão relacionados à d...

  5. Electron gain and electron loss radicals stabilized on the purine and pyrimidine of a cocrystal exhibiting base-base interstacking: ESR-ENDOR of X-irradiated adenosine:5-bromouracil

    International Nuclear Information System (INIS)

    Kar, L.; Bernhard, W.A.

    1983-01-01

    The predominant free radicals trapped in cocrystals of adenosine:5-bromouracil X-irradiated at 12 0 K were identified by ESR-ENDOR spectroscopy and the radical reactions were followed upon annealing to 480 0 K. The dominant electron abstraction and electron addition products stabilized on the bases at 12 0 K are observed to be the bromouracil π-cation and the adenine π-cation and π-anion. The formation of an anion on bromouracil is inferred from the presence of a radical formed by deuterium addition to C 6 of bromouracil at higher temperatures. Above 40 0 K the bromouracil π-cation appears to decay by recombination and is reduced to undetectable levels at approx.170 0 K. Both adenine π-ions are also observed to decay within the same temperature range. Above 200 0 K hydrogen adducts are stabilized on the bases. Experiments using partially deuterated cocrystals indicate that the H-adducts are formed via both hydrogen addition and protonation of the respective anions. Two hydrogen abstraction radicals stabilized on the sugar residue are detectable at temperatures above 200 0 K, but these may be present at much lower temperatures. The results presented here question the generally accepted hypothesis that, in the presence of purine:pyrimidine stacking interactions, holes are predominantly transferred to the purines while electrns are predominantly transferred to the pyrimidines

  6. The Effect of Speed Alterations on Tempo Note Selection.

    Science.gov (United States)

    Madsen, Clifford K.; And Others

    1986-01-01

    Investigated the tempo note preferences of 100 randomly selected college-level musicians using familiar orchestral music as stimuli. Subjects heard selections at increased, decreased, and unaltered tempi. Results showed musicians were not accurate in estimating original tempo and showed consistent preference for faster than actual tempo.…

  7. Chemical repair of trypsin-histidinyl radical

    International Nuclear Information System (INIS)

    Jovanovic, S.V.; Ruvarac, I.; Jankovic, I.; Josimovic, L.

    1991-01-01

    Oxyl radicals, such as hydroxyl, alkoxyl and peroxyl, react with biomolecules to produce bioradicals. Unless chemically repaired by suitable antioxidants, these bioradicals form stable products. This leads to loss of biological function of parent biomolecules with deleterious biological results, such as mutagenesis and cancer. Consequently, the understanding of the mechanisms of oxyl radical damage to biomolecules and chemical repair of such damage is crucial for the development of strategies for anticarcinogenesis and radioprotection. In this study the chemical repair of the histidinyl radical generated upon the trichloromethylperoxyl radical reaction with trypsin vas investigated by gamma radiolysis. The trypsin histidinyl radical is a resonance-stabilized heterocyclic free radical which was found to be unreactive with oxygen. The efficacy of the chemical repair of the trypsin-histidinyl radical by endogenous antioxidants which are electron donors (e.g. 5-hydroxytryptophan, uric acid) is compared to that of antioxidants which are H-atom donors (e. g. glutathione). 9 refs., 2 figs., 1 tab

  8. Intramolecular hydrogen bonding in malonaldehyde and its radical analogues.

    Science.gov (United States)

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

    2017-09-28

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

  9. La trama del cosmo spazio, tempo, realtà

    CERN Document Server

    Greene, Brian

    2004-01-01

    Dal regno immutabile di Newton, dove lo spazio e il tempo sono assoluti, alla concezione fluida dello spazio-tempo di Einstein, alle tesi della meccanica quantistica, il fisico americano mostra come il mondo sia molto diverso da quello che l'esperienza comune potrebbe far pensare. Concentrandosi sull'enigma del tempo, Greene stabilisce che nessuna regola fisica conferma l'idea che esso scorra in una particolare direzione. Attraverso l'analisi della teoria del big bang, dimostra quanto le recenti teorie delle superstringhe e la M-teoria possano conciliare ogni cosa, dalla più piccola particella al più grande buco nero. Una visione che culmina in un "multiverso" dove spazio e tempo possono dissolversi in entità più sottili e fondamentali.

  10. Absolute Memory for Tempo in Musicians and Non-Musicians.

    Directory of Open Access Journals (Sweden)

    Irene Gratton

    Full Text Available The ability to remember tempo (the perceived frequency of musical pulse without external references may be defined, by analogy with the notion of absolute pitch, as absolute tempo (AT. Anecdotal reports and sparse empirical evidence suggest that at least some individuals possess AT. However, to our knowledge, no systematic assessments of AT have been performed using laboratory tasks comparable to those assessing absolute pitch. In the present study, we operationalize AT as the ability to identify and reproduce tempo in the absence of rhythmic or melodic frames of reference and assess these abilities in musically trained and untrained participants. We asked 15 musicians and 15 non-musicians to listen to a seven-step `tempo scale' of metronome beats, each associated to a numerical label, and then to perform two memory tasks. In the first task, participants heard one of the tempi and attempted to report the correct label (identification task, in the second, they saw one label and attempted to tap the correct tempo (production task. A musical and visual excerpt was presented between successive trials as a distractor to prevent participants from using previous tempi as anchors. Thus, participants needed to encode tempo information with the corresponding label, store the information, and recall it to give the response. We found that more than half were able to perform above chance in at least one of the tasks, and that musical training differentiated between participants in identification, but not in production. These results suggest that AT is relatively wide-spread, relatively independent of musical training in tempo production, but further refined by training in tempo identification. We propose that at least in production, the underlying motor representations are related to tactus, a basic internal rhythmic period that may provide a body-based reference for encoding tempo.

  11. Tempos escolares e tempos de vida: (repensando práticas pedagógicas da EJA na contemporaneidade

    Directory of Open Access Journals (Sweden)

    Eufrázia Nenê Miranda

    2017-08-01

    Full Text Available As práticas estão desconsiderando os tempos de vida dos alunos. Isso está provocando uma crise na escola contemporânea, afetando a ordem dos discursos que, historicamente detém-se, tão somente, ao currículo, desconsiderando os tempos de vida dos sujeitos. Desse modo, não é sobre o produto do conhecimento que se deve recair o foco das discussões curriculares, mas sobre os processos de construção e consideração dos tempos escolares no currículo da EJA. Assim, ao longo do presente artigo, reforçaremos que as construções temporais melhor se desenvolvem e se estabilizam quando estas são afirmadas como resultado da interseção de políticas públicas e de práticas escolares, estruturando-o da seguinte forma: Iniciaremos com tema: Adultos Jovens – Jovens Alunos: uma relação transversal com o tempo, que trará alguns esclarecimentos acerca dos conceitos de adulto, jovem e sua relação com o tempo. Bem como, alguns tópicos relevantes sobre Currículo, Escola e Aluno. Em tempo, traremos algumas inferências a respeito dos tempos sombreados nos discursos escolares e, finalizaremos com uma análise, resultado do trabalho de campo se desenrolou entre junho 2014 a agosto de 2015, com visitas periódicas à unidade escolar NEEJA3. O trabalho de campo mesclou instrumentos de investigação (entrevistas e observações ligados às diversas dimensões constituintes do tempo escolar, que envolveram alunos das totalidades sete, oito e nove, que equivalem a séries fi nais do Ensino Médio, que estimou escores para tal. Palavras – chave: EJA. Currículo. Tempo School times and lifetimes: (re thinking pedagogical practices of the EJA in contemporary times ABSTRACT The practices are disregarding the lives of students times. This is causing a crisis in contemporary school, affecting the order of speeches that historically dwells, alone, to the curriculum, disregarding the lifetimes of subjects. Thus, it is not about the product knowledge

  12. Preferred Dance Tempo

    DEFF Research Database (Denmark)

    Dahl, Sofia; Huron, David; Brod, Garvin

    2014-01-01

    In two experiments participants tuned a drum machine to their preferred dance tempo. Measurements of height, shoulder width, leg length, and weight were taken for each participant, and their sex recorded. Using a multiple regression analysis, height and leg length combined was found to be the bes...

  13. Tempo Preferences of Different Age Music Listeners.

    Science.gov (United States)

    LeBlanc, Albert; And Others

    1988-01-01

    Measures the effect of four levels of tempo on the self-reported preferences of six different age-groups for traditional jazz music listening examples. Stated that listener age exerted a strong influence on overall preference scores. Reported an analysis of variance showing that there is a significant preference for increasingly faster tempo at…

  14. Carbon aerogels by pyrolysis of TEMPO-oxidized cellulose

    Science.gov (United States)

    Zhang, Sizhao; Feng, Jian; Feng, Junzong; Jiang, Yonggang; Ding, Feng

    2018-05-01

    Although carbon aerogels derived from naturally occurring materials have been developed extensively, a reasonable synthetic approach using cellulose-resource remains unclear. Here, we report a strategy to prepare carbon aerogels originated from cellulose position-selectively oxidized by TEMPO-oxidized process. Contrary to non-TEMPO-oxidized cellulose-derived carbon aerogels (NCCA) with relative loose structure, TEMPO-oxidized cellulose-derived carbon aerogels (TCCA) with tight fibrillar-continuous network are monitored, suggesting the importance of TEMPO-oxidized modification towards creating the architecture of subsequently produced carbon aerogels. TCCA endows a higher BET area despite owning slightly dense bulk density comparing with that of NCCA. The structural texture of TCCA could be maintained in a way in comparison to TEMPO-oxidized cellulose-derived aerogel, due to the integration and aggregation effect by losing the electric double layer repulsion via ionization of the surface carboxyl groups. FTIR and XPS analyses signify the evidence of non-functionalized carbon-skeleton network formation in terms of TCCA. Further, the mechanism concerning the creation of carbon aerogels is also established. These findings not only provide new insights into the production of carbon aerogels but also open up a new opportunity in the field of functional carbon materials.

  15. Sympathetic Tone Induced by High Acoustic Tempo Requires Fast Respiration.

    Directory of Open Access Journals (Sweden)

    Ken Watanabe

    Full Text Available Many studies have revealed the influences of music, and particularly its tempo, on the autonomic nervous system (ANS and respiration patterns. Since there is the interaction between the ANS and the respiratory system, namely sympatho-respiratory coupling, it is possible that the effect of musical tempo on the ANS is modulated by the respiratory system. Therefore, we investigated the effects of the relationship between musical tempo and respiratory rate on the ANS. Fifty-two healthy people aged 18-35 years participated in this study. Their respiratory rates were controlled by using a silent electronic metronome and they listened to simple drum sounds with a constant tempo. We varied the respiratory rate-acoustic tempo combination. The respiratory rate was controlled at 15 or 20 cycles per minute (CPM and the acoustic tempo was 60 or 80 beats per minute (BPM or the environment was silent. Electrocardiograms and an elastic chest band were used to measure the heart rate and respiratory rate, respectively. The mean heart rate and heart rate variability (HRV were regarded as indices of ANS activity. We observed a significant increase in the mean heart rate and the low (0.04-0.15 Hz to high (0.15-0.40 Hz frequency ratio of HRV, only when the respiratory rate was controlled at 20 CPM and the acoustic tempo was 80 BPM. We suggest that the effect of acoustic tempo on the sympathetic tone is modulated by the respiratory system.

  16. Sympathetic Tone Induced by High Acoustic Tempo Requires Fast Respiration.

    Science.gov (United States)

    Watanabe, Ken; Ooishi, Yuuki; Kashino, Makio

    2015-01-01

    Many studies have revealed the influences of music, and particularly its tempo, on the autonomic nervous system (ANS) and respiration patterns. Since there is the interaction between the ANS and the respiratory system, namely sympatho-respiratory coupling, it is possible that the effect of musical tempo on the ANS is modulated by the respiratory system. Therefore, we investigated the effects of the relationship between musical tempo and respiratory rate on the ANS. Fifty-two healthy people aged 18-35 years participated in this study. Their respiratory rates were controlled by using a silent electronic metronome and they listened to simple drum sounds with a constant tempo. We varied the respiratory rate-acoustic tempo combination. The respiratory rate was controlled at 15 or 20 cycles per minute (CPM) and the acoustic tempo was 60 or 80 beats per minute (BPM) or the environment was silent. Electrocardiograms and an elastic chest band were used to measure the heart rate and respiratory rate, respectively. The mean heart rate and heart rate variability (HRV) were regarded as indices of ANS activity. We observed a significant increase in the mean heart rate and the low (0.04-0.15 Hz) to high (0.15-0.40 Hz) frequency ratio of HRV, only when the respiratory rate was controlled at 20 CPM and the acoustic tempo was 80 BPM. We suggest that the effect of acoustic tempo on the sympathetic tone is modulated by the respiratory system.

  17. Effects of Tempo and Context on Transfer of Performance Skills.

    Science.gov (United States)

    Duke, Robert A.; Pierce, Michael A.

    1991-01-01

    Discusses research that examined the effects of melodic content and performance tempo on the ability of university music majors to perform previously learned music passages in new settings. Finds tempo accuracy and pitch accuracy were adversely affected by differences between originally learned tempo and tempi at which works were later performed.…

  18. Is expressive timing relational invariant under tempo transformation?

    NARCIS (Netherlands)

    Honing, H.

    2007-01-01

    This empirical study is concerned with examining the relation between tempo and expressive timing in music performance. This was investigated by asking listeners (N = 307) to distinguish between an original recording and a tempo-transformed version in a musical genre of their preference (jazz or

  19. Creative Potential and Conceptual Tempo in Preschool Children.

    Science.gov (United States)

    Broberg, Gayle Christensen; Moran, James D., III

    1988-01-01

    Individual stylistic variations of creative potential and conceptual tempo were investigated in 61 preschool children. No differences between reflective and impulsive preschoolers were found on the ideational fluency measure. Conceptual tempo scores revealed greater originality scores for the fast/accurate and slow/inaccurate groups compared to…

  20. Sniffer para redes Ethernet de tempo-real baseado em FPGA

    OpenAIRE

    Faria, João Pedro Puga

    2008-01-01

    A crescente utilização de sistemas distribuídos em aplicações de tempo-real tem levado á criação de protocolos de comunicação cada vez mais com- plexos e sofisticados. Apesar da rede Ethernet não apresentar característi- cas de tempo-real, devido ás suas vantagens, têm sido desenvolvidos muitos protocolos de comunicação tempo-real baseados em Ethernet. Nesta disser- tação é analisada a importância das arquitecturas distribuídas em aplicações de tempo-real, sendo apresentados...

  1. Template-Based Estimation of Time-Varying Tempo

    Directory of Open Access Journals (Sweden)

    Peeters Geoffroy

    2007-01-01

    Full Text Available We present a novel approach to automatic estimation of tempo over time. This method aims at detecting tempo at the tactus level for percussive and nonpercussive audio. The front-end of our system is based on a proposed reassigned spectral energy flux for the detection of musical events. The dominant periodicities of this flux are estimated by a proposed combination of discrete Fourier transform and frequency-mapped autocorrelation function. The most likely meter, beat, and tatum over time are then estimated jointly using proposed meter/beat subdivision templates and a Viterbi decoding algorithm. The performances of our system have been evaluated on four different test sets among which three were used during the ISMIR 2004 tempo induction contest. The performances obtained are close to the best results of this contest.

  2. INFLUENCIA DEL TEMPO DE LA MÚSICA EN LAS EMOCIONES

    Directory of Open Access Journals (Sweden)

    Jonathan Azael Caballero-Meneses

    2010-01-01

    Full Text Available Se sabe que la música puede influir en dos componentes de lasemociones: el arousal y la valencia. En particular, se ha reportadoque el tempo o rapidez de la música está directamenterelacionado con el arousal, aunque su relación con la valenciao medida de afecto no es aún clara. En este trabajo se analizóla influencia del tempo en ambos componentes mediante laexposición de 24 estudiantes de licenciatura a treinta extractosmusicales de distinto tempo. Además se evaluó la posiblemodulación de la relación tempo-valencia por el rasgo de personalidadextroversión/introversión. Los resultados confirmaronla influencia del tempo sobre el arousal, pero no sobrela valencia, así como una posible mediación de la dimensiónde personalidad introversión-extroversión sobre la valencia.

  3. Fios que Tecem o Tempo Escolar: do ritmo padrão à simultaneidade

    Directory of Open Access Journals (Sweden)

    Ana Sueli Teixeira de Pinho

    2017-09-01

    Full Text Available Este texto tem por objetivo tecer os fios que, de modo complexo, atam e desatam, de forma silenciosa, a constituição do tempo em duas escolas com classes multisseriadas da Ilha de Maré, problematizando a ideia de ritmo padrão e apontando a simultaneidade como possibilidade para o tempo escolar. Do ponto de vista metodológico foi adotada a narrativa (autobiográfica, e a técnica de pesquisa selecionada foi a entrevista narrativa. O estudo realizado aponta que o tempo escolar, das duas escolas pesquisadas, é convidado a reconhecer a existência e a legitimidade de outros tempos, para além do seu: o tempo da maré, o tempo do trabalho, o tempo das práticas simbólicas, o tempo livre e as temporalidades dos sujeitos.

  4. Tempo enhances heat-induced apoptosis by mitochondrial targeting of Bax

    International Nuclear Information System (INIS)

    Zhao, Q.-L.; Fujiwara, Y.; Kondo, T.

    2003-01-01

    A stable membrane-permeable nitroxide, Tempo, exerts an SOD-like antioxidant activity against ROS. Reportedly, Tempo inhibits ROS-induced thymocyte apoptosis, while 10 mM Tempo activates JNK1 to induce apoptosis in breast cancer cells. We have observed that nontoxic 5 mM Tempo enhances suboptimal hyperthermia (44 deg C/10 min)-induced apoptosis in U937 cells. Here we report the enhancing mechanism, focusing on activation and targeting of Bax to mitochondria and cytochrome c release. Methods: U937 cells were treated with either Tempo (5 mM, 37 deg C/10 min), heating (44 deg C/10 min), or Tempo-plus-heating, washed and incubated for various times up to 6 h, until assessing apoptosis, mitochondrial potential (ΔΨ>), and amount of superoxide by flow cytometry using Annexin V-FITC/PI, TMRM, and dihydroethidium, respectively. Bax, Bcl-2 and Bcl-XL, and cytochrome c were detected by western blotting, activated Bax was by immunoprecipitation, and ATP was by a luciferase assay. Bax targeting to and cytochrome c release from mitochorndria were also detected immunocytochemically under fluorescent microscopy. Results and Discussion: Treatment of U937 cells with 5 mM Tempo for 10 min at 37 deg C or suboptimal heating (44 deg C/ 10 min) alone did not induce apoptosis. The combined treatment with 5 mM Tempo and 44 deg C for 10 min dramatically induced ∼90% apoptosis in 6 h, as did the 44 deg C/30 min heating. During the enhanced apoptosis, cytochrome c release progressed. Although signals of Bcl-2, Bcl-XL and Bax in cell lysates were not altered, Bax was specifically activated and translocated to mitochondria after the combined treatment. Further, loss of ΔΨ>and decreases in superoxide and ATP progressed after the combined treatment, suggesting that the treatment may disturb mitochondrial electron transport. Thus, Tempo sensitizes the heat-induced apoptosis through (1) targeting of Bax to mitochondria and releasing cytochrome c, and (2) mitochondrial dysfunction

  5. Photodissociaton of allyl-d2 iodide excited at 193 nm: Stability of highly rotationally excited H2CDCH2 radicals to C-D fission

    International Nuclear Information System (INIS)

    Szpunar, D.E.; Liu, Y.; McCullagh, M.J.; Butler, L.J.; Shu, J.

    2003-01-01

    The photodissociation of allyl-d2 iodide (H2C=CDCH2I) and the dynamics of the nascent allyl-d2 radical (H2CCDCH2) were studied using photofragment translational spectroscopy. A previous study found the allyl radical stable at internal energies up to 15 kcal/mol higher than the 60 kcal/mol barrier to allene + H formation as the result of a centrifugal barrier. The deuterated allyl radical should then also show a stability to secondary dissociation at internal energies well above the barrier due to centrifugal effects. A comparison in this paper shows the allyl-d2 radical is stable to allene + D formation at energies of 2-3 kcal/mol higher than that of the non-deuterated allyl radical following photolysis of allyl iodide at 193 nm. This is most likely a result of a combination of the slight raising of the barrier from the difference in zero-point levels and a reduction of the impact parameter of the dissociative fragments due to the decrease in frequency of the C-D bending modes, and the refore allene + D product orbital angular momentum. Integrated signal taken at m/e = 40 (allene) and m/e = 41 (allene-d1 and propyne-d3) shows a minor fraction of the allyl-d2 radicals isomerize to the 2-propenyl radical, in qualitative support of earlier conclusions of the domination of direct allene + H formation over isomerization

  6. Passive listening to preferred motor tempo modulates corticospinal excitability.

    Science.gov (United States)

    Michaelis, Kelly; Wiener, Martin; Thompson, James C

    2014-01-01

    Rhythms are an essential characteristic of our lives, and auditory-motor coupling affects a variety of behaviors. Previous research has shown that the neural regions associated with motor system processing are coupled to perceptual rhythmic and melodic processing such that the perception of rhythmic stimuli can entrain motor system responses. However, the degree to which individual preference modulates the motor system is unknown. Recent work has shown that passively listening to metrically strong rhythms increases corticospinal excitability, as indicated by transcranial magnetic stimulation (TMS). Furthermore, this effect is modulated by high-groove music, or music that inspires movement, while neuroimaging evidence suggests that premotor activity increases with tempos occurring within a preferred tempo (PT) category. PT refers to the rate of a hypothetical endogenous oscillator that may be indicated by spontaneous motor tempo (SMT) and preferred perceptual tempo (PPT) measurements. The present study investigated whether listening to a rhythm at an individual's PT preferentially modulates motor system excitability. SMT was obtained in human participants through a tapping task in which subjects were asked to tap a response key at their most comfortable rate. Subjects listened a 10-beat tone sequence at 11 log-spaced tempos and rated their preference for each (PPT). We found that SMT and PPT measurements were correlated, indicating that preferred and produced tempos occurred at a similar rate. Crucially, single-pulse TMS delivered to left M1 during PPT judgments revealed that corticospinal excitability, measured by motor-evoked potentials (MEPs), was modulated by tempos traveling closer to individual PT. However, the specific nature of this modulation differed across individuals, with some exhibiting an increase in excitability around PT and others exhibiting a decrease. These findings suggest that auditory-motor coupling induced by rhythms is preferentially

  7. Tritiation and Stability Measurements of Nitroxide for Betavoltaic Cells

    Science.gov (United States)

    2016-09-01

    source compounds include low beta-flux power, intrinsic isotope leakage , and beta self-absorption. The figure of merit for a tritiated compound is...graphane, fully hydrogenated graphene. Graphane is not reactive in water or air; it has theoretical higher mechanical and thermal strength than graphene...bonded to the side group of the nitroxide radical TEMPO 6-membered ring. The ester-cleaved product is detectable and is used to assess the specific

  8. Effects of timbre and tempo change on memory for music.

    Science.gov (United States)

    Halpern, Andrea R; Müllensiefen, Daniel

    2008-09-01

    We investigated the effects of different encoding tasks and of manipulations of two supposedly surface parameters of music on implicit and explicit memory for tunes. In two experiments, participants were first asked to either categorize instrument or judge familiarity of 40 unfamiliar short tunes. Subsequently, participants were asked to give explicit and implicit memory ratings for a list of 80 tunes, which included 40 previously heard. Half of the 40 previously heard tunes differed in timbre (Experiment 1) or tempo (Experiment 2) in comparison with the first exposure. A third experiment compared similarity ratings of the tunes that varied in timbre or tempo. Analysis of variance (ANOVA) results suggest first that the encoding task made no difference for either memory mode. Secondly, timbre and tempo change both impaired explicit memory, whereas tempo change additionally made implicit tune recognition worse. Results are discussed in the context of implicit memory for nonsemantic materials and the possible differences in timbre and tempo in musical representations.

  9. Luz e tempo na melancolia I

    Directory of Open Access Journals (Sweden)

    Cláudio Soares Braga Furtado

    2009-12-01

    Full Text Available A comparação entre as artes possibilita figurar o tempo como elemento comum entre a gravura renascentista de Dürer, a escultura romana de Laocoonte e o conto de Guimarães Rosa. A partir da leitura dessas artes distantes em forma, meios, época e lugar, descobrem-se mistérios aludidos em sutis sinais, que, se ainda não despertos na consciência criativa, estimulam interpretações. O papel da luz como unificadora das entidades tempo/espaço restabelece o princípio clássico da ut pictura poesis na leitura moderna.

  10. Fenomenologia do tempo vivido no transtorno bipolar

    Directory of Open Access Journals (Sweden)

    Virginia Moreira

    Full Text Available Com base na tradição da psicopatologia fenomenológica, este artigo se propõe a contribuir para a compreensão do mundo vivido do paciente bipolar, marcado por uma forte alteração do tempo vivido. Realizamos uma descrição deste tempo vivido significado de forma diferente nas oscilações de humor chamadas de fase maníaca e fase melancólica. Pensado a partir da temporalidade, na fase melancólica, o bipolar parece parar no tempo, não se lança em um devir. Na fase maníaca, o sujeito vive demasiadamente um agora como se tivesse explodido sua biografia. Concluímos que estas fases, ou dois pólos opostos no funcionamento temporal patológico do sofrimento bipolar, constituem fundamentalmente um mesmo mundo vivido.

  11. The effect of music tempo on perceived crowding in retailing

    OpenAIRE

    Fiksdal, Taisiya; Hua, Wen

    2016-01-01

    Masteroppgave(MSc) in Master of Science in Strategic Marketing Management - Handelshøyskolen BI, 2016 In the marketing field the influence of in-store atmospherics on consumers’ shopping behavior is widely accepted. We seek to understand the effects of instore music tempo on perceived crowding and how music tempo can affect emotions, arousal and perceived control occurring in retail stores. Hence, our research questions are the following: Does music tempo influence the perce...

  12. Tempo no museu e o museu no tempo

    OpenAIRE

    Monteiro, Renata; Gouvêa, Guaracira

    2015-01-01

    Este estudo discute o tempo mediante o lugar e objeto nos museus de ciência e técnica, apresentando diferentes abordagens teóricas a partir de uma perspectiva física e social. Este aporte subsidia a análise de discursos do público espontâneo do Museu de Artes e Ofícios, que expõe objetos históricos relacionados ao universo do trabalho, técnicas e ofícios do período pré-industrial brasileiro. Os discursos analisados mediante a metodologia do Discurso do Sujeito Coletivo tiveram como ponto de p...

  13. Revisiting the relationship between exercise heart rate and music tempo preference.

    Science.gov (United States)

    Karageorghis, Costas I; Jones, Leighton; Priest, David-Lee; Akers, Rose I; Clarke, Adam; Perry, Jennifer M; Reddick, Benjamin T; Bishop, Daniel T; Lim, Harry B T

    2011-06-01

    In the present study, we investigated a hypothesized quartic relationship (meaning three inflection points) between exercise heart rate (HR) and preferred music tempo. Initial theoretical predictions suggested a positive linear relationship (Iwanaga, 1995a, 1995b); however, recent experimental work has shown that as exercise HR increases, step changes and plateaus that punctuate the profile of music tempo preference may occur (Karageorghis, Jones, & Stuart, 2008). Tempi bands consisted of slow (95-100 bpm), medium (115-120 bpm), fast (135-140 bpm), and very fast (155-160 bpm) music. Twenty-eight active undergraduate students cycled at exercise intensities representing 40, 50, 60, 70, 80, and 90% of their maximal HR reserve while their music preference was assessed using a 10-point scale. The Exercise Intensity x Music Tempo interaction was significant, F(6.16, 160.05) = 7.08, p music-tempo relationship (p music was not preferred at any exercise intensity, preference for fast tempo increased, relative to medium and very fast tempo music, as exercise intensity increased. The implications for the prescription of music in exercise and physical activity contexts are discussed.

  14. Fughe ‘dal’ tempo, fughe ‘nel’ tempo: Borges, McTaggart, Nabokov

    Directory of Open Access Journals (Sweden)

    Francesco Baucia

    2014-10-01

    Full Text Available Questo intervento presenta due diversi tipi di rapporto tra i concetti di ‘fuga’ e di ‘temporalità’, che sono esemplificati da due frasi tratte da una coppia di opere di V. Nabokov. Il primo tipo di rapporto esaminato può essere chiamato ‘fuga dal tempo’: si tratta di una relazione tra questi concetti che rivela una posizione filosofica scettica nei confronti dell’esistenza reale del tempo, posizione che è condivisa da scrittori come J.L. Borges e da filosofi come J.T. McTaggart. Il secondo tipo di rapporto può essere invece denominato ‘fuga nel tempo’: secondo Nabokov, la temporalità è la dimensione più decisiva per l’arte e la letteratura, e dunque non è possibile realizzare una ‘vera’ fuga dal tempo. Il vero obiettivo dell’artista deve essere pertanto quello di realizzare una fuga nell’elemento puro (medium della temporalità, ossia nella sua ‘tessitura’, piuttosto che nei suoi contenuti (nel suo ‘testo’.

  15. Heart rate responses induced by acoustic tempo and its interaction with basal heart rate.

    Science.gov (United States)

    Watanabe, Ken; Ooishi, Yuuki; Kashino, Makio

    2017-03-07

    Many studies have revealed the influences of music on the autonomic nervous system (ANS). Since previous studies focused on the effects of acoustic tempo on the ANS, and humans have their own physiological oscillations such as the heart rate (HR), the effects of acoustic tempo might depend on the HR. Here we show the relationship between HR elevation induced by acoustic tempo and individual basal HR. Since high tempo-induced HR elevation requires fast respiration, which is based on sympatho-respiratory coupling, we controlled the participants' respiration at a faster rate (20 CPM) than usual (15 CPM). We found that sound stimuli with a faster tempo than the individual basal HR increased the HR. However, the HR increased following a gradual increase in the acoustic tempo only when the extent of the gradual increase in tempo was within a specific range (around + 2%/min). The HR did not follow the increase in acoustic tempo when the rate of the increase in the acoustic tempo exceeded 3% per minute. These results suggest that the effect of the sympatho-respiratory coupling underlying the HR elevation caused by a high acoustic tempo depends on the basal HR, and the strength and the temporal dynamics of the tempo.

  16. Vibronic Spectroscopy of the Phenylcyanomethyl Radical

    Science.gov (United States)

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

    2011-06-01

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

  17. Aspirin degradation in surface-charged TEMPO-oxidized mesoporous crystalline nanocellulose.

    Science.gov (United States)

    Carlsson, Daniel O; Hua, Kai; Forsgren, Johan; Mihranyan, Albert

    2014-01-30

    TEMPO-mediated surface oxidation of mesoporous highly crystalline Cladophora cellulose was used to introduce negative surface charges onto cellulose nanofibrils without significantly altering other structural characteristics. This enabled the investigation of the influence of mesoporous nanocellulose surface charges on aspirin chemical stability to be conducted. The negative surface charges (carboxylate content 0.44±0.01 mmol/g) introduced on the mesoporous crystalline nanocellulose significantly accelerated aspirin degradation, compared to the starting material which had significantly less surface charge (0.06±0.01 mmol/g). This effect followed from an increased aspirin amorphisation ability in mesopores of the oxidized nanocellulose. These results highlight the importance of surface charges in formulating nanocellulose for drug delivery. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Influencia del tempo de la música en las emociones

    Directory of Open Access Journals (Sweden)

    Jonathan Azael Caballero-Meneses

    2010-01-01

    exposición de 24 estudiantes de licenciatura a treinta extractos musicales de distinto tempo. Además se evaluó la posible modulación de la relación tempo-valencia por el rasgo de personalidad extroversión/introversión. Los resultados confirmaron la influencia del tempo sobre el arousal, pero no sobre la valencia, así como una posible mediación de la dimensión de personalidad introversión-extroversión sobre la valencia.

  19. The Effect of Repetition on Tempo Preferences of Elementary Children.

    Science.gov (United States)

    Moskovitz, Elisa M.

    1992-01-01

    Reports on a study of children's preferences between slow and fast tempo classical music excerpts. Finds that students preferred music with a slow tempo. Concludes that repetition had a positive effect on children's preferences. (CFR)

  20. Alkyl Radicals as Hydrogen Bond Acceptors: Computational Evidence

    DEFF Research Database (Denmark)

    Hammerum, Steen

    2009-01-01

    Spectroscopic, energetic and structural information obtained by DFT and G3-type computational studies demonstrates that charged proton donors can form moderately strong hydrogen bonds to simple alkyl radicals. The presence of these bonds stabilizes the adducts and modifies their structure......, 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...... acceptors than formaldehyde molecules, while propyl radicals are as good as H2O. The hydrogen bond strength appears to depend on the proton affinity of the proton donor and on the ionization energy of the acceptor alkyl radical, not on the donor-acceptor proton affinity difference, reflecting...

  1. Twin-peak effect in both cardiac response and tempo of popular music.

    Science.gov (United States)

    Shih, Yi-Sen; Zhang, Wen-Chih; Lee, Yaw-Chern; Lei, Chun-Yang; Tseng, Cheng-Lung; Wang, Hui-Min; Huang, Sheng-Chieh

    2011-01-01

    How the musical tempo affects the performance of heart rate variability (HRV) was studied in this work. By understanding the relationship between the HRV response and the music tempo with decreasing tempo from 140 to 70 beats per minute (bpm) periodically in six successive weeks. There were two groups in the experiment, one was listening drum loop music 3 minutes in the middle of experiment and the other was just rest for 20 minutes. After the processed the information from the objects, the distribution of difference of HRV response between before and after listening various tempo drum loop was similar to the distribution of modern popular music in tempo. Both distributions have the twin peaks about 70-85 and 110-125 bpm.

  2. O tempo da escola: organização, ampliação e qualificação do tempo do ensino escolar

    Directory of Open Access Journals (Sweden)

    Antonio Chizzotti

    2016-12-01

    Full Text Available Este artigo analisa a organização administrativa e pedagógica do tempo escolar e avalia as discussões sobre a ampliação da jornada escolar e a qualificação desse tempo dispendido no ensino com a finalidade de criar melhores condições de aprendizagem e de bem-estar para todos os que estão comprometidos com a vida da escola. O texto levanta algumas controvérsias e iniciativas internacionais, que buscam encontrar alternativas para promover uma disposição mais adequada desse ritmo do tempo a fim de propiciar melhores condições do sucesso no ensino e de qualidade na duração da jornada escolar. O entendimento metodológico deste trabalho de conformidade com Gaussel (2013 pressupõe o reconhecimento de uma pluralidade de tempos educativos e múltiplos modos legítimos de aprendizagem e ensino. Toma-se o calendário como modelo de organização e gerenciamento das atividades escolares, e de observações e contatos pessoais com os atores educacionais em uma escola, para levantar algumas considerações críticas sobre a disposição do ritmo do tempo escolar a partir da análise do calendário de uma escola pública do Ensino Médio do sistema de ensino do Estado de São Paulo.

  3. Interactions between simple radicals and water

    International Nuclear Information System (INIS)

    Crespo-Otero, Rachel; Sanchez-Garcia, Elsa; Suardiaz, Reynier; Montero, Luis A.; Sander, Wolfram

    2008-01-01

    The interactions of the simple radicals CH 3 , NH 2 , OH, and F with water have been studied by DFT (UB3LYP/6-311++G(2d,2p)) and ab initio (RHF-UCCSD(T)/6-311++G(2d,2p)) methods. In this order the number of lone pairs (from zero to three), the electronegativity, and the strength of the X-H bonds increase (X = C, N, and O). The various minima of the radical-water complexes were located using the multiple minima hypersurface (MMH) approach which had previously been proven to be useful for closed-shell molecules. The role of the unpaired electron in hydrogen bonding was investigated using the natural bond orbital (NBO) analysis. A considerable contribution of the unpaired electron to the complex stabilization was only found for the methyl radical and the fluorine atom, whereas in the aminyl and the hydroxyl radical the role of the unpaired electron is negligible

  4. Analisi e variazioni di tempo: la Polacca op. 53 di Chopin

    Directory of Open Access Journals (Sweden)

    Giorgio Sanguinetti

    2013-12-01

    Full Text Available L'aspetto più difficile e sfuggente dell'esecuzione musicale è forse quello della scelta del tempo e delle sue variazioni. Qual è il tempo giusto per una composizione, e come va stabilito? E poi, una volta deciso il tempo generale, questo va osservato strettamente o l'esecutore può concedersi accelerandi e rallentandi occasionali, o addirittura cambiare il tempo in una data parte della composizione, per poi riprendere successivamente il tempo principale? In cosa consiste il rubato, e dove questa pratica trova legittimità? È giustificato introdurre una variazione agogica anche dove il compositore non l'ha prescritta? Domande di questo genere si pongono continuamente agli esecutori, e le risposte ovviamente dipendono da una gran quantità di fattori, prima di tutto dal contesto storico e stilistico nel quale il pezzo è originato, e dalla conoscenza della prassi esecutiva relativa alla sua epoca e alla sua tradizione locale.

  5. TEMPO-based catholyte for high-energy density nonaqueous redox flow batteries.

    Science.gov (United States)

    Wei, Xiaoliang; Xu, Wu; Vijayakumar, Murugesan; Cosimbescu, Lelia; Liu, Tianbiao; Sprenkle, Vincent; Wang, Wei

    2014-12-03

    A TEMPO-based non-aqueous electrolyte with the TEMPO concentration as high as 2.0 m is demonstrated as a high-energy-density catholyte for redox flow battery applications. With a hybrid anode, Li|TEMPO flow cells using this electrolyte deliver an energy efficiency of ca. 70% and an impressively high energy density of 126 W h L(-1) . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Tempo effects in mortality: An appraisal

    Directory of Open Access Journals (Sweden)

    Michel Guillot

    2006-01-01

    Full Text Available This study examines the existence of tempo effects in mortality and evaluates the procedure developed by Bongaarts and Feeney for calculating a tempo-adjusted life expectancy. It is shown that Bongaarts and Feeney's index can be interpreted as an indicator reflecting current mortality conditions under specific assumptions regarding the effects of changing period mortality conditions on the timing of future cohort deaths. It is argued, however, that currently there is no clear evidence about the existence of such effects in actual populations. This paper concludes that until the existence of these effects can be demonstrated, it is preferable to continue using the conventional life expectancy as an indicator of current mortality conditions.

  7. Quality management of cut carnation 'Tempo' with 1- MCP | Abadi ...

    African Journals Online (AJOL)

    Quality management of cut carnation 'Tempo' with 1- MCP. ... African Journal of Biotechnology ... time durations (3, 6 and 9 h) on the vaselife, water uptake, loss of fresh weight and chlorophyll index of cut carnation 'Tempo' which is an ...

  8. Efficient radical cation stabilization of PANI-ZnO and PANI-ZnO-GO composites and its optical activity

    Energy Technology Data Exchange (ETDEWEB)

    Mathavan, T., E-mail: tjmathavan@gmail.com; Divya, A.; Benial, A. Milton Franklin [PG & Research Department of Physics, N.M.S.S.Vellaichamy Nadar College, Madurai-625 019 (India); Archana, J. [Research Institute of Engineering, Shizuoka University (Japan); Ramasubbu, A. [PG & Research Department of Chemistry, Govt. Arts College, Coimbatore (India); Jothirajan, M. A. [Research Department of Physics, Arul Anandar College, Karumathur, Madurai-625 514 (India)

    2016-05-23

    Polyaniline (PANI) and its composites PANI-ZnO (Zinc oxide) and PANI-ZnO-GO (Graphene oxide) were successfully constructed. These materials were characterized by electron spin resonance (ESR) technique and ultraviolet visible spectrometry. The parameters such as line width, g-factor and spin concentration were deduced from ESR spectra, from the results the radical cation stabilization of PANI, PANI-ZnO and PANI-ZnO-GO composites were compared by the polaron and bipolaron formation. The absorption features obtained in the UV absorption spectra reveal the band gap of these modified PANI composites and also predicted the information of increasing and decreasing features of signal intensity and spin concentration.

  9. Efficient radical cation stabilization of PANI-ZnO and PANI-ZnO-GO composites and its optical activity

    International Nuclear Information System (INIS)

    Mathavan, T.; Divya, A.; Benial, A. Milton Franklin; Archana, J.; Ramasubbu, A.; Jothirajan, M. A.

    2016-01-01

    Polyaniline (PANI) and its composites PANI-ZnO (Zinc oxide) and PANI-ZnO-GO (Graphene oxide) were successfully constructed. These materials were characterized by electron spin resonance (ESR) technique and ultraviolet visible spectrometry. The parameters such as line width, g-factor and spin concentration were deduced from ESR spectra, from the results the radical cation stabilization of PANI, PANI-ZnO and PANI-ZnO-GO composites were compared by the polaron and bipolaron formation. The absorption features obtained in the UV absorption spectra reveal the band gap of these modified PANI composites and also predicted the information of increasing and decreasing features of signal intensity and spin concentration.

  10. Memory for musical tempo: Additional evidence that auditory memory is absolute

    OpenAIRE

    Levitin, Daniel J.; Cook, Perry R.

    1996-01-01

    We report evidence that long term memory retains absolute (accurate) features of perceptual events. Specifically, we show that memory for music seems to preserve the absolute tempo of the musical performance. In Experiment 1, 46 subjects sang popular songs from memory, and their tempos were compared to recorded versions of the songs. Seventy-two of the subjects came within 8% of the actual tempo on two consecutive trials (using different songs), demonstrating accuracy near the perceptual thre...

  11. INFLUENCIA DEL TEMPO DE LA MÚSICA EN LAS EMOCIONES

    OpenAIRE

    Jonathan Azael Caballero-Meneses; Marina Menez

    2010-01-01

    Se sabe que la música puede influir en dos componentes de las emociones: el arousal y la valencia. En particular, se ha reportado que el tempo o rapidez de la música está directamente relacionado con el arousal, aunque su relación con la valencia o medida de afecto no es aún clara. En este trabajo se analizó la influencia del tempo en ambos componentes mediante la exposición de 24 estudiantes de licenciatura a treinta extractos musicales de distinto tempo. Además se evaluó la posible m...

  12. A ADMINISTRAÇÃO DO TEMPO LIVRE

    OpenAIRE

    Musse, Ricardo

    2016-01-01

    Resumo A conferência de Theodor W. Adorno sobre o conceito e a prática do "tempo livre", publicada em Stichworte, em 1969, foi proferida numa época de pleno emprego. A gradativa redução da jornada normal de trabalho, sinalizando e consolidando uma tendência de longo prazo, inspirou uma série de conjecturas acerca de uma possível mudança nas estruturas até então assentadas como próprias do mundo moderno. Nesse contexto, a conferência-ensaio de Adorno organiza-se, ao mesmo tempo, como uma atual...

  13. Interaction with Mass Media: The Importance of Rhythm and Tempo.

    Science.gov (United States)

    Snow, Robert P.

    1987-01-01

    Stresses that understanding the impact of interaction with mass media requires conceptualizing media as an institutionalized social form. A critical feature of this process is the grammatical character of media interaction in the form of rhythm and tempo, because these rhythms and tempos become established in everyday routine. (SKC)

  14. Characterization of beer flavour stability (EPR - spin trapping)

    International Nuclear Information System (INIS)

    Stasko, A.; Liptakova, M.; Malik, F.

    1999-01-01

    The beer flavour stability is coupled with free radical degradation processes. Probably, aldehydes produced during the brewery but also generated by stalling are responsible for beer flavour as well as for its breaking down. The storing beer at the lower temperatures and in the dark place inhibits, and otherwise the rising temperature and illumination accelerate the rate of such radical processes. Beers contain naturally occurring radical scavengers - antioxidants which inhibit such unwanted reactions. Then depleting of scavengers results in the breaking down of the beer stability. EPR spin trapping technique was used as monitor such processes and for characterising so the flavour stability of beer. The probe was temperated at 60 grad C in the cavity of EPR spectrometer in the presence of spin trapping agent, N-tert.-butyl-α-phenyl nitrone (PBN) and EPR spectra were recorded for few hours. After beer antioxidants become depleted, free radicals formed by the beer degradation are scavenged by PBN spin trap and this point is characterised with a dramatically increased concentration of the free radicals trapped

  15. Tempo máximo de fonação /a/, tempo máximo de fonação previsto e tipo respiratório de mulheres adultas sem afecções laríngeas

    Directory of Open Access Journals (Sweden)

    Carla Aparecida Cielo

    2015-04-01

    Full Text Available OBJETIVO:verificar a diferença entre o tempo máximo de fonação /a/ e tempo máximo de fonação previsto em relação ao tipo respiratório, e correlacionar os tempos máximos em mulheres adultas com capacidade vital dentro da normalidade e sem afecções laríngeas.MÉTODOS:pesquisa transversal analítica, quantitativa e retrospectiva, em banco de dados, de 51 sujeitos do sexo feminino, com diagnóstico otorrinolaringológico de ausência de afecção laríngea, com idades entre 18 e 44 anos (média 27,64. Utilizaram-se os dados: maior valor de tempo máximo de fonação de /a/, tempo máximo de fonação previsto, capacidade vital e tipo respiratório. O valor do tempo máximo previsto para mulheres foi calculado multiplicando-se a capacidade vital por 0,0051, e o valor encontrado foi determinante para a classificação do tempo de /a/ em normal, abaixo ou acima do previsto.RESULTADOS:houve diferença significante entre tempo de fonação previsto e os tipos respiratórios superior (17,44s e misto (15,17s. Não houve diferença significante do tempo máximo de fonação /a/ nos diferentes tipos respiratórios, nem correlação entre tempo de fonação /a/ e tempo previsto.CONCLUSÃO:não houve correlação entre tempo de /a/ e tempo de fonação previsto e este último foi significantemente maior no tipo respiratório superior do que no misto na população estudada.

  16. Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery.

    Science.gov (United States)

    Wei, Xiaoliang; Xu, Wu; Huang, Jinhua; Zhang, Lu; Walter, Eric; Lawrence, Chad; Vijayakumar, M; Henderson, Wesley A; Liu, Tianbiao; Cosimbescu, Lelia; Li, Bin; Sprenkle, Vincent; Wang, Wei

    2015-07-20

    Nonaqueous redox flow batteries hold the promise of achieving higher energy density because of the broader voltage window than aqueous systems, but their current performance is limited by low redox material concentration, cell efficiency, cycling stability, and current density. We report a new nonaqueous all-organic flow battery based on high concentrations of redox materials, which shows significant, comprehensive improvement in flow battery performance. A mechanistic electron spin resonance study reveals that the choice of supporting electrolytes greatly affects the chemical stability of the charged radical species especially the negative side radical anion, which dominates the cycling stability of these flow cells. This finding not only increases our fundamental understanding of performance degradation in flow batteries using radical-based redox species, but also offers insights toward rational electrolyte optimization for improving the cycling stability of these flow batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Particle Filtering Applied to Musical Tempo Tracking

    Directory of Open Access Journals (Sweden)

    Macleod Malcolm D

    2004-01-01

    Full Text Available This paper explores the use of particle filters for beat tracking in musical audio examples. The aim is to estimate the time-varying tempo process and to find the time locations of beats, as defined by human perception. Two alternative algorithms are presented, one which performs Rao-Blackwellisation to produce an almost deterministic formulation while the second is a formulation which models tempo as a Brownian motion process. The algorithms have been tested on a large and varied database of examples and results are comparable with the current state of the art. The deterministic algorithm gives the better performance of the two algorithms.

  18. Cation radicals of xanthophylls.

    Science.gov (United States)

    Galinato, Mary Grace I; Niedzwiedzki, Dariusz; Deal, Cailin; Birge, Robert R; Frank, Harry A

    2007-10-01

    Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, beta-cryptoxanthin, beta-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing pi-chain length. However, zeaxanthin and beta-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of beta-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

  19. MUSIC TEMPO'S EFFECT ON EXERCISE PERFORMANCE: COMMENT ON DYER AND McKUNE.

    Science.gov (United States)

    Nakamura, Priscila Missaki

    2015-06-01

    Dyer and McKune (2013) stated that music tempo has no influence on performance, physiological, and psychophysical variables in well-trained cyclists during high intensity endurance tasks. However, there are important limitations in the methodology of the study. The participants' music preferences and tempo change were not well measured. It is not possible to affirm that music tempo does not influence athletes' performance. Potential areas of future research include: (a) use of instruments to assess the qualities of music; (b) standardizing music of tempo according to exercise type (e.g., running, cycling, etc.); (c) considering training level of the participants (i.e., athletes and non-athletes); and (d) use of instruments to assess concentration during exercise.

  20. The rhythm and tempo of the game of highly qualified teams

    Directory of Open Access Journals (Sweden)

    V’yacheslav Mulik

    2015-06-01

    Full Text Available Purpose: to set indicators of rhythm and tempo of the game teams of high qualification. Material and Methods: analysis of the scientific-methodical literature, registration of technical-tactical actions, methods of mathematical statistics. The study of competitive activities was conducted with participating teams of world championship 2014. Results: the acticle shows indicators of the rhythm and tempo of the game of well-qualified teams. Conclusions: teams-winners have surpassed teams that concede in terms of indicators of passes the ball, shots at goal, the rhythm of the game, tempo of game.

  1. Music genre preference and tempo alter alpha and beta waves in human non-musicians

    Directory of Open Access Journals (Sweden)

    Hunter Gentry

    2013-10-01

    Full Text Available This study examined the effects of music genre and tempo on brain activation patterns in 10 nonmusicians.Two genres (rock and jazz and three tempos (slowed, medium/normal, andquickened were examined using EEG recording and analyzed through Fast Fourier Transform(FFT analysis. When participants listened to their preferred genre, an increase in alpha waveamplitude was observed. Alpha waves were not significantly affected by tempo. Beta waveamplitude increased significantly as the tempo increased. Genre had no effect on beta waves. Thefindings of this study indicate that genre preference and artificially modified tempo do affectalpha and beta wave activation in non-musicians listening to preselected songs.

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

    Science.gov (United States)

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

    2016-07-01

    Dietary stilbenoids are associated with many benefits for human health, which depend on their bioavailability and bioaccessibility. The stilbenoid-human serum albumin (HSA) interactions are investigated to explore the structure-affinity relationship and influence on the stability, free radical scavenging activity and cell uptake of stilbenoids. The structure-affinity relationship of the stilbenoids-HSA interaction was found as: (1) the methoxylation enhanced the affinity, (2) an additional hydroxyl group increases the affinity and (3) the glycosylation significantly weakened the affinity. HSA obviously masked the free radical scavenging potential of stilbenoids. The stabilities of stilbenoids in different medium were determined as: HSA solution>human plasma>Dulbecco's modified Eagle's medium. It appears that the milk enhanced the cell uptake of stilbenoids with multi-hydroxyl groups and weakened the cell uptake of stilbenoids with methoxyl group on EA.hy 926 endothelial cells. The stilbenoids are hardly absorbed by human umbilical vein endothelial cells in the presence of milk. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Possíveis relações entre o contexto histórico e a recepção do behaviorismo radical

    Directory of Open Access Journals (Sweden)

    Robson Nascimento da Cruz

    Full Text Available O artigo discute a recepção do behaviorismo radical, em especial, na década de 70, e busca relacionar a polêmica em torno de algumas noções skinnerianas acerca da liberdade e da dignidade divulgadas no livro Para Além da Liberdade e Dignidade. Essa discussão foi orientada por três conjuntos de questões: a a incompatibilidade entre alguns aspectos históricos e a definição behaviorista radical de liberdade e dignidade; b os problemas em identificar o behaviorismo radical como uma abordagem solidária com os pressupostos de uma ideologia liberalista; c a linguagem utilizada por Skinner como fonte de problemas. Por fim, são discutidos as limitações e os problemas envolvidos em tentativas de esclarecimentos de possíveis mal-entendidos acerca do behaviorismo radical. Ao mesmo tempo, demonstra-se que a recepção do behaviorismo radical é perpassada por aspectos além daqueles relacionados à validade interna do sistema explicativo skinneriano, e que discordâncias acerca dessa abordagem nem sempre podem ser explicadas como desconhecimento e equívocos sobre a mesma.

  4. Does the Tempo of Music Impact Human Behavior Behind the Wheel?

    Science.gov (United States)

    Navarro, Jordan; Osiurak, François; Reynaud, Emanuelle

    2018-06-01

    Assess the influence of background music tempo on driving performance. Music with a fast tempo is known to increase the level of arousal, whereas the reverse is observed for slow music. The relationship between driving performance and level of arousal was expected to take the form of an inverted U-curve. Three experiments were undertaken to manipulate the musical background during driving. In Experiment 1, the driver's preferred music track played at its original and modified (plus or minus 30%) tempo were used together with the simple ticking of a metronome. In Experiment 2, music tracks of different tempos were played during driving. In Experiment 3, music tracks were categorized as arousing or relaxing based on the associated perceived level of arousal. Listening to music tended to influence drivers' performances in a car-following task by improving coherence and gain adjustments relative to the followed vehicle but simultaneously shortened the intervehicular time. Although the tempo of the music per se did not directly affect driving behavior, arousing music tracks improved drivers' adjustments to the followed vehicle (Experiment 3). The tempo of the music listened to behind the wheel was not found to influence driving behaviors. However, arousing music improved drivers' responsiveness to changes in the speed of the followed vehicle. However, this benefit was canceled out by a reduction in the drivers' intervehicle safety margin. Listening to arousing music while driving cannot be considered to improve road safety, at least in a car-following task without attentional impairments.

  5. Metal-Free α-C(sp3–H Functionalized Oxidative Cyclization of Tertiary N,N-Diaryl Amino Alcohols: Theoretical Approach for Mechanistic Pathway

    Directory of Open Access Journals (Sweden)

    Zakir Ullah

    2017-03-01

    Full Text Available The mechanistic pathway of TEMPO/I2-mediated oxidative cyclization of N,N-diaryl amino alcohols 1 was investigated. Based on direct empirical experiments, three key intermediates (aminium radical cation 3, α-aminoalkyl radical 4, and iminium 5, four types of reactive species (radical TEMPO, cationic TEMPO, TEMPO-I, and iodo radical, and three types of pathways ((1 SET/PCET mechanism; (2 HAT/1,6-H transfer mechanism; (3 ionic mechanism were assumed. Under the assumption, nine free energy diagrams were acquired through density functional theory calculations. From the comparison of solution-phase free energy, some possible mechanisms were excluded, and then the chosen plausible mechanisms were concretized using the more stable intermediate 7.

  6. Effects of lifting tempo on one repetition maximum and hormonal responses to a bench press protocol.

    Science.gov (United States)

    Headley, Samuel A; Henry, Kelley; Nindl, Bradley C; Thompson, Brian A; Kraemer, William J; Jones, Margaret T

    2011-02-01

    This study was carried out in 2 parts: part 1 was designed to measure the 1 repetition maximum (1RM) bench press with 2 different moderate-velocity tempos (2/0/2) vs. (2/0/4) in male lifters while part 2 compared the hormonal responses at the same tempos as described in part 1. In both parts 1 and 2, the 1RMs (lbs) were higher on the 2/0/2 tempo than on the 2/0/4 tempo. The change in plasma volume (PV) was greater after the 2/0/4 tempo (-5.7 ± 1.7% vs. 0.96 ± 1.2%, p < 0.05). All blood parameters were significantly (p < 0.05) higher post-exercise compared with baseline. With PV corrected, insulin-like growth factor 1 (IGF-1) (ng·mL⁻¹) was higher with the 2/0/2 tempo only (pre-exercise: 277.4 ± 21.8, post-exercise: 308.1 ± 22.9; 2/0/4 tempo pre-exercise: 277.2 ± 17.6, post-exercise: 284.8 ± 21.2). In conclusion, heavier loads can be lifted and more total work can be performed using a (2/0/2) tempo compared with a slower (2/0/4) tempo, but with the exception of IGF-1, the hormonal responses are similar. Individuals may get the same metabolic responses to training by using different tempos, but they will need to use less weight at a slower tempo.

  7. Robust data reconciliation with TEMPO

    International Nuclear Information System (INIS)

    Sunde, Svein; Banati, Jozsef

    2004-03-01

    The Halden Project's TEMPO system is devised to meet the increasing challenges facing utilities in performance monitoring and optimisation, among other things due to deregulation and market liberalisation. The data reconciliation mode is an important one in the TEMPO system. Data reconciliation is a method to provide reliable estimates of process states, parameters, the state of equipment and instruments, and efficiency. Data reconciliation follows maximum likelihood principles, and is usually based on a Gaussian error model for the data. Data reconciliation thus estimates the most likely state of the process, given the heat and mass balance and the current instrument readings. If the assumption of normally (Gaussian) distributed errors in the measurements break down, as it will in the case of gross errors (outliers) in the data set, this needs to be detected by the monitoring system. TEMPO does this by computing an overall test statistic subjected to a hypothesis test, resulting in the so-called goodness-of-fit. If the goodness-of-fit takes a too low value, a fault is probably present in the process. Identifying the location of the fault is more difficult, however. With the Gaussian error model this is still possible employing a so-called serial elimination method. The serial elimination method is, however, cumbersome to use and leads to quite lengthy calculations. The present report describes the application of alternative distributions in the maximum likelihood estimation in an attempt to directly identify the location of faulty sensors. For direct identification of sensor faults significant improvements over the method based on a Gaussian error model has been achieved. However, serial elimination still leads to the highest success rate for fault identification. All results were based on Monte Carlo simulations. (Author)

  8. ESR investigation of radicals formed in γ-irradiated vinylidene fluoride based copolymer: P(VDF-co-HFP)

    International Nuclear Information System (INIS)

    Dumas, Ludovic; Albela, Belén; Bonneviot, Laurent; Portinha, Daniel; Fleury, Etienne

    2013-01-01

    Samples of copolymer based on vinylidene fluoride and hexafluoropropene P(VDF-co-HFP) were exposed to γ-radiation performed under an inert atmosphere and the total amount of radicals was quantified by electron spin resonance spectroscopy (ESR). An in-depth study of recorded ESR spectra allowed the identification of several types of radical species formed during radiolysis. Starting from an ESR simulation model established for irradiated PVDF, seven radical species have been identified in the case of P(VDF-co-HFP): five of them are related to the VDF units while the two others are derived from the HFP unit. The model used to simulate the complex superimposed ESR signals is presented. The proportions of each species are discussed and correlated to the amount of HFP units contained in the copolymer, and to the stability of each species depending on their local environment. Furthermore, the evolution of radical density with radiation dose and the decay resulting from annealing at a given temperature are presented. Corresponding spectral evolution shows the progressive predominance of most stable species. - Highlights: ► ESR signal of γ-irradiated P(vinylidene fluoride-co-hexafluoropropene) containing 6 wt% of hexafluoropropene is modeled. ► The formation of seven major radical species is proposed for the first time. ► Despite a low comonomer content, 43% of radicals are localized on hexafluoropropene. ► Effect of dose and annealing highlight radical stability. ► Radical stability is found to depend on both chemical environment and chain location

  9. Speed on the dance floor: Auditory and visual cues for musical tempo.

    Science.gov (United States)

    London, Justin; Burger, Birgitta; Thompson, Marc; Toiviainen, Petri

    2016-02-01

    Musical tempo is most strongly associated with the rate of the beat or "tactus," which may be defined as the most prominent rhythmic periodicity present in the music, typically in a range of 1.67-2 Hz. However, other factors such as rhythmic density, mean rhythmic inter-onset interval, metrical (accentual) structure, and rhythmic complexity can affect perceived tempo (Drake, Gros, & Penel, 1999; London, 2011 Drake, Gros, & Penel, 1999; London, 2011). Visual information can also give rise to a perceived beat/tempo (Iversen, et al., 2015), and auditory and visual temporal cues can interact and mutually influence each other (Soto-Faraco & Kingstone, 2004; Spence, 2015). A five-part experiment was performed to assess the integration of auditory and visual information in judgments of musical tempo. Participants rated the speed of six classic R&B songs on a seven point scale while observing an animated figure dancing to them. Participants were presented with original and time-stretched (±5%) versions of each song in audio-only, audio+video (A+V), and video-only conditions. In some videos the animations were of spontaneous movements to the different time-stretched versions of each song, and in other videos the animations were of "vigorous" versus "relaxed" interpretations of the same auditory stimulus. Two main results were observed. First, in all conditions with audio, even though participants were able to correctly rank the original vs. time-stretched versions of each song, a song-specific tempo-anchoring effect was observed, such that sped-up versions of slower songs were judged to be faster than slowed-down versions of faster songs, even when their objective beat rates were the same. Second, when viewing a vigorous dancing figure in the A+V condition, participants gave faster tempo ratings than from the audio alone or when viewing the same audio with a relaxed dancing figure. The implications of this illusory tempo percept for cross-modal sensory integration and

  10. Radical fashion and radical fashion innovation

    NARCIS (Netherlands)

    Zhang, D.; Benedetto, Di A.C.

    2010-01-01

    This is a study of the related concepts of radical fashion and radical fashion innovation. Radical fashions are defined here as those that may never enter the market at all, and exist primarily on runway shows, in exhibitions and in publicity; by contrast, radical fashion innovations may be very

  11. Tempo é dinheiro’: Usabilidade é Produtividade

    Directory of Open Access Journals (Sweden)

    Antonio Mendes Silva Filho

    2012-09-01

    Full Text Available Benjamin Franklin foi um intelectual de sua época (1706-1790 e uma frase marcante dele que ultrapassa fronteiras é “Remember that time is money”. Lembre-se do que já disse: Tempo é o bem mais precioso que todo ser humano pode possuir, inclusive para aqueles que pensam nada ter. Tempo impacta a produtividade, tema esse explorado neste artigo que se concentra em discutir como a facilidade em realizar atividades utilizando tablets, smartphones, computadores e outros artefatos podem impactar a produtividade. Essa ‘facilidade em realizar atividades’ é denominada de usabilidade e, sesse sentido, este artigo explora como a inspeção por meio da análise e interpretação de dados podem auxiliar nessa tarefa.

  12. Role of tempo entrainment in psychophysiological differentiation of happy and sad music?

    Science.gov (United States)

    Khalfa, Stéphanie; Roy, Mathieu; Rainville, Pierre; Dalla Bella, Simone; Peretz, Isabelle

    2008-04-01

    Respiration rate allows to differentiate between happy and sad excerpts which may be attributable to entrainment of respiration to the rhythm or the tempo rather than to emotions [Etzel, J.A., Johnsen, E.L., Dickerson, J., Tranel, D., Adolphs, R., 2006. Cardiovascular and respiratory responses during musical mood induction. Int. J. Psychophysiol. 61(1), 57-69]. In order to test for this hypothesis, this study intended to verify whether fast and slow rhythm, and/or tempo alone are sufficient to induce differential physiological effects. Psychophysiological responses (electrodermal responses, facial muscles activity, blood pressure, heart and respiration rate) were then measured in fifty young adults listening to fast/happy and slow/sad music, and to two control versions of these excerpts created by removing pitch variations (rhythmic version) and both pitch and temporal variations (beat-alone). The results indicate that happy and sad music are significantly differentiated (happy>sad) by diastolic blood pressure, electrodermal activity, and zygomatic activity, while the fast and slow rhythmic and tempo control versions did not elicit such differentiations. In contrast, respiration rate was faster with stimuli presented at fast tempi relative to slow stimuli in the beat-alone condition. It was thus demonstrated that the psychophysiological happy/sad distinction requires the tonal variations and cannot be explained solely by entrainment to tempo and rhythm. The tempo entrainment exists in the tempo alone condition but our results suggest this effect may disappear when embedded in music or with rhythm.

  13. Long-term memory for music: infants remember tempo and timbre.

    Science.gov (United States)

    Trainor, Laurel J; Wu, Luann; Tsang, Christine D

    2004-06-01

    We show that infants' long-term memory representations for melodies are not just reduced to the structural features of relative pitches and durations, but contain surface or performance tempo- and timbre-specific information. Using a head turn preference procedure, we found that after a one week exposure to an old English folk song, infants preferred to listen to a novel folk song, indicating that they remembered the familiarized melody. However, if the tempo (25% faster or slower) or instrument timbre (harp vs. piano) of the familiarized melody was changed at test, infants showed no preference, indicating that they remembered the specific tempo and timbre of the melodies. The results are consistent with an exemplar-based model of memory in infancy rather than one in which structural features are extracted and performance features forgotten.

  14. TEMPO/viologen electrochemical heterojunction for diffusion-controlled redox mediation: a highly rectifying bilayer-sandwiched device based on cross-reaction at the interface between dissimilar redox polymers.

    Science.gov (United States)

    Tokue, Hiroshi; Oyaizu, Kenichi; Sukegawa, Takashi; Nishide, Hiroyuki

    2014-03-26

    A couple of totally reversible redox-active molecules, which are different in redox potentials, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and viologen (V(2+)), were employed to give rise to a rectified redox conduction effect. Single-layer and bilayer devices were fabricated using polymers containing these sites as pendant groups per repeating unit. The devices were obtained by sandwiching the redox polymer layer(s) with indium tin oxide (ITO)/glass and Pt foil electrodes. Electrochemical measurements of the single-layer device composed of polynorbornene-bearing TEMPO (PTNB) exhibited a diffusion-limited current-voltage response based on the TEMPO(+)/TEMPO exchange reaction, which was almost equivalent to a redox gradient through the PTNB layer depending upon the thickness. The bilayer device gave rise to the current rectification because of the thermodynamically favored cross-reaction between TEMPO(+) and V(+) at the polymer/polymer interface. A current-voltage response obtained for the bilayer device demonstrated a two-step diffusion-limited current behavior as a result of the concurrent V(2+)/V(+) and V(+)/V(0) exchange reactions according to the voltage and suggested that the charge transport process through the device was most likely to be rate-determined by a redox gradient in the polymer layer. Current collection experiments revealed a charge transport balance throughout the device, as a result of the electrochemical stability and robustness of the polymers in both redox states.

  15. Reaction time to changes in the tempo of acoustic pulse trains.

    Science.gov (United States)

    Smith, R. P.; Warm, J. S.; Westendorf, D. H.

    1973-01-01

    Investigation of the ability of human observers to detect accelerations and decelerations in the rate of presentation of pulsed stimuli, i.e., changes in the tempo of acoustic pulse trains. Response times to accelerations in tempo were faster than to decelerations. Overall speed of response was inversely related to the pulse repetition rate.

  16. 1,2-Fluorine Radical Rearrangements: Isomerization Events in Perfluorinated Radicals.

    Science.gov (United States)

    Van Hoomissen, Daniel J; Vyas, Shubham

    2017-11-16

    Devising effective degradation technologies for perfluoroalkyl substances (PFASs) is an active area of research, where the molecular mechanisms involving both oxidative and reductive pathways are still elusive. One commonly neglected pathway in PFAS degradation is fluorine atom migration in perfluoroalkyl radicals, which was largely assumed to be implausible because of the high C-F bond strength. Using density functional theory calculations, it was demonstrated that 1,2-F atom migrations are thermodynamically favored when the fluorine atom migrated from a less branched carbon center to a more branched carbon center. Activation barriers for these rearrangements were within 19-29 kcal/mol, which are possible to easily overcome at elevated temperatures or in photochemically activated species in the gas or aqueous phase. It was also found that the activation barriers for the 1,2-F atom migration are lowered as much as by 10 kcal/mol when common oxidative degradation products such as HF assisted the rearrangements or if the resulting radical center was stabilized by vicinal π-bonds. Natural bond orbital analyses showed that fluorine moves as a radical in a noncharge-separated state. These findings add an important reaction to the existing knowledge of mechanisms for PFAS degradation and highlights the fact that 1,2-F atom shifts may be a small channel for isomerization of these compounds, but upon availability of mineralization products, this isomerization process could become more prominent.

  17. Susceptibility of Iα- and Iβ-Dominated Cellulose to TEMPO-Mediated Oxidation.

    Science.gov (United States)

    Carlsson, Daniel O; Lindh, Jonas; Strømme, Maria; Mihranyan, Albert

    2015-05-11

    The susceptibility of Iα- and Iβ-dominated cellulose to TEMPO-mediated oxidation was studied in this work since the cellulose Iα-allomorph is generally considered to be thermodynamically less stable and therefore more reactive than the cellulose Iβ-allomorph. Highly crystalline Cladophora nanocellulose, which is dominated by the Iα-allomorph, was oxidized to various degrees with TEMPO oxidant via bulk electrolysis in the absence of co-oxidants. Further, the Cladophora nanocellulose was thermally annealed in glycerol to produce its Iβ-dominated form and then oxidized. The produced materials were subsequently studied using FTIR, CP/MAS (13)C NMR, XRD, and SEM. The solid-state analyses confirmed that the annealed Cladophora cellulose was successfully transformed from an Iα- to an Iβ-dominated form. The results of the analyses of pristine and annealed TEMPO-oxidized samples suggest that Iα- and Iβ-dominated cellulose do not differ in susceptibility to TEMPO-oxidation. This work hence suggests that cellulose from different sources are not expected to differ in susceptibility to the oxidation due to differences in allomorph composition.

  18. Ricardo, o tempo e o valor

    Directory of Open Access Journals (Sweden)

    Rogério Arthmar

    2014-03-01

    Full Text Available O artigo revisa a evolução da teoria ricardiana do valor em sua conexão com o elemento tempo. Inicialmente, procede-se breve inspeção da primeira proposta de Ricardo para a lei geral das trocas. Contempla-se, a seguir, uma ilustração numérica da fórmula original dos preços competitivos, esclarecendo-se como o fator tempo surgiu nas discussões sobre a teoria desenvolvida nos Principles. Examina-se ainda a versão simplificada da regra do valor introduzida na terceira edição do livro, assim como a proposição ricardiana fundamental de que as variações nos lucros teriam impacto mínimo nos preços. Mostra-se, na última seção, que a generalização do exemplo concebido por Ricardo, incluindo processos produtivos com múltiplos períodos, não sustenta tal asserção.

  19. Free radicals in dicarboxylic acids: an e.s.r. study of radical conversions in γ-irradiated single crystals of glutaric acid and glutaric-2,2,4,4-d4 acid

    International Nuclear Information System (INIS)

    Bergene, R.; Minegishi, A.; Riesz, P.

    1980-01-01

    The γ-radiation-induced free radicals in single crystals of glutaric acid and glutaric-2,2,4,4-d 4 acid were studied in the temperature range 77-300 K by e.s.r. techniques. At 77 K the decarboxylation radical and the anion are stabilized. At higher temperatures the decarboxylation radical is found to be converted into a hydrogen abstraction radical with an activation energy of 6.3 +- 0.5 kcal/mole for the non-deuterated crystal. This radical is stable at room temperature. The anion seems to be converted to a unidentified intermediate radical which in turn is converted to the σ-acyl radical. An analysis of the g-value anisotropy and of the 13 C hyperfine splitting variation for this radical in the deuterated crystal is consistent with the assigned radical structure. By heat treatment the σ-acyl radical is converted to another form of the hydrogen abstraction radical with an activation energy of 9.6 +- 0.6 kcal/mole in the deuterated crystal. U.V.-light (lambda= 254 nm) transforms one of the room temperature radicals into the other. (author)

  20. Ratings of speed in real music as a function of both original and manipulated beat tempo.

    Science.gov (United States)

    Madison, Guy; Paulin, Johan

    2010-11-01

    There is an apparent contradiction between the narrow range of tempi optimal for perceptual judgment and motor synchronization and the wide range of beat tempi found in real music. The relation between listeners' perception of speed and beat tempo was therefore investigated, both for real music excerpts (ME) and metronome sequences. Tempi ranged from 42 to 200 beats per minute (BPM), and some excerpts were further tempo manipulated in four levels from ±5 to ±20%. Regression analyses showed that speed was a shallower function of original tempo for fast (>150 BPM) and slow (tempo had twice as large an effect on speed as had original tempo. In contrast, speed was an almost linear function of tempo for metronome sequences. Taken together, these results show that the non-linearity stems from properties of the musical signal, rather than being a subjective perceptual effect. They indicate an inverse relation between tempo and relative event density in real music, and demonstrate that the perception of periodic signals is affected not only by the beat level, but also by faster and slower levels.

  1. Sensorimotor synchronization with tempo-changing auditory sequences: Modeling temporal adaptation and anticipation.

    Science.gov (United States)

    van der Steen, M C Marieke; Jacoby, Nori; Fairhurst, Merle T; Keller, Peter E

    2015-11-11

    The current study investigated the human ability to synchronize movements with event sequences containing continuous tempo changes. This capacity is evident, for example, in ensemble musicians who maintain precise interpersonal coordination while modulating the performance tempo for expressive purposes. Here we tested an ADaptation and Anticipation Model (ADAM) that was developed to account for such behavior by combining error correction processes (adaptation) with a predictive temporal extrapolation process (anticipation). While previous computational models of synchronization incorporate error correction, they do not account for prediction during tempo-changing behavior. The fit between behavioral data and computer simulations based on four versions of ADAM was assessed. These versions included a model with adaptation only, one in which adaptation and anticipation act in combination (error correction is applied on the basis of predicted tempo changes), and two models in which adaptation and anticipation were linked in a joint module that corrects for predicted discrepancies between the outcomes of adaptive and anticipatory processes. The behavioral experiment required participants to tap their finger in time with three auditory pacing sequences containing tempo changes that differed in the rate of change and the number of turning points. Behavioral results indicated that sensorimotor synchronization accuracy and precision, while generally high, decreased with increases in the rate of tempo change and number of turning points. Simulations and model-based parameter estimates showed that adaptation mechanisms alone could not fully explain the observed precision of sensorimotor synchronization. Including anticipation in the model increased the precision of simulated sensorimotor synchronization and improved the fit of model to behavioral data, especially when adaptation and anticipation mechanisms were linked via a joint module based on the notion of joint internal

  2. The effects of music tempo and loudness level on treadmill exercise.

    Science.gov (United States)

    Edworthy, Judy; Waring, Hannah

    2006-12-15

    This study examined the effects of loudness and tempo of background music on exercise performance. A total of 30 volunteers performed five 10-min exercise sessions on a treadmill. The music listened to whilst exercising was either fast/loud, fast/quiet, slow/loud, slow/quiet or absent. Measures of running speed, heart rate, perceived exertion and affect were taken. Significant effects and interactions were found for running speed and heart rate across the different music tempo and loudness levels. More positive affect was observed during the music condition in comparison to the 'no music' condition. No significant differences for perceived exertion were found across conditions. These results confirm that fast, loud music might be played to enhance optimal exercising, and show how loudness and tempo interact.

  3. Memory for surface features of unfamiliar melodies: independent effects of changes in pitch and tempo.

    Science.gov (United States)

    Schellenberg, E Glenn; Stalinski, Stephanie M; Marks, Bradley M

    2014-01-01

    A melody's identity is determined by relations between consecutive tones in terms of pitch and duration, whereas surface features (i.e., pitch level or key, tempo, and timbre) are irrelevant. Although surface features of highly familiar recordings are encoded into memory, little is known about listeners' mental representations of melodies heard once or twice. It is also unknown whether musical pitch is represented additively or interactively with temporal information. In two experiments, listeners heard unfamiliar melodies twice in an initial exposure phase. In a subsequent test phase, they heard the same (old) melodies interspersed with new melodies. Some of the old melodies were shifted in key, tempo, or key and tempo. Listeners' task was to rate how well they recognized each melody from the exposure phase while ignoring changes in key and tempo. Recognition ratings were higher for old melodies that stayed the same compared to those that were shifted in key or tempo, and detrimental effects of key and tempo changes were additive in between-subjects (Experiment 1) and within-subjects (Experiment 2) designs. The results confirm that surface features are remembered for melodies heard only twice. They also imply that key and tempo are processed and stored independently.

  4. O uso de manta térmica no intra-operatório de pacientes submetidos à prostatectomia radical está relacionado com a diminuição do tempo de recuperação pós-anestésica El uso de manta térmica en el intraoperatorio de pacientes sometidos a la prostatectomía radical está relacionado con la disminución del tiempo de recuperación pos anestésica The intraoperative use of warming blankets in patients undergoing radical prostatectomy is related with a reduction in post-anesthetic recovery time

    Directory of Open Access Journals (Sweden)

    Cláudia Panossian

    2008-06-01

    Full Text Available JUSTIFICATIVA E OBJETIVOS: A anestesia e o procedimento cirúrgico causam alterações térmicas substanciais. A hipotermia pode causar complicações cardiovasculares, distúrbios da coagulação, alterações imunológicas e hidroeletrolíticas, além de diminuir o metabolismo de fármacos aumentando o período de recuperação pós-anestésica (RPA. A circulação de ar aquecido (manta térmica é o método de aquecimento não-invasivo mais efetivo disponível atualmente. O objetivo do presente estudo foi comparar o tempo de permanência na RPA de pacientes submetidos à prostatectomia radical com e sem o uso de manta térmica no período intra-operatório. MÉTODO: Foram estudados pacientes ASA PS I, II, III, entre 45 e 75 anos, submetidos à prostatectomia radical sob anestesia geral no ano de 2004. Os dados coletados incluíram: idade, peso, estado físico, técnica anestésica, uso de manta térmica e tempo de permanência na RPA, que foram tabulados em planilha Excel e analisados pelo teste de Mann-Whitney. RESULTADOS: Os pacientes em que a manta térmica foi utilizada no período intra-operatório permaneceram em média 139,66 ± 58,6 minutos na RPA; já nos pacientes em que a manta térmica não foi utilizada o tempo de permanência foi em média 208,28 ± 65,8 minutos na RPA (p JUSTIFICATIVA Y OBJETIVOS: La anestesia y el procedimiento quirúrgico causan alteraciones térmicas ostensivas, y la hipotermia puede causar complicaciones cardiovasculares, disturbios de la coagulación, alteraciones inmunológicas, hidro electrolíticas, además de reducir el metabolismo de fármacos aumentando el período de recuperación pos anestésica (RPA. La circulación de aire caliente (manta térmica, es el método de calentamiento no invasivo más efectivo que está a disposición actualmente. El objetivo del presente estudio fue comparar el tiempo de permanencia en el RPA de pacientes sometidos a la prostatectomía radical con y sin el uso de

  5. Distribution of free radical products among the bases of x-irradiated DNA model systems: an ESR study

    International Nuclear Information System (INIS)

    Spalletta, R.A.

    1984-01-01

    Exposure of solid state DNA to ionizing radiation results in an ESR spectrum that has been attributed to a nonstoichiometric distribution of free radicals among the bases. At low temperatures radical cations appear to be stabilized on the purines while radical anions are stabilized on the pyrimidines. This distribution could arise from at least two different mechanisms. The first, charge transfer, involves the transfer of electrons and/or holes between stacked bases. In the second, saturation asymmetry, the free radical distribution arises from differences in the dose saturation characteristics of individual bases. The present study addresses the relative importance of charge transfer versus saturation asymmetry in the production of these population differences. Radicals formed by dissolving irradiated polycrystalline pyrimidines in aqueous solutions containing NtB or PBN spin traps were analyzed using ESR. The relative importance of the two free radical production and distribution mechanisms was assessed using DNA model systems. Saturation asymmetry plays a significant role in determining the free radical population while charge transfer was unambiguously observed in only one, the complex of dAMP and TMP. The results demonstrate that any quantitative analysis of charge transfer must take saturation asymmetry into account

  6. The thermal performance monitoring and optimisation system (TEMPO): lessons learnt

    International Nuclear Information System (INIS)

    Beere, W.H.Aa.

    2005-09-01

    The goal of condition monitoring, fault detection and diagnosis is to ensure the success of planned operations by recognizing anomalies in a plant. This is achieved by monitoring the condition of equipment and instrumentation, and by detection, identification, diagnosis and removal of faults. The method of using physical modelling for condition monitoring has been investigated at the Institutt for energiteknikk since 1998. The result of this work was the development of the TEMPO (ThErMal Performance monitoring and Optimisation) toolbox. In this toolbox plant wide models are built up of unit sub-models. These are then linked to measurements by using data reconciliation. This enables the comparison of calculated to measured values as well as an indication of the significance of any deviation. It also allows the calculation of unmeasured variables as well as an overall 'goodness of fit' indicator. Since its first release in 2000 the TEMPO toolbox has been used to model the turbine cycles of several NPPs. Installations include Forsmark 3 and Loviisa 2 with feasibility studies for Dukovany, Olkiluoto 2, Almaraz and Paks. The experience from creating and installing TEMPO at these plants has now been collated and is presented in this report. This experience is used to indicate which direction the further development of TEMPO should take. The experience of using TEMPO has shown that the data-reconciliation method can be applied to the turbine cycles of NPPs. Problems that have arose have primarily been connected to the usability of the toolbox. This has prompted a shift in the development emphasis from the task of developing the method to that of developing its usability. A summary of improvement proposals is given in this paper. The reader is welcome to comment on these proposals or to suggest alternative improvements. (Author)

  7. Rate constants for the reactions of free radicals with oxygen in solution

    International Nuclear Information System (INIS)

    Maillard, B.; Ingold, K.U.; Scaiano, J.C.

    1983-01-01

    The kinetics of the rections of several free radicals with oxygen have been examined in solution at 300 K using laser flash photolysis techniques. The reactions of resonance-stabilized radicals are only slightly slower than those of nonstabilized radicals: for example, for tert-butyl (in cyclohexane), 4.93 x 10 9 ; benzyl, 2.36 x 10 9 (in cyclohexane); cyclohexadienyl (in benzene), 1.64 x 10 9 M -1 s -1 . The reaction of butyl-tin (n-Bu 3 Sn.) radicals is unusually fast (7.5 x 10 9 M -1 s -1 ), a fact that has been tentatively attributed to a relaxation of spin selection rules due to heavy atom effects. 1 table

  8. Funzioni del tempo presente nella strategia narrativa

    Directory of Open Access Journals (Sweden)

    Aleksandra Koman

    2017-08-01

    Full Text Available La scelta del tempo verbale adatto a una determinata situazione dipende dal rapporto tra il momento dell’avvenimento e quello dell’enunciazione. Se coincidono abbiamo a che fare con il tempo presente (Bertinetto. È necessario, però, ricordare che il presente è in grado di riferirsi agli eventi passati come accade spesso nei testi narrativi. Per capire lo scopo di questa scelta si sono analizzati diversi tipi di scrittura comprovanti che il presente nella narrativa può servire a sottolineare la posizione temporale del narratore (Il fu Mattia Pascal; a evidenziare un momento importante dal punto di vista dello svolgimento dell’azione (Se questo è un uomo; a costruire descrizioni (Vita oppure far entrare il lettore nel vivo del racconto (Gli Italiani in Polonia nei secoli, dando l’impressione che egli sia un testimone diretto degli eventi raccontati.

  9. Structure, stability, and properties of the trans peroxo nitrate radical: the importance of nondynamic correlation.

    Science.gov (United States)

    Dutta, Achintya Kumar; Dar, Manzoor; Vaval, Nayana; Pal, Sourav

    2014-02-27

    We report a comparative single-reference and multireference coupled-cluster investigation on the structure, potential energy surface, and IR spectroscopic properties of the trans peroxo nitrate radical, one of the key intermediates in stratospheric NOX chemistry. The previous single-reference ab initio studies predicted an unbound structure for the trans peroxo nitrate radical. However, our Fock space multireference coupled-cluster calculation confirms a bound structure for the trans peroxo nitrate radical, in accordance with the experimental results reported earlier. Further, the analysis of the potential energy surface in FSMRCC method indicates a well-behaved minima, contrary to the shallow minima predicted by the single-reference coupled-cluster method. The harmonic force field analysis, of various possible isomers of peroxo nitrate also reveals that only the trans structure leads to the experimentally observed IR peak at 1840 cm(-1). The present study highlights the critical importance of nondynamic correlation in predicting the structure and properties of high-energy stratospheric NOx radicals.

  10. Escolas de tempo integral e atividades extracurriculares: universos à espera da Psicologia brasileira

    Directory of Open Access Journals (Sweden)

    Neyfsom Carlos Fernandes Matias

    2009-12-01

    Full Text Available Observa-se que, no Brasil, diversas ações vêm sendo desenvolvidas com o intuito de se implantar uma educação em tempo integral. Sabe-se que as atividades ligadas ao esporte, às artes e culturais podem contribuir significativamente nesse sentido. Com base nisso, este artigo apresenta algumas iniciativas que visavam à execução de escolas de tempo integral e como as atividades extracurriculares podem ser úteis na efetivação de uma educação em tempo integral. O objetivo deste estudo foi o de verificar o que já se tem publicado sobre as escolas de tempo integral e atividades extracurriculares, desde uma pesquisa bibliográfica, nos periódicos “Psicologia: teoria e pesquisa”; “Psicologia: reflexão e crítica”; “Psicologia escolar e educacional”. As considerações finais apontam que o estudo sobre as atividades extracurriculares e escolas de tempo integral ainda é embrionário no Brasil e que urge a realização de pesquisas empíricas sobre atividades extracurriculares no País

  11. Visualizing the Past: The Design of a Temporally Enabled Map for Presentation (TEMPO

    Directory of Open Access Journals (Sweden)

    Nathan Prestopnik

    2012-01-01

    Full Text Available We present a design case for a prototype visualization tool called the Temporally Enabled Map for Presentation (TEMPO. Designed for use in the lecture classroom, TEMPO is an interactive animated map that addressed a common problem in military history: the shortcomings of traditional static (non-interactive, non-animated maps. Static maps show spatial elements well, but cannot do more than approximate temporal events using multiple views, movement arrows, and the like. TEMPO provides a more complete view of past historical events by showing them from start to finish. In our design case we describe our development process, which included consultation with military history domain experts, classroom observations, application of techniques derived from visualization and Human-Computer Interaction (HCI literature and theory. Our design case shows how the design of an educational tool can motivate scholarly evaluation, and we describe how some theories were first embraced and then rejected as design circumstances required. Finally, we explore a future direction for TEMPO, tools to support creative interactions with visualizations where students or instructors can learn by visualizing historical events for themselves. A working version of the finished TEMPO artifact is included as an interactive element in this document.

  12. The Effect of Concurrent Music Reading and Performance on the Ability to Detect Tempo Change.

    Science.gov (United States)

    Ellis, Mark Carlton

    1989-01-01

    Measures the ability of three groups of musicians to detect tempo change while reading and performing music. Compares this ability with that of the same musicians to detect tempo change while listening only. Found that for all groups the ability to detect tempo changes was inhibited by the playing task, although to different degrees for each…

  13. TEMPO E HISTÓRIA – revisitando uma discussão conceitual

    Directory of Open Access Journals (Sweden)

    José D'Assunção Barros

    2011-07-01

    Full Text Available RESUMO:Busca-se examinar a relação entre Tempo e História, particularmente atentando para os principais conceitos referidos a esta relação: temporalidade, duração, evento, processo e outros. Em um segundo momento, desenvolve-se um contraste entre o conceito aristotélico e o conceito agostiniano de tempo, de modo a preparar as outras duas discussões do artigo: a relação entre ‘tempo da ação’ e ‘tempo da narrativa’ na construção da História, de acordo com Paul Ricoeur, e as relações entre Futuro e Passado na constituição do Presente, de acordo com as contribuições de Koselleck.PALAVRAS-CHAVE: Tempo; Narrativa; História.ABSTRACT:This article aims to examine the relation between Time and History, attempting in particular to the mainly concepts referred to this relation: Temporality, duration, event, process, and others. In a second moment, it’s developed a contrast between the Aristotelian concept and the Augustinian concept of time, in order to prepare the two other discussions of the article: the relation between ‘action time’ and ‘narrative time’ in the construction of History, according Paul Ricoeur, and the relations between Future and Past in the constitution of Present, according the contributions of Koselleck.KEYWORDS: Time, Narrative; History.Recebido: 06/02/2011         Aceito: 05/04/2011

  14. Radical intermediates of low temperature radiolysis of di-tert-butylcyclohexano-18-crown-6/1-octanol extractant

    International Nuclear Information System (INIS)

    Zakurdaeva, O.A.; Nesterov, S.V.; Moscow State Univ.; Feldman, V.I.

    2013-01-01

    Intermediates of low temperature (77 K) X-rays radiolysis of 1-octanol and di-tert-butylcyclohexano-18-crown-6 solutions in 1-octanol were studied by ESR spectroscopy. Hydroxyalkyl CH 3 (CH 2 ) 6 C circle HOH and interior-type alkyl R 1 C circle HR 2 OH radicals were found to be main paramagnetic products stabilized in 1-octanol irradiated at 77 K. In addition to abovementioned radicals, macrocyclic -O-CH 2 -C circle H- and acyclic -C circle H-C(H)=O radicals produced from crown ether were identified in irradiated 1.0 M DtBuCH18C6 solution in octanol. No deviation in radiation-chemical yield of the stabilized acyclic radicals from the value expected in accord with 'additive' rule was observed in the latter case. It was supposed that macrocycle cleavage in DtBuCH18C6 occurred at early stages of radiolysis rather than in secondary radical reactions between products of 1-octanol radiolysis and crown ether. Meanwhile, alkyl radicals formed from 1-octanol can react with crown ether, resulting in formation of macrocyclic products of radiolysis. (orig.)

  15. Radical intermediates of low temperature radiolysis of di-tert-butylcyclohexano-18-crown-6/1-octanol extractant

    Energy Technology Data Exchange (ETDEWEB)

    Zakurdaeva, O.A.; Nesterov, S.V. [Russian Academy of Sciences, Moscow (Russian Federation). Enikolopov Institute of Synthetic Polymer Materials; Moscow State Univ. (Russian Federation). Dept. of Chemistry; Feldman, V.I. [Moscow State Univ. (Russian Federation). Dept. of Chemistry

    2013-03-01

    Intermediates of low temperature (77 K) X-rays radiolysis of 1-octanol and di-tert-butylcyclohexano-18-crown-6 solutions in 1-octanol were studied by ESR spectroscopy. Hydroxyalkyl CH{sub 3}(CH{sub 2}){sub 6}C {sup circle} HOH and interior-type alkyl R{sub 1}C {sup circle} HR{sub 2}OH radicals were found to be main paramagnetic products stabilized in 1-octanol irradiated at 77 K. In addition to abovementioned radicals, macrocyclic -O-CH{sub 2}-C {sup circle} H- and acyclic -C {sup circle} H-C(H)=O radicals produced from crown ether were identified in irradiated 1.0 M DtBuCH18C6 solution in octanol. No deviation in radiation-chemical yield of the stabilized acyclic radicals from the value expected in accord with 'additive' rule was observed in the latter case. It was supposed that macrocycle cleavage in DtBuCH18C6 occurred at early stages of radiolysis rather than in secondary radical reactions between products of 1-octanol radiolysis and crown ether. Meanwhile, alkyl radicals formed from 1-octanol can react with crown ether, resulting in formation of macrocyclic products of radiolysis. (orig.)

  16. Super-pnicogen bonding in the radical anion of the fluorophosphine dimer

    Science.gov (United States)

    Setiawan, Dani; Cremer, Dieter

    2016-10-01

    The LUMO of the pnicogen-bonded fluoro-phosphine dimer has PP bonding character. Radical anion and dianion form relatively strong pnicogen bonds with some covalent character where however the dianion turns out to be a second order transition state. The binding energy of (FPH 2)2- is 30.4 kcal/mol (CCSD(T)/aug-cc-pVTZ; CASPT2(5,8): 30.7 kcal/mol) and the bond strength order measured with the local PP bond stretching force constant increases from 0.055 for the neutral dimer to 0.187 thus revealing that the stabilization of the radical anion is to a large extend a result of one-electron six-center delocalization. Pnicogen-bonded complexes have a stabilizing electron affinity.

  17. Cochlear implant users rely on tempo rather than on pitch information during perception of musical emotion.

    Science.gov (United States)

    Caldwell, Meredith; Rankin, Summer K; Jiradejvong, Patpong; Carver, Courtney; Limb, Charles J

    2015-09-01

    The purpose of this study was to investigate the extent to which cochlear implant (CI) users rely on tempo and mode in perception of musical emotion when compared with normal hearing (NH) individuals. A test battery of novel four-bar melodies was created and adapted to four permutations with alterations of tonality (major vs. minor) and tempo (presto vs. largo), resulting in non-ambiguous (major key/fast tempo and minor key/slow tempo) and ambiguous (major key/slow tempo, and minor key/fast tempo) musical stimuli. Both CI and NH participants listened to each clip and provided emotional ratings on a Likert scale of +5 (happy) to -5 (sad). A three-way ANOVA demonstrated an overall effect for tempo in both groups, and an overall effect for mode in the NH group. The CI group rated stimuli of the same tempo similarly, regardless of changes in mode, whereas the NH group did not. A subgroup analysis indicated the same effects in both musician and non-musician CI users and NH listeners. The results suggest that the CI group relied more heavily on tempo than mode in making musical emotion decisions. The subgroup analysis further suggests that level of musical training did not significantly impact this finding. CI users weigh temporal cues more heavily than pitch cues in inferring musical emotion. These findings highlight the significant disadvantage of CI users in comparison with NH listeners for music perception, particularly during recognition of musical emotion, a critically important feature of music.

  18. Novel Profluorescent Nitroxides for Monitoring Alkyl Radical Reactions During Radiation Degradation

    International Nuclear Information System (INIS)

    George, G.

    2006-01-01

    Hindered amine stabilizers (HAS) are effective at retarding the photo-oxidative and high energy radiation degradation of PP and in certain circumstances, also thermo-oxidative degradation. The effectiveness of HAS as retarders of oxidation relies on the oxidation of the N-C bond by polymer hydroperoxide, ROOH, to form the nitroxyl group -NO which is the scavenger of polymer alkyl radicals, R. This reaction, which produces the alkoxy amine: -NO-R, must be competitive with the reaction of R with oxygen (which gives the chain-carrying peroxy radical, RO 2 ) if this stabilization mechanism is to be important in the inhibition of radiation-induced oxidative degradation of polyolefins by HAS. The rate of this reaction is high and in solution the rate coefficient is from 1 to 9x10 8 l mol - 1 s - 1. The efficient radical trapping by nitroxides has been widely employed in spin-trapping studies by electron spin resonance (esr) spectroscopy]. In addition to the hindered piperidine structure of commercial HAS, more rigid aromatic systems have been studied that are more stable to oxidative degradation and are more efficient at scavenging alkyl radicals. One such family is the iso-indoline nitroxide system, TMDBIO, shown below which, as it contains the phenanthrene fluorophore, is termed phenanthrene nitroxide. This nitroxide only becomes fluorescent when it reacts with alkyl radicals or is reduced and is termed profluorescent. TMDBIO has a vanishingly small fluorescence quantum yield (φ∼10 - 4) due to the enhanced intersystem crossing from the first excited singlet state to the ground state due to electron exchange interactions of the nitroxyl radical. When the nitroxide traps an alkyl radical, R, the resulting alkoxy amine is fluorescent (φ∼10 - 1) and the emission intensity is a measure of the number of reactions that have occurred. This property may be exploited by using quantitative fluorescence spectroscopy to follow the reaction of the nitroxide with alkyl radicals

  19. Role of distonic dimer radical cations in the radiation-induced polymerisation of vinyl ethers

    International Nuclear Information System (INIS)

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

    2005-01-01

    The experimental low-temperature EPR results and the quantum chemical calculations suggest that dimer radical cations of cyclic and aliphatic vinyl ethers (VE) plays a key role in starting of radiation-induced polymerisation. The main species observed at high 2,3-dihydrofuran (DHF), 2,3-dihydropyran (DHP) and VE concentration is the dimer radical cation. In the case of cyclic VE the dimer radical cation transforms through H-abstraction from neutral molecule into a carbocation and radical, which could start both cationic and free-radical polymerisation. However, in the case of aliphatic VE no further reactive species, which could start polymerisation, were observed. This is caused (in agreement with experiment and quantum chemical calculations) by the very high stability of dimer radical cation and calculated endothermity of H-abstraction reaction by dimer radical cation from monomer

  20. Tango or Waltz?: Putting Ballroom Dance Style into Tempo Detection

    Directory of Open Access Journals (Sweden)

    Gerhard Rigoll

    2008-05-01

    Full Text Available Rhythmic information plays an important role in Music Information Retrieval. Example applications include automatically annotating large databases by genre, meter, ballroom dance style or tempo, fully automated D.J.-ing, and audio segmentation for further retrieval tasks such as automatic chord labeling. In this article, we therefore provide an introductory overview over basic and current principles of tempo detection. Subsequently, we show how to improve on these by inclusion of ballroom dance style recognition. We introduce a feature set of 82 rhythmic features for rhythm analysis on real audio. With this set, data-driven identification of the meter and ballroom dance style, employing support vector machines, is carried out in a first step. Next, this information is used to more robustly detect tempo. We evaluate the suggested method on a large public database containing 1.8 k titles of standard and Latin ballroom dance music. Following extensive test runs, a clear boost in performance can be reported.

  1. WACANA KEAGAMAAN SYIAH-SUNNI DALAM MAJALAH TEMPO DAN SUARA HIDAYATULLAH

    Directory of Open Access Journals (Sweden)

    Dadang S Anshori

    2014-07-01

    Full Text Available This study aims to describe the language use as representation of mass media attitudes towards Shia-Sunni conflicts. It employed the qualitative method using Fowler’s critical discourse analysis. The data source was news on Shia-Sunni conflicts in Sampang reported in Tempo and Suara Hidayatullah magazines. The findings are as follows. First, Shia-Sunni conflicts are described in news headings and points of view. Tempo describes the conflicts using the point of view of ‘devil attack’ while Suara Hidayatullah presents them as conflicts of religious understanding. Second, expressions such as ‘belief forcing’, ‘Shia cleansing’, ‘devil attack’, and ‘intolerance’ represent Tempo’s attitudes while expressions such as ‘heretical’, ‘misleading’, ‘hijacking’, ‘deifying something’, and ‘infidel’ represent Suara Hidayatullah’s attitudes. Third, based on the use of vocabulary and sentences, Tempo tends to back the Shia group while Suara Hidayatullah tends to back the Sunni group.

  2. Electron spin resonance characterization of radical components in irradiated black pepper skin and core

    International Nuclear Information System (INIS)

    Yamaoki, Rumi; Kimura, Shojiro; Ohta, Masatoshi

    2011-01-01

    Characteristics of free radical components of irradiated black pepper fruit (skin) and the pepper seed (core) were analyzed using electron spin resonance. A weak signal near g=2.005 was observed in black pepper before irradiation. Complex spectra near g=2.005 with three lines (the skin) or seven lines (the core) were observed in irradiated black pepper (both end line width; ca. 6.8 mT). The spectral intensities decreased considerably at 30 days after irradiation, and continued to decrease steadily thereafter. The spectra simulated on the basis of the content and the stability of radical components derived from plant constituents, including fiber, starch, polyphenol, mono- and disaccharide, were in good agreement with the observed spectra. Analysis showed that the signal intensities derived from fiber in the skin for an absorbed dose were higher, and the rates of decrease were lower, than that in the core. In particular, the cellulose radical component in the skin was highly stable. - Highlights: → We identified the radical components in irradiated black pepper skin and core. → The ESR spectra near g=2.005 with 3-7 lines were emerged after irradiation. → Spectra simulated basing on the content and the stability of radical from the plant constituents. → Cellulose radical component in black pepper skin was highly stable. → Single signal near g=2.005 was the most stable in black pepper core.

  3. Nilai Eksklusivitas Dalam Karya Foto Cover Majalah Tempo Edisi 4351 Tentang Kasus Bom Sarinah 2016

    Directory of Open Access Journals (Sweden)

    Yohanes Christiansen Tanjung

    2017-12-01

    Full Text Available Visualization towards a news which is not limited on animation or photographic works in electronic media, online, and printed media has purposively been as additional information and becomes a complement of news. Particularly in spot news of the photojournalism works, every occurrence happens quite quickly. Due to photography, every moment can be recorded and well documented, as well as providing answers to what is actually happening on a rapid occurrence. One example is the use of photographs on a printed media, namely Tempo. This Research aims to observe hidden meaning in the works of photojournalism on the cover of Tempo magazine 4351 edition wether it is objective or subjective meaning that be received by the public after seeing the photo on the cover. The method used is descriptive qualitative method by conducting analysis of Peirce semiotics on the cover photo of Tempo magazine issue of 4351. Based on the research which has been done, it can be concluded that the application of visualization conducted by Tempo referred to the works of photojournalism in the cover of Tempo magazine issue of 4351 created exclusivity both in objective and subjective meaning Visualisasi pada suatu pemberitaan baik itu animasi maupun karya foto dalam media elektronik, online, dan pastinya media cetak, mempunyai tujuan sebagai informasi tambahan serta pemanis suatu berita. Khususnya pada karya foto jurnalistik spot news, setiap peristiwa yang terjadi dengan sangat cepat. Oleh karena fotografi, setiap kejadian dapat direkam dan didokumentasikan dengan baik, serta memberikan jawaban atas apa yang sebenarnya terjadi pada suatu peristiwa yang berlangsung dengan cepat. Salah satu contohnya adalah pemakaian karya foto pada sebuah cover media cetak, yaitu Tempo. Penelitian bertujuan untuk mengetahui makna yang tersembunyi dalam karya foto jurnalistik pada cover majalah Tempo edisi 4351 baik berupa makna obyektif maupun subyektif yang diterima publik setelah melihat

  4. Estimates of the Tempo-adjusted Total Fertility Rate in Western and Eastern Germany, 1955-2008

    Directory of Open Access Journals (Sweden)

    Marc Luy

    2011-09-01

    Full Text Available In this article we present estimates of the tempo-adjusted total fertility rate in Western and Eastern Germany from 1955 to 2008. Tempo adjustment of the total fertility rate (TFR requires data on the annual number of births by parity and age of the mother. Since official statistics do not provide such data for West Germany as well as Eastern Germany from 1990 on we used alternative data sources which include these specific characteristics. The combined picture of conventional TFR and tempo-adjusted TFR* provides interesting information about the trends in period fertility in Western and Eastern Germany, above all with regard to the differences between the two regions and the enormous extent of tempo effects in Eastern Germany during the 1990s. Compared to corresponding data for populations from other countries, our estimates of the tempo-adjusted TFR* for Eastern and Western Germany show plausible trends. Nevertheless, it is important to note that the estimates of the tempo-adjusted total fertility rate presented in this paper should not be seen as being on the level of or equivalent to official statistics since they are based on different kinds of data with different degrees of quality.

  5. Thermal stability of carbonyl radicals. Part II. Reactions of methylglyoxyl and methylglyoxylperoxy radicals at 1 bar in the temperature range 275-311 K.

    Science.gov (United States)

    Jagiella, Stefan; Zabel, Friedhelm

    2008-04-07

    Reactions of methylglyoxyl and methylglyoxylperoxy radicals were investigated at a total pressure of 1 bar in oxygen. Methylglyoxyl radicals were generated by stationary photolysis of Br2-CH3C(O)C(O)H-NO2-O2-N2 mixtures at wavelengths > or =480 nm and of Cl2-CH3C(O)C(O)H-NO2-O2-N2 mixtures in the wavelength range 315-460 nm. In the bromine system, rate constant ratios for the reactions CH3C(O)CO --> CH3CO + CO (kdis) and CH3C(O)CO + O2 --> CH3C(O)C(O)O2 (kO2) were measured as a function of temperature in the range 275-311 K. Assuming the constant value kO2 = 5.1 x 10(-12) cm3 molecule(-1) s(-1) for our reaction conditions, kdis = 1.2 x 10(10.0+/-0.7) x exp(-11.7 +/- 3.8 kJ mol(-1)/RT) s(-1) (2sigma errors) was obtained for ptot = 1 bar (M = O2), in good agreement with the kinetic parameters calculated by Méreau et al. [R. Méreau, M.-T. Rayez, J.-C. Rayez, F. Caralp and R. Lesclaux, Phys. Chem. Chem. Phys., 2001, 3, 4712]. CH3C(O)C(O)O2 radicals oxidise NO2, forming NO3, CH3CO and CO2. This experimental result is supported by DFT and ab initio calculations. Possible mechanisms for the observed formation of several % of ketene and bromoacetyl peroxynitrate are discussed. Use of Cl rather than Br atoms to abstract the aldehydic H atom from methylglyoxal leads to chemically activated CH3C(O)CO radicals, thus substantially increasing the fraction of CH3C(O)CO radicals that decompose rather than add O2.

  6. Children's Preference for Sequenced Accompaniments: The Influence of Style and Perceived Tempo.

    Science.gov (United States)

    Brittin, Ruth V.

    2000-01-01

    Explores the influence of tempo on musical preference for students in grades 2-6, focusing on the effects of various styles using a MIDI keyboard. Explains that the students listened to 10 musical selections identifying their preferences and perceptions of tempo. Reveals that the preferred styles were Hip-Hop, Heavy Rock Shuffle, Samba, and Funk2.…

  7. Importance of A Priori Vertical Ozone Profiles for TEMPO Air Quality Retrievals

    Science.gov (United States)

    Johnson, M. S.; Sullivan, J. T.; Liu, X.; Zoogman, P.; Newchurch, M.; Kuang, S.; McGee, T. J.; Leblanc, T.

    2017-12-01

    Ozone (O3) is a toxic pollutant which plays a major role in air quality. Typically, monitoring of surface air quality and O3 mixing ratios is conducted using in situ measurement networks. This is partially due to high-quality information related to air quality being limited from space-borne platforms due to coarse spatial resolution, limited temporal frequency, and minimal sensitivity to lower tropospheric and surface-level O3. The Tropospheric Emissions: Monitoring of Pollution (TEMPO) satellite is designed to address the limitations of current space-based platforms and to improve our ability to monitor North American air quality. TEMPO will provide hourly data of total column and vertical profiles of O3 with high spatial resolution to be used as a near-real-time air quality product. TEMPO O3 retrievals will apply the Smithsonian Astrophysical Observatory profile algorithm developed based on work from GOME, GOME-2, and OMI. This algorithm is suggested to use a priori O3 profile information from a climatological data-base developed from long-term ozone-sonde measurements (tropopause-based (TB-Clim) O3 climatology). This study evaluates the TB-Clim dataset and model simulated O3 profiles, which could potentially serve as a priori O3 profile information in TEMPO retrievals, from near-real-time data assimilation model products (NASA GMAO's operational GEOS-5 FP model and reanalysis data from MERRA2) and a full chemical transport model (CTM), GEOS-Chem. In this study, vertical profile products are evaluated with surface (0-2 km) and tropospheric (0-10 km) TOLNet observations and the theoretical impact of individual a priori profile sources on the accuracy of TEMPO O3 retrievals in the troposphere and at the surface are presented. Results indicate that while the TB-Clim climatological dataset can replicate seasonally-averaged tropospheric O3 profiles, model-simulated profiles from a full CTM resulted in more accurate tropospheric and surface-level O3 retrievals from

  8. Optimal Tempo for Groove: Its Relation to Directions of Body Movement and Japanese nori

    Directory of Open Access Journals (Sweden)

    Takahide Etani

    2018-04-01

    Full Text Available The tendency for groove-based music to induce body movements has been linked to multiple acoustical factors. However, it is unclear how or whether tempo affects groove, although tempo significantly affects other aspects of music perception. To address this issue, the present study investigated effects of tempo, specific rhythmic organizations of patterns, and syncopation on groove and the induction of the sensation of wanting to move. We focused on the directions of body movement in particular by taking into account nori, which is an indigenous Japanese musical term used not only synonymously with groove, but also as a spatial metaphor indicating vertical or horizontal movement directions. Thus, the present study explored how groove was felt and defined, as well as how musical factors induced the sensation of wanting to move in cross-cultural context. A listening experiment was conducted using drum breaks as stimuli. Stimuli consisted of various rhythm patterns at six tempi from 60 to 200 BPM. The main findings are that: (1 an optimal tempo for groove existed for drum breaks at around 100–120 BPM, (2 an optimal tempo existed for the sensation of wanting to move the body in specific directions (i.e., back-and-forth and side-to-side, (3 groove and nori shared a similar concept of wanting to move but differed on several points (i.e., association with sense of pulse and fast tempo. Overall, the present study suggests that there is an optimal tempo for body movement related to groove. This finding has implications for the use of music or rhythmic stimuli to induce smooth motion in rehabilitation, therapy, or dance.

  9. Optimal Tempo for Groove: Its Relation to Directions of Body Movement and Japanese nori.

    Science.gov (United States)

    Etani, Takahide; Marui, Atsushi; Kawase, Satoshi; Keller, Peter E

    2018-01-01

    The tendency for groove-based music to induce body movements has been linked to multiple acoustical factors. However, it is unclear how or whether tempo affects groove, although tempo significantly affects other aspects of music perception. To address this issue, the present study investigated effects of tempo, specific rhythmic organizations of patterns, and syncopation on groove and the induction of the sensation of wanting to move. We focused on the directions of body movement in particular by taking into account nori , which is an indigenous Japanese musical term used not only synonymously with groove, but also as a spatial metaphor indicating vertical or horizontal movement directions. Thus, the present study explored how groove was felt and defined, as well as how musical factors induced the sensation of wanting to move in cross-cultural context. A listening experiment was conducted using drum breaks as stimuli. Stimuli consisted of various rhythm patterns at six tempi from 60 to 200 BPM. The main findings are that: (1) an optimal tempo for groove existed for drum breaks at around 100-120 BPM, (2) an optimal tempo existed for the sensation of wanting to move the body in specific directions (i.e., back-and-forth and side-to-side), (3) groove and nori shared a similar concept of wanting to move but differed on several points (i.e., association with sense of pulse and fast tempo). Overall, the present study suggests that there is an optimal tempo for body movement related to groove. This finding has implications for the use of music or rhythmic stimuli to induce smooth motion in rehabilitation, therapy, or dance.

  10. Effect of antioxidant properties of lecithin emulsifier on oxidative stability of encapsulated bioactive compounds.

    Science.gov (United States)

    Pan, Yuanjie; Tikekar, Rohan V; Nitin, N

    2013-06-25

    Oxidation of encapsulated bioactive compounds in emulsions is one of the key challenges that limit shelf life of emulsion containing products. Oxidation in these emulsions is triggered by permeation of free radicals generated at the emulsion interface. The objective of this study was to evaluate the role of antioxidant properties of common emulsifiers (lecithin and Tween 20) in reducing permeation of free radicals across the emulsion interface. Radical permeation rates were correlated with oxidative stability of a model bioactive compound (curcumin) encapsulated in these emulsions. Rate of permeation of peroxyl radicals from the aqueous phase to the oil phase of emulsion was inversely proportional to the antioxidant properties of emulsifiers. The rate of radical permeation was significantly higher (plecithin compared to native lecithin that showed higher antioxidant activity. Free radical permeation rate correlated with stability of curcumin in emulsions and was significantly higher (plecithin stabilized emulsions as compared to Tween 20 emulsions. Overall, this study demonstrates that antioxidant activity of emulsifiers significantly influences permeation of free radicals across the emulsion interface and the rate of oxidation of bioactive encapsulant. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Tempos históricos, tempos físicos, tempos epidemiológicos: prováveis contribuições de Fernand Braudel e Ilya Prigogine ao pensamento epidemiológico Historical times, physical times, epidemiological times: probable contributions of Fernand Braudel and Ilya Prigogine to epidemiological thinking

    Directory of Open Access Journals (Sweden)

    Gil Sevalho

    1997-01-01

    Full Text Available O texto é uma abordagem acerca do tempo enquanto categoria científica para a epidemiologia. A partir do aforismo tempo-lugar-pessoa, o tempo é apontado como elemento pouco pensado pela epidemiologia, embora esteja presente em vários dos seus conceitos. No entanto, o tema tem sido objeto de reflexão importante na movimentação recente de várias disciplinas, tais como a história, a geografia, a biologia e a física, e deve por isto representar para a epidemiologia um ponto de vista interessante, tanto no que concerne ao diálogo interdisciplinar quanto ao estabelecimento de um olhar crítico voltado para a própria disciplina. Com o objetivo de argumentar a respeito destes aspectos, apresenta-se o tempo histórico de Fernand Braudel e o tempo físico de Ilya Prigogine, construções teóricas que serão comparadas com um provável tempo epidemiológico. Ao final, usando a questão das infecções emergentes como exemplo, faz-se considerações sobre a aparente inadequação epistemológica do tempo epidemiológico para reconhecer e lidar com os aspectos sociais e históricos envolvidos na complexidade do adoecer humano coletivo.The text is an approach on time as a scientific category in epidemiology. Considering the aphorism time-place-person, time is pointed out as an element with little theoretical concern, despite its presence in main epidemiological concepts. While a topic connected to important changes in other disciplines, such as history, geography, biology and physics, time represents an interesting point of view to the interdisciplinary dialogue and its relevance for a critical knowledge in epidemiology. To argue about this idea, the historical and physical time constructions of Fernand Braudel and Ilya Prigogine are presented. These time theoretical constructions are compared with a probable epidemiological time. Finally, using the emerging infectious diseases as an example, some considerations are made about an apparent

  12. Metal-free TEMPO-promoted C(sp³)-H amination to afford multisubstituted benzimidazoles.

    Science.gov (United States)

    Xue, Ding; Long, Ya-Qiu

    2014-05-16

    An efficient TEMPO-air/cat. TEMPO-O2 oxidative protocol was developed to synthesize multisubstituted or fused tetracyclic benzimidazoles via a metal-free oxidative C-N coupling between the sp(3) C-H and free N-H of readily available N(1)-benzyl/alkyl-1,2-phenylenediamines.

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

    Science.gov (United States)

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

    2018-04-01

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

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

    Science.gov (United States)

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

    2018-04-01

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

  15. The free radical species in polyacrylonitrile fibers induced by γ-radiation and their decay behaviors

    International Nuclear Information System (INIS)

    Liu Weihua; Wang Mouhua; Xing Zhe; Wu Guozhong

    2012-01-01

    Free radicals in vacuum, air and oxygen atmospheres were studied using electron spin resonance (ESR). Mainly two types of radicals, namely alkyl radicals and polyimine radicals, are formed in polyacrylonitrile (PAN) fibers after γ-ray irradiation. The G value of the radical formation was calculated to be 2.1 (number of radicals per 100 eV absorbed) in air at room temperature based on the ESR measurements. The radical stability and decay behaviors at room temperature and elevated temperatures were also investigated under different atmospheres. The alkyl radicals were found to be rather stable when stored in vacuum at room temperature, but they decayed via reaction with oxygen when stored in air. The alkyl radicals disappeared completely after a thermal treatment at 110 °C in vacuum, but only 15% of the polyimine radicals decayed; this indicates that polyimine radicals are more stable compared to the alkyl radicals due to their lower mobility. - Highlights: ► Radicals formed by radiation were assigned to polyimine and alkyl radicals. ► G-value of radicals was measured to be 2.1 per 100 eV. ► The radicals were found to be extremely stable in vacuum at room temperature. ► Effect of oxygen on radical decay under various conditions was studied.

  16. On the time behaviour of the concentration of pyrazinium radical cations in the early stage of the Maillard reaction

    Science.gov (United States)

    Stoesser, Reinhard; Klein, Jeannette; Peschke, Simone; Zehl, Andrea; Cämmerer, Bettina; Kroh, Lothar W.

    2007-08-01

    During the early stage of the Maillard reaction pyrazinium radical cations were detected by ESR within the reaction system D-glucose/glycine. The spectra were characterized by completely resolved hyperfine structure. The partial pressure of oxygen and the radical concentrations were measured directly in the reaction mixture by ESR using solutions of the spin probe TEMPOL and of DPPH, respectively. There are quantitative and qualitative relations of the actual concentration of the radical ions to the partial pressure of oxygen, the temperature-time regime and the mechanical mixing of the reaction system. These macroscopic parameters significantly affect both the induction period and the velocity of the time-dependent formation of free radicals. From in situ variations of p(O 2) and p(Ar) including the connected mixing effects caused by the passing the gases through the reaction mixture, steric and chemical effects of the stabilization of the radical ions were established. The determination of suitable and relevant conditions for stabilization and subsequent radical reactions contributes to the elucidation of the macroscopically known antioxidant activity of Maillard products.

  17. Relationship between heart rate and preference for tempo of music.

    Science.gov (United States)

    Iwanaga, M

    1995-10-01

    People prefer music with tempi ranging from 70 to 100 cycles per minute similar to that of adults' heart rate within normal daily situations. Previous studies of the relation between preferred tempi and heart rates using a pure tone also have indicated that subjects tended to prefer tempi similar to their heart rates. The present study examined this relationship using a musical piece (the theme of "It's a small world") as a stimulus. 14 undergraduate women were subjects who searched for their favorite tempi by controlling the musical tempo by themselves. The most preferred tempo was close to their cycle of heart beats, however, tempi that were one and a half and twice as fast as the heart rate were less preferred in the present study than in a previous study using a tone. Subjects preferred faster tempi in the descending series of stimuli than in the ascending one, and hence were influenced by the initial value of the tempo in the trial sequence. The effects due to the differences of the meaning of the stimuli are considered.

  18. Beating time: How ensemble musicians' cueing gestures communicate beat position and tempo.

    Science.gov (United States)

    Bishop, Laura; Goebl, Werner

    2018-01-01

    Ensemble musicians typically exchange visual cues to coordinate piece entrances. "Cueing-in" gestures indicate when to begin playing and at what tempo. This study investigated how timing information is encoded in musicians' cueing-in gestures. Gesture acceleration patterns were expected to indicate beat position, while gesture periodicity, duration, and peak gesture velocity were expected to indicate tempo. Same-instrument ensembles (e.g., piano-piano) were expected to synchronize more successfully than mixed-instrument ensembles (e.g., piano-violin). Duos performed short passages as their head and (for violinists) bowing hand movements were tracked with accelerometers and Kinect sensors. Performers alternated between leader/follower roles; leaders heard a tempo via headphones and cued their partner in nonverbally. Violin duos synchronized more successfully than either piano duos or piano-violin duos, possibly because violinists were more experienced in ensemble playing than pianists. Peak acceleration indicated beat position in leaders' head-nodding gestures. Gesture duration and periodicity in leaders' head and bowing hand gestures indicated tempo. The results show that the spatio-temporal characteristics of cueing-in gestures guide beat perception, enabling synchronization with visual gestures that follow a range of spatial trajectories.

  19. o-Iminobenzosemiquinonate and o-imino-p-methylbenzosemiquinonate anion radicals coupled VO2+ stabilization.

    Science.gov (United States)

    Roy, Amit Saha; Saha, Pinaki; Adhikary, Nirmal Das; Ghosh, Prasanta

    2011-03-21

    The diamagnetic VO(2+)-iminobenzosemiquinonate anion radical (L(R)(IS)(•-), R = H, Me) complexes, (L(-))(VO(2+))(L(R)(IS)(•-)): (L(1)(-))(VO(2+))(L(H)(IS)(•-))•3/2MeOH (1•3/2MeOH), (L(2)(-))(VO(2+))(L(H)(IS)(•-)) (2), and (L(2)(-))(VO(2+))(L(Me)(IS)(•-))•1/2 L(Me)(AP) (3•1/2 L(Me)(AP)), incorporating tridentate monoanionic NNO-donor ligands {L = L(1)(-) or L(2)(-), L(1)H = (2-[(phenylpyridin-2-yl-methylene)amino]phenol; L(2)H = 1-(2-pyridylazo)-2-naphthol; L(H)(IS)(•-) = o-iminobenzosemiquinonate anion radical; L(Me)(IS)(•-) = o-imino-p-methylbenzosemiquinonate anion radical; and L(Me)(AP) = o-amino-p-methylphenol} have been isolated and characterized by elemental analyses, IR, mass, NMR, and UV-vis spectra, including the single-crystal X-ray structure determinations of 1•3/2MeOH and 3•1/2 L(Me)(AP). Complexes 1•3/2MeOH, 2, and 3•1/2 L(Me)(AP) absorb strongly in the visible region because of intraligand (IL) and ligand-to-metal charge transfers (LMCT). 1•3/2MeOH is luminescent (λ(ext), 333 nm; λ(em), 522, 553 nm) in frozen dichloromethane-toluene glass at 77 K due to π(diimine→)π(diimine)* transition. The V-O(phenolato) (cis to the V═O) lengths, 1.940(2) and 1.984(2) Å, respectively, in 1•3/2MeOH and 3•1/2 L(Me)(AP) are consistent with the VO(2+) description. The V-O(iminosemiquinonate) (trans to the V═O) lengths, 2.1324(19) in 1•3/2MeOH and 2.083(2) Å in 3•1/2 L(Me)(AP), are expectedly ∼0.20 Å longer due to the trans influence of the V═O bond. Because of the stronger affinity of the paramagnetic VO(2+) ion to the L(H)(IS)(•-) or L(Me)(IS)(•-), the V-N(iminosemiquinonate) lengths, 1.908(2) and 1.921(2) Å, respectively, in 1•3/2MeOH and 3•1/2 L(Me)(AP), are unexpectedly shorter. Density functional theory (DFT) calculations using B3LYP, B3PW91, and PBE1PBE functionals on 1 and 2 have established that the closed shell singlet (CSS) solutions (VO(3+)-amidophenolato (L(R)(AP)(2-)) coordination) of these

  20. Oltre lo spazio e il tempo la nuova fisica

    CERN Document Server

    Lachièze-Rey, Marc

    2004-01-01

    Oggi la fisica si fonda, allo stesso tempo, sulla meccanica quantistica e sulla relatività generale. Ma, in quanto veri e propri sistemi di pensiero, queste due teorie suggeriscono due distinte visioni del mondo, non conciliabili nel quadro di una descrizione unificata. Se dunque la fisica attuale si rivela inadeguata, occorre costruirne una nuova, percorrendo fino in fondo la via geometrica. Supersimmetria, stringhe e superstringhe, gravità e cosmologia quantistiche, geometria non commutativa: nuove audaci ipotesi al servizio di nuove teorie che rinnovano la nostra concezione dello spazio, del tempo, della materia e dell'Universo, e che trovano nel volume una presentazione chiara e accessibile anche a un pubblico di non specialisti.

  1. Environmentally Persistent Free Radicals in Soils of Past Coking Sites: Distribution and Stabilization.

    Science.gov (United States)

    Jia, Hanzhong; Zhao, Song; Nulaji, Gulimire; Tao, Kelin; Wang, Fu; Sharma, Virender K; Wang, Chuanyi

    2017-06-06

    This study presents the existence of environmentally persistent free radicals (EPFRs) in soils of past coking sites, mainly contaminated by polycyclic aromatic hydrocarbons (PAHs). Measurements of EPFRs were conducted by electron paramagnetic resonance (EPR) technique with numerous soil samples, which were collected from different distances (0-1000 m) and different depths (0-30 cm) of three contaminant sources. EPR signals with ∼3 × 10 17 radicals/g of the soil samples were obtained, which are very similar to that generated in PAHs contaminated clays, that is, g = 2.0028-2.0036. Concentrations of PAHs and soil components were determined to understand their role in producing EPFRs. PAHs, clay, and iron predominately contributed to generating EPRFs. Meanwhile, organic matter negatively influenced the production of EPRFs. The effects of environmental factors (moisture and oxic/anoxic) were also studied to probe the persistency of EPFRs under various simulated conditions. The EPFRs are stable under relatively dry and oxic conditions. Under anoxic conditions without O 2 and H 2 O, the spin densities decrease initially, followed by gradual increase before attaining constant values in two months period time. The present work implies that continuous formation of EPFRs induced by PAHs is largely responsible for the presence of relatively stable radicals in soils of coking sites.

  2. Evaluating A Priori Ozone Profile Information Used in TEMPO Tropospheric Ozone Retrievals

    Science.gov (United States)

    Johnson, Matthew S.; Sullivan, John T.; Liu, Xiong; Newchurch, Mike; Kuang, Shi; McGee, Thomas J.; Langford, Andrew O'Neil; Senff, Christoph J.; Leblanc, Thierry; Berkoff, Timothy; hide

    2016-01-01

    Ozone (O3) is a greenhouse gas and toxic pollutant which plays a major role in air quality. Typically, monitoring of surface air quality and O3 mixing ratios is primarily conducted using in situ measurement networks. This is partially due to high-quality information related to air quality being limited from space-borne platforms due to coarse spatial resolution, limited temporal frequency, and minimal sensitivity to lower tropospheric and surface-level O3. The Tropospheric Emissions: Monitoring of Pollution (TEMPO) satellite is designed to address these limitations of current space-based platforms and to improve our ability to monitor North American air quality. TEMPO will provide hourly data of total column and vertical profiles of O3 with high spatial resolution to be used as a near-real-time air quality product. TEMPO O3 retrievals will apply the Smithsonian Astrophysical Observatory profile algorithm developed based on work from GOME, GOME-2, and OMI. This algorithm uses a priori O3 profile information from a climatological data-base developed from long-term ozone-sonde measurements (tropopause-based (TB) O3 climatology). It has been shown that satellite O3 retrievals are sensitive to a priori O3 profiles and covariance matrices. During this work we investigate the climatological data to be used in TEMPO algorithms (TB O3) and simulated data from the NASA GMAO Goddard Earth Observing System (GEOS-5) Forward Processing (FP) near-real-time (NRT) model products. These two data products will be evaluated with ground-based lidar data from the Tropospheric Ozone Lidar Network (TOLNet) at various locations of the US. This study evaluates the TB climatology, GEOS-5 climatology, and 3-hourly GEOS-5 data compared to lower tropospheric observations to demonstrate the accuracy of a priori information to potentially be used in TEMPO O3 algorithms. Here we present our initial analysis and the theoretical impact on TEMPO retrievals in the lower troposphere.

  3. Evaluating A Priori Ozone Profile Information Used in TEMPO Tropospheric Ozone Retrievals

    Science.gov (United States)

    Johnson, M. S.; Sullivan, J. T.; Liu, X.; Newchurch, M.; Kuang, S.; McGee, T. J.; Langford, A. O.; Senff, C. J.; Leblanc, T.; Berkoff, T.; Gronoff, G.; Chen, G.; Strawbridge, K. B.

    2016-12-01

    Ozone (O3) is a greenhouse gas and toxic pollutant which plays a major role in air quality. Typically, monitoring of surface air quality and O3 mixing ratios is primarily conducted using in situ measurement networks. This is partially due to high-quality information related to air quality being limited from space-borne platforms due to coarse spatial resolution, limited temporal frequency, and minimal sensitivity to lower tropospheric and surface-level O3. The Tropospheric Emissions: Monitoring of Pollution (TEMPO) satellite is designed to address these limitations of current space-based platforms and to improve our ability to monitor North American air quality. TEMPO will provide hourly data of total column and vertical profiles of O3 with high spatial resolution to be used as a near-real-time air quality product. TEMPO O3 retrievals will apply the Smithsonian Astrophysical Observatory profile algorithm developed based on work from GOME, GOME-2, and OMI. This algorithm uses a priori O3 profile information from a climatological data-base developed from long-term ozone-sonde measurements (tropopause-based (TB) O3 climatology). It has been shown that satellite O3 retrievals are sensitive to a priori O3 profiles and covariance matrices. During this work we investigate the climatological data to be used in TEMPO algorithms (TB O3) and simulated data from the NASA GMAO Goddard Earth Observing System (GEOS-5) Forward Processing (FP) near-real-time (NRT) model products. These two data products will be evaluated with ground-based lidar data from the Tropospheric Ozone Lidar Network (TOLNet) at various locations of the US. This study evaluates the TB climatology, GEOS-5 climatology, and 3-hourly GEOS-5 data compared to lower tropospheric observations to demonstrate the accuracy of a priori information to potentially be used in TEMPO O3 algorithms. Here we present our initial analysis and the theoretical impact on TEMPO retrievals in the lower troposphere.

  4. Research progress on trifluoromethyl-based radical reaction process

    Science.gov (United States)

    Song, Hao

    2017-12-01

    Due to the unique properties imparted by the trifluoromethyl group, such as high electron density and strong lipotropy, which effectively improve acidity, lipophilicity and metabolic stability of the molecule itself, trifluoromethyl-substituted organic compounds are becoming increasingly important as structural motifs in pharmaceuticals, agrochemicals and organic materials. In this review, we present several methods developed for the direct introduction of a trifluoromethyl group, beginning with its rich and storied history. Then the present article addresses mechanism and process in carbon-carbon bond forming reaction based on radical process which is divided into three parts according to the way of CF3 radical generation. Finally, challenges and opportunities of researches on trifluoromethylation reactions facing are prospected.

  5. Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions.

    Science.gov (United States)

    Williams, Peggy E; Marshall, David L; Poad, Berwyck L J; Narreddula, Venkateswara R; Kirk, Benjamin B; Trevitt, Adam J; Blanksby, Stephen J

    2018-06-04

    In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions. Graphical Abstract.

  6. Manipulating Greek musical modes and tempo affects perceived musical emotion in musicians and nonmusicians.

    Science.gov (United States)

    Ramos, D; Bueno, J L O; Bigand, E

    2011-02-01

    The combined influence of tempo and mode on emotional responses to music was studied by crossing 7 changes in mode with 3 changes in tempo. Twenty-four musicians aged 19 to 25 years (12 males and 12 females) and 24 nonmusicians aged 17 to 25 years (12 males and 12 females) were required to perform two tasks: 1) listening to different musical excerpts, and 2) associating an emotion to them such as happiness, serenity, fear, anger, or sadness. ANOVA showed that increasing the tempo strongly affected the arousal (F(2,116) = 268.62, mean square error (MSE) = 0.6676, P effects were found between tempo and mode (F (1,58) = 115.6, MSE = 0.6428, P effects. This finding demonstrates that small changes in the pitch structures of modes modulate the emotions associated with the pieces, confirming the cognitive foundation of emotional responses to music.

  7. A developmental study of the affective value of tempo and mode in music.

    Science.gov (United States)

    Dalla Bella, S; Peretz, I; Rousseau, L; Gosselin, N

    2001-07-01

    Do children use the same properties as adults in determining whether music sounds happy or sad? We addressed this question with a set of 32 excerpts (16 happy and 16 sad) taken from pre-existing music. The tempo (i.e. the number of beats per minute) and the mode (i.e. the specific subset of pitches used to write a given musical excerpt) of these excerpts were modified independently and jointly in order to measure their effects on happy-sad judgments. Adults and children from 3 to 8 years old were required to judge whether the excerpts were happy or sad. The results show that as adults, 6--8-year-old children are affected by mode and tempo manipulations. In contrast, 5-year-olds' responses are only affected by a change of tempo. The youngest children (3--4-year-olds) failed to distinguish the happy from the sad tone of the music above chance. The results indicate that tempo is mastered earlier than mode to infer the emotional tone conveyed by music.

  8. Tempo e Trânsito na Experiência Subjetiva de Motoristas

    OpenAIRE

    Ana Inez Oka Elvas de Lima; Sylvia Cavalcante

    2015-01-01

    Esta pesquisa investiga como são percebidos e vivenciados o tempo e a pressa no trânsito por motoristas de Fortaleza, identificando e analisando seus estados subjetivos e comportamentos associados a essa experiência. Para a coleta de dados, organizaram-se quatro grupos focais, a partir dos quais emergiram diversos elementos relacionados ao tempo e à pressa e à incidência de comportamentos inadequados no trânsito, segundo o sexo e a idade dos participantes. Para analisar os dados obtidos nas d...

  9. Effect of solid phase on the selectivity of alkyl radical formation by gamma-irradiation of branched alkanes

    International Nuclear Information System (INIS)

    Koizumi, Hitoshi; Hashino, Masatoshi; Ichikawa, Tsuneki; Yoshida, Hiroshi

    1992-01-01

    ESR and electron spin echo measurements of alkyl radicals generated by γ-irradiation of glassy and crystalline branched alkanes C 10 ∼ C 13 have been carried out to elucidate the effect of molecular structure and solid phase on the selectivity of alkyl radical formation. Alkyl radicals generated and stabilized at 77 K in the glassy alkanes are secondary penultimate radicals. Tertiary radicals and secondary radicals other than the penultimate one are not generated either by hydrogen abstraction or from ionized or excited molecules. In the crystalline alkanes, however, a small amount of secondary internal radicals are generated in addition to the predominant formation of the secondary penultimate radicals. It is concluded that the detachment of C-H hydrogen preferentially takes place at the location where the motion of carbon atoms assisting the detachment of the C-H hydrogen easily occurs. (author)

  10. Ultra-low fertility in South Korea: The role of the tempo effect

    Directory of Open Access Journals (Sweden)

    Sam Hyun Yoo

    2018-02-01

    Full Text Available Background: The total fertility rate (TFR in South Korea has fallen below 1.3 since 2001. The role of the rapid shift toward a late-childbearing pattern in driving Korean fertility decline to this ultra-low level has been little explored until now. Objective: We provide an in-depth analysis of period fertility trends by birth order in South Korea from 1981 to 2015, when the period TFR fell from 2.57 to extremely low levels. Methods: We combine census and birth registration data to estimate period and cohort fertility indicators by birth order. We compare changes in conventional TFR with tempo- and parity-adjusted total fertility rate (TFRp* and their birth-order-specific components. Results: The tempo effect linked to the shift toward delayed childbearing has had a strong and persistent negative influence on period TFRs in South Korea since the early 1980s. Without the shift to later childbearing, period fertility rates in South Korea would consistently stay higher and decline more gradually, reaching a threshold of very low fertility, 1.5, only in 2014. The postponement of childbearing and the resulting tempo effect were strongest in the early 2000s, when Korean TFR reached the lowest levels. More recently, Korean fertility has been characterized by a diminishing tempo effect and falling first and second birth rates. This trend marks a break with the previous pattern of almost universal fertility and a strong two-child family model. Contribution: Our study demonstrates the importance of the tempo effect in explaining the shift to ultra-low fertility in South Korea and in East Asia

  11. A TEMPO-free copper-catalyzed aerobic oxidation of alcohols.

    Science.gov (United States)

    Xu, Boran; Lumb, Jean-Philip; Arndtsen, Bruce A

    2015-03-27

    The copper-catalyzed aerobic oxidation of primary and secondary alcohols without an external N-oxide co-oxidant is described. The catalyst system is composed of a Cu/diamine complex inspired by the enzyme tyrosinase, along with dimethylaminopyridine (DMAP) or N-methylimidazole (NMI). The Cu catalyst system works without 2,2,6,6-tetramethyl-l-piperidinoxyl (TEMPO) at ambient pressure and temperature, and displays activity for un-activated secondary alcohols, which remain a challenging substrate for catalytic aerobic systems. Our work underscores the importance of finding alternative mechanistic pathways for alcohol oxidation, which complement Cu/TEMPO systems, and demonstrate, in this case, a preference for the oxidation of activated secondary over primary alcohols. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Exame do líquido cefalorraquidiano: influência da temperatura, tempo e preparo da amostra na estabilidade analítica Cerebrospinal fluid exam: influence of sample preparation, temperature and time on analytical stability

    Directory of Open Access Journals (Sweden)

    Luciana Ferreira Dimas

    2008-04-01

    Full Text Available O líquido cefalorraquidiano (LCR é um fluido biológico que está em íntima relação com o sistema nervoso central (SNC. Por isso, o exame do LCR constitui um método de grande valia para o diagnóstico e o acompanhamento de diversas afecções neurológicas. Entretanto, existem poucos estudos sobre a estabilidade de seus analitos durante a etapa pré-analítica. OBJETIVO: Identificar dados existentes sobre a influência da temperatura e do tempo de estocagem, dos ciclos de congelamento/descongelamento e pré-tratamentos (centrifugação, desnaturação, adição de soro na estabilidade dos analitos do LCR. MÉTODO: Foi realizada uma revisão sistemática de artigos da literatura, usando palavras-chave da língua inglesa como storage, cerebrospinal fluid, CSF, stability, temperature e period, com base nos serviços de dados de PubMed, Highwire Press, Lilacs e Amazonas Library, os quais permitem a pesquisa bibliográfica de citações e artigos científicos. RESULTADO: A busca encontrou nove artigos, resultado da escassez de trabalhos sobre o assunto. Os analitos do LCR estudados incluíram células (número e morfologia, proteínas totais, glicose, lactato, aminoácidos, creatina, creatinina, biomarcadores e enzimas. As metodologias se basearam em microscopia óptica, ensaio imunossorvente ligado à enzima (ELISA, Imunoblot/SDS-PAGE e fotometria. CONCLUSÃO: A revisão da literatura confirma que a estabilidade da amostra de LCR sofre influência da temperatura, do tempo de estocagem e das condições de preparo pré-analítico. Os achados desta revisão sistemática podem contribuir para a ampliação dos conhecimentos no exame do LCR, assim como o melhor entendimento sobre a estabilidade da amostra.The cerebrospinal fluid (CSF is a biological fluid that is in close relation with the central nervous system (CNS. Therefore, the CSF examination constitutes an invaluable method in the diagnosis and monitoring of countless neurological diseases

  13. Tempos de infância, tempos de escola: a ordenação do tempo escolar no ensino público paulista (1892-1933 Childhood times, school times: the ordering of school time in the São Paulo State School System (1892-1933

    Directory of Open Access Journals (Sweden)

    Rosa Fátima de Souza

    1999-07-01

    Full Text Available O texto analisa a ordenação do tempo nas escolas primárias paulistas no final do século XIX e início do século XX, período em que se institui e se consolida a arquitetura temporal escolar. Compreende, pois, as primeiras prescrições detalhadas sobre o tempo constantes na reforma republicana da instrução pública de 1892, as regulamentações instituídas no decorrer da Primeira República, até o momento de criação do Código de Educação de São Paulo em 1933, quando se inaugura uma nova fase da instrução pública no estado. O texto busca mostrar como o tempo constitui uma ordem que se experimenta e se aprende na escola. Para a realização deste estudo foram utilizadas fontes documentais, especialmente a legislação e textos oficiais da administração do ensino. As análises incidem sobre dois aspectos: a formulação política do tempo escolar e a organização pedagógica e disciplinar do tempo na escola. Em relação ao primeiro aspecto, mostra como a ordenação do tempo pautou-se pela aspiração de uniformização e controle. Nesse sentido, as autoridades do ensino público procuraram regulamentar a obrigatoriedade do ensino, a freqüência, a duração do curso primário e a jornada escolar. Em relação à organização pedagógica e disciplinar do tempo, põe em destaque a ordenação minuciosa do emprego do tempo compreendendo a racionalização curricular - a seleção e distribuição do conhecimento por séries, aulas, lições, e a definição dos horários.This text analyzes the ordering of time in primary state schools of the State of São Paulo at the end of the 19th century and beginning of the 20th century, a period in which the school time architecture is instated and consolidated. The paper thus starts with the first detailed instructions related to time at schools, which are part of the Republican Reform of Public Schooling of 1892. It continues with the regulations elaborated during the First Republic

  14. Effect of Melodic Rhythm on Elementary Students' and College Undergraduates' Perceptions of Relative Tempo.

    Science.gov (United States)

    Duke, Robert A.

    1989-01-01

    Uses extant musical examples as stimuli in order to assess the effect of melodic rhythm as a determinant of relative tempo as perceived by college undergraduates and elementary students. Results indicate that subjects responded to the melodic rhythm as well as the beat when making tempo judgments. (LS)

  15. Determinação da Distribuição de Tempos de Residência em Tempo Real no Processamento Reativo de Blendas Poliméricas

    Directory of Open Access Journals (Sweden)

    Mélo Tomás J. A. de

    2002-01-01

    Full Text Available Determinou-se por transmissão de luz a distribuição de tempos de residência (DTR em tempo real em uma extrusora com rosca dupla co-rotativa e autolimpante onde o sinal do detetor é sensível à presença da segunda fase dispersa, usada como traçador. Vários traçadores foram utilizados em diferentes concentrações: dois pigmentos (TiO2 e ftalocianina e dois polímeros (poliestireno PS e poliamida-6 PA6 sendo adicionados na forma de um pulso em um fluxo de polipropileno (PP. Os parâmetros temporais (tempos de residência inicial, t i e médio t n e a variância normalizada s q² medidos nas mesmas condições de processamento são muito próximos, dentro do erro experimental, indicando que a dispersão axial neste tipo de extrusora é independente do traçador. Por outro lado curvas de DTR medidas usando-se um polímero traçador (PS disperso em um polímero de fluxo (PP ficam deslocadas no tempo quando a situação é invertida, ou seja, usando-se PP como traçador em um fluxo de PS. Os parâmetros temporais são dependentes das características reológicas do polímero de fluxo, assim diferentes tipos de um mesmo polímero apresentam DTR com formas diferentes e deslocadas no tempo. A intensidade do sinal produzido pelo detetor é dependente não só da concentração mas também das características ópticas do par polímero/traçador, ou polímero/fase dispersa. Misturas poliméricas reativas (PP/PA6/PP-g-AA e não reativas (PP/PA6 apresentaram diferenças na intensidade do sinal da DTR, devido à ocorrência da reação de graftização com conseqüente mudança na morfologia e no comportamento reológico. Estes resultados foram corroborados com medidas "off-line" por espectroscopia no infravermelho.

  16. Infrared spectroscopy, vibrational predissociation dynamics and stability of the hydrogen trioxy (HOOO) radical and estimation of its abundance in the atmosphere

    Science.gov (United States)

    Derro, Erika L.

    The hydrogen trioxy (HOOO) radical has been implicated as an important intermediate in key processes in the atmosphere. In the present studies, HOOO is produced by the combination of O2 and photolytically generated OH radicals in the collisional region of a pulsed supersonic expansion. Rotationally cooled HOOO is probed in the effectively collision-free region of the expansion using infrared action spectroscopy, an infrared-pump, ultraviolet-probe technique, in which HOOO is vibrationally excited and the nascent OH products of vibrational predissociation are probed via laser-induced fluorescence. High resolution infrared spectra of HOOO and DOOO were observed in the fundamental and overtone OH/D stretching regions (nui and 2nu 1), which comprise a rotationally structured band attributed to the trans conformer, and an unstructured component assigned to the cis conformer. Infrared spectra of HOOO and DOOO combination bands composed of the OH stretch and a low frequency mode (nu1 + nun) were also observed. This allowed identification of vibrational frequencies for five of the six modes for trans-H/DOOO and four of the six modes for cis-HOOO and DOOO. Identification of low frequency modes provides critical information on the vibrational dynamics and thermochemical properties of the HOOO radical, and furthermore, provides a potential means for detecting HOOO in situ in the atmosphere. In addition, the nascent OH X2pi products following vibrational predissociation of HOOO have been investigated. The product state distributions reveal a distinct preference for population of pi(A ') Λ-doublets in OH that is indicative of a planar dissociation of trans-HOOO in which the symmetry of the bonding orbital is maintained. The highest observed OH quantum state allows determination of the stability of HOOO relative to the OH + O 2 asymptote using a conservation of energy approach. In conjunction with a similar investigation of DOOO, the binding energy is determined to be ≤ 5

  17. Relational invariance of expressive microstructure across global tempo changes in music performance: an exploratory study.

    Science.gov (United States)

    Repp, B H

    1994-01-01

    This study addressed the question of whether the expressive microstructure of a music performance remains relationally invariant across moderate (musically acceptable) changes in tempo. Two pianists played Schumann's "Träumerei" three times at each of three tempi on a digital piano, and the performance data were recorded in MIDI format. In a perceptual test, musically trained listeners attempted to distinguish the original performances from performances that had been artificially speeded up or slowed down to the same overall duration. Accuracy in this task was barely above chance, suggesting that relational invariance was largely preserved. Subsequent analysis of the MIDI data confirmed that each pianist's characteristic timing patterns were highly similar across the three tempi, although there were statistically significant deviations from perfect relational invariance. The timing of (relatively slow) grace notes seemed relationally invariant, but selective examination of other detailed temporal features (chord asynchrony, tone overlap, pedal timing) revealed no systematic scaling with tempo. Finally, although the intensity profile seemed unaffected by tempo, a slight overall increase in intensity with tempo was observed. Effects of musical structure on expressive microstructure were large and pervasive at all levels, as were individual differences between the two pianists. For the specific composition and range of tempi considered here, these results suggest that major (cognitively controlled) temporal and dynamic features of a performance change roughly in proportion with tempo, whereas minor features tend to be governed by tempo-independent motoric constraints.

  18. Delocalization model of regioselectivity and reactivity of free radicals in reactions of addition to olefins

    International Nuclear Information System (INIS)

    Volovik, S.V.; Dyadyusha, G.G.; Staninets, V.I.

    1987-01-01

    On the basis of the concept of polarity (philicity) of free radicals as proposed by the authors, within the framework of methods of qualitative surfaces of potential energy (linear combinations of configurations of fragments) and stabilization energy, an effective model has been developed for the regioselectivity and reactivity of radicals in processes of addition. A critical examination is made of certain key aspects of the change in regiochemistry and reactivity with changes in the electronic structure of the free radical and substrate. The dominant trends in regioselectivity and reactivity in processes of free-radical addition to olefins are controlled by electronic effects and can be predicted by analyzing interactions of diabatic potential energy surfaces or orbital interactions for a system consisting of a free radical and an unsaturated substrate

  19. Lokasi Dan Kelompok Teater Indonesia 2001-2005 (Analisis Rubrik Teater Majalah Tempo

    Directory of Open Access Journals (Sweden)

    Nurhadi Nurhadi

    2010-06-01

    Full Text Available Artikel ini bertujuan mendeskripsikan kelompok-kelompok teater yang berkecimpung dalam pementasan teater di Indonesia dan peta lokasi pementasan sebagaimana diulas dalam majalah Tempo tahun 2001-2005. Hasil penelitian ini menunjukan kelompok teater yang paling konsisten dalam mementaskan suatu naskah setiap tahunnya adalah Teater Koma. Kelompok teater berikutnya yang relatif banyak berkiprah dari tahun 2001-2005 berdasarkan artikel rubrik teater Tempo yaitu Teater Mandiri, Teater Garasi, dan Actors Unlimited Bandung. Kelompok teater pada jajaran berikutnya yang mementaskan lebih dari satu kali pada periode 2001-2005, yaitu Teater Gandrik, Bengkel Teater, dan Mainteater Jakarta. Lokasi pementasan teater selama 2001-2005 berdasarkan rubrik teater majalah Tempo sebagian besar berlangsung di berbagai gedung teater di Jakarta. Perbandingan jumlah lokasi pertunjukannya adalah sebagai berikut: Jakarta (50 pementasan, Yogyakarta (6 pementasan, Surakarta (2 pementasan dan Bandung (1 pementasan. Abstract: This article aims to describe the theater groups being active in theater performances in Indonesia and the performance location map as reviewed in Tempo magazine in 2001-2005. The research result has shown that the most consistent theater group in performing a script each year is Teater Koma. The next group which have relatively many performances in 2001-2005 according to Tempo’s articles are Teater Mandiri, Teater Garasi, and Actors Unlimited Bandung. The next level groups which have more than one performance in 2001-2005 are Teater Gandrik, Bengkel Teater, and Mainteater Jakarta. The theater performance locations in 2001-2005, according to Tempo’s articles, mostly took place in Jakarta’s theater houses. The ratio of performance locations amount is as follows: Jakarta (50 performances, Yogyakarta (6 performances, Surakarta (2 performances, and Bandung (1 performance. Key Words: theater performance location, theater group, Tempo magazine

  20. Dureza knoop de resinas compostas em função do número relativo de radicais livres Relative number of free radicals and knoop hardness of composites

    Directory of Open Access Journals (Sweden)

    Marco Aurélio de MENEZES

    1998-07-01

    Full Text Available A pesquisa teve a finalidade de determinar o número relativo de radicais livres e a dureza Knoop de três resinas compostas (Z100, Silux Plus e Heliomolar RO. Para o ensaio dos radicais livres, as irradiações foram: 110, 180, 300, 580 mW/cm2, pelos tempos de 10, 20, 30, 40, 50, 60, 80 e 90 segundos. As durezas foram determinadas com as cores claras com irradiação de 110 e 300 mW/cm2, por 20, 40, 60 e 80 segundos, nas faces da frente e do fundo, nas idades de 5 minutos, 1 hora, 1 dia, 1 semana e 1 mês. As conclusões foram: a resina Z100 apresentou cerca de 3 vezes mais radicais livres do que as outras; o número relativo de radicais livres aumenta com a intensidade e tempo de exposição; maior intensidade de luz aumentou a dureza; maior tempo de exposição aumentou as durezas das resinas Silux Plus e Heliomolar, mas não da Z100; a dureza aumentou com a idade até 1 mês; o lado da irradiação apresentou maior dureza do que o do fundo; a resina Z100 foi bem mais dura e sofreu menos a influência da irradiação.The present study had the purpose of determining the relative number of free radicals of three composites with clear and dark colors. Intensities of irradiation were: 110, 180, 300, and 580 mW/cm2, for 10, 20, 30, 40, 50, 60, 80 and 90 seconds. Hardness was determined for the clear colors of the composites, using 110 and 300 mW/cm2 irradiation intensities, for 20, 40, 60, and 80 seconds, on front and deep surfaces, at the ages of 5 minutes, 1 hour, 1 day, 1 week, and 1 month. The conclusions were that: depending on the resin, clear colors present more free radicals; the number of free radicals increases with higher intensity and longer irradiation time; composite Z100 is much richer in free radicals than Silux Plus and Heliomolar RO; higher intensity of irradiation leads to increasing hardness; longer irradiation time increases hardness of Silux Plus and Heliomolar RO, but not that of Z100; hardness increases with age; in depth

  1. Síntese de copolímeros em bloco de p-acetoxiestireno com isopreno através de polimerização "viva" via radical livre Synthesis of block copolymers from p-acetoxystyrene and isoprene by "living" free radical polymerization

    Directory of Open Access Journals (Sweden)

    José Carlos Moreira

    2004-09-01

    Full Text Available Neste trabalho, é mostrada a síntese de homopolímeros de p-acetoxiestireno e copolímeros diblocos de p-acetoxiestireno com isopreno, utilizando um iniciador TEMPO-modificado, por um processo de polimerização "viva" via radical livre. As análises de GPC indicaram a formação de copolímeros em bloco com massas molares e polidispersão mais altas quando comparadas aos dos homopolímeros correspondentes. Os copolímeros em bloco poli(p-acetoxiestireno-b-isopreno foram preparados com controle de composição e massa molar até 94500 u.m.a. As análises de DSC mostraram que a transição vítrea do bloco de p-acetoxiestireno foi de 5 a 18 °C mais baixa que aquelas obtidas para os homopolímeros correspondentes. A transição vítrea do bloco de isopreno apresentou valores similares àqueles dos homopolímeros de poliisopreno (-67 a -55 °C.In this work we show the synthesis of homopolymers and diblock copolymers of p-acetoxystyrene and isoprene by using TEMPO-modified free radical initiator. The GPC analyses have shown an increase in the molar masses and in the polydispersity of the copolymers in comparison with their corresponding homopolymer. Poly(p-acetoxystyrene-b-isoprene were prepared with good control of composition and molar mass up to 94,500 a.m.u. DSC analyses have shown a glass transition temperature decrease of 5-18 °C for the poly(p-acetoxystyrene segment in copolymers compared to that observed for the parent homopolymer. The glass transition temperature of polyisoprene segment in copolymers remained similar to those observed for the homopolymers (-67 to -55 °C.

  2. Representasi Pemberitaan Wanita Pelaku Kejahatan di Media Massa (Analisis Karikatur dan Konten Berita Malinda Dee di Majalah TEMPO)

    OpenAIRE

    Lubis, Ghassani S.

    2015-01-01

    This research titled “Representation of Women Offenders Reporting in Mass Media”. A Study of semiotics analysis of TEMPO magazine‟s front covers and news content on editions in April 4th and 11th 2011. Caricature cover and news content of TEMPO has been analyzed to discover the meaning and myths and representation of Malinda Dee in TEMPO magazine. Malinda cover design TEMPO edition number 05/40 (4th April 2011) and 06/40 (11th April 2011), depicting two historical females in the world that is...

  3. Tempo e Trânsito na Experiência Subjetiva de Motoristas

    Directory of Open Access Journals (Sweden)

    Ana Inez Oka Elvas de Lima

    2015-03-01

    Full Text Available Esta pesquisa investiga como são percebidos e vivenciados o tempo e a pressa no trânsito por motoristas de Fortaleza, identificando e analisando seus estados subjetivos e comportamentos associados a essa experiência. Para a coleta de dados, organizaram-se quatro grupos focais, a partir dos quais emergiram diversos elementos relacionados ao tempo e à pressa e à incidência de comportamentos inadequados no trânsito, segundo o sexo e a idade dos participantes. Para analisar os dados obtidos nas discussões grupais utilizaram-se os critérios da Análise Clássica de Conteúdo. Os resultados levaram à conclusão de que a questão do tempo e da pressa constitui um potencial gerador de erros e violações na condução de veículos, pois exerce influência decisiva sobre os comportamentos dos motoristas e configura uma realidade importante para se compreender os fatores humanos envolvidos na dinâmica do trânsito e do ambiente urbano como um todo.

  4. Directed Motor-Auditory EEG Connectivity Is Modulated by Music Tempo.

    Science.gov (United States)

    Nicolaou, Nicoletta; Malik, Asad; Daly, Ian; Weaver, James; Hwang, Faustina; Kirke, Alexis; Roesch, Etienne B; Williams, Duncan; Miranda, Eduardo R; Nasuto, Slawomir J

    2017-01-01

    Beat perception is fundamental to how we experience music, and yet the mechanism behind this spontaneous building of the internal beat representation is largely unknown. Existing findings support links between the tempo (speed) of the beat and enhancement of electroencephalogram (EEG) activity at tempo-related frequencies, but there are no studies looking at how tempo may affect the underlying long-range interactions between EEG activity at different electrodes. The present study investigates these long-range interactions using EEG activity recorded from 21 volunteers listening to music stimuli played at 4 different tempi (50, 100, 150 and 200 beats per minute). The music stimuli consisted of piano excerpts designed to convey the emotion of "peacefulness". Noise stimuli with an identical acoustic content to the music excerpts were also presented for comparison purposes. The brain activity interactions were characterized with the imaginary part of coherence (iCOH) in the frequency range 1.5-18 Hz (δ, θ, α and lower β) between all pairs of EEG electrodes for the four tempi and the music/noise conditions, as well as a baseline resting state (RS) condition obtained at the start of the experimental task. Our findings can be summarized as follows: (a) there was an ongoing long-range interaction in the RS engaging fronto-posterior areas; (b) this interaction was maintained in both music and noise, but its strength and directionality were modulated as a result of acoustic stimulation; (c) the topological patterns of iCOH were similar for music, noise and RS, however statistically significant differences in strength and direction of iCOH were identified; and (d) tempo had an effect on the direction and strength of motor-auditory interactions. Our findings are in line with existing literature and illustrate a part of the mechanism by which musical stimuli with different tempi can entrain changes in cortical activity.

  5. Directed Motor-Auditory EEG Connectivity Is Modulated by Music Tempo

    Directory of Open Access Journals (Sweden)

    Nicoletta Nicolaou

    2017-10-01

    Full Text Available Beat perception is fundamental to how we experience music, and yet the mechanism behind this spontaneous building of the internal beat representation is largely unknown. Existing findings support links between the tempo (speed of the beat and enhancement of electroencephalogram (EEG activity at tempo-related frequencies, but there are no studies looking at how tempo may affect the underlying long-range interactions between EEG activity at different electrodes. The present study investigates these long-range interactions using EEG activity recorded from 21 volunteers listening to music stimuli played at 4 different tempi (50, 100, 150 and 200 beats per minute. The music stimuli consisted of piano excerpts designed to convey the emotion of “peacefulness”. Noise stimuli with an identical acoustic content to the music excerpts were also presented for comparison purposes. The brain activity interactions were characterized with the imaginary part of coherence (iCOH in the frequency range 1.5–18 Hz (δ, θ, α and lower β between all pairs of EEG electrodes for the four tempi and the music/noise conditions, as well as a baseline resting state (RS condition obtained at the start of the experimental task. Our findings can be summarized as follows: (a there was an ongoing long-range interaction in the RS engaging fronto-posterior areas; (b this interaction was maintained in both music and noise, but its strength and directionality were modulated as a result of acoustic stimulation; (c the topological patterns of iCOH were similar for music, noise and RS, however statistically significant differences in strength and direction of iCOH were identified; and (d tempo had an effect on the direction and strength of motor-auditory interactions. Our findings are in line with existing literature and illustrate a part of the mechanism by which musical stimuli with different tempi can entrain changes in cortical activity.

  6. Directed Motor-Auditory EEG Connectivity Is Modulated by Music Tempo

    Science.gov (United States)

    Nicolaou, Nicoletta; Malik, Asad; Daly, Ian; Weaver, James; Hwang, Faustina; Kirke, Alexis; Roesch, Etienne B.; Williams, Duncan; Miranda, Eduardo R.; Nasuto, Slawomir J.

    2017-01-01

    Beat perception is fundamental to how we experience music, and yet the mechanism behind this spontaneous building of the internal beat representation is largely unknown. Existing findings support links between the tempo (speed) of the beat and enhancement of electroencephalogram (EEG) activity at tempo-related frequencies, but there are no studies looking at how tempo may affect the underlying long-range interactions between EEG activity at different electrodes. The present study investigates these long-range interactions using EEG activity recorded from 21 volunteers listening to music stimuli played at 4 different tempi (50, 100, 150 and 200 beats per minute). The music stimuli consisted of piano excerpts designed to convey the emotion of “peacefulness”. Noise stimuli with an identical acoustic content to the music excerpts were also presented for comparison purposes. The brain activity interactions were characterized with the imaginary part of coherence (iCOH) in the frequency range 1.5–18 Hz (δ, θ, α and lower β) between all pairs of EEG electrodes for the four tempi and the music/noise conditions, as well as a baseline resting state (RS) condition obtained at the start of the experimental task. Our findings can be summarized as follows: (a) there was an ongoing long-range interaction in the RS engaging fronto-posterior areas; (b) this interaction was maintained in both music and noise, but its strength and directionality were modulated as a result of acoustic stimulation; (c) the topological patterns of iCOH were similar for music, noise and RS, however statistically significant differences in strength and direction of iCOH were identified; and (d) tempo had an effect on the direction and strength of motor-auditory interactions. Our findings are in line with existing literature and illustrate a part of the mechanism by which musical stimuli with different tempi can entrain changes in cortical activity. PMID:29093672

  7. Stability of radicals in electron-irradiated fluoropolymer film for the preparation ofgraft copolymer fuel cell electrolyte membranes

    DEFF Research Database (Denmark)

    Larsen, Mikkel Juul; Ma, Yue; Qian, Huan

    2010-01-01

    The content of radicals in the base polymer film before and after grafting is an important issue in theproduction and use of membranes for electrochemical devices by radiation grafting. In this work a methodhas been developed for determination of relative radical content in fluoropolymer films us...

  8. Tempo resposta de um serviço de atendimento móvel de urgência

    OpenAIRE

    Rosane Mortari Ciconet

    2015-01-01

    O tempo resposta é um indicador usado para avaliação da qualidade de serviços de atendimento pré-hospitalar (APH). Consiste no intervalo de tempo entre a expressão do pedido de socorro até a chegada da equipe à cena do evento. Assim, o objetivo do estudo foi analisar o tempo resposta de um SAMU, referente aos chamados para atendimentos clínicos e traumáticos demandados à Central de Regulação de Urgências. Os agravos clínicos foram compostos pelas síndromes neurológicas, cardiovasculares e res...

  9. Hydroxyl-radical-induced oxidation of cyclic dipeptides: Reactions of free peptide radicals and their peroxyl radicals

    International Nuclear Information System (INIS)

    Mieden, O.J.

    1989-01-01

    In the course of this study investigations were carried out into the reactions of hydroxyl radicals and hydrogen atoms with cyclic dipeptides as well as the subsequent reactions of peptide radicals and their peroxyl radicals in aqueous solution. The radiolysis products formed in the absence and presence of oxygen or transient metal complexes were characterized and determined on a quantitative basis. The linking of information from product analyses to the kinetic data for transient species obtained by time-resolving UV/VIS and conductivity measurements (pulse radiolysis) as well as computer-assisted simulations of individual events during the reaction permitted an evaluation of the mechanisms underlying the various processes and an identification of interim products with short life-times, which did or did not belong to the group of radicals. Through the characterization of key reactions of radicals and peroxyl radicals of this substance class a major advance has been made towards a better understanding of the role of radicals in the peptide compound and the mechanisms involved in indirect radiation effects on long-chain peptides and proteins. (orig.) [de

  10. A radical approach to radical innovation

    NARCIS (Netherlands)

    D. Deichmann (Dirk); J.C.M. van den Ende (Jan)

    2014-01-01

    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?

  11. Radiation-induced free radical reactions in polymer/drug systems for controlled release: an EPR investigation

    Energy Technology Data Exchange (ETDEWEB)

    Faucitano, A. E-mail: chemrad@unipv.it; Buttafava, A.; Montanari, L.; Cilurzo, F.; Conti, B.; Genta, I.; Valvo, L

    2003-05-01

    The primary and secondary free radical intermediates in the gamma radiolysis of poly(D,L-lactide-co-glycolide) (PLGA) and clonazepam loaded PLGA microspheres were investigated by matrix EPR spectroscopy in the temperature range 77-298 K. Drug-polymer interactions were found to be important leading to significant deviations of the G(radicals) from the additivity law. In particular, in the mixed system a stabilization of the polymer matrix with respect to the radiation damage was detected, witnessed by a decrease of the overall polymer radicals yield which is accompanied by an increase of the drug radicals yield. These effects have been attributed to the scavenging properties of the nitro group with respect to electrons and polymer radicals. It is conceivable that such conclusions be of general application for all pharmaceutical formulations containing drugs bearing nitro groups in their chemical structure.

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

    Directory of Open Access Journals (Sweden)

    Bahir ahmad

    2015-08-01

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

  13. Predictive rhythmic tapping to isochronous and tempo changing metronomes in the nonhuman primate.

    Science.gov (United States)

    Gámez, Jorge; Yc, Karyna; Ayala, Yaneri A; Dotov, Dobromir; Prado, Luis; Merchant, Hugo

    2018-04-30

    Beat entrainment is the ability to entrain one's movements to a perceived periodic stimulus, such as a metronome or a pulse in music. Humans have a capacity to predictively respond to a periodic pulse and to dynamically adjust their movement timing to match the varying music tempos. Previous studies have shown that monkeys share some of the human capabilities for rhythmic entrainment, such as tapping regularly at the period of isochronous stimuli. However, it is still unknown whether monkeys can predictively entrain to dynamic tempo changes like humans. To address this question, we trained monkeys in three tapping tasks and compared their rhythmic entrainment abilities with those of humans. We found that, when immediate feedback about the timing of each movement is provided, monkeys can predictively entrain to an isochronous beat, generating tapping movements in anticipation of the metronome pulse. This ability also generalized to a novel untrained tempo. Notably, macaques can modify their tapping tempo by predicting the beat changes of accelerating and decelerating visual metronomes in a manner similar to humans. Our findings support the notion that nonhuman primates share with humans the ability of temporal anticipation during tapping to isochronous and smoothly changing sequences of stimuli. © 2018 New York Academy of Sciences.

  14. Stabilization of oxidovanadium(IV) by organic radicals.

    Science.gov (United States)

    Kundu, Suman; Maity, Suvendu; Maity, Amarendra Nath; Ke, Shyue-Chu; Ghosh, Prasanta

    2013-04-07

    o-Imino-p-R'-benzosemiquinone anion radical (L(R')(IS)(˙-)) complexes of oxidovanadium(IV) of type [(L(1)(R-))(VO(2+))(L(R')(IS)(˙-))] (R = H, R' = H, 1; R = H, R' = -CMe(3), 2; R = -CMe(3), R' = H, 3 and R = -CMe(3), R' = -CMe(3), 4) incorporating the redox-innocent tridentate NNO-donor L(1)(R-) ligands (L(1)(R)H = 2,4-di-R-6-{(2-(pyridin-2-yl)hydrazono)methyl}phenol) were isolated and substantiated by elemental analyses, IR, mass, NMR and UV-vis spectra including the single crystal X-ray structure determinations. The V-O(phenolato) (cis to the V=O) lengths spanning 1.905(3)-1.9355(15) Å in 1-4 are consistent with the coordination to the [VO](2+) state. The V-O(IS) (trans to the V=O) lengths, 2.1505(17)-2.1869(15) Å, in 1-4 are longer due to the trans influence of the V=O bond. The V-N(IS) lengths, 1.906(3)-1.924(2) Å, in 1-4 are comparatively shorter due to the higher affinity of the paramagnetic [VO](2+) ion towards the L(R')(IS)(˙-) anion radicals. Density functional theory (DFT) calculations using B3LYP, B3PW91 and PBE1PBE functionals on 1 and 2 authenticated that the closed shell singlet (CSS) solutions (dianionic o-amido-p-R'-phenolates (L(R')(AP)(2-)) coordinated to VO(3+), Type I) of 1-4 are unstable with respect to the open shell singlet (OSS) perturbations. Broken symmetry, BS (1,1) M(s) = 0 (L(R')(IS)(˙-) coordinated to the VO(2+) ion, Type III) solutions of 1-4 are stable and reproduce the experimental bond parameters. Frozen glasses EPR spectra of [1-4](+) ions (e.g. g(||) = 1.948, g(⊥) = 1.978, A(||) = 184 (22 G), A(⊥) = 62(15 G) for [2](+)) and unrestricted DFT calculations on [1](+), [2](+), [1](-) and [2](-) ions using doublet spin state elucidated that the reversible anodic waves at [0.15-0.31] V of 1-4 complexes are due to the oxidation of L(R')(IS)(˙-) generating [(L(1)(R-))(VO(2+))(L(R')(IQ))]+ complexes (L(R')(IQ) = o-imino-p-R'-benzoquinone) coordinated to the [VO](2+) ion (Type V) while the irreversible cathodic waves at -[1

  15. Distribution of stable free radicals among amino acids of isolated soy proteins.

    Science.gov (United States)

    Lei, Qingxin; Liebold, Christopher M; Boatright, William L; Shah Jahan, M

    2010-09-01

    Application of deuterium sulfide to powdered isolated soy proteins (ISP) was used to quench stable free radicals and produce a single deuterium label on amino acids where free radicals reside. The deuterium labels rendered increases of isotope ratio for the specific ions of radical-bearing amino acids. Isotope ratio measurements were achieved by gas chromatography/mass spectrometry (GC/MS) analyses after the amino acids were released by acidic hydrolysis and converted to volatile derivatives with propyl chloroformate. The isotope enrichment data showed the stable free radicals were located on Ala, Gly, Leu, Ile, Asx (Asp+Asn), Glx (Glu+Gln), and Trp but not on Val, Pro, Met, Phe, Lys, and His. Due to the low abundance of Ser, Thr, and Cys derivatives and the impossibility to accurately measure their isotope ratios, the radical bearing status for these amino acids remained undetermined even though their derivatives were positively identified from ISP hydrolysates. The relative isotope enrichment for radical-bearing amino acids Ala, Gly, Leu, Ile, Asx (Asp+Asn), Glx (Glu+Gln), and Trp were 8.67%, 2.96%, 2.90%, 3.94%, 6.03%, 3.91%, and 21.48%, respectively. Isotope ratio increase for Tyr was also observed but further investigation revealed such increase was mainly from nonspecific deuterium-hydrogen exchange not free radical quenching. The results obtained from the present study provide important information for a better understanding of the mechanisms of free radical formation and stabilization in "dry" ISP.

  16. Electron spin resonance study on γ-ray-induced radical species in ethylene hydrate

    International Nuclear Information System (INIS)

    Takeya, Kei; Sugahara, Takeshi; Ohgaki, Kazunari; Tani, Atsushi

    2007-01-01

    Electron spin resonance (ESR) study on γ-irradiated synthetic ethylene hydrate was performed to investigate induced radicals and their thermal stability. ESR spectra of induced 3-butenyl radical (.CH 2 C 2 H 3 =CH 2 ,g=2.0039±0.0005,A α =2.2±0.1mTandA β =3.0±0.1mT) and induced ethyl radical (.C 2 H 5 , g=2.0044±0.0005, A α =2.2±0.1mT and A β =2.7±0.1mT) were observed in irradiated ethylene hydrate. The decay of the 3-butenyl radicals was observed above 200 K with the activation energy of 51.9±4.4kJ/mol. The obvious decay of ethyl radicals starts above 240 K that is close to the dissociation temperature of ethylene hydrate at atmospheric pressure. The activation energy of the ethyl radical decay is estimated as 63.4±8.2kJ/mol and nearly equal to the enthalpy change of ethylene hydrate into liquid water and gaseous ethylene. It is suggested that the decay of ethyl radicals would be caused by the hydrate dissociation and that ethylene hydrate dissociates into water (supercooled) and ethylene at 240-265 K.

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

    Science.gov (United States)

    Dugas, Michelle; Kruglanski, Arie W

    2014-01-01

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

  18. Tempo: A Toolkit for the Timed Input/Output Automata Formalism

    National Research Council Canada - National Science Library

    Lynch, Nancy A; Shvartsman, Alex Allister

    2008-01-01

    Report developed under STTR contract for topic AFO4-T023. This Phase II project developed an integrated development environment, called Tempo, for specifying, analyzing, and verifying complex distributed system designs...

  19. Pengembangan alat tempo trainer untuk membantu efisiensi gerakan lengan gaya bebas cabang olahraga renang

    Directory of Open Access Journals (Sweden)

    Bahtiyar Heru Susanto

    2017-09-01

    This research aimed to develop the tools of Tempo Trainer to help efficiency of arm freestyle movement on the branch of swimming. Small-scale trials were conducted on four coaches and 10 athletes in the swimming association Tirta Alvita and Yuso. Large-scale trial was conducted on 10 coaches and 25 athletes in the swimming association Tirta Alvita, Yuso, Dolphin, Caesar, and Arowana. The instrument used to collect data was a questionnaire based on the analysis PIECES (Performance, Information, Economic, Control, Efficiency, Services. The assessment result of experts, coaches, and athletes toward Tempo Trainer tool shows that the assessment categoryis good, valid and reliable. Based of the resultsthat Tempo Trainer tool developed can count the number of cycles of freestyle movement, a sound that can be heard by coaches and athletes, can be used for more than one athlete, as well as it is more affordable. The coaches assessment shows valid results with every indicator PIECES obtain value rxy > r table = 0.632, with reliable results rxy = 0.908. The assessment of Tempo Trainer draft tool by athletes is good and valid with the result of the rxy > r table = 0.750.

  20. Diálogos acerca da concepção de tempo homogêneo e heterogêneo em Einstein e Bergson

    Directory of Open Access Journals (Sweden)

    Lara Emanuele da Luz

    2017-03-01

    Full Text Available O problema sobre o tempo é um tema complexo e bastante estudado tanto no âmbito científico como na tradição filosófica. Henri Bergson, utilizando-se do tempo proposto por Albert Einstein, traça diferenças entre o tempo heterogêneo, ou cronológico, e o tempo homogêneo, ou durée, sendo este segundo, o menos estudado pelo físico. Foi a partir da duração que o filósofo propõe-se a mostrar como se dá a concepção do tempo durée e como esta forma responde a um questionamento einsteiniano. O presente artigo pretende estabelecer um diálogo entre a concepção de tempo de ambos autores, ressaltando a novidade da duração bergsoniana.

  1. Quality management of cut carnation 'Tempo' with 1- MCP

    African Journals Online (AJOL)

    STORAGESEVER

    2009-10-19

    Oct 19, 2009 ... carnation 'Tempo' which is an ethylene-sensitive flower, were evaluated. The effects of 1-MCP .... rolling of the petals. Water uptake rate (ml g-1 .... The studies of Chamani (2006) on Rosa 'First red' cut flowers revealed that ...

  2. Synchronization to metrical levels in music depends on low-frequency spectral components and tempo.

    Science.gov (United States)

    Burger, Birgitta; London, Justin; Thompson, Marc R; Toiviainen, Petri

    2017-07-15

    Previous studies have found relationships between music-induced movement and musical characteristics on more general levels, such as tempo or pulse clarity. This study focused on synchronization abilities to music of finely-varying tempi and varying degrees of low-frequency spectral change/flux. Excerpts from six classic Motown/R&B songs at three different tempos (105, 115, and 130 BPM) were used as stimuli in this experiment. Each was then time-stretched by a factor of 5% with regard to the original tempo, yielding a total of 12 stimuli that were presented to 30 participants. Participants were asked to move along with the stimuli while being recorded with an optical motion capture system. Synchronization analysis was performed relative to the beat and the bar level of the music and four body parts. Results suggest that participants synchronized different body parts to specific metrical levels; in particular, vertical movements of hip and feet were synchronized to the beat level when the music contained large amounts of low-frequency spectral flux and had a slower tempo, while synchronization of head and hands was more tightly coupled to the weak flux stimuli at the bar level. Synchronization was generally more tightly coupled to the slower versions of the same stimuli, while synchronization showed an inverted u-shape effect at the bar level as tempo increased. These results indicate complex relationships between musical characteristics, in particular regarding metrical and temporal structure, and our ability to synchronize and entrain to such musical stimuli.

  3. catalysed selective oxidation of benzyl alcohols using TEMPO

    Indian Academy of Sciences (India)

    oxygen provides excellent results in terms of yields and reaction time. SiO2-Cu(II) was very ... lytic systems using transition metal complexes and ter- minal oxidants are well ... dry toluene, TEMPO (0.5 mmol), potassium carbonate. (1.5 mmol) and ... The conditioning of the catalyst was done in water, ethanol and toluene to.

  4. Experiência subjetiva do tempo e sua influência no comportamento: revisão e modelos

    Directory of Open Access Journals (Sweden)

    Alejandro Vásquez Echeverría

    Full Text Available Pesquisadores têm tentado explicar, desde o início da psicologia, a experiência temporal das pessoas e sua influência nas cognições, emoções e comportamentos. Trata-se de uma das dimensões mais complexas e influentes da psique, que tem sido abordada a partir de concepções diferentes e sem uma estrutura consensual. Este artigo tem o objetivo de contribuir na sistematização da psicologia do tempo, ampliando um modelo de quatro níveis, aprofundando na percepção do tempo vital ou tempo III. Trabalhos incluídos foram selecionados segundo a sua importância na historia da psicologia ou índice de citação. Sugere-se um modelo explicativo do Tempo III, que inclui discussão e debate e visa integrar os diferentes modelos existentes na literatura.

  5. Manipulating radicals: Using cobalt to steer radical reactions

    OpenAIRE

    Chirilă, A.

    2017-01-01

    This thesis describes research aimed at understanding and exploiting metallo-radical reactivity and explores reactions mediated by square planar, low-spin cobalt(II) complexes. A primary goal was to uncover novel reactivity of discrete cobalt(III)-bound carbene radicals generated upon reaction of the cobalt(II) catalysts with carbene precursors. Another important goal was to replace cobalt(II)-porphyrin catalysts with cheaper and easier to prepare metallo-radical analogues. Therefore the cata...

  6. Revisiting the electrochemical formation, stability and structure of radical and biradical anionic structures in dinitrobenzenes

    International Nuclear Information System (INIS)

    Hernandez-Munoz, Lindsay S.; Gonzalez, Felipe J.; Gonzalez, Ignacio; Goulart, Marilia O.F.; Abreu, Fabiane Caxico de; Ribeiro, Adriana Santos; Ribeiro, Rogerio Tavares; Longo, Ricardo L.; Navarro, Marcelo; Frontana, Carlos

    2010-01-01

    The effects of the position of a second nitroaromatic group (orthovs.paravs.meta) during reduction of nitrobenzenes were analysed. Cyclic voltammetric experiments in acetonitrile solution revealed that ortho-, meta- and para-dinitrobenzenes show two reversible reduction processes. An Electrochemical-Electron Spin Resonance (E-ESR) study showed that the corresponding radical anions of the ortho and para derivatives, electrogenerated during the first electron transfer uptake, remain the same even after the second monoelectronic process, increasing their intensity due to the presence of a comproportionation process (A 2- + A → 2A· - ). For the case of the meta derivative, the electrogenerated radical anion at the first reduction peak is consumed at the second reduction step, forming a secondary radical species. During the electrochemical study of methyl 3,5-dinitrobenzoate, two successive and reversible electron processes were also observed; however, in this case, a very rare biradical dianion structure was found. The use of ESR-spectroelectrochemistry shed some light on controversial aspects of nitroaromatic reduction, especially concerning the second and further waves. These results were corroborated and interpreted with quantum chemical calculations of the molecular and electronic structures, electron affinities and spin densities. As a result, electrochemical mechanisms are presented and discussed.

  7. Free radical inactivation of trypsin

    International Nuclear Information System (INIS)

    Cudina, Ivana; Jovanovic, S.V.

    1988-01-01

    Reactivities of free radical oxidants, radical OH, Br2-anion radical and Cl 3 COO radical and a reductant, CO2-anion radical, with trypsin and reactive protein components were determined by pulse radiolysis of aqueous solutions at pH 7, 20 0 C. Highly reactive free radicals, radical OH, Br2-anion radical and CO2-anion radical, react with trypsin at diffusion controlled rates. Moderately reactive trichloroperoxy radical, k(Cl 3 COO radical + trypsin) preferentially oxidizes histidine residues. The efficiency of inactivation of trypsin by free radicals is inversely proportional to their reactivity. The yields of inactivation of trypsin by radical OH, Br2-anion radical and CO2-anion radical are low, G(inactivation) = 0.6-0.8, which corresponds to ∼ 10% of the initially produced radicals. In contrast, Cl 3 COO radical inactivates trypsin with ∼ 50% efficiency, i.e. G(inactivation) = 3.2. (author)

  8. Quantifying auditory temporal stability in a large database of recorded music.

    Science.gov (United States)

    Ellis, Robert J; Duan, Zhiyan; Wang, Ye

    2014-01-01

    "Moving to the beat" is both one of the most basic and one of the most profound means by which humans (and a few other species) interact with music. Computer algorithms that detect the precise temporal location of beats (i.e., pulses of musical "energy") in recorded music have important practical applications, such as the creation of playlists with a particular tempo for rehabilitation (e.g., rhythmic gait training), exercise (e.g., jogging), or entertainment (e.g., continuous dance mixes). Although several such algorithms return simple point estimates of an audio file's temporal structure (e.g., "average tempo", "time signature"), none has sought to quantify the temporal stability of a series of detected beats. Such a method--a "Balanced Evaluation of Auditory Temporal Stability" (BEATS)--is proposed here, and is illustrated using the Million Song Dataset (a collection of audio features and music metadata for nearly one million audio files). A publically accessible web interface is also presented, which combines the thresholdable statistics of BEATS with queryable metadata terms, fostering potential avenues of research and facilitating the creation of highly personalized music playlists for clinical or recreational applications.

  9. Revealing spatio-spectral electroencephalographic dynamics of musical mode and tempo perception by independent component analysis.

    Science.gov (United States)

    Lin, Yuan-Pin; Duann, Jeng-Ren; Feng, Wenfeng; Chen, Jyh-Horng; Jung, Tzyy-Ping

    2014-02-28

    Music conveys emotion by manipulating musical structures, particularly musical mode- and tempo-impact. The neural correlates of musical mode and tempo perception revealed by electroencephalography (EEG) have not been adequately addressed in the literature. This study used independent component analysis (ICA) to systematically assess spatio-spectral EEG dynamics associated with the changes of musical mode and tempo. Empirical results showed that music with major mode augmented delta-band activity over the right sensorimotor cortex, suppressed theta activity over the superior parietal cortex, and moderately suppressed beta activity over the medial frontal cortex, compared to minor-mode music, whereas fast-tempo music engaged significant alpha suppression over the right sensorimotor cortex. The resultant EEG brain sources were comparable with previous studies obtained by other neuroimaging modalities, such as functional magnetic resonance imaging (fMRI) and positron emission tomography (PET). In conjunction with advanced dry and mobile EEG technology, the EEG results might facilitate the translation from laboratory-oriented research to real-life applications for music therapy, training and entertainment in naturalistic environments.

  10. Tempo and walking speed with music in the urban context.

    Science.gov (United States)

    Franěk, Marek; van Noorden, Leon; Režný, Lukáš

    2014-01-01

    The study explored the effect of music on the temporal aspects of walking behavior in a real outdoor urban setting. First, spontaneous synchronization between the beat of the music and step tempo was explored. The effect of motivational and non-motivational music (Karageorghis et al., 1999) on the walking speed was also studied. Finally, we investigated whether music can mask the effects of visual aspects of the walking route environment, which involve fluctuation of walking speed as a response to particular environmental settings. In two experiments, we asked participants to walk around an urban route that was 1.8 km in length through various environments in the downtown area of Hradec Králové. In Experiment 1, the participants listened to a musical track consisting of world pop music with a clear beat. In Experiment 2, participants were walking either with motivational music, which had a fast tempo and a strong rhythm, or with non-motivational music, which was slower, nice music, but with no strong implication to movement. Musical beat, as well as the sonic character of the music listened to while walking, influenced walking speed but did not lead to precise synchronization. It was found that many subjects did not spontaneously synchronize with the beat of the music at all, and some subjects synchronized only part of the time. The fast, energetic music increases the speed of the walking tempo, while slower, relaxing music makes the walking tempo slower. Further, it was found that listening to music with headphones while walking can mask the influence of the surrounding environment to some extent. Both motivational music and non-motivational music had a larger effect than the world pop music from Experiment 1. Individual differences in responses to the music listened to while walking that were linked to extraversion and neuroticism were also observed. The findings described here could be useful in rhythmic stimulation for enhancing or recovering the features of

  11. Tempo and walking speed with music in the urban context

    Directory of Open Access Journals (Sweden)

    Marek eFranek

    2014-12-01

    Full Text Available The study explored the effect of music on the temporal aspects of walking behavior in a real outdoor urban setting. First, spontaneous synchronization between the beat of the music and step tempo was explored. The effect of motivational and non-motivational music (Karageorghis et al. 1999 on the walking speed was also studied. Finally, we investigated whether music can mask the effects of visual aspects of the walking route environment, which involve fluctuation of walking speed as a response to particular environmental settings. In two experiments, we asked participants to walk around an urban route through various environments in the downtown area of Hradec Králové. In Experiment 1, the participants listened to a musical track consisting of world pop music with a clear beat. In Experiment 2, participants were walking either with motivational music, which had a fast tempo and a strong rhythm, or with non-motivational music, which was slower, nice music, but with no strong implication to movement. Musical beat, as well as the sonic character of the music listened to while walking, influenced walking speed but did not lead to precise synchronization. It was found that many subjects did not spontaneously synchronize with the beat of the music at all, and some subjects synchronized only part of the time. The fast, energetic music increases the speed of the walking tempo, while slower, relaxing music makes the walking tempo slower. Further, it was found that listening to music with headphones while walking can mask the influence of the surrounding environment to some extent. Both motivational music and non-motivational music had a larger effect than the music from Experiment 1. Individual differences in responses to the music listened to while walking that were linked to extraversion and neuroticism were also observed. The findings described here could be useful in rhythmic stimulation for enhancing or recovering the features of movement

  12. Tempo and walking speed with music in the urban context

    Science.gov (United States)

    Franěk, Marek; van Noorden, Leon; Režný, Lukáš

    2014-01-01

    The study explored the effect of music on the temporal aspects of walking behavior in a real outdoor urban setting. First, spontaneous synchronization between the beat of the music and step tempo was explored. The effect of motivational and non-motivational music (Karageorghis et al., 1999) on the walking speed was also studied. Finally, we investigated whether music can mask the effects of visual aspects of the walking route environment, which involve fluctuation of walking speed as a response to particular environmental settings. In two experiments, we asked participants to walk around an urban route that was 1.8 km in length through various environments in the downtown area of Hradec Králové. In Experiment 1, the participants listened to a musical track consisting of world pop music with a clear beat. In Experiment 2, participants were walking either with motivational music, which had a fast tempo and a strong rhythm, or with non-motivational music, which was slower, nice music, but with no strong implication to movement. Musical beat, as well as the sonic character of the music listened to while walking, influenced walking speed but did not lead to precise synchronization. It was found that many subjects did not spontaneously synchronize with the beat of the music at all, and some subjects synchronized only part of the time. The fast, energetic music increases the speed of the walking tempo, while slower, relaxing music makes the walking tempo slower. Further, it was found that listening to music with headphones while walking can mask the influence of the surrounding environment to some extent. Both motivational music and non-motivational music had a larger effect than the world pop music from Experiment 1. Individual differences in responses to the music listened to while walking that were linked to extraversion and neuroticism were also observed. The findings described here could be useful in rhythmic stimulation for enhancing or recovering the features of

  13. Emotional and psychophysiological responses to tempo, mode, and percussiveness

    NARCIS (Netherlands)

    van der Zwaag, Marjolein; Westerink, Joyce H.D.M.; van den Broek, Egon

    People often listen to music to influence their emotional state. However, the specific musical characteristics which cause this process are not yet fully understood. We have investigated the influence of the musical characteristics of tempo, mode and percussiveness on our emotions. In a quest

  14. Involvement of oxygen free radicals in the respiratory uncoupling induced by free calcium and ADP-magnesium in isolated cardiac mitochondria: comparing reoxygenation in cultured cardiomyocytes.

    Science.gov (United States)

    Meynier, Alexandra; Razik, Hafida; Cordelet, Catherine; Grégoire, Stéphane; Demaison, Luc

    2003-01-01

    Recently, we have observed that the simultaneous application of free calcium (fCa) and ADP-magnesium (Mg) reduced the ADP:O ratio in isolated cardiac mitochondria. The uncoupling was prevented by cyclosporin A, an inhibitor of the permeability transition pore. The purpose of this study was to know if the generation of oxygen free radicals (OFR) is involved in this phenomenon and if it occurs during reoxygenation (Reox) of cultured cardiomyocytes. Cardiac mitochondria were harvested from male Wistar rats. Respiration was assessed in two media with different fCa concentrations (0 or 0.6 microM) with palmitoylcarnitine and ADP-Mg as respiration substrates. The production of Krebs cycle intermediates (KCI) was determined. Without fCa in the medium, the mitochondria displayed a large production of citrate + isocitrate + alpha-ketoglutarate. fCa drastically reduced these KCI and promoted the accumulation of succinate. To know if OFR are involved in the respiratory uncoupling, the effect of 4OH-TEMPO (250 microM), a hydrosoluble scavenger of OFR, was tested. 4OH-TEMPO completely abolished the fCa- and ADP-Mg-induced uncoupling. Conversely, vitamin E contributed to further decreasing the ADP:O ratio. Since no hydrosoluble electron acceptor was added in our experiment, the oxygen free radical-induced oxidized vitamin E was confined near the mitochondrial membranes, which should reduce the ADP:O ratio by opening the permeability transition pore. The generation of OFR could result from the matrix accumulation of succinate. Taken together, these results indicate that mitochondrial Ca uptake induces a slight increase in membrane permeability. Thereafter, Mg enters the matrix and, in combination with Ca, stimulates the isocitrate and/or alpha-ketoglutarate dehydrogenases. Matrix succinate favors oxygen free radical generation that further increases membrane permeability and allows respiratory uncoupling through proton leakage. To determine whether the phenomenon takes place

  15. Os Usos do Tempo Livre entre Jovens de Classes Populares

    Directory of Open Access Journals (Sweden)

    Manoela Pagotto Martins Nodari

    Full Text Available RESUMO O presente estudo, de caráter quantitativo, pretendeu investigar aspectos relacionados ao tempo livre de jovens de classes populares. Participaram da pesquisa 291 jovens (53,3% meninas, de 15 a 19 anos (M = 16,3; DP = 1,09, estudantes de ensino médio em escolas públicas da Grande Vitória, ES. Os dados foram coletados através de questionário e analisados através do software SPSS. Os resultados apontaram, principalmente, para os diferentes fatores envolvidos nas formas de apropriação do tempo livre entre esses jovens, não relacionados estritamente à renda, mas também a aspectos como gênero, meio em que vivem, estilos de vida e grupos de que participam.

  16. Does Listening to Slow Tempo Classical Music During Independent Writing Affect Children's On-Task Performance?

    Science.gov (United States)

    McKnight, Rosemary

    This project explored the effects of slow tempo classical music on children's on-task performance during independent writing. The project sample consisted of 24 students from a first grade classroom in the New York City Public School System. The students' on-task behavior was observed with and without use of slow tempo classical music playing, and…

  17. Individual differences in boys' and girls' timing and tempo of puberty: modeling development with nonlinear growth models.

    Science.gov (United States)

    Marceau, Kristine; Ram, Nilam; Houts, Renate M; Grimm, Kevin J; Susman, Elizabeth J

    2011-09-01

    Pubertal development is a nonlinear process progressing from prepubescent beginnings through biological, physical, and psychological changes to full sexual maturity. To tether theoretical concepts of puberty with sophisticated longitudinal, analytical models capable of articulating pubertal development more accurately, we used nonlinear mixed-effects models to describe both the timing and tempo of pubertal development in the sample of 364 White boys and 373 White girls measured across 6 years as part of the National Institute of Child Health and Human Development Study of Early Child Care and Youth Development. Individual differences in timing and tempo were extracted with models of logistic growth. Differential relations emerged for how boys' and girls' timing and tempo of development were related to physical characteristics (body mass index, height, and weight) and psychological outcomes (internalizing problems, externalizing problems, and risky sexual behavior). Timing and tempo are associated in boys but not girls. Pubertal timing and tempo are particularly important for predicting psychological outcomes in girls but only sparsely related to boys' psychological outcomes. Results highlight the importance of considering the nonlinear nature of puberty and expand the repertoire of possibilities for examining important aspects of how and when pubertal processes contribute to development.

  18. Effects of Modeling and Tempo Patterns as Practice Techniques on the Performance of High School Instrumentalists.

    Science.gov (United States)

    Henley, Paul T.

    2001-01-01

    Examines the effect of modeling conditions and tempo patterns on high school instrumentalists' performance. Focuses on high school students (n=60) who play wind instruments. Reports that the with-model condition was superior in rhythm and tempo percentage gain when compared to the no-model condition. Includes references. (CMK)

  19. Predictive and tempo-flexible synchronization to a visual metronome in monkeys.

    Science.gov (United States)

    Takeya, Ryuji; Kameda, Masashi; Patel, Aniruddh D; Tanaka, Masaki

    2017-07-21

    Predictive and tempo-flexible synchronization to an auditory beat is a fundamental component of human music. To date, only certain vocal learning species show this behaviour spontaneously. Prior research training macaques (vocal non-learners) to tap to an auditory or visual metronome found their movements to be largely reactive, not predictive. Does this reflect the lack of capacity for predictive synchronization in monkeys, or lack of motivation to exhibit this behaviour? To discriminate these possibilities, we trained monkeys to make synchronized eye movements to a visual metronome. We found that monkeys could generate predictive saccades synchronized to periodic visual stimuli when an immediate reward was given for every predictive movement. This behaviour generalized to novel tempi, and the monkeys could maintain the tempo internally. Furthermore, monkeys could flexibly switch from predictive to reactive saccades when a reward was given for each reactive response. In contrast, when humans were asked to make a sequence of reactive saccades to a visual metronome, they often unintentionally generated predictive movements. These results suggest that even vocal non-learners may have the capacity for predictive and tempo-flexible synchronization to a beat, but that only certain vocal learning species are intrinsically motivated to do it.

  20. Manipulating Greek musical modes and tempo affects perceived musical emotion in musicians and nonmusicians

    Directory of Open Access Journals (Sweden)

    D. Ramos

    2011-02-01

    Full Text Available The combined influence of tempo and mode on emotional responses to music was studied by crossing 7 changes in mode with 3 changes in tempo. Twenty-four musicians aged 19 to 25 years (12 males and 12 females and 24 nonmusicians aged 17 to 25 years (12 males and 12 females were required to perform two tasks: 1 listening to different musical excerpts, and 2 associating an emotion to them such as happiness, serenity, fear, anger, or sadness. ANOVA showed that increasing the tempo strongly affected the arousal (F(2,116 = 268.62, mean square error (MSE = 0.6676, P < 0.001 and, to a lesser extent, the valence of emotional responses (F(6,348 = 8.71, MSE = 0.6196, P < 0.001. Changes in modes modulated the affective valence of the perceived emotions (F(6,348 = 4.24, MSE = 0.6764, P < 0.001. Some interactive effects were found between tempo and mode (F (1,58 = 115.6, MSE = 0.6428, P < 0.001, but, in most cases, the two parameters had additive effects. This finding demonstrates that small changes in the pitch structures of modes modulate the emotions associated with the pieces, confirming the cognitive foundation of emotional responses to music.

  1. Ion pairing of radical ions of aromatic alkenes and alkynes studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Yamamoto, Satoshi; Yamamoto, Yukio; Hayashi, Koichiro

    1991-01-01

    Pulse radiolysis of 1,2-dichloroethane solutions of trans,trans-1,4-bis(2-phenylethenyl)benzene and 1,4-bis(2-phenylethynyl)benzene was undertaken in the presence of Bu 4 NPF 6 (Bu=butyl) to investigate the effect of ion pairing of the solute radical cations with PF 6 - . It was also undertaken for the tetrahydrofuran solutions of the above compounds in the presence of Bu 4 NPF 6 and NaBPh 4 , where the solute radical anions are generated and form ion pairs with Bu 4 N + and Na + . The decay of the radical ions, which is due to neutralization, is retarded by the ion pairing. The rate constants for the neutralization reactions in the free-ion and ion-paired states were determined. Also presented are the data for the radical ions of trans-stilbene, diphenylacetylene, trans,trans-1,4-diphenyl-1,3-butadiene, and diphenylbutadiene. The radical ions of the aromatic alkynes are less stabilized by the ion pairing than those of the aromatic alkenes having the same carbon skeletons probably because of more extensive charge delocalization of the former radical ions. Spectral shifts to shorter wavelengths caused by the ion pairing are appreciable for the radical anions. Dependence of the spectral shifts on the size of the radical anions is described. (author)

  2. Effects of Tempo and Performing Medium on Children's Music Preference.

    Science.gov (United States)

    LeBlanc, Albert; Cote, Richard

    1983-01-01

    This study measured the effect of three levels of tempo and two levels of performing medium, vocal and instrumental, on the expressed preference of fifth- and sixth-grade students for traditional jazz music listening examples. (Author/SR)

  3. Conversion of alkyl radicals to allyl radicals in irradiated single crystal mats of polyethylene

    International Nuclear Information System (INIS)

    Fujimura, T.; Hayakawa, N.; Kuriyama, I.

    1978-01-01

    The decay of alkyl radicals, the conversion of alkyl radicals to allyl radicals and the trapping of allyl radicals in irradiated single crystal mats of polyethylene have been studied by electron spin resonance (e.s.r.). It has been suggested that in the crystal core alkyl radicals react with trans-vinylene double bonds and are converted into trans-vinylene allyl radicals; at the crystal surface, alkyl radicals react with vinyl end groups and are converted into allyl radicals with vinyl end groups. The decay of radical pairs and the formation of trans-vinylene double bonds are discussed. (author)

  4. Effects of tempo and timing of simple musical rhythms

    NARCIS (Netherlands)

    Repp, B.H.; Windsor, W.L.; Desain, P.W.M.

    2002-01-01

    In this study we investigated whether and how the timing of musical rhythms changes with tempo. Twelve skilled pianists played a monophonic 8-bar melody in 21 different rhythmic versions at 4 different tempi. Within bars, the rhythms represented all possible ordered pairs and triplets of note values

  5. Revisiting the electrochemical formation, stability and structure of radical and biradical anionic structures in dinitrobenzenes

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez-Munoz, Lindsay S.; Gonzalez, Felipe J. [Departamento de Quimica, Centro de Investigacion y Estudios Avanzados, Av. I.P.N. 2508. Col. San Pedro Zacatenco, 07360, D.F. (Mexico); Gonzalez, Ignacio [Departamento de Quimica, Universidad Autonoma Metropolitana-Iztapalapa, Area de Electroquimica, Apartado Postal 55-534, 09340, D.F. (Mexico); Goulart, Marilia O.F.; Abreu, Fabiane Caxico de; Ribeiro, Adriana Santos [Instituto de Quimica e Biotecnologia, Universidade Federal de Alagoas, Tabuleiro do Martins, Maceio, AL, 57072-970 (Brazil); Ribeiro, Rogerio Tavares; Longo, Ricardo L. [Departamento de Quimica Fundamental, Universidade Federal de Pernambuco, Av. Prof. Luiz Freire, s/n, Cid. Universitaria, Recife, PE, 50740-540 (Brazil); Navarro, Marcelo, E-mail: navarro@ufpe.b [Departamento de Quimica Fundamental, Universidade Federal de Pernambuco, Av. Prof. Luiz Freire, s/n, Cid. Universitaria, Recife, PE, 50740-540 (Brazil); Frontana, Carlos, E-mail: ultrabuho@yahoo.com.m [Departamento de Quimica, Centro de Investigacion y Estudios Avanzados, Av. I.P.N. 2508. Col. San Pedro Zacatenco, 07360, D.F. (Mexico)

    2010-11-30

    The effects of the position of a second nitroaromatic group (orthovs.paravs.meta) during reduction of nitrobenzenes were analysed. Cyclic voltammetric experiments in acetonitrile solution revealed that ortho-, meta- and para-dinitrobenzenes show two reversible reduction processes. An Electrochemical-Electron Spin Resonance (E-ESR) study showed that the corresponding radical anions of the ortho and para derivatives, electrogenerated during the first electron transfer uptake, remain the same even after the second monoelectronic process, increasing their intensity due to the presence of a comproportionation process (A{sup 2-} + A {yields} 2A{center_dot}{sup -}). For the case of the meta derivative, the electrogenerated radical anion at the first reduction peak is consumed at the second reduction step, forming a secondary radical species. During the electrochemical study of methyl 3,5-dinitrobenzoate, two successive and reversible electron processes were also observed; however, in this case, a very rare biradical dianion structure was found. The use of ESR-spectroelectrochemistry shed some light on controversial aspects of nitroaromatic reduction, especially concerning the second and further waves. These results were corroborated and interpreted with quantum chemical calculations of the molecular and electronic structures, electron affinities and spin densities. As a result, electrochemical mechanisms are presented and discussed.

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

    Directory of Open Access Journals (Sweden)

    Donatella Della Porta

    2012-05-01

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

  7. Metal-catalyzed living radical polymerization and radical polyaddition for precision polymer synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, M; Satoh, K [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kamigaito, M, E-mail: kamigait@apchem.nagoya-u.ac.j

    2009-08-01

    The metal-catalyzed radical addition reaction can be evolved into two different polymerization mechanisms, i.e.; chain- and step-growth polymerizations, while both the polymerizations are based on the same metal-catalyzed radical formation reaction. The former is a widely employed metal-catalyzed living radical polymerization or atom transfer radical polymerization of common vinyl monomers, and the latter is a novel metal-catalyzed radical polyaddition of designed monomer with an unconjugated C=C double bond and a reactive C-Cl bond in one molecule. The simultaneous ruthenium-catalyzed living radical polymerization of methyl acrylate and radical polyaddition of 3-butenyl 2-chloropropionate was achieved with Ru(Cp*)Cl(PPh{sub 3}){sub 2} to afford the controlled polymers, in which the homopolymer segments with the controlled chain length were connected by the ester linkage.

  8. Oxidation of cashew tree gum exudate polysaccharide with TEMPO reagent

    International Nuclear Information System (INIS)

    Cunha, Pablyana L.R.; Maciel, Jeanny S.; Paula, Regina C.M. de; Feitosa, Judith P.A.; Sierakowski, Maria Rita

    2007-01-01

    Cashew gum (CG), an exudate polysaccharide from Anacardium occidentale trees, was oxidized with TEMPO reagent and the product (CGOX) characterized by spectroscopic techniques (FTIR and NMR), chromatographic analyses (HPLC and GPC), viscosity measurements and thermal analysis (TGA). The yield of the reaction product was 96%. The uronic acid content in starting gum (7.2 m%) was increased to 36 m%. The degree of oxidation based on free galactose and glucose units was 68%. NMR data show that oxidation occurred preferentially at primary carbons of galactose units. High degradation degree after oxidation was estimated by the difference on the expected and observed η CGOX /η CG ratio. The presence of organic and inorganic impurities in the new polyelectrolyte was detected by TGA. A less thermally stable cashew gum is formed after the oxidation with TEMPO based on initial decomposition temperature and IPDT. (author)

  9. Conscientiousness and Extraversion relate to responsiveness to tempo in dance.

    Science.gov (United States)

    Carlson, Emily; Burger, Birgitta; London, Justin; Thompson, Marc R; Toiviainen, Petri

    2016-10-01

    Previous research has shown broad relationships between personality and dance, but the relationship between personality and specific structural features of music has not been explored. The current study explores the influence of personality and trait empathy on dancers' responsiveness to small tempo differences between otherwise musically identical stimuli, measured by difference in the amount in acceleration of key joints. Thirty participants were recorded using motion capture while dancing to excerpts from six popular songs that were time-stretched to be slightly faster or slower than their original tempi. Analysis revealed that higher conscientiousness and lower extraversion both correlated with greater responsiveness to tempo change. Partial correlation analysis revealed that conscientiousness remained significantly correlated with responsiveness when extraversion was controlled, but not vice versa. No effect of empathy was found. Implications are discussed. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Effect of Music Tempo on Attentional Focus and Perceived Exertion during Self-selected Paced Walking.

    Science.gov (United States)

    Silva, Aldo Coelho; Dos Santos Ferreira, Sandro; Alves, Ragami Chaves; Follador, Lucio; DA Silva, Sergio Gregorio

    2016-01-01

    This study investigated the influence of music on the rating of perceived exertion (RPE) and attentional focus during walking at a self-selected pace. Fifteen overweight and obese women volunteered to participate in the study. They underwent four sessions: the first for incremental maximal test and anthropometric measurement followed by three experimental sessions. After the first session, they were exposed to three 30-minute walking sessions at a self-selected pace in a counterbalanced order: fast-tempo music (FT), medium-tempo music (MT) and no-music control (NM). Borg's RPE Scale and an Attentional Focus Questionnaire were used to measure the perceptual response and attentional focus, respectively. Results showed that the RPE was higher in the no-music control than in the medium-tempo music (12.05 ± 0.6 vs. 10.5 ± 0.5). Furthermore, dissociative attentional focus was greater for both conditions with music in comparison with the no-music control (NM= 39.0 ± 4.1; MT= 48.4 ± 4.1 and FT= 47.9 ± 4.5). The results indicated that the use of music during walking can modulate attentional focus, increasing dissociative thought, and medium-tempo music can reduce the RPE.

  11. Radical Surgery of Only the Anterior Elements of the Spine at the Posterior Element Fusion Level due to Metastatic Thyroid Cancer

    Directory of Open Access Journals (Sweden)

    Ryuto Tsuchiya

    2017-01-01

    Full Text Available Spinal metastasis of differentiated thyroid cancer can have a favorable prognosis if radical surgery is performed. We encountered a case of spinal metastasis involving three anterior vertebral bodies at the posterior element fusion level and successfully achieved adequate stability by radical surgery involving only the anterior elements. A 67-year-old woman who had numbness and muscle weakness in the lower limbs caused by metastatic spinal tumor at the posterior element fusion level of L1–L3 vertebrae was treated with radical surgery of only the anterior element to gain stability. Similar situations may occur in cases involving other malignant tumor metastases or spinal primary tumors. If such a case occurs, this method could be useful in preventing metastasis to the posterior element.

  12. Gli incerti confini del cosmo dai buchi neri alle macchine del tempo

    CERN Document Server

    De Felice, Fernando

    2000-01-01

    Il libro mostra come la gravitazione abbia un ruolo determinante nei fenomeni cosmici che più ci impressionano, da quelli relativamente vicini alla nostra esperienza (come la formazione delle stelle) a quelli meno intuibili (come la formazione dei buchi neri), alla struttura dell'Universo nel suo insieme. Oltre a spiegare, in modo qualitativo, concetti come la geometria dello spazio-tempo, la relatività del tempo e i coni di luce, l'autore formula un'ipotesi innovativa tendente a spiegare l'origine della gravitazione e con essa quella dei fenomeni circondati ancora da un alone di mistero: la materia oscura dell'Universo e il destino della materia alla fine del collasso gravitazionale.

  13. Polymer-Based Black Phosphorus (bP) Hybrid Materials by in Situ Radical Polymerization: An Effective Tool To Exfoliate bP and Stabilize bP Nanoflakes

    Science.gov (United States)

    2018-01-01

    Black phosphorus (bP) has been recently investigated for next generation nanoelectronic multifunctional devices. However, the intrinsic instability of exfoliated bP (the bP nanoflakes) toward both moisture and air has so far overshadowed its practical implementation. In order to contribute to fill this gap, we report here the preparation of new hybrid polymer-based materials where bP nanoflakes (bPn) exhibit a significantly improved stability. The new materials have been prepared by different synthetic paths including: (i) the mixing of conventionally liquid-phase exfoliated bP (in dimethyl sulfoxide, DMSO) with poly(methyl methacrylate) (PMMA) solution; (ii) the direct exfoliation of bP in a polymeric solution; (iii) the in situ radical polymerization after exfoliating bP in the liquid monomer (methyl methacrylate, MMA). This last methodology concerns the preparation of stable suspensions of bPn–MMA by sonication-assisted liquid-phase exfoliation (LPE) of bP in the presence of MMA followed by radical polymerization. The hybrids characteristics have been compared in order to evaluate the bP dispersion and the effectiveness of the bPn interfacial interactions with polymer chains aimed at their long-term environmental stabilization. The passivation of the bPn is particularly effective when the hybrid material is prepared by in situ polymerization. By using this synthetic methodology, the nanoflakes, even if with a gradient of dispersion (size of aggregates), preserve their chemical structure from oxidation (as proved by both Raman and 31P-solid state NMR studies) and are particularly stable to air and UV light exposure. The feasibility of this approach, capable of efficiently exfoliating bP while protecting the bPn, has been then verified by using different vinyl monomers (styrene and N-vinylpyrrolidone), thus obtaining hybrids where the nanoflakes are embedded in polymer matrices with a variety of intriguing thermal, mechanical, and solubility characteristics.

  14. On the role of resonantly stabilized radicals in polycyclic aromatic hydrocarbon (PAH) formation: pyrene and fluoranthene formation from benzyl-indenyl addition.

    Science.gov (United States)

    Sinha, Sourab; Rahman, Ramees K; Raj, Abhijeet

    2017-07-26

    Resonantly stabilized radicals, such as propargyl, cyclopentadienyl, benzyl, and indenyl, play a vital role in the formation and growth of polycyclic aromatic hydrocarbons (PAHs) that are soot precursors in engines and flames. Pyrene is considered to be an important PAH, as it is thought to nucleate soot particles, but its formation pathways are not well known. This paper presents a reaction mechanism for the formation of four-ring aromatics, pyrene and fluoranthene, through the combination of benzyl and indenyl radicals. The intermediate species and transition structures involved in the elementary reactions of the mechanism were studied using density functional theory, and the reaction kinetics were evaluated using transition state theory. The barrierless addition of benzyl and indenyl to form the adduct, 1-benzyl-1H-indene, was found to be exothermic with a reaction energy of 204.2 kJ mol -1 . The decomposition of this adduct through H-abstraction and H 2 -loss was studied to determine the possible products. The rate-of-production analysis was conducted to determine the most favourable reactions for pyrene and fluoranthene formation. The premixed laminar flames of toluene, ethylbenzene, and benzene were simulated using a well-validated hydrocarbon fuel mechanism with detailed PAH chemistry after adding the proposed reactions to it. The computed and experimentally observed species profiles were compared to determine the effect of the new reactions for pyrene and fluoranthene formation on their concentration profiles. The role of benzyl and indenyl combination in PAH formation and growth is highlighted.

  15. Cadernos encadeados: uma descrição sobre o encadeamento do tempo em uma turma alfabetizadora

    Directory of Open Access Journals (Sweden)

    Flávia Anastácio de Paula

    Full Text Available Nas últimas duas décadas tem se discutido sobre as tematizações, as normatizações e as concretizações do tema alfabetização na escola. Entretanto, poucos são os trabalhos que se dedicam às concretizações do uso do tempo escolar para mediações alfabetizadoras que levem ao sucesso. Este artigo apresenta um dos modos de como se produzem usos do tempo por uma alfabetizadora experiente. Partindo de uma proposta metodológica etnográfica, escolhemos um elemento para descrição e compreensão: os cadernos. A problemática exemplifica um dos desafios na pesquisa em alfabetização: documentar práticas, artefatos, usos atuais (ou não significativos para as professoras no aprendizado da leitura e da escrita. A especificidade da análise adota algumas das dimensões de tempo elaboradas por Heller e recai sobre um aspecto da temporalidade: o encadeamento. Objetiva-se descrever e refletir sobre como professoras experientes organizam o tempo para ensinar.

  16. Fifteen years of experience radical cystectomy and intestinal urinary diversion

    Directory of Open Access Journals (Sweden)

    M. I. Vasil’chenko

    2017-01-01

    Full Text Available Objective. Examination of the results of surgical treatment and analysis of the surgical technique and perioperative parameters in a series of radical cystectomy on the basis of its own 15 years of experience in the formation of orthotopic and heterotopic urinary reservoir of the ileum segment by developed and patented techniques in different versions: open radical cystectomy, laparoscopic radical cystectomy and robotassisted radical cystectomy.Materials and methods. A retrospective analysis of 310 radical cystectomy performed from 2000 to 2015, on the occasion of various pathologies of the bladder and prostate, as well as cancers of other organs (uterus, colon with involvement in the process of bladder tumor. Plastics of the bladder was performed from the segment of the terminal ileum. Formation of orthotopic bladder was performed by the method of M.I. Vasilchenko (RF patent for invention № 2337630 “Method of orthotopic bladder plastics” by M.I. Vasilchenko. The ureters are implanted by antireflux procedure. If unable to perform orthotopic bladder plastics recovery and self-urination, patients underwent the formation of heterotopic enteral reservoir with a holding valve.Results. It assesses the functionality and viability of organic shaped orthotopic and heterotopic urinary neocystis in the early and late postoperative periods in different versions. The proposed techniques have a beneficial effect on the improvement of the functional state and stabilization of the upper urinary tract. Analysis of morbidity and mortality was determined according to the classification of surgical complications on the Clavien–Dindo. This approach allowed to identify most of the complications and prevent an underestimation of the main negative results. Estimated oncologic efficacy of minimally invasive interventions laparoscopic radical cystectomy and robot-assisted radical cystectomy not inferior open radical cystectomy.Conclusions. Formation of

  17. The determination of the radical power - an in vitro test for the evaluation of cosmetic products.

    Science.gov (United States)

    Herrling, T; Seifert, M; Sandig, G; Jung, K

    2016-06-01

    Cosmetic formulations are influenced by environmental impacts and ageing, resulting in rancidity and change of colour and structure. These changes are caused by free radicals (FRs). The sensitivity of cosmetics generating FRs is a metric for its quality and should be determined. Electron spin resonance spectroscopy in combination with UV irradiation tested cosmetics such as creams, milks, lotions and fragrances. The probes were directly measured without expensive preparation. Nine formulations are tested for its radical generation and ranked corresponding to the radical power. The transformation of the FR properties of three formulations to skin is measured by the radical skin status factor (RSF) method. It shows that the higher the radical power (RP) is, the lower the radical status RSF of skin will be. The knowledge of the sensitivity of cosmetics to generate FRs is necessary for its stabilization and prevention of potential damages to skin. It is a new way in development of cosmetics which has to be considered. © 2015 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

  18. Stability of rhenium-188 labeled antibody

    International Nuclear Information System (INIS)

    Lim, B. K.; Jung, J. M.; Jung, J. K.; Lee, D. S.; Lee, M. C.

    1999-01-01

    For clinical application of beta-emitter labeled antibody, high specific activity is important. Carrier-free Re-188 from W-188/Re-188 generator is an ideal radionuclide for this purpose. However, low stability of Re-188 labeled antibody, especially in high specific activity, due to radiolytic decomposition by high energy (2.1 MeV) beta ray was problem. We studied the stability of Re-188 labeled antibody, and stabilizing effect of several nontoxic radical-quenching agents. Pre-reduced monoclonal antibody (CEA79.4) was labeled with Re-188 by incubating with generator-eluted Re-188-perrhenate in the presence of stannous tartrate for 2 hr at room temperature. Radiochemical purity of each preparation was determined by chromatography (ITLC-SG/acetone, ITLC-SG/Umezawa, Whatman No.1/saline). Human serum albumin was added to the labeled antibodies(2%). Stability of Re-188-CEA79.4 was investigated in the presence of vitamin C, ethanol, or Tween 80 as radical-quenching agents. Specific activities of 4.29∼5.11 MBq/μg were obtained. Labeling efficiencies were 88±4%(n=12). Very low stability after removal of stannous tartrate from the preparation was observed. If stored after purging with N 2 , all the preparations were stable for 10 hr. However, if contacted with air, stability decreased. Perrhenate and Re-188-tartrate was major impurity in declined preparation (12∼47 and 9∼38% each, after 10 hr). Colloid-formation was not a significant problem in all cases. Addition of vitamin C stabilized the labeled antibodies either under N 2 or under air by reducing the formation of perrhenate. High specific activity Re-188 labeled antibody is unstable, especially, in the presence of oxygen. Addition of vitamin C increased the stability

  19. Portando uma aplicação de sistema embarcado com arquitetura super Loop para operar com sistema operacional em tempo real

    Directory of Open Access Journals (Sweden)

    Edielson Prevato Frigieri

    2014-08-01

    Full Text Available Atualmente, a utilização dos sistemas operacionais, principalmente os sistemas de tempo real (RTOS, tem sido de grande importância no desenvolvimento de sistemas embarcados. Cada vez mais, diferentes e variadas funcionalidades são requisitos dos projetos de sistemas embarcados, como interfaces de comunicação com e sem fio, interfaces com o usuário através de displays, interfaces de acesso de dado como USB, serial, etc. Com o aumento da complexidade, fica extremamente difícil construir um sistema que seja estável e que atenda aos requisitos de tempo a partir de estruturas de programas comuns como o Super Loop. A fim de demonstrar os problemas inerentes deste tipo de arquitetura, foi desenvolvida uma aplicação utilizando o Super Loop e a mesma foi portada para uma solução baseada em RTOS demonstrando os principais conceitos que envolvem um sistema operacional, como utilizá-lo, e os benefícios obtidos com a sua utilização, como estabilidade do sistema, sincronização entre tarefas e cumprimento dos requisitos de tempo. Palavras-chave: Sistemas operacionais de tempo real. Sistemas embarcados. Escalonamento.Porting an embedded system application with super loop architecture to operate with real-time operating systemCurrently, the use of operating systems, especially real-time systems (RTOS, has been of great importance in the development of embedded systems. Increasingly, different and varied features are requirements for embedded system projects, as wired and wireless communication interfaces; user interfaces through displays; data access interfaces such as USB, serial, etc. With the increase in complexity, it becomes extremely difficult to build a system that is stable and that meets the time requirements from common program structures like Super Loop. In order to demonstrate the inherent problems of this type of architecture, an application was developed using Super Loop and it was ported to a solution based on RTOS

  20. Music tempo estimation in dancing robot%舞蹈机器人中音乐节拍的识别

    Institute of Scientific and Technical Information of China (English)

    何晓亮

    2013-01-01

    音乐节拍是音乐的重要特征之一,对音乐节拍的提取是音乐识别的重要研究内容.小波变换方法可以实现对音乐节拍特征进行有效的提取与识别.文中对音乐节拍的分析采用双尺度小波变换(DWT)方法,即离散小波变换,提取音乐信号的自相关包络,对自相关包络信息进行分析,从而实现对音乐节拍信息的识别.实验证明,文中提出的方法可以有效地对音乐信号的节拍信息进行识别.%Music tempo is an important feature of music, Extraction of the tempo of music is an important research in music recognition. Wavelet transform can characteristics of music tempo extraction and identification effective. This paper analyzes the music tempo by two-scale wavelet transform (DWT) method, that is discrete wavelet transform. Extracted from the music signal, the autocorrelation envelope of music is analyzed in order to estimat the music tempo information. Experimental results show that the proposed method can effectively estimat music tempo information.

  1. Oxidation of cashew tree gum exudate polysaccharide with TEMPO reagent

    Energy Technology Data Exchange (ETDEWEB)

    Cunha, Pablyana L.R.; Maciel, Jeanny S.; Paula, Regina C.M. de; Feitosa, Judith P.A. [Universidade Federal do Ceara, Fortaleza, CE (Brazil). Dept. de Quimica Organica e Inorganica; Sierakowski, Maria Rita [Universidade Federal do Parana, Curitiba, PR (Brazil). Dept. de Quimica]. E-mail: judith@dqoi.ufc.br

    2007-07-01

    Cashew gum (CG), an exudate polysaccharide from Anacardium occidentale trees, was oxidized with TEMPO reagent and the product (CGOX) characterized by spectroscopic techniques (FTIR and NMR), chromatographic analyses (HPLC and GPC), viscosity measurements and thermal analysis (TGA). The yield of the reaction product was 96%. The uronic acid content in starting gum (7.2 m%) was increased to 36 m%. The degree of oxidation based on free galactose and glucose units was 68%. NMR data show that oxidation occurred preferentially at primary carbons of galactose units. High degradation degree after oxidation was estimated by the difference on the expected and observed {eta}{sub CGOX}/{eta}{sub CG} ratio. The presence of organic and inorganic impurities in the new polyelectrolyte was detected by TGA. A less thermally stable cashew gum is formed after the oxidation with TEMPO based on initial decomposition temperature and IPDT. (author)

  2. A nonconjugated radical polymer glass with high electrical conductivity

    Science.gov (United States)

    Joo, Yongho; Agarkar, Varad; Sung, Seung Hyun; Savoie, Brett M.; Boudouris, Bryan W.

    2018-03-01

    Solid-state conducting polymers usually have highly conjugated macromolecular backbones and require intentional doping in order to achieve high electrical conductivities. Conversely, single-component, charge-neutral macromolecules could be synthetically simpler and have improved processibility and ambient stability. We show that poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl), a nonconjugated radical polymer with a subambient glass transition temperature, underwent rapid solid-state charge transfer reactions and had an electrical conductivity of up to 28 siemens per meter over channel lengths up to 0.6 micrometers. The charge transport through the radical polymer film was enabled with thermal annealing at 80°C, which allowed for the formation of a percolating network of open-shell sites in electronic communication with one another. The electrical conductivity was not enhanced by intentional doping, and thin films of this material showed high optical transparency.

  3. E. P. R. spectroscopic study of nitroxide mono- and bi-radicals

    International Nuclear Information System (INIS)

    Lemaire, H.

    1966-09-01

    A nitroxide is a molecule containing the group N-O where the oxygen atom made only one bond instead of the usual two. The main advantage of these radicals is their exceptional stability; this allows the study of well defined chemical structures while varying at will the experimental conditions. Studies by electron paramagnetic resonance of nitroxide mono-radicals have given the principal directions and the principal values of the electron-nitrogen nucleus hyperfine tensor and of the anisotropic g-factor tensor. The results were then related to the electronic structure of radicals. An understanding was obtained of the influence of the solvent on the principal values of the tensors, and the marked differences observed in the broadening of hyperfine lines when the medium become viscous. In the nitroxide biradicals, the hyperfine spectra depends not only on the magnetic interactions relative to each monomer, but also on the magnitude of the exchange interaction between the singlet and the triplet states of the dimer; the biradicals studied here are the first organic compounds which show clearly the influence of this exchange on the hyperfine structure. The two unpaired electrons also interact by a magnetic dipolar interaction: in the intermediate case, this can be used to derive the sign of the exchange interaction if the bi-radical is studied in a liquid crystal. Just as for mono-radicals, the hyperfine spectra of bi-radicals show selective broadening in viscous media, which is caused by an overall motional modulation of the anisotropic tensors. This gives another way to determine the sign of the exchange interaction. (author) [fr

  4. CONSIDERAÇÕES SOBRE LAZER, TRABALHO E TEMPO LIVRE

    Directory of Open Access Journals (Sweden)

    Luiz César Teixeira dos Santos

    2008-06-01

    Full Text Available O objetivo deste trabalho é discutir o lazer a partir dos conceitos de trabalho e tempo livre. O tema é abordado com base em estudos recentes que tratam os assuntos relacionados ao lazer em uma perspectiva que sugere, mediante o crescente nível do desemprego em escala global, um aumento significativo do tempo livre do trabalhador. Rifkin (1995, ao tratar da questão do fim do emprego, aponta para um cenário onde milhares de trabalhadores se colocam favoráveis a uma maior disponibilidade para a família e o lazer, ainda que isso signifique uma redução dos níveis de renda. O mesmo autor, no entanto, descortina um sério problema para as futuras gerações, uma vez que, com o declínio das ofertas de emprego, um número maior de homens, sem trabalho (e em conseqüência disso, sem condições materiais tendem a uma situação de miserabilidade, onde a própria condição para o lazer se vê comprometida. Dessa forma, verifica-se que há uma potencialização para a prática do lazer que nem sempre se concretiza, pois as possibilidades para sua efetiva realização não se expandem em proporções similares ao aumento do tempo livre. A temática do lazer se insere ainda em um contexto onde o apelo ao consumo se tornou o principal protagonista da história do mundo contemporâneo. Por isso, o próprio lazer passou a ser visto como uma mercadoria em potencial e, enquanto tal, sujeito às frias e duras regras do mercado.

  5. Free radical generation from an aniline derivative in HepG2 cells: a possible captodative effect.

    Science.gov (United States)

    Horinouchi, Yuya; Summers, Fiona A; Ehrenshaft, Marilyn; Mason, Ronald P

    2015-01-01

    Xenobiotic metabolism can induce the generation of protein radicals, which are believed to play an important role in the toxicity of chemicals and drugs. It is therefore important to identify chemical structures capable of inducing macromolecular free radical formation in living cells. In this study, we evaluated the ability of four structurally related environmental chemicals, aniline, nitrosobenzene, N,N-dimethylaniline, and N,N-dimethyl-4-nitrosoaniline (DMNA), to induce free radicals and cellular damage in the hepatoma cell line HepG2. Cytotoxicity was assessed using lactate dehydrogenase assays, and morphological changes were observed using phase contrast microscopy. Protein free radicals were detected by immuno-spin trapping using in-cell western experiments and confocal microscopy to determine the subcellular locale of free radical generation. DMNA induced free radical generation, lactate dehydrogenase release, and morphological changes in HepG2 cells, whereas aniline, nitrosobenzene, N,N-dimethylaniline did not. Confocal microscopy showed that DMNA induced free radical generation mainly in the cytosol. Preincubation of HepG2 cells with N-acetylcysteine and 2,2'-dipyridyl significantly prevented free radical generation on subsequent incubation with DMNA, whereas preincubation with apocynin and dimethyl sulfoxide had no effect. These results suggest that DMNA is metabolized to reactive free radicals capable of generating protein radicals which may play a critical role in DMNA toxicity. We propose that the captodative effect, the combined action of the electron-releasing dimethylamine substituent, and the electron-withdrawing nitroso substituent, leads to a thermodynamically stabilized radical, facilitating enhanced protein radical formation by DMNA. Copyright © 2014 Elsevier Inc. All rights reserved.

  6. Spontaneous movement tempo is influenced by observation of rhythmical actions.

    Science.gov (United States)

    Bove, Marco; Tacchino, Andrea; Pelosin, Elisa; Moisello, Clara; Abbruzzese, Giovanni; Ghilardi, M Felice

    2009-09-28

    Observation of people performing movements facilitates motor planning, execution and memory formation. Tempo, a crucial aspect involved in the execution of rhythmic movements, is normally perceived and learned through auditory channels. In this work, we ascertained whether: first, the frequency of self-paced finger movements (SPMs), which in normal subjects is around 2 Hz, is modified by prior observation of movements performed at either 1 or 3 Hz; second, such changes are lasting; third, there is an effect of time interval between observation and performance. We finally determined the effect of providing explicit information about the upcoming motor task. Seventy-two normal subjects (12 groups) performed a simple finger sequence at different intervals after observation of videos of either landscapes or finger opposition movements. Both with and without information about the upcoming task, observation influenced the tempo of SPMs and led to memory formation. With knowledge of the upcoming task, such changes occurred at all observation-execution intervals, while without instructions, changes took place only when SPMs were performed immediately after observation. Compared to explicit instructions, the absence of instructions produced tempo's changes that more closely resembled the observed rhythms. We conclude that learning requires a prompt comparison between visual and sensorimotor representations of movements; moreover, learning with explicit instructions is more efficient, as activity in both the dorsal and ventral streams might be potentiated by the chatecholaminergic attentional systems that promote long-term potentiation. These results provide the bases for novel neurorehabilitation strategies in terms of temporal re-organization of movement.

  7. Unidirectional adaptation in tempo in pairs of chimpanzees during simultaneous tapping movement: an examination under face-to-face setup.

    Science.gov (United States)

    Yu, Lira; Tomonaga, Masaki

    2016-04-01

    Many studies have reported a spontaneous nature to synchronized movement in humans and in non-human primates. However, it is not yet clear whether individuals mutually adapt their movement to each other or whether one individual significantly changes to synchronize with the other. In the current study, we examined a directionality of the tempo adaptation to understand an introductive process of interactional synchrony in pairs of chimpanzees. Four pairs, consisting of five female chimpanzees, produced a finger-tapping movement under a face-to-face experimental setup where both auditory and visual cues of the partner's movement were available. Two test conditions were prepared: alone and paired. An analysis of the tapping tempo depending on condition showed that only one chimpanzee in each pair significantly changed their tapping tempo in the direction of the partner's tapping tempo in the paired condition compared with the alone condition. The current study demonstrated that unidirectional adaptation in tempo occurs in pairs of chimpanzees when they simultaneously produce the tapping movement under auditory and visual interaction.

  8. Radical Change by Entrepreneurial Design

    National Research Council Canada - National Science Library

    Roberts, Nancy C

    1998-01-01

    .... How radical change in public policy has occurred in the past is then documented. We find examples of radical change by chance, radical change by consensus, radical change by learning, and radical change by entrepreneurial design...

  9. The effect of near-infrared MLS laser radiation on cell membrane structure and radical generation.

    Science.gov (United States)

    Kujawa, Jolanta; Pasternak, Kamila; Zavodnik, Ilya; Irzmański, Robert; Wróbel, Dominika; Bryszewska, Maria

    2014-09-01

    The therapeutic effects of low-power laser radiation of different wavelengths and light doses are well known, but the biochemical mechanism of the interaction of laser light with living cells is not fully understood. We have investigated the effect of MLS (Multiwave Locked System) laser near-infrared irradiation on cell membrane structure, functional properties, and free radical generation using human red blood cells and breast cancer MCF-4 cells. The cells were irradiated with low-intensity MLS near-infrared (simultaneously 808 nm, continuous emission and 905 nm, pulse emission, pulse-wave frequency, 1,000 or 2,000 Hz) laser light at light doses from 0 to 15 J (average power density 212.5 mW/cm(2), spot size was 3.18 cm(2)) at 22 °C, the activity membrane bound acetylcholinesterase, cell stability, anti-oxidative activity, and free radical generation were the parameters used in characterizing the structural and functional changes of the cell. Near-infrared low-intensity laser radiation changed the acetylcholinesterase activity of the red blood cell membrane in a dose-dependent manner: There was a considerable increase of maximal enzymatic rate and Michaelis constant due to changes in the membrane structure. Integral parameters such as erythrocyte stability, membrane lipid peroxidation, or methemoglobin levels remained unchanged. Anti-oxidative capacity of the red blood cells increased after MLS laser irradiation. This irradiation induced a time-dependent increase in free radical generation in MCF-4 cells. Low-intensity near-infrared MLS laser radiation induces free radical generation and changes enzymatic and anti-oxidative activities of cellular components. Free radical generation may be the mechanism of the biomodulative effect of laser radiation.

  10. Effect of Music Tempo on Attentional Focus and Perceived Exertion during Self-selected Paced Walking

    Science.gov (United States)

    SILVA, ALDO COELHO; DOS SANTOS FERREIRA, SANDRO; ALVES, RAGAMI CHAVES; FOLLADOR, LUCIO; DA SILVA, SERGIO GREGORIO

    2016-01-01

    This study investigated the influence of music on the rating of perceived exertion (RPE) and attentional focus during walking at a self-selected pace. Fifteen overweight and obese women volunteered to participate in the study. They underwent four sessions: the first for incremental maximal test and anthropometric measurement followed by three experimental sessions. After the first session, they were exposed to three 30-minute walking sessions at a self-selected pace in a counterbalanced order: fast-tempo music (FT), medium-tempo music (MT) and no-music control (NM). Borg’s RPE Scale and an Attentional Focus Questionnaire were used to measure the perceptual response and attentional focus, respectively. Results showed that the RPE was higher in the no-music control than in the medium-tempo music (12.05 ± 0.6 vs. 10.5 ± 0.5). Furthermore, dissociative attentional focus was greater for both conditions with music in comparison with the no-music control (NM= 39.0 ± 4.1; MT= 48.4 ± 4.1 and FT= 47.9 ± 4.5). The results indicated that the use of music during walking can modulate attentional focus, increasing dissociative thought, and medium-tempo music can reduce the RPE. PMID:27990220

  11. A medida do tempo: intuição e inteligência em Bergson

    OpenAIRE

    Monteiro, Geovana da Paz

    2008-01-01

    110f. Investigar a natureza do tempo real é, de acordo com Henri Bergson, perscrutar um objeto fugidio, uma vez que, ao tentarmos apreendê-lo, já se escoou em seu fluxo contínuo. Caberia à consciência compreendê-lo na passagem que lhe é própria. Doravante, uma dificuldade se mostra ao filósofo: tempo e espaço, sendo qualitativamente distintos, aparecem, quer para a filosofia, quer para a ciência, como faces de uma mesma moeda. O pensamento bergsoniano percebe, então, na espacialização do t...

  12. Fronteiras, violência e o trabalho do tempo: alguns temas wittgensteinianos

    Directory of Open Access Journals (Sweden)

    Das Veena

    1999-01-01

    Full Text Available Trabalhos recentes sugerem que, quando se contempla a violência, atinge-se uma espécie de limite da capacidade de representar. O caso da Partição da Índia, em 1947, fornece um desses "dramas de horror", por seus atos hediondos de grande escala. Este ensaio trata da domesticação da violência, atualizada na história de uma família urbana do Punjabi, e da necessidade do "trabalho do tempo" para permitir sua cicatrização. Recuperando idéias de Wittgenstein para a Antropologia, a autora mostra como o trabalho do tempo, não sua imagem ou representação, serve para testar o sentido do que é humano quando a linguagem falha ou simplesmente não existe.

  13. The Effects of Learning Procedure, Tempo, and Performance Condition on Transfer of Rhythm Skills in Instrumental Music.

    Science.gov (United States)

    Pierce, Michael A.

    1992-01-01

    Describes study of effects of learning procedures and performance tempo on ability of 64 middle school students to perform previously learned rhythmic passages. Reviews the four learning procedures used for each rhythmic passage. Finds no evidence attributed to learning procedure but significant adverse differences if the tempo was changed from…

  14. TEMPO E FILOSOFIA NO ROMANCE "PEDRO PÁRAMO", DE JUÁN RULFO

    Directory of Open Access Journals (Sweden)

    Profª Drª Cláudia Falluh Balduino Ferreira

    2012-01-01

    Full Text Available Considerando que a questão filosófica expressa pela composição narrativa visa às relações e as tensões entre o tempo da narrativa e o da vida, e que várias disciplinas são convocadas a este amplo debate, o presente artigo quer ilustrar ao modo como se dão a aliança entre os processos mnemônicos e de anamnese e a experiência do tempo no romance do escritor mexicano Ruan Rulfo, empregando as noções filosóficas de anamnese conforme Platão e a questão do temporal segundo Paul Ricoeur.

  15. Human brain basis of musical rhythm perception: common and distinct neural substrates for meter, tempo, and pattern.

    Science.gov (United States)

    Thaut, Michael H; Trimarchi, Pietro Davide; Parsons, Lawrence M

    2014-06-17

    Rhythm as the time structure of music is composed of distinct temporal components such as pattern, meter, and tempo. Each feature requires different computational processes: meter involves representing repeating cycles of strong and weak beats; pattern involves representing intervals at each local time point which vary in length across segments and are linked hierarchically; and tempo requires representing frequency rates of underlying pulse structures. We explored whether distinct rhythmic elements engage different neural mechanisms by recording brain activity of adult musicians and non-musicians with positron emission tomography (PET) as they made covert same-different discriminations of (a) pairs of rhythmic, monotonic tone sequences representing changes in pattern, tempo, and meter, and (b) pairs of isochronous melodies. Common to pattern, meter, and tempo tasks were focal activities in right, or bilateral, areas of frontal, cingulate, parietal, prefrontal, temporal, and cerebellar cortices. Meter processing alone activated areas in right prefrontal and inferior frontal cortex associated with more cognitive and abstract representations. Pattern processing alone recruited right cortical areas involved in different kinds of auditory processing. Tempo processing alone engaged mechanisms subserving somatosensory and premotor information (e.g., posterior insula, postcentral gyrus). Melody produced activity different from the rhythm conditions (e.g., right anterior insula and various cerebellar areas). These exploratory findings suggest the outlines of some distinct neural components underlying the components of rhythmic structure.

  16. Sucrose tricarboxylate by sonocatalysed TEMPO-mediated oxidation.

    Science.gov (United States)

    Lemoine, S; Thomazeau, C; Joannard, D; Trombotto, S; Descotes, G; Bouchu, A; Queneau, Y

    2000-06-16

    Oxidation of sucrose by the NaOCl/TEMPO system provided sucrose tricarboxylate without the addition of sodium bromide as co-catalyst when high-frequency (500 kHz) ultrasound was applied, in contrast to very limited conversion without sonication. In the presence of sodium bromide, sonication also caused acceleration of the oxidation. The rate increase due to sonication of the oxidant system prior to sucrose addition suggests that ultrasound acts at the level of the formation of the nitrosonium ion, the active oxidising species in the catalytic cycle.

  17. Oficinas de Gestão do Tempo com Estudantes Universitários

    Directory of Open Access Journals (Sweden)

    Clarissa Tochetto de Oliveira

    Full Text Available Resumo Buscou-se descrever a experiência de oficinas de gestão do tempo realizadas junto a acadêmicos de uma universidade pública no interior do Rio Grande do Sul. Foram realizados oito encontros com o objetivo de avaliar e discutir a forma como os participantes costumam organizar o seu tempo. Participaram 85 alunos de graduação e pós-graduação. Os tópicos abordados incluíram estratégias utilizadas para organização, identificação de problemas, metas e objetivos e oferecimento de dicas. Foram descritos os procedimentos e as ferramentas utilizadas nas oficinas. As dificuldades vivenciadas pelos estudantes estavam relacionadas à procrastinação, à incapacidade de dizer “não” às demandas alheias, à carga horária de seus cursos e à conciliação entre estudos, convivência familiar e lazer. A participação na oficina foi um primeiro momento de reflexão sobre a temática para muitos participantes. Pesquisas que investiguem os “motivos” das dificuldades na gestão do tempo nessa população podem subsidiar futuras intervenções junto a esse público.

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

    OpenAIRE

    Walton, J.C.; Williams, F.

    2015-01-01

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

  19. Time resolved resonance Raman spectra of anilino radical and aniline radical cation

    International Nuclear Information System (INIS)

    Tripathi, G.N.R.; Schuler, R.H.

    1987-01-01

    We report, in this paper, submicrosecond time resolved resonance Raman spectra of anilino radical and its radical cation as observed in pulse radiolytic studies of the oxidation of aniline in aqueous solution. By excitation in resonance with the broad and weak electronic transition of anilino radical at 400 nm (ε--1250 M -1 cm -1 ) we have observed, for the first time, the vibrational features of this radical. The Wilson ν 8 /sub a/ ring stretching mode at 1560 cm -1 is most strongly resonance enhanced. The ν 7 /sub a/ CN stretching band at 1505 cm -1 , which is shifted to higher frequency by 231 cm -1 with respect to aniline, is also prominent. The frequency of this latter mode indicates that the CN bond in the radical has considerable double bond character. The Raman spectrum of aniline radical cation, excited in resonance with the --425 nm electronic absorption (ε--4000 M -1 cm -1 ), shows features which are similar to phenoxyl radical. Most of the observed frequencies of this radical in solution are in good agreement with vibrational energies determined by recent laser photoelectron spectroscopic studies in the vapor phase. The bands most strongly enhanced in the resonance Raman spectrum are, however, weak in the photoelectron spectrum. While the vibrational frequencies observed for anilino radical and its isoelectronic cation are quite similar, the resonance enhancement patterns are very different. In particular the ν 14 b 2 mode of anilino radical observed at 1324 cm -1 is highly resonance enhanced because of strong vibronic coupling between the 400 nm 2 A 2 -- 2 B 1 and the higher 2 B 1 -- 2 B 1 electronic transitions

  20. Does expressive timing in music performance scale proportionally with tempo?

    NARCIS (Netherlands)

    Desain, P.; Honing, H.

    1994-01-01

    Evidence is presented that expressive timing in music is not relationally invariant with global tempo. Our results stem from an analysis of repeated performances of Beethoven's variations on a Paisiello theme. Recordings were made of two pianists playing the pieces at three tempi. In contrast with

  1. Effects of music tempo upon submaximal cycling performance.

    Science.gov (United States)

    Waterhouse, J; Hudson, P; Edwards, B

    2010-08-01

    In an in vivo laboratory controlled study, 12 healthy male students cycled at self-chosen work-rates while listening to a program of six popular music tracks of different tempi. The program lasted about 25 min and was performed on three occasions--unknown to the participants, its tempo was normal, increased by 10% or decreased by 10%. Work done, distance covered and cadence were measured at the end of each track, as were heart rate and subjective measures of exertion, thermal comfort and how much the music was liked. Speeding up the music program increased distance covered/unit time, power and pedal cadence by 2.1%, 3.5% and 0.7%, respectively; slowing the program produced falls of 3.8%, 9.8% and 5.9%. Average heart rate changes were +0.1% (faster program) and -2.2% (slower program). Perceived exertion and how much the music was liked increased (faster program) by 2.4% and 1.3%, respectively, and decreased (slower program) by 3.6% and 35.4%. That is, healthy individuals performing submaximal exercise not only worked harder with faster music but also chose to do so and enjoyed the music more when it was played at a faster tempo. Implications of these findings for improving training regimens are discussed.

  2. Tempo, ciência e consenso: os diferentes tempos que envolvem a pesquisa científica, a decisão política e a opinião pública

    Directory of Open Access Journals (Sweden)

    José Aparecido de Oliveira

    2009-06-01

    Full Text Available Este trabalho analisa a assimétrica relação entre o tempo da pesquisa científica e o tempo dos diferentes segmentos interessados em seus resultados, sobretudo com a crescente demanda de se construir consenso técnico sobre campos da ciência que exigem rigorosas investigações e exaustivos testes. Destacam-se, sobretudo nos últimos anos, as pressões de setores da sociedade civil, interessados em participar do processo decisório que orienta os rumos da ciência, entre eles: o jornalismo científico, o poder legislativo e a opinião pública. Como exemplo, foi analisado o processo decisório do projeto de Lei de Biossegurança, que permite pesquisas com células-tronco embrionárias no Brasil. Os resultados permitem concluir que essa relação assimétrica entre os diferentes tempos (da ciência, da divulgação científica, da opinião pública e do poder público contribui para o amadurecimento do diálogo sobre política científica e a construção de consenso sobre os rumos da ciência, com vistas a democratizar o fazer científico.

  3. Tempo, ciência e consenso: os diferentes tempos que envolvem a pesquisa científica, a decisão política e a opinião pública

    Directory of Open Access Journals (Sweden)

    José Aparecido de Oliveira

    Full Text Available Este trabalho analisa a assimétrica relação entre o tempo da pesquisa científica e o tempo dos diferentes segmentos interessados em seus resultados, sobretudo com a crescente demanda de se construir consenso técnico sobre campos da ciência que exigem rigorosas investigações e exaustivos testes. Destacam-se, sobretudo nos últimos anos, as pressões de setores da sociedade civil, interessados em participar do processo decisório que orienta os rumos da ciência, entre eles: o jornalismo científico, o poder legislativo e a opinião pública. Como exemplo, foi analisado o processo decisório do projeto de Lei de Biossegurança, que permite pesquisas com células-tronco embrionárias no Brasil. Os resultados permitem concluir que essa relação assimétrica entre os diferentes tempos (da ciência, da divulgação científica, da opinião pública e do poder público contribui para o amadurecimento do diálogo sobre política científica e a construção de consenso sobre os rumos da ciência, com vistas a democratizar o fazer científico.

  4. La liberazione del tempo

    CERN Document Server

    Selleri, Franco

    2003-01-01

    Negli ultimi dieci anni ho lavorato alla descrizione dei fenomeni naturali da parte di osservatori in movimento. E' un problema che molti credono risolto una volta per tutte dalle trasformazioni di Lorentz della teoria della relatività speciale (TRS nel seguito), ma che in realtà era rimasto aperto per una serie di ragioni che esporrò. Sento di dover dire che ho trovato risultati molto importanti, anche se il giudizio finale sul loro valore non può certo essere il mio. Infatti la conclusione di questa ricerca è duplice: una spiegazione dei dati empirici migliore di quella relativistica, e l'eliminazione di quegli aspetti della TRS che fanno a pugni con il buon senso; il tutto grazie alla liberazione del tempo dall'asservimento alle coordinate spaziali cui era stato costretto nello spazio a quattro dimensioni di Minkowski. La faccenda è raccontata con dovizia di particolari in un libro recente [FS]. Nel presente articolo espongo gli aspetti salienti della ricerca lasciando da parte quelli matematici.

  5. Free radical transfer in polymers

    International Nuclear Information System (INIS)

    Sonntag, C. von; Bothe, E.; Ulanski, P.

    1998-01-01

    For the present study of free-radical transfer in polymers pulse radiolysis and product studies have been carried out in aqueous solutions using thus far only the water-soluble polymers polyacrylic acid, polymethacrylic acid and polyvinyl alcohol. When OH radicals, generated in the radiolysis of N 2 O-saturated aqueous solutions, react with polymers the lifetime of the polymer radical thus created very much depends on the number of radicals per polymer chain. When there are a large number of radicals per chain their bimolecular decay may be faster than the corresponding (diffusion controlled) decay of monomeric radicals, but when the macromolecule contains only few or even just one radical their lifetime is considerably prolonged. Highly charged polymers such as polyacrylic acid at high pH attain a rod-like conformation which again favors a long lifetime of the radicals. Under such conditions, radical transfer reactions can occur. For example, in polyacrylic acid OH radicals generate two kinds of radicals side by side. The radical in β-position to the carboxylate group converts into the thermodynamically more stable α-radicals by an H-transfer reaction as can be followed by spectrophotometry. Besides radical transfer reactions β-fragmentation reactions occur causing chain scission. Such reactions can be followed in a pulse radiolysis experiment by conductometry, because counter ions are released upon chain scission. Such a process is especially effective in the case of polymethacrylic acid, where it results in a chain depolymerization. An intramolecular H-abstraction is also observed in the γ-radiolysis of polyacrylic acid with the corresponding peroxyl radicals. This causes a chain reaction to occur. The resulting hydroperoxides are unstable and decarboxylate given rise to acetylacetone-like products. In polyvinyl alcohol the peroxyl radicals in α-position to the alcohol function undergo HO 2 -elimination. This prevents a scission of the polymer chain in the

  6. Development and Lability in the Parent-Child Relationship During Adolescence: Associations With Pubertal Timing and Tempo

    Science.gov (United States)

    Marceau, Kristine; Ram, Nilam; Susman, Elizabeth

    2014-01-01

    Adolescents' and parents' reactions to pubertal development are hypothesized to contribute to changes in family dynamics. Using 7-year longitudinal data from the NICHD-SECCYD (488 boys, 475 girls) we examined relations between pubertal development (timing, tempo) and trajectories (developmental change and year-to-year lability) of parent-child conflict and closeness from age 8.5 to 15.5 years. Changes were mostly characterized by year-to-year fluctuations – lability. Parent-child conflict increased and closeness decreased some with age. Pubertal timing and tempo were more consistently associated with lability in parent-child relationships than with long-term trends, although faster tempo was associated with steeper decreases in parent-child closeness. Findings provide a platform for examining how puberty contributes to both long-term and transient changes in adolescents' relationships and adjustment. PMID:26321856

  7. North American pollution measurements from geostationary orbit with Tropospheric Emissions: Monitoring of Pollution (TEMPO)

    Science.gov (United States)

    Chance, K.

    2017-12-01

    TEMPO is the first NASA Earth Venture Instrument. It launches between 2019 and 2021 to measure atmospheric pollution from Mexico City and Cuba to the Canadian oil sands, and from the Atlantic to the Pacific, hourly at high spatial resolution, 10 km2. Geostationary daytime measurements capture the variability in the diurnal cycle of emissions and chemistry at sub-urban scale to improve emission inventories, monitor population exposure, and enable emission-control strategies.TEMPO measures UV/visible Earth reflectance spectra to retrieve O3, NO2, SO2, H2CO, C2H2O2, H2O, BrO, OClO, IO, aerosols, cloud parameters, and UVB radiation. It tracks aerosol loading. It provides near-real-time air quality products. TEMPO is the North American component of the upcoming the global geostationary constellation for pollution monitoring, together with the European Sentinel-4 and the Korean Geostationary Environmental Monitoring Spectrometer (GEMS).TEMPO science studies include: Intercontinental pollution transport; Solar-induced fluorescence from chlorophyll over land and in the ocean to study tropical dynamics, primary productivity and carbon uptake, to detect red tides, and to study phytoplankton; measurements of stratospheric intrusions that cause air quality exceedances; measurements at peaks in vehicle travel to capture the variability in emissions from mobile sources; measurements of thunderstorm activity, including outflow regions to better quantify lightning NOx and O3 production; cropland measurements to follow the temporal evolution of emissions after fertilizer application and from rain-induced emissions from semi-arid soils; investigating the chemical processing of primary fire emissions and the secondary formation of VOCs and ozone; examining ocean halogen emissions and their impact on the oxidizing capacity of coastal environments; measuring spectra of nighttime lights as markers for human activity, energy conservation, and compliance with outdoor lighting standards

  8. Synthesis of Zirconium-Containing Polyhedral Oligometallasilsesquioxane as an Efficient Thermal Stabilizer for Silicone Rubber

    Directory of Open Access Journals (Sweden)

    Jiedong Qiu

    2018-05-01

    Full Text Available Free radicals play a negative role during the thermal degradation of silicone rubber (SR. Quenching free radicals is proposed to be an efficient way to improve the thermal-oxidative stability of SR. In this work, a novel zirconium-containing polyhedral oligometallasilsesquioxane (Zr-POSS with free-radical quenching capability was synthesized and characterized. The incorporation of Zr-POSS effectively improved the thermal-oxidative stability of SR. The T5 (temperature at 5% weight loss of SR/Zr-POSS significantly increased by 31.7 °C when compared to the unmodified SR. Notably, after aging 12 h at 280 °C, SR/Zr-POSS was still retaining about 65%, 60%, 75%, and 100% of the tensile strength, tear strength, elongation at break, and hardness before aging, respectively, while the mechanical properties of the unmodified SR were significantly decreased. The possible mechanism of Zr-POSS for improving the thermal-oxidative stability of SR was intensively studied and it was revealed that the POSS structure could act as a limiting point to suppress the random scission reaction of backbone. Furthermore, Zr could quench the free radicals by its empty orbital and transformation of valence states. Therefore, it effectively suppressed the thermal-oxidative degradation and crosslinking reaction of the side chains.

  9. Adaptabilidade do tempo de trabalho, banco de horas e horário concentrado

    OpenAIRE

    Verdasca, Daniela Vieira

    2017-01-01

    No presente trabalho pretendemos analisar os regimes de adaptabilidade, banco de horas e horário concentrado, bem como ponderar a sua contribuição para os princípios sempre presentes na temática da duração do trabalho, que por vezes se revelam antagónicos: a proteção do trabalhador, a tutela da sua saúde e da sua vida familiar e pessoal, uma vez que estes mecanismos permitem a variação do tempo de trabalho e logo dos tempos de não trabalho, e a salvaguarda dos interesses de gestão, sendo que ...

  10. Stability evaluation of resveratrol submitted to ionizing radiation

    Energy Technology Data Exchange (ETDEWEB)

    Momesso, Roberta G.R.A.P.; Silva, Mariana L. da; Spencer, Patrick J.; Sousa, Jose M. de; Rogero, Jose R.; Rogero, Sizue O.; Lugao, Ademar B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN-CNEN/SP), Sao Paulo, SP (Brazil)], e-mail: robertapassarelli@yahoo.com.br

    2009-07-01

    The polyphenol trans-resveratrol (trans-3, 4',5-trihydroxystilbene) is a natural phytoalexin, reported to exert different biological activities, such as antioxidant properties. In the attempt to make possible the topic administration of resveratrol it will be immobilized in a hydrogel matrix obtained by gamma radiation crosslinking process which can cause undesirable hydrolysis reactions in the active compound. The aim of this work was to verify the aqueous/ethanol resveratrol solution stability and antioxidant activity after irradiation at 20 kGy. The integrity and stability were compared with nature one by High Performance Liquid Chromatography (HPLC) technique. The antioxidant activity was determined by the free radical scavenging method, using 2,2-Diphenyl-1-picrylhydrazyl (DPPH.) as free radical. The results demonstrated the decomposition of resveratrol and reduction of antioxidant capacity after irradiation at 20 kGy dose. (author)

  11. Stability evaluation of resveratrol submitted to ionizing radiation

    International Nuclear Information System (INIS)

    Momesso, Roberta G.R.A.P.; Silva, Mariana L. da; Spencer, Patrick J.; Sousa, Jose M. de; Rogero, Jose R.; Rogero, Sizue O.; Lugao, Ademar B.

    2009-01-01

    The polyphenol trans-resveratrol (trans-3, 4',5-trihydroxystilbene) is a natural phytoalexin, reported to exert different biological activities, such as antioxidant properties. In the attempt to make possible the topic administration of resveratrol it will be immobilized in a hydrogel matrix obtained by gamma radiation crosslinking process which can cause undesirable hydrolysis reactions in the active compound. The aim of this work was to verify the aqueous/ethanol resveratrol solution stability and antioxidant activity after irradiation at 20 kGy. The integrity and stability were compared with nature one by High Performance Liquid Chromatography (HPLC) technique. The antioxidant activity was determined by the free radical scavenging method, using 2,2-Diphenyl-1-picrylhydrazyl (DPPH.) as free radical. The results demonstrated the decomposition of resveratrol and reduction of antioxidant capacity after irradiation at 20 kGy dose. (author)

  12. The effects of tempo and familiarity on children's affective interpretation of music.

    Science.gov (United States)

    Mote, Jasmine

    2011-06-01

    When and how does one learn to associate emotion with music? This study attempted to address this issue by examining whether preschool children use tempo as a cue in determining whether a song is happy or sad. Instrumental versions of children's songs were played at different tempos to adults and children ages 3 to 5 years. Familiar and unfamiliar songs were used to examine whether familiarity affected children's identification of emotion in music. The results indicated that adults, 4 year olds and 5 year olds rated fast songs as significantly happier than slow songs. However, 3 year olds failed to rate fast songs differently than slow songs at above-chance levels. Familiarity did not significantly affect children's identification of happiness and sadness in music.

  13. ESR Study Applied To Thermal Stability Of Radiation-Induced Species Of Solid Ketoprofen

    International Nuclear Information System (INIS)

    Maltar-Strmecki, N.; Katusin-Razem, B.; Razem, D.

    2015-01-01

    Ketoprofen [2-(3-benzoylphenyl) propionic acid] is a non-steroidal anti-inflammatory drug. It has been widely used in human and veterinary medicine. Radiation processing of drugs and its ingredients is recognized as a safe and effective method among the existing technologies for sterilization and protocols that can be found in ISO 11137-1. Radiosterilization of drugs or other medical products by a suitable dose of ionizing radiation conducted in an appropriate environment ensures sterile conditions by destroying or removing vegetative and sporulating microbes from the ingredients or environment. In earlier studies the effects of gamma radiation was evaluated by selected physico-chemical methods and the observations showed that solid ketoprofen is relatively stable toward ionizing irradiation and that radiosterilization might be a suitable method for the sterilization of solid ketoprofen. The studies reported in this work were undertaken to analyse thermal stability of free radicals by accelerated aging method with a view to the determination of shelf-life. The expiration date (shelf-life) of a product is based on evaluation of both, thermal stability of free radicals, as well as on the time evolution of stable radiolysis products. Namely, storage time is determined by the time required by any degradation product in the dosage form to achieve a sufficient level to represent a risk to the patient. This work shows that ESR spectroscopy provides means for determination of thermal stability of radicals induced by gamma-irradiation in solid drugs. Therefore, despite the complex mixture of individual free radicals induced by gamma-irradiation in solid ketoprofen, the overall lifetime of free radicals could be determined by using isothermal and isochronal annealing. This study shows that radicals induced by gamma-irradiation in solid ketoprofen are stable for at least about 6 months. (author).

  14. The Effect of Articulation Style on Perception of Modulated Tempo

    Science.gov (United States)

    Geringer, John M.; Madsen, Clifford K.; MacLeod, Rebecca B.; Kevin Droe

    2006-01-01

    We investigated the effect of legato and staccato articulation styles on the perception of modulated tempos. Ninety music majors served as participants. Listeners heard music examples that had been selected from two pieces, each of which included staccato and legato passages. Excerpts were presented to listeners in three conditions of tempo…

  15. Spectroscopic characterization of the ethyl radical-water complex.

    Science.gov (United States)

    Lin, Chen; Finney, Brian A; Laufer, Allan H; Anglada, Josep M; Francisco, Joseph S

    2016-10-14

    An ab initio investigation has been employed to determine the structural and spectroscopic parameters, such as rotational constants, vibrational frequencies, vertical excitation energies, and the stability of the ethyl-water complex. The ethyl-water complex has a binding energy of 1.15 kcal⋅mol -1 . The interaction takes place between the hydrogen of water and the unpaired electron of the radical. This interaction is found to produce a red shift in the OH stretching bands of water of ca. 84 cm -1 , and a shift of all UV absorption bands to higher energies.

  16. Diffusion of 1,4-butanedithiol radicals on Au(111) and Au(100): A DFT-based comparison

    Energy Technology Data Exchange (ETDEWEB)

    Franke, Andreas; Pehlke, Eckhard [Institut fuer Theoretische Physik und Astrophysik, Universitaet Kiel, 24098 Kiel (Germany)

    2010-07-01

    Organic molecules chemisorbed on surfaces hold the perspective of surface functionalization. The 1,4-butanedithiol radical chemisorbed at the Au(111) or Au(100) surface serves as a model system for the S-Au molecule-substrate bond. Density functional total-energy calculations have been carried out for the chemisorption of the radical on the unreconstructed Au surfaces, which are both known to be stabilized under electrochemical conditions. Local minima with close-by energies indicate multi-valley potential-energy surfaces, which originate from the interplay between the two S-Au adsorbate-substrate bonds and the internal degrees of freedom of the butanedithiol radical. Diffusion paths of the radical on both Au surfaces have been calculated within DFT using VASP. The diffusion barriers for translation and rotation of the radical differ. They can be fine-tuned by varying the applied potential in the electrochemical cell. This is considered theoretically by inspecting the variation of the dipole moment along the reaction paths. Consequences for the dynamics of succeeding diffusion hops are discussed.

  17. Measurement of antioxidant activity with trifluoperazine dihydrochloride radical cation

    Directory of Open Access Journals (Sweden)

    M.N. Asghar

    2008-06-01

    Full Text Available A novel, rapid and cost-effective trifluoperazine dihydrochloride (TFPH decolorization assay is described for the screening of antioxidant activity. A chromogenic reaction between TFPH and potassium persulfate at low pH produces an orange-red radical cation with maximum absorption at 502 nm in its first-order derivative spectrum. TFPH was dissolved in distilled water to give a 100 mM solution. The TFPH radical cation solution was made by reacting 0.5 mL of the solution with K2S2O8 (final concentration: 0.1 mM and diluting to 100 mL with 4 M H2SO4 solution. A linear inhibition of color production was observed with linearly increasing amounts of antioxidants, with correlation coefficients (R² ranging from 0.999 to 0.983. The antioxidant capacity of standard solutions of an antioxidant was evaluated by comparing with the inhibition curve using Trolox as the standard. Comparison of antioxidant capacity determined with this newly developed TFPH assay and with the well-known 2,2'-azinobis-[3-ethylbenzthiazoline-6-sulfonic acid] (ABTS-persulfate decolorization assay indicated the efficacy and sensitivity of the procedure. The proposed assay is less expensive (costs about US$4 per 100 assays and requires only 20 min for preparation of radical cation solution in comparison with ABTS assay, in which almost 12-16 h are required for preparation of a stable ABTS radical cation solution. The present assay has the advantage over ABTS assay that it can be used to measure the antioxidant activity of the samples, which are naturally found at a pH as low as 1, because the radical cation itself has been stabilized at low pH.

  18. Photochemistry and reactivity of the phenyl radical-water system: a matrix isolation and computational study.

    Science.gov (United States)

    Mardyukov, Artur; Crespo-Otero, Rachel; Sanchez-Garcia, Elsa; Sander, Wolfram

    2010-08-02

    The reaction of the phenyl radical 1 with water has been investigated by using matrix isolation spectroscopy and quantum chemical calculations. The primary thermal product of the reaction between 1 and water is a weakly bound complex stabilized by an OH...pi interaction. This complex is photolabile, and visible-light irradiation (lambda>420 nm) results in hydrogen atom transfer from water to radical 1 and the formation of a highly labile complex between benzene and the OH radical. This complex is stable under the conditions of matrix isolation, however, continuous irradiation with lambda>420 nm light results in the complete destruction of the aromatic system and formation of an acylic unsaturated ketene. The mechanisms of all reaction steps are discussed in the light of ab initio and DFT calculations.

  19. 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.

  20. Musicians are more consistent: Gestural cross-modal mappings of pitch, loudness and tempo in real-time.

    Science.gov (United States)

    Küssner, Mats B; Tidhar, Dan; Prior, Helen M; Leech-Wilkinson, Daniel

    2014-01-01

    Cross-modal mappings of auditory stimuli reveal valuable insights into how humans make sense of sound and music. Whereas researchers have investigated cross-modal mappings of sound features varied in isolation within paradigms such as speeded classification and forced-choice matching tasks, investigations of representations of concurrently varied sound features (e.g., pitch, loudness and tempo) with overt gestures-accounting for the intrinsic link between movement and sound-are scant. To explore the role of bodily gestures in cross-modal mappings of auditory stimuli we asked 64 musically trained and untrained participants to represent pure tones-continually sounding and concurrently varied in pitch, loudness and tempo-with gestures while the sound stimuli were played. We hypothesized musical training to lead to more consistent mappings between pitch and height, loudness and distance/height, and tempo and speed of hand movement and muscular energy. Our results corroborate previously reported pitch vs. height (higher pitch leading to higher elevation in space) and tempo vs. speed (increasing tempo leading to increasing speed of hand movement) associations, but also reveal novel findings pertaining to musical training which influenced consistency of pitch mappings, annulling a commonly observed bias for convex (i.e., rising-falling) pitch contours. Moreover, we reveal effects of interactions between musical parameters on cross-modal mappings (e.g., pitch and loudness on speed of hand movement), highlighting the importance of studying auditory stimuli concurrently varied in different musical parameters. Results are discussed in light of cross-modal cognition, with particular emphasis on studies within (embodied) music cognition. Implications for theoretical refinements and potential clinical applications are provided.

  1. The speed of our mental soundtracks: Tracking the tempo of involuntary musical imagery in everyday life.

    Science.gov (United States)

    Jakubowski, Kelly; Farrugia, Nicolas; Halpern, Andrea R; Sankarpandi, Sathish K; Stewart, Lauren

    2015-11-01

    The study of spontaneous and everyday cognitions is an area of rapidly growing interest. One of the most ubiquitous forms of spontaneous cognition is involuntary musical imagery (INMI), the involuntarily retrieved and repetitive mental replay of music. The present study introduced a novel method for capturing temporal features of INMI within a naturalistic setting. This method allowed for the investigation of two questions of interest to INMI researchers in a more objective way than previously possible, concerning (1) the precision of memory representations within INMI and (2) the interactions between INMI and concurrent affective state. Over the course of 4 days, INMI tempo was measured by asking participants to tap to the beat of their INMI with a wrist-worn accelerometer. Participants documented additional details regarding their INMI in a diary. Overall, the tempo of music within INMI was recalled from long-term memory in a highly veridical form, although with a regression to the mean for recalled tempo that parallels previous findings on voluntary musical imagery. A significant positive relationship was found between INMI tempo and subjective arousal, suggesting that INMI interacts with concurrent mood in a similar manner to perceived music. The results suggest several parallels between INMI and voluntary imagery, music perceptual processes, and other types of involuntary memories.

  2. Individual differences in the biomechanical effect of loudness and tempo on upper-limb movements during repetitive piano keystrokes.

    Science.gov (United States)

    Furuya, Shinichi; Aoki, Tomoko; Nakahara, Hidehiro; Kinoshita, Hiroshi

    2012-02-01

    The present study addressed the effect of loudness and tempo on kinematics and muscular activities of the upper extremity during repetitive piano keystrokes. Eighteen pianists with professional music education struck two keys simultaneously and repetitively with a combination of four loudness levels and four tempi. The results demonstrated a significant interaction effect of loudness and tempo on peak angular velocity for the shoulder, elbow, wrist and finger joints, mean muscular activity for the corresponding flexors and extensors, and their co-activation level. The interaction effect indicated greater increases with tempo when eliciting louder tones for all joints and muscles except for the elbow velocity showing a greater decrease with tempo. Multiple-regression analysis and K-means clustering further revealed that 18 pianists were categorized into three clusters with different interaction effects on joint kinematics. These clusters were characterized by either an elbow-velocity decrease and a finger-velocity increase, a finger-velocity decrease with increases in shoulder and wrist velocities, or a large elbow-velocity decrease with a shoulder-velocity increase when increasing both loudness and tempo. Furthermore, the muscular load considerably differed across the clusters. These findings provide information to determine muscles with the greatest potential risk of playing-related disorders based on movement characteristics of individual pianists. Copyright © 2011 Elsevier B.V. All rights reserved.

  3. tempo astorico e spazio mitologico nella riflessione e nella pratica ...

    African Journals Online (AJOL)

    User

    Tempo astorico” e “spazio mitologico” in Pirandello? Esiste dunque un Pirandello mitologico? È possibile parlare non tanto di miti ma di vera e propria mitologia per uno scrittore come l'Agrigentino che è, senz'ombra di dubbio, il massimo drammaturgo italiano della modernità ed è conosciuto internazionalmente come ...

  4. Análise do tempo de ventilação mecânica e internamento em pacientes submetidos a cirurgia cardíaca

    Directory of Open Access Journals (Sweden)

    André Luiz Lisboa Cordeiro

    2017-04-01

    Full Text Available Introdução: Pacientes submetidos à cirurgia cardíaca (CC necessitam de ventilação mecânica invasiva (VMI após o procedimento cirúrgico, sendo que um tempo prolongado de VMI pode levar a um aumento do tempo de permanência na Unidade de Terapia Intensiva (UTI. Objetivo: Verificar se o tempo de VMI interfere no tempo de internação em UTI. Métodos: Foram analisados, prospectivamente, pacientes submetidos à CC e que permaneceram por um tempo inferior a 24 horas na VMI. Foram selecionados 69 pacientes, os quais foram admitidos na UTI e acompanhados até o momento da extubação. Com esse dado encontrou-se o tempo que permaneceram em VMI e, depois, quantos dias permaneceram internados na UTI até o momento da alta da unidade. Resultados: A maior parte dos pacientes submetidos à CC foi do sexo masculino (56,5%; a idade média foi de 55,93±14,29 anos; o tipo de cirurgia mais prevalente foi a revascularização miocárdica (71,0%; o tempo médio de circulação extracorpórea (CEC foi de 65,05±20,06 minutos; o tempo médio de internação na UTI foi de 2,18±1,10 dias; o tempo de VMI foi de 7,32±2,66 horas. Não se verificou significância estatística entre essas duas últimas variáveis com um p=0,43. Conclusão: Pode-se concluir que não houve correlação entre o tempo de ventilação mecânica e tempo de internação em UTI em pacientes que não apresentaram complicações pós-operatórias imediatas e que permaneceram menos de 12 horas sob ventilação mecânica.

  5. Development of a new free radical absorption capacity assay method for antioxidants: aroxyl radical absorption capacity (ARAC).

    Science.gov (United States)

    Nagaoka, Shin-ichi; Nagai, Kanae; Fujii, Yuko; Ouchi, Aya; Mukai, Kazuo

    2013-10-23

    A new free radical absorption capacity assay method is proposed with use of an aroxyl radical (2,6-di-tert-butyl-4-(4'-methoxyphenyl)phenoxyl radical) and stopped-flow spectroscopy and is named the aroxyl radical absorption capacity (ARAC) assay method. The free radical absorption capacity (ARAC value) of each tocopherol was determined through measurement of the radical-scavenging rate constant in ethanol. The ARAC value could also be evaluated through measurement of the half-life of the aroxyl radical during the scavenging reaction. For the estimation of the free radical absorption capacity, the aroxyl radical was more suitable than the DPPH radical, galvinoxyl, and p-nitrophenyl nitronyl nitroxide. The ARAC value in tocopherols showed the same tendency as the free radical absorption capacities reported previously, and the tendency was independent of an oxygen radical participating in the scavenging reaction and of a medium surrounding the tocopherol and oxygen radical. The ARAC value can be directly connected to the free radical-scavenging rate constant, and the ARAC method has the advantage of treating a stable and isolable radical (aroxyl radical) in a user-friendly organic solvent (ethanol). The ARAC method was also successfully applied to a palm oil extract. Accordingly, the ARAC method would be useful in free radical absorption capacity assay of antioxidative reagents and foods.

  6. Proposta de arquitetura de hardware e software para sistemas tempo-real distribuídos

    OpenAIRE

    Marcelo Gotz

    2001-01-01

    Um sistema tempo-real caracteriza-se por possuir requisitos temporais para execução de suas atividades, e de acordo com a sua tolerância ao atendimento destes requisitos é classificado em hard-real-time ou soft-real-time. O presente trabalho se propõe a apresentar uma arquitetura de hardware e software para suporte a sistemas tempo-real embarcados de baixo custo com objetivo de aplicação em pesquisas no meio acadêmico e que possa ser usado até em ambientes hard-real-time. A motivação para est...

  7. Atom-transfer radical polymerization of methyl methacrylate (MMA) using CuSCN as the catalyst

    NARCIS (Netherlands)

    Singha, N.K.; Klumperman, B.

    2000-01-01

    The effect of CuSCN as a catalyst in atom-transfer radical polymerization (ATRP) was investigated. CuSCN can successfully be used for the ATRP of MMA. Substituted bipyridines as well as imines can be used to stabilize the copper complex in solution. CuSCN induces faster polymerization compared to

  8. The application of radiation-induced free radicals signals in retrospective dosimetry

    International Nuclear Information System (INIS)

    Liu Zhongchao; Zhang Wenyi; Jiao Ling

    2013-01-01

    For some materials and biological samples, free radicals can be induced after ionizing radiation. Electron spin resonance (ESR) spectroscopy can detect free radical signal and its intensity can reflect the dose of the ionizing radiation. It is a typical way to estimate the radiation dosimetry by using the ESR spectroscopy of teeth. In recent years, many researchers studied on ESR of easy-getting materials such as finger (toe) nail, hair, cell phone screen, in order to investigate the relationship between signal intensity and radiation dose. The aim of this paper is to survey the current literature about methodologies and the materials on background signal, linearity of dose-response relationship, minimum detection limit and post-irradiation signal stability, so that more data will be provided for nuclear accident dose estimation. (authors)

  9. Physiology of free radicals

    Directory of Open Access Journals (Sweden)

    Stevanović Jelka

    2011-01-01

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

  10. Long-Term Memory for Music: Infants Remember Tempo and Timbre

    Science.gov (United States)

    Trainor, Laurel J.; Wu, Luann; Tsang, Christine D.

    2004-01-01

    We show that infants' long-term memory representations for melodies are not just reduced to the structural features of relative pitches and durations, but contain surface or performance tempo- and timbre-specific information. Using a head turn preference procedure, we found that after a one week exposure to an old English folk song, infants…

  11. Abstraction of iodine from aromatic iodides by alkyl radicals: steric and electronic effects.

    Science.gov (United States)

    Dolenc, Darko; Plesnicar, Bozo

    2006-10-13

    Abstraction of the iodine atom from aryl iodides by alkyl radicals takes place in some cases very efficiently despite the unfavorable difference in bond dissociation energies of C-I bonds in alkyl and aryl iodides. The abstraction is most efficient in iodobenzenes, ortho-substituted with bulky groups. The ease of abstraction can be explained by the release of steric strain during the elimination of the iodine atom. The rate of abstraction correlates fairly well with the strain energy, calculated by density functional theory (DFT) and Hartree-Fock (HF) methods as a difference in the total energy of ortho and para isomers. However, besides the steric bulk, the presence of some other functional groups in an ortho substituent also influences the rate. The stabilization of the transition state, resembling a 9-I-2 iodanyl radical, by electron-withdrawing groups seems to explain a positive sign of the Hammett rho value in the radical abstraction of halogen atoms.

  12. Effects of music tempo on performance, psychological, and physiological variables during 20 km cycling in well-trained cyclists.

    Science.gov (United States)

    2013-10-01

    Few studies have investigated the effects of music on trained athletes during high intensity endurance tasks. Therefore, this study investigated the effects of different music tempi on performance, psychological, and physiological responses of well-trained cyclists to time trial cycling. 10 male road cyclists (M age = 35 yr., SD = 7), with a minimum of three years racing experience, performed four 20-km time trials on a Computrainer Pro 3D indoor cycle trainer over a period of four weeks. The time-trials were spaced one week apart. The music conditions for each trial were randomised between fast-tempo (140 bpm), medium-tempo (120 bpm), slow-tempo (100 bpm), and no music. Performance (completion time, power output, average speed and cadence), physiological (heart rate, oxygen consumption, breathing frequency and respiratory exchange ratio), psychophysical (RPE), and psychological (mood states) data were collected for each trial. Results indicated no significant changes in performance, physiological, or psychophysical variables. Total mood disturbance and tension increased significantly in the fast-tempo trial when compared with medium and no-music conditions.

  13. Vinylcyclopropylacyl and polyeneacyl radicals. Intramolecular ketene alkyl radical additions in ring synthesis.

    Science.gov (United States)

    De Boeck, Benoit; Herbert, Nicola M A; Harrington-Frost, Nicole M; Pattenden, Gerald

    2005-01-21

    Treatment of a variety of substituted vinylcyclopropyl selenyl esters, e.g. 11, with Bu(3)SnH-AIBN in refluxing benzene leads to the corresponding acyl radical intermediates, which undergo rearrangement and intramolecular cyclisations via their ketene alkyl radical equivalents producing cyclohexenones in 50-60% yield. By contrast, treatment of conjugated triene selenyl esters, e.g. 32, with Bu(3)SnH-AIBN produces substituted 2-cyclopentenones via intramolecular cyclisations of their ketene alkyl radical intermediates. Under the same radical-initiating conditions the selenyl esters derived from o-vinylbenzoic acid and o-vinylcinnamic acid undergo intramolecular cyclisations producing 1-indanone and 5,6-dihydrobenzocyclohepten-7-one respectively in 60-70% yields. A tandem radical cyclisation from the alpha,beta,gamma,delta-diene selenyl ester 31 provides an expeditious synthesis of the diquinane 35 in 69% yield.

  14. Intra- and intersubject comparison of cochlear implant systems using the Esprit and the Tempo+ behind-the-ear speech processor.

    Science.gov (United States)

    Kompis, Martin; Jenk, Martin; Vischer, Mattheus W; Seifert, Eberhard; Häusler, Rudolf

    2002-12-01

    A patient with bilateral profound deafness was implanted with a Nucleus CI24M cochlear implant (CI) and used an Esprit behind-the-ear (BTE) speech processor. Thirteen months later, the implant had to be removed because of a cholesteatoma. As the same electrode could not be reinserted, a Medel combi40s CI was implanted in the same ear, and the patient used a Tempo+ BTE processor. After 1 year of use of the Combi40s/Tempo+ system, speech recognition was better and was rated better subjectively than with the CI24M/Esprit system. Speech recognition and subjective ratings were also assessed for two matched groups of nine CI users each, using either an Esprit or a Tempo+ processor. On average, speech recognition scores were higher for the group of Tempo+ users, but the difference was not statistically significant. Users of the Esprit processors rated their device higher in terms of cosmetic appearance and comfort of wearing.

  15. Serum Hydroxyl Radical Scavenging Capacity as Quantified with Iron-Free Hydroxyl Radical Source

    Science.gov (United States)

    Endo, Nobuyuki; Oowada, Shigeru; Sueishi, Yoshimi; Shimmei, Masashi; Makino, Keisuke; Fujii, Hirotada; Kotake, Yashige

    2009-01-01

    We have developed a simple ESR spin trapping based method for hydroxyl (OH) radical scavenging-capacity determination, using iron-free OH radical source. Instead of the widely used Fenton reaction, a short (typically 5 seconds) in situ UV-photolysis of a dilute hydrogen peroxide aqueous solution was employed to generate reproducible amounts of OH radicals. ESR spin trapping was applied to quantify OH radicals; the decrease in the OH radical level due to the specimen’s scavenging activity was converted into the OH radical scavenging capacity (rate). The validity of the method was confirmed in pure antioxidants, and the agreement with the previous data was satisfactory. In the second half of this work, the new method was applied to the sera of chronic renal failure (CRF) patients. We show for the first time that after hemodialysis, OH radical scavenging capacity of the CRF serum was restored to the level of healthy control. This method is simple and rapid, and the low concentration hydrogen peroxide is the only chemical added to the system, that could eliminate the complexity of iron-involved Fenton reactions or the use of the pulse-radiolysis system. PMID:19794928

  16. Strength and tempo of directional selection in the wild

    OpenAIRE

    Hoekstra, H. E.; Hoekstra, J. M.; Berrigan, D.; Vignieri, S. N.; Hoang, A.; Hill, C. E.; Beerli, P.; Kingsolver, J. G.

    2001-01-01

    Directional selection is a major force driving adaptation and evolutionary change. However, the distribution, strength, and tempo of phenotypic selection acting on quantitative traits in natural populations remain unclear across different study systems. We reviewed the literature (1984–1997) that reported the strength of directional selection as indexed by standardized linear selection gradients (β). We asked how strong are viability and sexual selection, and whether strength of selection is ...

  17. Radical transfer between proteins: role of tyrosine, tryptophan and protein peroxyl radicals

    International Nuclear Information System (INIS)

    Irwin, J.A.; Ostdal, H.; Davies, M.J.

    1998-01-01

    Reaction of the Fe(III) forms of the heme proteins myoglobin (Mb) and horseradish peroxidase (HRP) with H 2 O 2 gives rise to high-oxidation-state heme-derived species which can be described as a Fe(IV)-oxo porphyrin radical-cation ('Compound 1'). In the case of Mb, the Fe(IV)-oxo porphyrin radical-cation undergoes rapid electron transfer with the surrounding protein to give protein (globin)-derived radicals and an Fe(lV)-oxo species ('Compound 2'). The globin-derived radicals have been shown to be located at two (or more) sites: Tyr-103 or Trp-14, with the latter radical known to react with oxygen to give a Trp-derived peroxyl radical (Mb-Trp-OO*). With HRP, the Fe(lV)-oxo porphyrin radical-cation carries out two successive one-electron oxidation reactions at the exposed heme edge to give firstly 'Compound 2' [the Fe(lV)oxo species] and then the resting Fe(III) state of the enzyme. n this study we have investigated whether the Trp-14 peroxyl radical from Mb and the Compound 1 and 2 species from HRP (in the absence and presence of free Tyr) can oxidise amino acids, peptides and proteins. Such reactions constitute intermolecular protein-to-protein radical transfer reactions and hence protein chain-oxidation. We have also examined whether these oxidants react with antioxidants. Reaction of these heme-protein derived oxidants with amino acids, proteins and antioxidants has been carried out at room temperature for defined periods of time before freeze-quenching to 77K to halt reaction. The radical species present in the reaction system at the time of freezing were subsequently examined by EPR spectroscopy at 77K. Three free amino acids, Tyr, Trp and Cys (with Cys the least efficient) have been shown to react rapidly with Mb-Trp-OO*, as evidenced by the loss of the characteristic EPR features of Mb-Trp-OO* on inclusion of increasing concentrations of the amino acids. All other amino acids are much less reactive. Evidence has also been obtained for (inefficient) hydrogen

  18. Phytoplankton Biogeography and Community Stability in the Ocean

    Science.gov (United States)

    Cermeño, Pedro; de Vargas, Colomban; Abrantes, Fátima; Falkowski, Paul G.

    2010-01-01

    Background Despite enormous environmental variability linked to glacial/interglacial climates of the Pleistocene, we have recently shown that marine diatom communities evolved slowly through gradual changes over the past 1.5 million years. Identifying the causes of this ecological stability is key for understanding the mechanisms that control the tempo and mode of community evolution. Methodology/Principal Findings If community assembly were controlled by local environmental selection rather than dispersal, environmental perturbations would change community composition, yet, this could revert once environmental conditions returned to previous-like states. We analyzed phytoplankton community composition across >104 km latitudinal transects in the Atlantic Ocean and show that local environmental selection of broadly dispersed species primarily controls community structure. Consistent with these results, three independent fossil records of marine diatoms over the past 250,000 years show cycles of community departure and recovery tightly synchronized with the temporal variations in Earth's climate. Conclusions/Significance Changes in habitat conditions dramatically alter community structure, yet, we conclude that the high dispersal of marine planktonic microbes erases the legacy of past environmental conditions, thereby decreasing the tempo of community evolution. PMID:20368810

  19. Homegrown religious radicalization

    DEFF Research Database (Denmark)

    Khawaja, Iram

    It has been reported that a growing number of youngsters from Western Europe are engaging in conflicts motivated by religious and political conflicts in the Middle East. This paper explores the reasons behind this seemingly religious radicalization from the point of view of the youngsters...... youngsters and parents of youngsters who have chosen a radicalized path in life. The paper will shed light on how the sense of and yearning for belonging and recognition have to be taken into account in our understanding of homegrown religious radicalization...

  20. Laparoscopic radical trachelectomy.

    Science.gov (United States)

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

    2012-01-01

    The standard treatment for patients with early-stage cervical cancer has been radical hysterectomy. However, for women interested in future fertility, radical trachelectomy is now considered a safe and feasible option. The use of minimally invasive surgical techniques to perform this procedure has recently been reported. We report the first case of a laparoscopic radical trachelectomy performed in a developing country. The patient is a nulligravid, 30-y-old female with stage IB1 adenocarcinoma of the cervix who desired future fertility. She underwent a laparoscopic radical trachelectomy and bilateral pelvic lymph node dissection. The operative time was 340 min, and the estimated blood loss was 100mL. There were no intraoperative or postoperative complications. The final pathology showed no evidence of residual disease, and all pelvic lymph nodes were negative. At 20 mo of follow-up, the patient is having regular menses but has not yet attempted to become pregnant. There is no evidence of recurrence. Laparoscopic radical trachelectomy with pelvic lymphadenectomy in a young woman who desires future fertility may also be an alternative technique in the treatment of early cervical cancer in developing countries.

  1. Marxismo, a alienação e o tempo histórico da barbárie social do capital Marxism, Alienation and the Historic Time of the Social Barbarity of Capital

    Directory of Open Access Journals (Sweden)

    Giovanni Alves

    2013-06-01

    Full Text Available O objetivo do ensaio é expor a alienação/estranhamento como o problema crucial do nosso tempo histórico, buscando salientar os significados do conceito de "autotranscendência positiva da alienação", considerada por István Meszáros, como sendo o eixo da reflexão marxiana nos Manuscritos econômico-filosóficos. Para tanto, discorre sobre o novo registro histórico da Aufhebung nas condições da crise estrutural do capital e a vigência do capitalismo global como capitalismo manipulatório. Aborda a centralidade ontológica da problemática da vida cotidiana e o estranhamento na perspectiva da crítica radical do trabalho. Finalmente, coloca elementos para refletir, na perspectiva do marxismo radical, sobre a transição como sendo o problema de produção dos sujeitos humanos, capazes da autotranscendência positiva da alienação.The purpose of this essay is to explore alienation as a crucial problem of our historic time, seeking to emphasize the meanings of the concept of "positive self-transcendence of alienation", which is considered by István Meszáros as the central axis of Marxian reflection in the Economic-Philosophic Manuscripts. To do so, it looks at the new historic registration of Aufhebung considering the conditions of the structural crisis of capital and the rule of global capitalism as manipulative capitalism. It addresses the ontological centrality of the problematic of everyday life and alienation from the perspective of the radical criticism of work. Finally, it raises elements for reflection, from a radical Marxist perspective, about the transition as being the problem of production of human subjects, capable of positive self-transcendence from alienation.

  2. Radical Evil

    Directory of Open Access Journals (Sweden)

    Carlos Manrique

    2007-12-01

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

  3. Considerações sobre a idéia de tempo em Sto. Agostinho, Hume e Kant

    Directory of Open Access Journals (Sweden)

    Marcelo Carbone Carneiro

    2004-08-01

    Full Text Available Discute-se sobre o tempo buscando entendê-lo a partir dos referenciais que o tomam como elaboração subjetiva, ou seja, como não possuindo qualquer realidade fora do sujeito. Entende-se que, na história da Filosofia, esta reflexão inicia-se com a filosofia de Sto. Agostinho e tem seu ápice no pensamento moderno, sobretudo em Hume e Kant. O tempo seria uma construção ou elaboração do espírito, sem existência fora dele (Sto. Agostinho ou uma apreensão empírica regular de relações causais de antes e depois (Hume ou uma intuição pura do espírito (Kant. Pretende-se, com esta análise, evidenciar uma forma clássica de conceber o tempo como elaboração realizada pelo sujeito (subjetiva.

  4. Adopting a music-to-heart rate alignment strategy to measure the impact of music and its tempo on human heart rate

    OpenAIRE

    Van Dyck, Edith; Six, Joren; Soyer, Esin Nisa; Denys, Marlies; Bardijn, Ilka; Leman, Marc

    2017-01-01

    Music is frequently used as a means of relaxation. Conversely, it is used as a means of arousal in sports and exercise contexts. Previous research suggests that tempo is one of the most significant determinants of music-related arousal and relaxation effects. Here we investigate the specific effect of music tempo, but also more generally, the influence of music on human heart rate. We took the pulses of 32 participants in silence, and then we played them non-vocal, ambient music at a tempo co...

  5. N-tert-butylmethanimine N-oxide is an efficient spin-trapping probe for EPR analysis of glutathione thiyl radical

    Science.gov (United States)

    Scott, Melanie J.; Billiar, Timothy R.; Stoyanovsky, Detcho A.

    2016-01-01

    The electron spin resonance (EPR) spin-trapping technique allows detection of radical species with nanosecond half-lives. This technique is based on the high rates of addition of radicals to nitrones or nitroso compounds (spin traps; STs). The paramagnetic nitroxides (spin-adducts) formed as a result of reactions between STs and radical species are relatively stable compounds whose EPR spectra represent “structural fingerprints” of the parent radical species. Herein we report a novel protocol for the synthesis of N-tert-butylmethanimine N-oxide (EBN), which is the simplest nitrone containing an α-H and a tertiary α′-C atom. We present EPR spin-trapping proof that: (i) EBN is an efficient probe for the analysis of glutathione thiyl radical (GS•); (ii) β-cyclodextrins increase the kinetic stability of the spin-adduct EBN/•SG; and (iii) in aqueous solutions, EBN does not react with superoxide anion radical (O2−•) to form EBN/•OOH to any significant extent. The data presented complement previous studies within the context of synthetic accessibility to EBN and efficient spin-trapping analysis of GS•. PMID:27941944

  6. Tempo e patrimônio Temporality and patrimony

    Directory of Open Access Journals (Sweden)

    François Hartog

    2006-12-01

    Full Text Available O artigo discute a redefinição da "memória" e do "patrimônio" dentro do novo "regime de historicidade" que o Ocidente vive após a Queda do Muro de Berlim (1989. Estas palavras-chave são tratadas como indícios, sintomas, de nossa relação com o tempo, como testemunhas da "crise" da ordem presente do tempo. O problema abordado: um novo regime de historicidade, centrado sobre o presente, estaria se formulando? Para o autor, ocorreu um crescimento rápido da categoria do presente e se impôs a evidência de um presente onipresente, que ele nomeia "presentismo", onde se vive entre a amnésia e a vontade de nada esquecer.This article discusses the redefinition of "memory" and "patrimony" within the new "regime of historicity" set in motion in the West after the fall of the Berlin Wall (1989. These keywords are treated as indicators or symptoms of our relation with time, as witnesses of the "crises" of the present order of time. The question that is approached is the following: is a new regime of historicity, one based on the present, taking shape? In the author's view, the category of present has grown rather fast and imposed an omnipotent present, which he names "presentism". This condition causes one to be torn between amnesia and the desire not to forget.

  7. Effects of Style, Tempo, and Performing Medium on Children's Music Preference.

    Science.gov (United States)

    LeBlanc, Albert

    1981-01-01

    Fifth-graders listened to a tape incorporating fast and slow vocal and instrumental excerpts within the generic styles of rock/pop, country, older jazz, newer jazz, art music, and band music. A preference hierarchy emerged favoring the popular styles. Across pooled styles, faster tempos and instrumentals were slightly preferred. (Author/SJL)

  8. Gestão do tempo como apoio ao planejamento estratégico pessoal Time management and support to personal strategic planning

    Directory of Open Access Journals (Sweden)

    Cristiano Descovi Schimith

    2011-08-01

    Full Text Available Este estudo parte do pressuposto de que a gestão do tempo pode auxiliar o planejamento estratégico pessoal, sistematizando sua implantação. Desta forma, o objetivo do trabalho consiste em propor um modelo de gestão do tempo que contribua com a implantação do planejamento estratégico pessoal. Para atingi-lo, o estudo tem seus fundamentos teóricos no Planejamento Estratégico, no Planejamento Estratégico Pessoal e na Gestão do Tempo. A análise da literatura permitiu identificar elementos essenciais para a composição do modelo proposto. Os resultados obtidos revelam um Modelo de Gestão do Tempo, lógico e sequencial, que envolve fatores técnicos e comportamentais, composto por três fases: auditoria do tempo (situação real, alavancagem do tempo (situação ideal e enquadramento do tempo (planejamento semanal, planejamento diário e priorização. This study assumes that time management can support the personal strategic planning, streamlining its implementation. So the objective of this study is to propose a model of time management that contributes to the implementation of the strategic planning personal. To achieve it, the study has its theoretical foundations in Strategic Planning, Strategic Planning Personal and Time Management. The literature review identified key elements in the composition of the proposed model. The results reveal a Model of Time Management, logical and sequential, which involves technical and behavioral factors. The model consists of three phases: audit of time (real situation, leverage the time (ideal situation and the time frame (weekly planning, daily planning and prioritizing.

  9. UM ESTUDO SOBRE O TEMPO-PADRÃO NO PROCESSO PRODUTIVO DE RECAPAGEM DE PNEUS EM UMA CONCESSIONÁRIA DE VEÍCULOS

    Directory of Open Access Journals (Sweden)

    Andreas Dittmar Weise

    2013-01-01

    Full Text Available Em um contexto de um mercado cada vez mais competitivo, as empresas necessitam manter-se em constante busca por aperfeiçoamento em seus processos. Para isso, a administração eficaz dos seus processos produtivos e das operações desenvolvidas traz consigo elementos voltados para o alcance dos objetivos estratégicos, podendo ocasionar sucessivas reduções de uso desnecessário dos recursos, de tempo e, consequentemente, de capital, o que poderá gerar mais ganhos financeiros e menor desperdício. Assim, este artigo tem como objetivo analisar o processo produtivo da recapagem de pneus em uma concessionária de veículos através do estudo do tempo-padrão das operações. O estudo desenvolveu-se por meio de um estudo de caso, com abordagens qualitativa e quantitativa, do tipo descritiva. Primeiramente, através de observação in loco, analisaram-se, durante o processo de recapagem de pneus, o tempo normal e o tempo-padrão das atividades desempenhadas e, posteriormente, todas as etapas foram devidamente cronometradas, mediante doze repetições, para, então, se chegar ao cálculo do tempo médio de cada etapa do processo de recapagem. Como resultados, destaca-se que, em grande parte das etapas do processo, o tempo médio e o tempo-padrão identificados são semelhantes, não apresentando discrepância significativa entre os valores encontrados. No entanto, o problema referente à rotatividade de colaboradores no setor é uma questão que precisa ser analisada com mais atenção por parte dos gestores da empresa. Palavras-chave: Gestão da produção. Gerenciamento de processos. Planejamento de recursos.

  10. Influência do tempo de aclimatação na resposta do cajueiro à salinidade

    OpenAIRE

    Brilhante, Jean C. A.; Silveira, Joaquim A. G.; Rocha, Iza M. A.; Morais, Déborah L. de; Viégas, Ricardo A.

    2007-01-01

    A resposta das plantas à salinidade depende de fatores fisiológicos, bioquímicos e genéticos. Com este trabalho, objetivou-se estudar o impacto do tempo de aclimatação à solução nutritiva sobre a resposta do cajueiro à salinidade. Plantas de Anarcadium occidentale L., CCP06, cultivadas em vermiculita durante 28 dias, foram transferidas para solução nutritiva de Hoagland com 1/10 de sua força iônica, onde permaneceram por 1 e 7 dias. Ao final dos dois tempos, a solução nutritiva foi suplementa...

  11. Practical Aerobic Oxidations of Alcohols and Amines with Homogeneous Cu/TEMPO and Related Catalyst Systems

    Science.gov (United States)

    Ryland, Bradford L.; Stahl, Shannon S.

    2014-01-01

    Alcohol and amine oxidations are common reactions in laboratory and industrial synthesis of organic molecules. Aerobic oxidation methods have long been sought for these transformations, but few practical methods exist that offer advantages over traditional oxidation methods. Recently developed homogeneous Cu/TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidinyl-N-oxyl) and related catalyst systems appear to fill this void. The reactions exhibit high levels of chemoselectivity and broad functional-group tolerance, and they often operate efficiently at room temperature with ambient air as the oxidant. These advances, together with their historical context and recent applications, are highlighted in this minireview. PMID:25044821

  12. Radical constructivism: Between realism and solipsism

    Science.gov (United States)

    Martínez-Delgado, Alberto

    2002-11-01

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

  13. Romancização ou serialização: ou diferentes formas de tempo

    Directory of Open Access Journals (Sweden)

    Peter Hitchcock

    2015-11-01

    Full Text Available Este artigo explora a noção bakhtiniana de romancização no que se refere à sua teoria de tempo e serialização. Bakhtin, para quem o romance é histórico, mas sem história, remonta à Grécia antiga para traçar a história do romance. Sem dar a ele uma identidade fixa, compreende-o em termos de tendências e crises. A romancização, para Bakhtin, é um meio de tornar a história literária acessível a uma análise mais dialógica da forma e um modo discursivo para avaliar ideologias criticamente. Ele enfatiza a habilidade desestabilizadora do romance, sua descentralização do discurso e sua acomodação de vozes não oficiais e estrangeiras. Seu sugestivo relato histórico do desenvolvimento do romance nos permite estender seu pensamento e esboçar a romancização mais como uma condição futura do que uma lei genérica. Bakhtin oferece uma versão problemática de modernidade, na qual o romance ativa a influência do tempo sobre o presente; no entanto, por causa da propensão à crise da modernidade, o tempo é suspenso. O artigo também examina um cronotopo do romance sobre o qual Bakhtin tem pouco a dizer: o tempo/espaço da nação. Benedict Anderson e Etienne Balibar, cujos interesses incluem temas relacionados ao comparatismo, ao multiculturalismo e ao pós-colonialismo, questionam a ideia de nação por meio de análises em que o gênero romanesco é privilegiado.

  14. Studies of initial stage in coal liquefaction. 4. Radical formation and structural change with thermal decomposition of coal; Ekika hanno no shoki katei ni kansuru kenkyu. 4. Netsubunkai ni tomonau radical seisei kyodo to kozo henka

    Energy Technology Data Exchange (ETDEWEB)

    Kanaji, M.; Kaneko, T.; Shimasaki, K. [Nippon Brown Coal Liquefaction Co. Ltd., Tokyo (Japan); Kumagai, H.; Chiba, T. [Hokkaido University, Sapporo (Japan). Center for Advanced Research of Energy Technology

    1996-10-28

    In relation to coal liquefaction reaction, the effect of the coexistence of transferable hydrogen (TH) from process solvent on reduction of radical concentration and the effect of pre-heat treatment on average structure of coals were studied. In experiment, change in radical concentration with temperature rise was measured using the system composed of Yallourn coal and process solvent. The results are as follows. Process solvent with a wide boiling point range of 180-420{degree}C is effective in suppressing an increase in radical concentration even at higher temperature. The effect of hydrogen-donating solvent increases with TH. It was also suggested that high-boiling point constituents in solvent stabilize radicals even over 400{degree}C by vapor phase hydrogenation. The experimental results of pre-heat treatment are as follows. Although the conversion improvement effect of TH is equivalent to that of the model solvent, TH tends to produce soluble products with smaller ring numbers. It was thus suggested that pre-heat treatment in process solvent is effective to inhibit retrogressive reactions. 6 refs., 5 figs., 1 tab.

  15. O regime de dedicação exclusiva e a gestão do tempo: estudo de caso com docentes universitários.

    Directory of Open Access Journals (Sweden)

    Leonardo de Brito Quevedo

    2013-12-01

    Full Text Available Esta pesquisa propôs investigar o comportamento dos docentes atuantes sob regime dededicação exclusiva na UNIPAMPA, frente à gestão do tempo de trabalho e tempo livre. Oestudo teve caráter exploratório e descritivo, pois procurou compreender o comportamento deum grupo particular, configurando-se, portanto, como um estudo de caso. Escolheu-se comotécnica de coleta de dados a entrevista semiestruturada. Doze docentes foram entrevistados.Conclui-se que todos os docentes mantêm uma gestão do tempo de trabalho e do tempo livre,evidenciando que a atividade docente interfere na vida pessoal dos mesmos, principalmentena quantidade de tarefas do trabalho levadas para casa.

  16. Salvage robotic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Samuel D Kaffenberger

    2014-01-01

    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.

  17. PERFIL SENSORIAL DE CULTIVARES DE FEIJÃO SOB DIFERENTES TEMPOS DE COZIMENTO

    Directory of Open Access Journals (Sweden)

    Viviani Ruffo de OLIVEIRA

    2013-04-01

    Full Text Available O objetivo deste trabalho foi determinar o tempo necessário de cozimento de cultivares de feijão de grãos preto e carioca, em panela de pressão doméstica, para a identificação de cultivares de melhor perfil sensorial para o consumo. Para tanto, utilizaram-se grãos de quatro cultivares de feijão: BRS Expedito, BRS Campeiro, Pérola e Carioca e o cozimento foi realizado em panela de pressão doméstica por 15, 20, 25 e 30 minutos. A avaliação do perfil sensorial foi efetuada em três etapas: seleção, treinamento para a Análise Descritiva Quantitativa (ADQ e ADQ propriamente dita, com sete avaliadores treinados. Os avaliadores reconheceram diferenças para as cultivares de feijão quanto à uniformidade da cor do grão, cor do caldo, à viscosidade, à dureza e a granulosidade. A ruptura no tegumento dos grãos foi maior à medida que se aumentou o tempo de cozimento. A dureza e a granulosidade apresentaram maiores intensidades conforme aumentou o tempo de cozimento dos grãos de feijão. A utilização de 20 a 25 minutos de cozimento em panela de pressão doméstica possibilita a identificação de cultivares de feijão de grãos preto e carioca com melhor perfil sensorial para o consumo, mantendo a integridade dos grãos cozidos.

  18. Muoniated acyl and thioacyl radicals

    International Nuclear Information System (INIS)

    McKenzie, Iain; Brodovitch, Jean-Claude; Ghandi, Khashayar; Percival, Paul W.

    2006-01-01

    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 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 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

  19. Muoniated acyl and thioacyl radicals

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-03-31

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

  20. Muonium and muonic radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Geeson, D.; Symons, M.C.R.

    1985-01-01

    An energetic positive muon which is injected in a liquid sample of substrate molecules (S) creates an ionization track consisting of substrate cations (S + ) and electrons. Near the end of this track the muon may combine with an electron to form muonium (Mu) which is observable in inert liquids, but which reacts by addition to form a radical. Alternatively, the electron can add to S to form S - , which then combines with the muon to form the radical. Furthermore, instead of ending up in Mu or in a radical the muon may stay in a diamagnetic environment as a solvated muon, or as a muon substituting a proton in a molecule. Of interest in these schemes are the mechanisms and rates of formation of muonated radicals and in particular the rate constants for their reactions to products. Investigations are based on the observation of Mu and the radical by means of the μSR technique in transverse magnetic fields. (Auth.)

  1. Leghemoglobin-derived radicals. Evidence for multiple protein-derived radicals and the initiation of peribacteroid membrane damage

    DEFF Research Database (Denmark)

    Moreau, S; Davies, Michael Jonathan; Mathieu, C

    1996-01-01

    , with the consequent generation of lipid-derived radicals. The formation of such radicals may result in the depletion of membrane antioxidants and the initiation of lipid peroxidation. This transfer of damage from the heme center via the protein surface to neighboring membranes may be of considerable biological......-derived phenoxyl radical present at Tyr-133 in the soybean protein and Tyr-138 in the lupin protein. To obtain further information on these protein radicals and their potential interaction with the physiologically important peribacteroid membrane (which surrounds the microsymbiont in vivo), EPR spin trapping......); these radicals may be side chain- or alpha-carbon-derived, their exact sites have not been determined. Some of these radicals are on the protein surface and may be key intermediates in the formation of protein dimers. These radicals have been shown to be capable of reacting with peribacteroid membrane fractions...

  2. Addressing Emerging Risks: Scientific and Regulatory Challenges Associated with Environmentally Persistent Free Radicals.

    Science.gov (United States)

    Dugas, Tammy R; Lomnicki, Slawomir; Cormier, Stephania A; Dellinger, Barry; Reams, Margaret

    2016-06-08

    Airborne fine and ultrafine particulate matter (PM) are often generated through widely-used thermal processes such as the combustion of fuels or the thermal decomposition of waste. Residents near Superfund sites are exposed to PM through the inhalation of windblown dust, ingestion of soil and sediments, and inhalation of emissions from the on-site thermal treatment of contaminated soils. Epidemiological evidence supports a link between exposure to airborne PM and an increased risk of cardiovascular and pulmonary diseases. It is well-known that during combustion processes, incomplete combustion can lead to the production of organic pollutants that can adsorb to the surface of PM. Recent studies have demonstrated that their interaction with metal centers can lead to the generation of a surface stabilized metal-radical complex capable of redox cycling to produce ROS. Moreover, these free radicals can persist in the environment, hence their designation as Environmentally Persistent Free Radicals (EPFR). EPFR has been demonstrated in both ambient air PM2.5 (diameter challenges associated with regulating this new, emerging contaminant.

  3. Studies of radiation-produced radicals and radical ions. Progress report, June 1, 1981-August 31, 1982

    International Nuclear Information System (INIS)

    Williams, T.F.

    1982-01-01

    The discovery and characterization of novel radical ions produced by the γ irradiation of solids continues to be a fertile field for investigation. This Progress Report describes the generation and ESR identification of several new paramagnetic species, some of which have long been sought as important intermediates in radiation chemistry. We have also contributed to a general theoretical problem in ESR spectroscopy. Solid-state studies of electron attachment reactions, both non-dissociative and dissociative, reveal interesting structural and chemical information about the molecular nature of these processes for simple compounds. In particular, ESR measurements of the spin distribution in the products allow a fairly sharp distinction to be drawn between radical anions and radical-anion pairs or adducts. Dimer radical anion formation can also take place but the crystal structure plays a role in this process, as expected. Some radical anions undergo photolysis to give radical-anion pairs which may then revert back to the original radical anion by a thermal reaction. The chemistry of these reversible processes is made more intricate by a competing reaction in which the radical abstracts a hydrogen atom from a neighboring molecule. However, the unraveling of this complication has also served to extend our knowledge of the role of quantum tunneling in chemical reactions. The results of this investigation testify to the potential of solid-state techniques for the study of novel and frangible radical ions. Progress in this field shows no sign of abating, as witness the recent discovery of perfluorocycloalkane radical anions and alkane radical cations

  4. The Effect of Montessori Method on Cognitive Tempo of Kindergarten Children

    Science.gov (United States)

    Kayili, Gökhan

    2018-01-01

    This study was undertaken to discover the effect of the Montessori Method on the cognitive tempo of 4-5-year-old children. Using an experimental pre-test-post-test paired control group design, the study sample included 60 children attending Ihsan Dogramaci Applied Nursery School (affiliated to Selcuk University, Department of Health Sciences) in…

  5. Prenatal influences on size, velocity and tempo of infant growth: findings from three contemporary cohorts.

    Directory of Open Access Journals (Sweden)

    Costanza Pizzi

    Full Text Available Studying prenatal influences of early life growth is relevant to life-course epidemiology as some of its features have been linked to the onset of later diseases.We studied the association between prenatal maternal characteristics (height, age, parity, education, pre-pregnancy body mass index (BMI, smoking, gestational diabetes and hypertension and offspring weight trajectories in infancy using SuperImposition by Translation And Rotation (SITAR models, which parameterize growth in terms of three biologically interpretable parameters: size, velocity and tempo. We used data from three contemporary cohorts based in Portugal (GXXI, n=738, Italy (NINFEA, n=2,925, and Chile (GOCS, n=959.Estimates were generally consistent across the cohorts for maternal height, age, parity and pre-pregnancy overweight/obesity. Some exposures only affected one growth parameter (e.g. maternal height (per cm: 0.4% increase in size (95% confidence interval (CI:0.3; 0.5, others were either found to affect size and velocity (e.g. pre-pregnancy underweight vs normal weight: smaller size (-4.9%, 95% CI:-6.5; -3.3, greater velocity (5.9%, 95% CI:1.9;10.0, or to additionally influence tempo (e.g. pre-pregnancy overweight/obesity vs normal weight: increased size (7.9%, 95% CI:4.9;10.8, delayed tempo (0.26 months, 95% CI:0.11;0.41, decreased velocity (-4.9%, 95% CI: -10.8;0.9.By disentangling the growth parameters of size, velocity and tempo, we found that prenatal maternal characteristics, especially maternal smoking, pre-pregnancy overweight and underweight, parity and gestational hypertension, are associated with different aspects of infant weight growth. These results may offer insights into the mechanisms governing infant growth.

  6. Experimentação do tempo e estilo de vida em contexto de trabalho imaterial

    Directory of Open Access Journals (Sweden)

    Carmem Ligia Iochins Grisci

    Full Text Available Este artigo buscou responder, em contexto de trabalho imaterial, que estilo de vida decorre do uso do tempo permeado pelas tecnologias da informação e comunicação. O estudo qualitativo contou com a participação de 18 docentes horistas de instituições de ensino superior privadas. A coleta de dados se deu por meio de entrevista individual semiestruturada, com foco no uso das tecnologias da informação e comunicação e no exercício do trabalho imaterial, considerando o tempo de trabalho e de não trabalho. A análise de conteúdo partiu dos dados coletados. Os resultados, em consonância com a literatura ( em especial, Bauman (2008b, Deleuze (1998, Giddens (2002, Gorz (2005 e Lazzarato e Negri (2001 (apontaram que, em contexto de trabalho imaterial, o estilo de vida é instrumentalizado pelo modo de trabalhar e pelo uso das tecnologias de informação e comunicação. Ele se configura como uma imposição aos sujeitos que o toma na perspectiva de uma estratégia existencial consumista. Mesmo contratado por tempo fracionado em horas, o trabalho dos docentes horistas exige-lhes disponibilidade e mobilização total para o desempenho das atividades laborais, requerendo dedicação em tempo integral. Os estilos de trabalho produzem estilo de vida e sugerem que a vida está sendo convertida em trabalho nos dias de hoje, tanto pela intensificação do trabalho, como pelo prolongamento da jornada.

  7. Anthraquinone derivatives as organic stabilizers for rigid poly (vinyl chloride) against photo-degradation

    International Nuclear Information System (INIS)

    Sabaa, M.W.; Mohamed, R.R.

    2005-01-01

    Anthraquinone derivatives have been prepared and investigated as photo-stabilizers for rigid PVC by measuring the extent of weight loss (%), the amount of gel formation as well as the intrinsic viscosity of the soluble fractions of the degraded polymer. The results indicated a reasonable stabilizing effect of these derivatives compared with UV-commorcially used stabilizers. A synergistic effect is achieved when the Anthraquinone derivatives are mixed with UV-absorbers in a weight ratio of 75 % of investigated organic stabilizer and 25 % of reference stabilizer. A probable radical mechanism is proposed to account for the stabilizing action of the organic investigated materials

  8. Muonium-containing vinyl radicals

    International Nuclear Information System (INIS)

    Rhodes, C.J.; Symons, M.C.R.; Roduner, E.; Heming, M.

    1987-01-01

    Exposure of trimethylsilylacetylene and bis(trimethylsilyl)acetylene to positive muons gave radicals whose muon-electron hyperfine coupling constants establish that the corresponding vinyl radicals were formed. (author)

  9. TEMPO functionalized C60 fullerene deposited on gold surface for catalytic oxidation of selected alcohols

    International Nuclear Information System (INIS)

    Piotrowski, Piotr; Pawłowska, Joanna; Sadło, Jarosław Grzegorz; Bilewicz, Renata; Kaim, Andrzej

    2017-01-01

    C 60 TEMPO 10 catalytic system linked to a microspherical gold support through a covalent S-Au bond was developed. The C 60 TEMPO 10 @Au composite catalyst had a particle size of 0.5–0.8 μm and was covered with the fullerenes derivative of 2.3 nm diameter bearing ten nitroxyl groups; the organic film showed up to 50 nm thickness. The catalytic composite allowed for the oxidation under mild conditions of various primary and secondary alcohols to the corresponding aldehyde and ketone analogues with efficiencies as high as 79–98%, thus giving values typical for homogeneous catalysis, while retaining at the same time all the advantages of heterogeneous catalysis, e.g., easy separation by filtration from the reaction mixture. The catalytic activity of the resulting system was studied by means of high pressure liquid chromatography. A redox mechanism was proposed for the process. In the catalytic cycle of the oxidation process, the TEMPO moiety was continuously regenerated in situ with an applied primary oxidant, for example, O 2 /Fe 3+ system. The new intermediate composite components and the final catalyst were characterized by various spectroscopic methods and thermogravimetry.

  10. ANÁLISE DE DESEMPENHO EM REDES IEEE 802.3 APLICADO PARA SISTEMA DE TEMPO REAL

    Directory of Open Access Journals (Sweden)

    Ricardo Alexsandro de Medeiros Valentim

    2011-06-01

    Full Text Available A tecnologia Ethernet domina o mercado de rede local de computadores. No entanto, não foi estabelecida como uma tecnologia para automação industrial, onde o determinismo procura os requisitos com um desempenho de tempo real. Muitas soluções têm sido propostas para resolver o problema do determinismo não, que se baseiam principalmente no TDMA (acesso múltiplo por divisão de tempo, passagem de token e mestre-escravo. É neste contexto que este trabalho é realizado, através de medidas de desempenho em redes de comunicação que utilizam o padrão IEEE 802.3, observando o comportamento destas redes, quando submetidos a diferentes cenários de sobrecarga. Para isso, as variações foram aprovadas em ambiente de teste, que será baseado em Shared Ethernet (Hub, Ethernet e Ethernet Switch com prioridade (IEEE 802.1Q. Desta forma, é possível indicar quais os dispositivos analisados pelos testes de desempenho demonstrado um comportamento mais adequado para suportar as aplicações com requisitos de tempo real.

  11. A teia, a tela e o tempo: internet e história do tempo presente

    Directory of Open Access Journals (Sweden)

    Pedro Eurico Rodrigues

    2014-09-01

    Full Text Available O enfoque deste artigo será uma apresentação da pesquisa em história e Internet, pensando esta como um documento dentro dos estudos da História da Cultura Escrita e da Leitura. Ao propiciar novas formas de ler e escrever na contemporaneidade, a Internet perpassa por várias modalidades tais como os comunicadores instantâneos (MIRC e MSN, as redes sociais (Orkut, Facebook, notícias, vídeos entre outros. Com destaque a novos mecanismos de sociabilidade que funcionam como mediadores para interação entre grupos que utilizam as redes sociais. Os documentos são abordados na perspectiva da História do Tempo Presente, que possibilita pensarmos um passado-presente, em que os recuos e aproximações com as fontes são possibilitados pelas escolhas do historiador que problematiza este Presente Palavras-chave: História; Escrita; Leitura; Redes de Relações Sociais.

  12. Electron paramagnetic resonance of radicals and metal complexes. 2. international conference of the Polish EPR Association. Warsaw 9-13 September 1996

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-12-31

    The conference of Electron Paramagnetic Resonance of Radicals and Metal Complexes has been held in Warsaw from 9 to 13 September 1996. It was the Second International Conference of the Polish EPR Association. The very extensive group of systems containing paramagnetic species has been studied by means of ESR or other magnetic techniques like ENDOR, Spin Echo etc. By radiation or photochemically generated radicals have been stabilized in low temperatures or being detected by means of very fast pulsed techniques. The chemical reactions, reaction kinetics of radicals as well as spin interaction with matrices have been studied and discussed. Over 100 lectures and posters have been presented.

  13. Electron paramagnetic resonance of radicals and metal complexes. 2. international conference of the Polish EPR Association. Warsaw 9-13 September 1996

    International Nuclear Information System (INIS)

    1996-01-01

    The conference of Electron Paramagnetic Resonance of Radicals and Metal Complexes has been held in Warsaw from 9 to 13 September 1996. It was the Second International Conference of the Polish EPR Association. The very extensive group of systems containing paramagnetic species has been studied by means of ESR or other magnetic techniques like ENDOR, Spin Echo etc. By radiation or photochemically generated radicals have been stabilized in low temperatures or being detected by means of very fast pulsed techniques. The chemical reactions, reaction kinetics of radicals as well as spin interaction with matrices have been studied and discussed. Over 100 lectures and posters have been presented

  14. Electron paramagnetic resonance of radicals and metal complexes. 2. international conference of the Polish EPR Association. Warsaw 9-13 September 1996

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-31

    The conference of Electron Paramagnetic Resonance of Radicals and Metal Complexes has been held in Warsaw from 9 to 13 September 1996. It was the Second International Conference of the Polish EPR Association. The very extensive group of systems containing paramagnetic species has been studied by means of ESR or other magnetic techniques like ENDOR, Spin Echo etc. By radiation or photochemically generated radicals have been stabilized in low temperatures or being detected by means of very fast pulsed techniques. The chemical reactions, reaction kinetics of radicals as well as spin interaction with matrices have been studied and discussed. Over 100 lectures and posters have been presented.

  15. Radicals in arithmetic

    NARCIS (Netherlands)

    W.J. Palenstijn (Willem Jan)

    2014-01-01

    htmlabstractLet K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement

  16. Selective Exposure to and Acquisition of Information from Educational Television Programs as a Function of Appeal and Tempo of Background Music.

    Science.gov (United States)

    Wakshlag, Jacob J.; And Others

    1982-01-01

    The effect of educational television background music on selective exposure and information acquisition was studied. Background music of slow tempo, regardless of its appeal, had negligible effects on attention and information acquisition. Rhythmic, fast-tempo background music, especially when appealing, significantly reduced visual attention to…

  17. Ascorbyl radical disproportionation in reverse micellar systems

    Science.gov (United States)

    Gębicki, J. L.; Szymańska-Owczarek, M.; Pacholczyk-Sienicka, B.; Jankowski, S.

    2018-04-01

    Ascorbyl radical was generated by the pulse radiolysis method and observed with the fast kinetic spectrophotometry within reverse micelles stabilized by AOT in n-heptane or by Igepal CO-520 in cyclohexane at different water to surfactant molar ratio, w0. Rate constants for the disproportionation of the ascorbyl radicals were smaller than those for intermicellar exchange for both type of reverse micelles and slower than those in homogeneous aqueous solutions. However, they increased with increasing w0 for AOT/n-heptane system, while they decreased for Igepal CO-520 system. The absorption spectra of ascorbic acid AOT/n-heptane reverse micellar system showed that the "pH" sensed by this molecule is lower than that in respective homogeneous aqueous solutions. The obtained results were rationalized taking into account three main factors (i) preferential location of ascorbic acid molecules in the interfacial region of the both types of reverse micelles; (ii) postulate that the pH of the interface is lower than that of the water pool of reverse micelles and (iii) different structure of the interface of the reverse micelles made by AOT in n-heptane and those formed by Igepal CO-520 I cyclohexane. Some possible consequences of these findings are discussed.

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

    Science.gov (United States)

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

    2015-01-20

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

  19. Multiple free-radical scavenging capacity in serum

    Science.gov (United States)

    Oowada, Shigeru; Endo, Nobuyuki; Kameya, Hiromi; Shimmei, Masashi; Kotake, Yashige

    2012-01-01

    We have developed a method to determine serum scavenging-capacity profile against multiple free radical species, namely hydroxyl radical, superoxide radical, alkoxyl radical, alkylperoxyl radical, alkyl radical, and singlet oxygen. This method was applied to a cohort of chronic kidney disease patients. Each free radical species was produced with a common experimental procedure; i.e., uv/visible-light photolysis of free-radical precursor/sensitizer. The decrease in free-radical concentration by the presence of serum was quantified with electron spin resonance spin trapping method, from which the scavenging capacity was calculated. There was a significant capacity change in the disease group (n = 45) as compared with the healthy control group (n = 30). The percent values of disease’s scavenging capacity with respect to control group indicated statistically significant differences in all free-radical species except alkylperoxyl radical, i.e., hydroxyl radical, 73 ± 12% (p = 0.001); superoxide radical, 158 ± 50% (p = 0.001); alkoxyl radical, 121 ± 30% (p = 0.005); alkylperoxyl radical, 123 ± 32% (p>0.1); alkyl radical, 26 ± 14% (p = 0.001); and singlet oxygen, 57 ± 18% (p = 0.001). The scavenging capacity profile was illustrated using a radar chart, clearly demonstrating the characteristic change in the disease group. Although the cause of the scavenging capacity change by the disease state is not completely understood, the profile of multiple radical scavenging capacities may become a useful diagnostic tool. PMID:22962529

  20. Nos tempos de Asclépio: a suposta engenharia genética de Platão

    Directory of Open Access Journals (Sweden)

    Sussumo Matsui

    2016-01-01

    Full Text Available A descrição do papel da medicina no Livro III da República pode facilmente deixar o leitor constrangido. O trecho defende que a medicina deveria se espelhar nas práticas do tempo de Asclépio. Neste tempo, a medicina tinha um papel político de não prolongar a vida dos cidadãos tomados pela doença e nem deixá-los procriar. Frente a estas declarações, surgiram várias interpretações que vão desde o totalitarismo de Popper até a ironia de Strauss. Para uma melhor compreensão do texto, seria necessária a interlocução com a medicina hipocrática e com as práticas médicas do tempo dos séculos V e IV aEN. Contudo, a passagem em questão não se reduz ao contexto histórico, mas apresenta uma crítica válida ainda na atualidade.

  1. Preoperative radiochemotherapy and radical surgery in comparison with radical surgery alone

    International Nuclear Information System (INIS)

    Mohr, C.; Schettler, D.; Bohndorf, W.

    1994-01-01

    A multicentric, randomized study of squamous cell carcinoma (SCC) of the oral cavity and the oropharynx has been undertaken by DOeSAK. The results after radical surgery alone have been compared with the results of combined preoperative radiochemotherapy followed by radical surgery. Patients with primary (biopsy proven) SCC of the oral cavity or the oropharynx with tumor nodes metastasis (TNM) stages T2-4, N0-3, M0 were included in the study. A total of 141 patients were treated by radical surgery alone, whereas 127 patients were treated by radical surgery preceded by preoperative radiochemotherapy. The pre-operative treatment consisted of conventionally fractioned irradiation on the primary and the regional lymph nodes with a total dose of 36 Gy (5 x 2 Gy per week) and low-dose cisplatin chemotherapy with 5 x 12.5 mg cisplatin per m 2 of body surface during the first week of treatment. Radical surgery according to be DOeSAK definitions (DOeSAK, 1982) was performed after a delay of 10-14 days. During the follow-up period, 28.2% of all patients suffered from locoregional recurrence, and 27.2% of the patients died. The percentages were higher after radical surgery alone for locoregional recurrence (31% and 15.6%) and for death (28% and 18.6%). The life-table analysis showed improved survival rates of 4.5% after 1 year and 8.3% after 2 years in the group of patients treated with combined therapy. The demonstrated improvement appeared to be significant with the Gehan-Wilcoxon test as well as with the log rank test below a P value of 5%. (au) (29 refs.)

  2. Radicals in arithmetic

    NARCIS (Netherlands)

    Palenstijn, Willem Jan

    2014-01-01

    Let K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement group. We give

  3. Radicalization as a Vector: Exploring Non-Violent and Benevolent Processes of Radicalization.

    Directory of Open Access Journals (Sweden)

    Ken Reidy

    2018-03-01

    Full Text Available Successful radicalization posits three outcomes: extremism, terrorism or both. As these are undesirable, radicalization is understood as wholly malevolent and governments work to prevent and/or stop it. Nonetheless, a handful of scholars have recognized that the same radicalization process which results in either outcome may, theoretically at least, also have beneficial outcomes such as environmental awareness or human rights. This article explores one such outcome. Based on interviews with British Muslim aid workers (n=6 operating in Jihadist conflict zones post Arab spring and using constructivist grounded theory, it illustrates how the research participants radicalized to humanitarianism which resulted in them assisting the most plighted of Muslims by deploying to the most wanton of areas: ones commonly referred to as Jihadist conflict zones. Evidently, these destinations are shared with Jihadists and given the array of other observable similarities (socio-demographics and [pre-]mobilization behaviours, these morally opposed groups become conflated by the security services. This is further compounded by the fact that Jihadists manipulate and/or impersonate aid workers so as to funnel people and funds. To distinguish both, this article documents the benevolent pathway of the research participants and juxtaposes it to scholarly knowledge on Jihadist pathways. Socialization was revealed to be the key distinguishing feature rather than descriptive risk factors (such as ideology or moral outrage because the process of radicalization was not found to be the start of the radicalized pathway. It concludes that benevolently radicalized Islamic groups constitute an effective means of pathway divergence for particular typologies by offering an attractive and prosocial alternative to Jihadism. This strengths-based preventative approach (“what’s right” takes the form of a community-centric market competitor to Jihadism rather than a problem

  4. Mitochondria-Targeted Antioxidant Mito-Tempo Protects Against Aldosterone-Induced Renal Injury In Vivo

    Directory of Open Access Journals (Sweden)

    Wei Ding

    2017-11-01

    Full Text Available Background/Aims: Growing evidence suggests mitochondrial dysfunction (MtD and the Nlrp3 inflammasome play critical roles in chronic kidney disease (CKD progression. We previously reported that Aldosterone (Aldo-induced renal injury in vitro is directly caused by mitochondrial reactive oxygen species (mtROS-mediated activation of the Nlrp3 inflammasome. Here we aimed to determine whether a mitochondria-targeted antioxidant (Mito-Tempo could prevent Aldo-induced kidney damage in vivo. Methods: C57BL/6J mice were treated with Aldo and/or Mito-Tempo (or ethanol as a control for 4 weeks. Renal injury was evaluated by Periodic Acid-Schiff reagent or Masson’s trichrome staining and electron microscopy. ROS were measured by DCFDA fluorescence and ELISA. MtD was determined by real-time PCR and electron microscopy. Activation of the Nlrp3 inflammasome and endoplasmic reticulum stress (ERS was detected via western blot. Results: Compared with control mice, Aldo-infused mice showed impaired renal function, increased mtROS production and MtD, Nlrp3 inflammasome activation, and elevated ERS. We showed administration of Mito-Tempo significantly improved renal function and MtD, and reduced Nlrp3 inflammasome activation and ERS in vivo. Conclusion: Mitochondria-targeted antioxidants may attenuate Aldo-infused renal injury by inhibiting MtD, the Nlrp3 inflammasome, and ERS in vivo. Therefore, targeting mtROS might be an effective strategy for preventing CKD.

  5. Identifying the distinct features of geometric structures for hole trapping to generate radicals on rutile TiO₂(110) in photooxidation using density functional theory calculations with hybrid functional.

    Science.gov (United States)

    Wang, Dong; Wang, Haifeng; Hu, P

    2015-01-21

    Using density functional theory calculations with HSE 06 functional, we obtained the structures of spin-polarized radicals on rutile TiO2(110), which is crucial to understand the photooxidation at the atomic level, and further calculate the thermodynamic stabilities of these radicals. By analyzing the results, we identify the structural features for hole trapping in the system, and reveal the mutual effects among the geometric structures, the energy levels of trapped hole states and their hole trapping capacities. Furthermore, the results from HSE 06 functional are compared to those from DFT + U and the stability trend of radicals against the number of slabs is tested. The effect of trapped holes on two important steps of the oxygen evolution reaction, i.e. water dissociation and the oxygen removal, is investigated and discussed.

  6. Stability of [MeBu3N][Tf2N] under gamma irradiation

    International Nuclear Information System (INIS)

    Bosse, E.; Berthon, L.; Zorz, N.; Monget, J.; Berthon, C.; Bisel, I.; Legand, S.; Moisy, P.

    2008-01-01

    The stability of the ionic liquid [MeBu 3 N][Tf 2 N], dry or after contact with water (where [MeBu 3 N] + is the methyl-tributyl-ammonium cation and [Tf 2 N] - is the bistriflimide anion), was studied under 137 Cs gamma irradiation in argon and in air. In a quantitative study with an absorbed dose of 2 MGy this ionic liquid was highly stable regardless of the radiolysis conditions. The radiolytic disappearance yields determined by ESI-MS were -0.38 and -0.25 μmolJ -1 for the cation and anion, respectively. ESI-MS, NMR, and liquid chromatography coupled with ESI-MS identified a large number of degradation products in very small quantities for the same dose. The cation radicals were formed by the loss of a Bu-radical group, the Me-radical group, or two H-radical atoms to form a double bond with the butyl chain. Radiolysis of the anion produced mainly F-radical and CF 3 -radicals. The anion radicals recombined with the cation to form a wide range of secondary degradation products regardless of the radiolysis conditions. (authors)

  7. Radical cations of quadricyclane and norbornadiene in polar ZSM-5 matrices: Radical cation photochemical transformations without photons

    International Nuclear Information System (INIS)

    Barnabas, M.V.; Trifunac, A.D.

    1994-01-01

    Radical cations of quadricyclane (Q) and norbornadiene (NBD) are produced by γ-radiolysis in zeolites. In polar ZSM-5, only one radical cation is initially observed below 100K. Increasing the temperature above 200K gives rise to the cyclopentadiene radical cation. Higher temperatures (>360K) give rise to the cyclopenten-4-yl radical. The observation of cyclopentadiene radical cation implies the occurrence of the reverse Diels-Alder reaction. This is a thermally forbidden, photochemically allowed, process, which is made possible by the interaction of the polar zeolite matrix sites with parent NBD and Q radical cations

  8. Reactions of organic free radicals at colloidal silver in aqueous solution. Electron pool effect and water decomposition

    International Nuclear Information System (INIS)

    Henglein, A.

    1979-01-01

    Organic free radicals of high negative redox potential such as α-alcohol radicals were found to transfer electrons to colloidal silver particles stabilized by sodium dodecyl sulfate in aqueous solution. The colloidal particles thus became a pool of stored electrons that could reduce water to form hydrogen or react with suitable acceptors in solution. The organic radicals were produced by irradiation, using suitable scavengers for the primary radicals from the radiolysis of the aqueous solvent. The solutions initially contained silver ions at 1 x 10 -4 - 2 x 10 -3 M. At doses below 10 5 rd, the silver ions were completely reduced to form the colloidal catalyst. In this dose range, the corresponding hydrogen yield amounted to 1 molecule per 100 eV. It increased steeply at higher doses up to 3 molecules per 100 eV. The H 2 yield decreased with increasing dose rate and with increasing pH in alkaline solutions. It was highest at a concentration of sodium dodecyl sulfate of 1 x 10 -3 M, i.e., far below the critical micelle concentration of this surfactant. Changes in the absorption spectrum of the colloid are attributed to changes in the size of the silver particles upon charging up with electrons. The competition of radical-colloid reactions with radical-radical deactivation in the bulk of solution or at the surface of the colloidal particles is also discussed. 11 figures

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

    Science.gov (United States)

    Craciun, Smaranda; Donald, Kelling J

    2009-07-06

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

  10. Presente: o tempo do jornalismo e seus desdobramentos

    OpenAIRE

    Dalmonte, Edson

    2010-01-01

    p. 328-344 Discute a noção de temporalidade no campo do jornalismo. Partindo do princípio de que a atualidade é a base da narrativa jornalística, reflete acerca dos dispositivos empregados para dar densidade ao presente: o passado, como elemento da memória e o futuro, como projeção. Dessa forma, procura entender os modos a partir dos quais o jornalismo estabelece estratégias capazes de criar o sentido de "presentificação", simulando a ideia de atualidade, o que coloca num mesmo plano tempo...

  11. Fate of free radicals generated during one-electron reductions of 4-alkyl-1,4-peroxyquinols by cytochrome P-450

    International Nuclear Information System (INIS)

    Yumibe, N.P.; Thompson, J.A.

    1988-01-01

    Free radicals resulting from the one-electron reduction and subsequent homolytic cleavage of oxygen-oxygen bonds by heme proteins are likely to be responsible for some aspects of the toxicity of organic hydroperoxides. In the present work, effects of the 4-alkyl substituent of 2,6-di-tert-butyl-4-alkyl-4-hydroperoxycytohexa-2,5-dienones on radical production were investigated with microsomal cytochrome P-450 from rat liver. Quinoxy radicals from homolysis of the peroxyquinols underwent β-scission to produce a quinone and an alkyl radical, and this process occurred with increasing frequency as the stability of the alkyl radical increased. The fate of benzyl and 2-phenylethyl radicals generated from the appropriately substituted peroxyquinols was investigated also. The former was converted to benzyl alcohol, benzaldehyde, and toluene and the latter to 2-phenylethanol, phenylacetaldehyde, ethylbenzene, styrene, and benzaldehyde. Oxygen-18 labeling studies demonstrate that 80-85% of the benzyl alcohol incorporated oxygen from the hydroperoxide and the balance from molecular oxygen. This indicates that the predominant reaction pathway involved recombination between the benzyl radical and the iron-bound hydroxyl radical of the P-450 intermediate complex. By contrast, about 50% of 2-phenylethanol from the 2-phenylethyl radical incorporated oxygen from water and the balance from O 2 . Two alternative mechanisms are proposed to explain the formation of 2-phenylethanol that contained oxygen from water and the concurrent formation of styrene: (a) oxygen exchange of the P-450 intermediate with water, followed by hydrogen abstraction and radical recombination reactions with the P-450 complex, or (b) oxidation of the radical to the 2-phenylethyl cation followed by proton elimination and hydration

  12. Food-web stability signals critical transitions in temperate shallow lakes

    NARCIS (Netherlands)

    Kuiper, Jan J.; van Altena, Cassandra; de Ruiter, P.C.; Van Gerven, Luuk P.A.; Janse, Jan H.; Mooij, Wolf M.

    2015-01-01

    A principal aim of ecologists is to identify critical levels of environmental change beyond which ecosystems undergo radical shifts in their functioning. Both food-web theory and alternative stable states theory provide fundamental clues to mechanisms conferring stability to natural systems. Yet, it

  13. Food-web stability signals critical transitions in temperate shallow lakes

    NARCIS (Netherlands)

    Kuiper, J.J.; Altena, Van Cassandra; Ruiter, De P.C.; Gerven, Van L.P.A.; Janse, J.H.; Mooij, W.M.

    2015-01-01

    A principal aim of ecologists is to identify critical levels of environmental change beyond which ecosystems undergo radical shifts in their functioning. Both food-web theory and alternative stable states theory provide fundamental clues to mechanisms conferring stability to natural systems. Yet,

  14. Youth De-Radicalization: A Canadian Framework

    Directory of Open Access Journals (Sweden)

    Hafal (Haval Ahmad

    2017-09-01

    Full Text Available Youth radicalization leading to violence has become a growing fear among Canadians, as terrorist attacks are carried out in Western states. Although Canada has suffered relatively fewer acts of violence, this fear has intensified and a de-radicalization strategy is needed in the Canadian context. In a qualitative case study methodology, interviews were conducted with school counsellors, religious leaders, and academics to explore solutions to youth radicalization. Youth de-radicalization approaches from the United Kingdom were analyzed and found that community-based initiatives were missing from programming. Social identity theory is used to explain that youth join radicalized groups to feel a sense of belonging and have to be provided an alternative and moderate group identity to de-radicalize. This study found youth de-radicalization in Canada is best served through a community collaboration approach.

  15. Syntheses and study of pyrrolidinic nitroxide free radicals. Preparation of a nitroxide-type stable bi-radical; Synthese et etudes de radicaux libres nitroxydes pyrrolidiniques. Preparation d'un biradical stable du type nitroxyde

    Energy Technology Data Exchange (ETDEWEB)

    Dupeyre, R M [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires, Laboratoire de chimie organique physique

    1967-12-01

    Syntheses and study of pyrrolidinic nitroxide free radicals: These radicals are obtained by oxidation, with hydrogen peroxide, of pyrrolidinic amines prepared from triacetonamine by ring contraction. The U. V,, I. R, and E.P.R. spectral characteristics have been determined. The oxidation of these amines with hydrogen peroxide has led also to rupture of the pentagonal ring; some of the decomposition products have been identified. The high chemical stability of the nitroxide group has made it possible to synthesize and study a stable bi-radical. (author) [French] Syntheses et etudes de radicaux libres nitroxydes pyrrolidiniques: Ces radicaux sont obtenus par oxydation l'eau oxygenee d'amines pyrrolidiniques preparees a partir de la triacetonamine par contraction de cycle. Les caracteristiques spectroscopiques ultra-violettes, infra-rouge et resonance paramagnetique sont determinees. Cependant, 1'oxydation de ces amines a l'eau oxygenee a entraine la coupure du cycle pentagonal et identification de certaines substances de decomposition obtenues. La grande stabilite chimique de groupement nitroxyde a permis la synthese et l'etude d'un biradical stable. (auteur)

  16. Intermolecular effects on the radiogenic formation of electron-capture phosphorus-centered radicals. A single-crystal ESR study of diastereoisomeric precursors

    Energy Technology Data Exchange (ETDEWEB)

    Aagaard, O.M.; Janssen, R.A.J.; de Waal, B.F.M.; Buck, H.M. (Eindhoven Univ. of Technology (Netherlands))

    1990-01-31

    ESR experiments on X-irradiated single crystals of the 2R,4S,5R and 2S,4S,5R diastereoisomers of 2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide reveal that the yield of radiogenic electron-capture reactions in the solid state strongly depends on intermolecular interactions in the crystal. In the present case a high yield of P-Cl three-electron-bond phosphoranyl radical anions is found in crystals of the 2R,4S,5R isomer, whereas no radical formation can be detected for the 2S,4S,5R isomer. An analysis of nonbonded interactions with neighboring molecules reveals that the geometry relaxation necessary for the radical stabilization is easily accommodated in crystals of the 2R,4S,SR isomer but not in the 2S,4S,5R isomer, explaining the observed difference in electron-capture efficiency. Experiments on radical formation in a MeTHF host matrix give further insight into the importance of the environment on radiogenic radical formation. The possible concurrent effect of the matrix on the electronic configuration and spin density distribution of the resulting phosphoranyl radical is discussed.

  17. Intermolecular effects on the radiogenic formation of electron-capture phosphorus-centered radicals. A single-crystal ESR study of diastereoisomeric precursors

    International Nuclear Information System (INIS)

    Aagaard, O.M.; Janssen, R.A.J.; de Waal, B.F.M.; Buck, H.M.

    1990-01-01

    ESR experiments on X-irradiated single crystals of the 2R,4S,5R and 2S,4S,5R diastereoisomers of 2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide reveal that the yield of radiogenic electron-capture reactions in the solid state strongly depends on intermolecular interactions in the crystal. In the present case a high yield of P-Cl three-electron-bond phosphoranyl radical anions is found in crystals of the 2R,4S,5R isomer, whereas no radical formation can be detected for the 2S,4S,5R isomer. An analysis of nonbonded interactions with neighboring molecules reveals that the geometry relaxation necessary for the radical stabilization is easily accommodated in crystals of the 2R,4S,SR isomer but not in the 2S,4S,5R isomer, explaining the observed difference in electron-capture efficiency. Experiments on radical formation in a MeTHF host matrix give further insight into the importance of the environment on radiogenic radical formation. The possible concurrent effect of the matrix on the electronic configuration and spin density distribution of the resulting phosphoranyl radical is discussed

  18. GRAMSCI E A FILOSOFIA POLÍTICA DE SEU TEMPO

    OpenAIRE

    José Carlos Freire

    2011-01-01

    O presente artigo procura refletir sobre o modo pelo qual Gramsci debate com os autores de seu tempo, a fim de recolocar o marxismo no terreno da história e da dialética. Tomamos como referência o confronto de Gramsci com o neo-idealismo italiano, representado por Benedetto Croce, e com o marxismo economicista, representado por Nicolai Bukharin. Com isso, procuraremos analisar se Gramsci seria autenticamente um marxista ou, dito de outro modo, até que ponto ele teria se afastado de Marx pela ...

  19. Relationship between exercise heart rate and music tempo preference

    OpenAIRE

    Karageorghis, CI; Jones, L; Low, DC

    2006-01-01

    The present study examined the predicted positive and linear relationship (Iwanaga, 1995a,1995b) between exercise heart rate and music tempo preference. Initially, 128 undergraduates (M 3 age = 20.0 years, SD = 0.9 years) were surveyed to establish their three favorite music artists of all time. A separate experimental group of 29 undergraduates (M age = 20.3 years, SD = 1.2 years) selected the music of a single artist from a choice of the three highest-rated artists from the earlier survey. ...

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

    Science.gov (United States)

    El-Agamey, Ali; McGarvey, David J

    2016-01-01

    The reactions of acetylperoxyl radicals with different carotenoids (7,7'-dihydro-β-carotene and ζ-carotene) in SDS and CTAC microemulsions of different compositions were investigated using laser flash photolysis (LFP) coupled with kinetic absorption spectroscopy. The primary objective of this study was to explore the influence of microemulsion composition and the type of surfactant used on the yields and kinetics of various transients formed from the reaction of acetylperoxyl radicals with carotenoids. Also, the influence of the site (hydrocarbon phases or aqueous phase) of generation of the peroxyl radical precursor was examined by using 4-acetyl-4-phenylpiperidine hydrochloride (APPHCl) and 1,1-diphenylacetone (11DPA) as water-soluble and lipid-soluble peroxyl radical precursors, respectively. LFP of peroxyl radical precursors with 7,7'-dihydro-β-carotene (77DH) in different microemulsions gives rise to the formation of three distinct transients namely addition radical (λmax=460 nm), near infrared transient1 (NIR, λmax=700 nm) and 7,7'-dihydro-β-carotene radical cation (77DH(•+), λmax=770 nm). In addition, for ζ-carotene (ZETA) two transients (near infrared transient1 (NIR1, λmax=660 nm) and ζ-carotene radical cation (ZETA(•+), λmax=730-740 nm)) are generated following LFP of peroxyl radical precursors in the presence of ζ-carotene (ZETA) in different microemulsions. The results show that the composition of the microemulsion strongly influences the observed yield and kinetics of the transients formed from the reactions of peroxyl radicals (acetylperoxyl radicals) with carotenoids (77DH and ZETA). Also, the type of surfactant used in the microemulsions influences the yield of the transients formed. The dependence of the transient yields and kinetics on microemulsion composition (or the type of surfactant used in the microemulsion) can be attributed to the change of the polarity of the microenvironment of the carotenoid. Furthermore, the nature of

  1. Glutathione as a radical scavenger and the biological consequences of thiyl radical production

    International Nuclear Information System (INIS)

    Winterbourn, C.C.

    1996-01-01

    A large number of compounds that have toxic effects can be metabolised to free radicals and secondary reactive oxygen species. These may be directly damaging or affect cell function by altering regulatory mechanisms through changing redox status. Protection is provided by an integrated system of antioxidant defenses. This includes reduced glutathione (GSH), one of the functions of which is as a free radical scavenger. For GSH to be an effective radical scavenging antioxidant, therefore, it must act in concert with superoxide dismutase to remove the superoxide so generated. Superoxide is produced in a variety of metabolic processes. It is also a secondary product of radicals reacting with oxygen either directly or through GSH. The biological reactivity of superoxide has been the subject of much debate ever since the discovery of superoxide dismutase in 1968. It has more recently become apparent that its rapid reaction with nitric oxide to give peroxynitrite, and its ability to reversibly oxidise and inactivate iron sulphur enzymes, contribute to the toxicity of superoxide. Another mechanism that could be important involves addition reactions of superoxide with other radicals to give organic peroxides. This reaction, to form a tyrosine peroxide, has come to authors attention through the study of the scavenging of tyrosyl radicals by GSH. It is also shown that a tyrosine peroxide is a major product of the oxidation of tyrosine by neutrophils

  2. Taking a radical position: Evidence for position specific radical representations in Chinese character recognition using masked priming ERP

    Directory of Open Access Journals (Sweden)

    I-Fan eSu

    2012-09-01

    Full Text Available In the investigation of orthographic representation of Chinese characters, one question that has stimulated much research is whether radicals (character components are specified for spatial position in a character (e.g. Ding, Peng, & Taft, 2004; Tsang & Chen, 2009. Differing from previous work, component or radical position information in this study is conceived in terms of relative frequency across different positions of characters containing it. A lexical decision task in a masked priming paradigm focusing on radicals with preferred position of occurrence was conducted. A radical position that encompasses more characters than other positions was identified to be the preferred position of a particular radical. The prime that was exposed for 96ms might share a radical with the target in the same or different positions. Moreover, the shared radical appeared either in its preferred or non-preferred position in the target. While response latencies only revealed the effect of graphical similarity, both effects of graphical similarity and radical position preference were found in the ERP results. The former effect was reflected in greater positivity in occipital P1 and greater negativity in N400 for radicals in different positions in prime and target characters. The latter effect manifested as greater negativity in occipital N170 and greater positivity in frontal P200 in the same time window elicited by radicals in their non-preferred position. Equally interesting was the reversal of the effect of radical position preference in N400 with greater negativity associated with radicals in preferred position. These findings identify the early ERP components associated with activation of position-specific radical representations in the orthographic lexicon, and reveal the change in the nature of competition from processing at the radical level to the lexical level.

  3. TEMPO-oxidized Konjac glucomannan as appliance for the preparation of hard capsules

    NARCIS (Netherlands)

    Chen, Yuying; Zhao, Huiying; Liu, Xianwu; Li, Zusen; Liu, Bin; Wu, Jiande; Shi, Mengxuan; Norde, Willem; Li, Yuan

    2016-01-01

    TEMPO-oxidized Konjac glucomannan (OKGM) was developed as new material for preparing vegetarian hard capsules. OKGM of different degrees of oxidation: DO30%, DO50%, and DO80% were prepared to select optimum DO for capsule formation. FT-IR results proved that the primary alcohol groups on KGM were

  4. Effects of Articulation Styles on Perception of Modulated Tempos in Violin Excerpts

    Science.gov (United States)

    Geringer, John M.; Madsen, Clifford K.; Macleod, Rebecca B.

    2007-01-01

    We investigated effects of legato, staccato and pizzicato articulation styles on the perception of modulated tempos. Seventy-two music majors served as participants. Two solo violin excerpts were chosen with contrasting rhythmic rates and were recorded in all three articulation styles. Examples were presented to listeners in three conditions of…

  5. Radical production in biological systems

    International Nuclear Information System (INIS)

    Johnson, J.R.; Akabani, G.

    1994-10-01

    This paper describes our effort to develop a metric for radiation exposure that is more fundamental than adsorbed dose and upon which a metric for exposure to chemicals could be based. This metric is based on the production of radicals by the two agents. Radicals produced by radiation in biological systems commonly assumed to be the same as those produced in water despite the presence of a variety of complex molecules. This may explain why the extensive efforts to describe the relationship between energy deposition (track structure) and molecular damage to DNA, based on the spectrum of radicals produced, have not been successful in explaining simple biological effects such as cell killing. Current models assume that DNA and its basic elements are immersed in water-like media and only model the production and diffusion of water-based radicals and their interaction with DNA structures; these models lack the cross sections associated with each macro-component of DNA and only treat water-based radicals. It has been found that such models are not realistic because DNA is not immersed in pure water. A computer code capable of simulating electron tracks, low-energy electrons, energy deposition in small molecules, and radical production and diffusion in water like media has been developed. This code is still in at a primitive stage and development is continuing. It is being used to study radical production by radiation, and radical diffusion and interactions in simple molecular systems following their production. We are extending the code to radical production by chemicals to complement our PBPK modeling efforts. It therefore has been developed primarily for use with radionuclides that are in biological materials, and not for radiation fields

  6. Practical aerobic oxidations of alcohols and amines with homogeneous copper/TEMPO and related catalyst systems.

    Science.gov (United States)

    Ryland, Bradford L; Stahl, Shannon S

    2014-08-18

    Oxidations of alcohols and amines are common reactions in the synthesis of organic molecules in the laboratory and industry. Aerobic oxidation methods have long been sought for these transformations, but few practical methods exist that offer advantages over traditional oxidation methods. Recently developed homogeneous Cu/TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidinyl-N-oxyl) and related catalyst systems appear to fill this void. The reactions exhibit high levels of chemoselectivity and broad functional-group tolerance, and they often operate efficiently at room temperature with ambient air as the oxidant. These advances, together with their historical context and recent applications, are highlighted in this Minireview. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. A filled duration illusion in music: Effects of metrical subdivision on the perception and production of beat tempo.

    Science.gov (United States)

    Repp, Bruno H; Bruttomesso, Meijin

    2010-01-13

    This study replicates and extends previous findings suggesting that metrical subdivision slows the perceived beat tempo (Repp, 2008). Here, musically trained participants produced the subdivisions themselves and were found to speed up, thus compensating for the perceived slowing. This was shown in a synchronization-continuation paradigm (Experiment 1) and in a reproduction task (Experiment 2a). Participants also judged the tempo of a subdivided sequence as being slower than that of a preceding simple beat sequence (Experiment 2b). Experiment 2 also included nonmusician participants, with similar results. Tempo measurements of famous pianists' recordings of two variation movements from Beethoven sonatas revealed a strong tendency to play the first variation (subdivided beats) faster than the theme (mostly simple beats). A similar tendency was found in musicians' laboratory performances of a simple theme and variations, despite instruc-tions to keep the tempo constant (Experiment 3a). When playing melodic sequences in which only one of three beats per measure was subdivided, musicians tended to play these beats faster and to perceive them as longer than adjacent beats, and they played the whole sequence faster than a sequence without any subdivisions (Experiments 3b and 3c). The results amply demonstrate a filled duration illusion in rhythm perception and music performance: Intervals containing events seem longer than empty intervals and thus must be shortened to be perceived as equal in duration.

  8. A concepção do tempo em Bergson e sua relação com a teoria da relatividade de Einstein

    OpenAIRE

    Daniel Siqueira Pereira

    2008-01-01

    A presente dissertação trata da relação entre o conceito de tempo tal como foi pensado pelo filósofo francês Henri Bergson (1859-1941) e pelo físico alemão Albert Einstein (1879-1955). Ambos foram contemporâneos e tiveram a chance de confrontar suas opiniões discordantes sobre a natureza do tempo. Em seu polêmico ensaio Duração e Simultaneidade (1922), Bergson expôs sua teoria sobre tempo, pensado enquanto duração, já levando em conta a teoria da relatividade de Einstein. O ob...

  9. A STUDY OF TIME MANAGEMENT EFFECTIVE AS A TOOL FOR INCREASED PRODUCTIVITY AND WORK-LIFE BALANCE AND PERSONAL ADMINISTRAÇÃO DO TEMPO: UM ESTUDO SOBRE A GESTÃO EFICAZ DO TEMPO COMO FERRAMENTA PARA O AUMENTO DA PRODUTIVIDADE E WORK LIFE BALANCE

    Directory of Open Access Journals (Sweden)

    Maria do Carmo Ferreira Lima

    2011-05-01

    Full Text Available

    Time Management has been a topic of high relevance, and subject of extensive discussion, especially in the corporate world. Since the first studies of Classical Administration, as for example the "Motion and Time Study," conducted by Taylor, at the time of the Industrial Revolution, through the Technological Revolution in the early 1990s until today, there have always been questions about how it would be possible to better manage time. The challenge is not to manage time, but relationships managed by professionals. The aim of this study was to understand how the adoption of techniques of Time Management can serve as a tool for increasing productivity and balance the career versus personal life. The literature review was supported by a survey in two stages. The first step applied as descriptive, with the intention of identifying what were called "time wasters" most common within the sample surveyed and diagnose the profile time management of all the participants. In the later stage, we performed a case study, in which, for a period of 30 days, voluntary participants were instructed to use some tools such as software and forms available on the market for organization and effective time management. The results proved that a considerable number of people do not know how to manage and take their time and suffering from the negative effects of work overload and lack of motivation that is constantly tied to this scenario. The outcome of the case study found that the tools of organization and time management are available and promote good improvement in how you manage time. But you need commitment and discipline that uses these mechanisms, since the change in how they manage their time is primarily a behavioral change.

    A Administração do Tempo vem sendo um tema de alta relevância, e muito discutido, principalmente no mundo corporativo. Desde os primeiros estudos da Administração Clássica, como o

  10. Poesia e cinema: uma forma de representação do mundo e do tempo

    Directory of Open Access Journals (Sweden)

    Ana Lúcia Costa Barbosa

    2016-09-01

    Full Text Available Este artigo visa a analisar a técnica compositiva de três poemas de Carlos Drummond de Andrade, a saber: “Consideração do poema” “Procura de poesia” e “Canto ao homem do povo Charlie Chaplin”, presentes em A rosa do povo, escrito entre 1943 a 1945. Os dois primeiros poemas mereceram de diferentes críticos análises diversas. Alguns assumem posições divergentes, reconhecendo-se no primeiro a função predominante da linguagem, enquanto o outro estaria mais atrelado ao compromisso social. Outras tendências críticas defendem que os dois poemas compõem um todo coerente, estando, ambos, erigidos de acordo com a concepção dialética de gênero lírico. Propõe-se, também, a discutir as relações entre poesia e cinema, entendendo-os como formas de representação cultural de um tempo histórico. O “Canto ao homem do povo Charlie Chaplin” estabelece um diálogo com seu tempo, abordando temas como a luta pela sobrevivência, o protesto contra a fome e a brutalidade dos tempos modernos.

  11. Influence of the medium on the reaction rate of the t-butoxyl radical with iron(II)

    International Nuclear Information System (INIS)

    Mihaljevic, B.; Razem, D.

    2002-01-01

    Complete text of publication follows. Tert-butoxyl radicals (t-BuO.) were generated by homolytic photodecomposition of di-tert-butylperoxide using ruby laser flashes at 347 nm. The reaction of t-BuO. radicals with Fe 2+ was studied under pseudo-first order conditions. The quantum yield Φ(Fe 3+ ) was determined by measuring the absorbance of Fe 3+ ion as [FeCl] 2+ complex at 360 nm 2 μs after the flash. According to the equation derived from the reaction scheme, the rate constant k 3 was obtained from the relative rate constant k r (k r =k 0 /k 3 ) and the value of k 0 ; the latter refers to the overall rate of the competing disappearance of t-BuO. radicals from the system (reaction 2), including the highest contribution of β-cleavage. The rate constant k 0 was determined using diphenylmethanol instead of Fe 2+ . The known rate constant of the reaction of t-BuO. radical with diphenylmethanol giving ketyl radicals (6.9 x 10 6 dm 3 mol -1 s -1 ) was applied. The quantum yield of ketyl radicals was determined by measuring the maximum of absorbance at 535 nm. At acid concentration of 0.023 mol dm -3 HCl the rate constant k 3 = 3.4 x 10 8 dm 3 mol -1 s -1 was determined. The relative rate constant increased with an increase of the hydrochloric acid concentration which has been ascribed to the lower stability of t-BuO. radical at higher acidity of the medium. The effect of polarity of the medium on the reaction rate was also determined. Decreasing k 3 in media of increasing polarity were explained by increasing of the β-scission rate of t-BuO. radical with increasing polarity of the medium

  12. Plants, Pollution and Public Engagement with Atmospheric Chemistry: Sharing the TEMPO Story Through Ozone Garden Activities

    Science.gov (United States)

    Reilly, L. G.; Pippin, M. R.; Malick, E.; Summers, D.; Dussault, M. E.; Wright, E. A.; Skelly, J.

    2016-12-01

    What do a snap-bean plant and a future NASA satellite instrument named TEMPO have in common? They are both indicators of the quality of the air we breathe. Scientists, educators, and museum and student collaborators of the Tropospheric Emissions: Monitoring Pollution (TEMPO) instrument team are developing a program model to engage learners of all ages via public ozone garden exhibits and associated activities. TEMPO, an ultraviolet and visible spectroscopy instrument due for launch on a geostationary host satellite between 2019 and 2021, will scan North America hourly to measure the major elements in the tropospheric ozone chemistry cycle, providing near real-time data with high temporal and spatial resolution. The TEMPO mission provides a unique opportunity to share the story of the effects of air quality on living organisms. A public ozone garden exhibit affords an accessible way to understand atmospheric science through a connection with nature, while providing a visual representation of the impact of ozone pollution on living organisms. A prototype ozone garden exhibit was established at the Virginia Living Museum in partnership with NASA Langley, and has served as a site to formatively evaluate garden planting and exhibit display protocols, hands-on interpretive activities, and citizen science data collection protocols for learners as young as 3 to 10 as well as older adults. The fun and engaging activities, optimized for adult-child interaction in informal or free-choice learning environments, are aimed at developing foundational science skills such as observing, comparing, classifying, and collecting and making sense of data in the context of thinking about air quality - all NGSS-emphasized scientific practices, as well as key capabilities for future contributing members of the citizen science community. As the launch of TEMPO approaches, a major public engagement effort will include disseminating this ozone garden exhibit and program model to a network of

  13. Gnosticism and Radical Feminism

    DEFF Research Database (Denmark)

    Cahana, Jonathan

    2016-01-01

    and radical feminism would easily fall under this definition. There is, however, one major difference: since radical feminism is a relatively recent phenomenon which also benefited from modern modes of text production and preservation, almost all of the sources are still with us. This, in turn, may allow us...... to use radical feminism to make certain aspects of ancient Gnosticism re-emerge from their long submersion, provided that enough similarities can be independently drawn between the two phenomena to merit such a comparison. This paper therefore presents a comparison between concepts and positions...

  14. Radical's view of sciences

    International Nuclear Information System (INIS)

    Mittal, J.P.

    2004-01-01

    Full text: General concept in radiation biology is that free radicals are highly reactive and they can damage vital cellular molecules leading to injurious effects. However, in this talk, evidence will be presented through the techniques of electron paramagnetic resonance ( EPR ) and pulse radiolysis that free radicals can be highly selective in their reaction with the target molecules. In addition, attempts will be made to present a brief account of emerging scenario of free radical generation, identification and their involvement in radiation damage mechanisms in chemical and biological systems

  15. Modifications induced by swift heavy ions on poly(hydroxybutyrate-hydroxyvalerate) (PHB/HV) and poly(ε-caprolactone) (PCL). Part 2. Radicals characterization

    International Nuclear Information System (INIS)

    Rouxhet, L.; Mestdagh, M.; Legras, R.

    2000-01-01

    Modifications induced by different energetic heavy ions ( 40 Ar 9+ , 80 Kr 15+ , 129 Xe 24+ , 208 Pb 53+ and 208 Pb 56+ ) on poly(ε-caprolactone) (PCL) and poly(hydroxybutyrate-hydroxyvalerate) (PHB/HV) have been investigated by electron spin resonance (ESR). Indeed, film irradiation by heavy ions leads to, among other phenomena, the formation of radicals in the ion tracks. Thanks to ESR, it is possible to detect these radicals and to identify them or at least to characterize them by following the evolution of the radical signal as a function of parameters, like temperature, or the kinetic of disappearance of the radical species at ambient temperature in vacuum or ambient atmosphere. This study confirmed the generation of radicals by the irradiation of PHB/HV samples with energetic heavy ions reported in the literature. The study on PCL was not pursued after a few preliminary studies, revealing the presence of an ESR signal in the non-irradiated sample. Electronic stopping power has a major influence on radical decrease at ambient temperature. The ion used for the irradiation did not modify very much the radical signal and the evolution of the radicalar signal intensity with temperature. Different reasoning and experiments revealed that the glass transition temperature is a key temperature above which irreversible recombinations of the most stable radicals take place. A simulation study indicated that the most stable radical produced was probably a tertiary radical formed by the stabilization of the secondary radical resulting from the abstraction of a highly mobile hydrogen adjacent to the carbonyl

  16. Radiolytic degradation and stability of polycarbonate

    International Nuclear Information System (INIS)

    Araujo, E.S. de.

    1993-01-01

    The radiolytic stability of polycarbonate was studied using national commercial additives, employed in the photo and thermo-oxidative stabilization of polymers. Among several additives tested only two showed the efficiency to radiolytic protection: one quencher and one radical scavenger. It was derived a linear relation that provides by slope of the straight line the degree of degradation (scissions), G, and the factors of radiolytic protection P (degree of protection) and CE (capture of energy) conferred by radioprotector additive easily. Therefore the method developed in this work (viscosity) to study the molecular degradation and stability of polymers is a simply and precise method. The synergic mixture of two additives (1% of weight total) confers at polycarbonate excellent radiolytic protection of 98% (20 - 40 kGy) reducing the G value of 16.7 to only 0.4. (author). 69 refs, 31 figs, 17 tabs

  17. Musicians are more consistent: Gestural cross-modal mappings of pitch, loudness and tempo in real-time

    Science.gov (United States)

    Küssner, Mats B.; Tidhar, Dan; Prior, Helen M.; Leech-Wilkinson, Daniel

    2014-01-01

    Cross-modal mappings of auditory stimuli reveal valuable insights into how humans make sense of sound and music. Whereas researchers have investigated cross-modal mappings of sound features varied in isolation within paradigms such as speeded classification and forced-choice matching tasks, investigations of representations of concurrently varied sound features (e.g., pitch, loudness and tempo) with overt gestures—accounting for the intrinsic link between movement and sound—are scant. To explore the role of bodily gestures in cross-modal mappings of auditory stimuli we asked 64 musically trained and untrained participants to represent pure tones—continually sounding and concurrently varied in pitch, loudness and tempo—with gestures while the sound stimuli were played. We hypothesized musical training to lead to more consistent mappings between pitch and height, loudness and distance/height, and tempo and speed of hand movement and muscular energy. Our results corroborate previously reported pitch vs. height (higher pitch leading to higher elevation in space) and tempo vs. speed (increasing tempo leading to increasing speed of hand movement) associations, but also reveal novel findings pertaining to musical training which influenced consistency of pitch mappings, annulling a commonly observed bias for convex (i.e., rising–falling) pitch contours. Moreover, we reveal effects of interactions between musical parameters on cross-modal mappings (e.g., pitch and loudness on speed of hand movement), highlighting the importance of studying auditory stimuli concurrently varied in different musical parameters. Results are discussed in light of cross-modal cognition, with particular emphasis on studies within (embodied) music cognition. Implications for theoretical refinements and potential clinical applications are provided. PMID:25120506

  18. Musicians are more consistent: Gestural cross-modal mappings of pitch, loudness and tempo in real-time

    Directory of Open Access Journals (Sweden)

    Mats B. Küssner

    2014-07-01

    Full Text Available Cross-modal mappings of auditory stimuli reveal valuable insights into how humans make sense of sound and music. Whereas researchers have investigated cross-modal mappings of sound features varied in isolation within paradigms such as speeded classification and forced-choice matching tasks, investigations of representations of concurrently varied sound features (e.g., pitch, loudness and tempo with overt gestures—accounting for the intrinsic link between movement and sound—are scant. To explore the role of bodily gestures in cross-modal mappings of auditory stimuli we asked sixty-four musically trained and untrained participants to represent pure tones—continually sounding and concurrently varied in pitch, loudness and tempo—with gestures while the sound stimuli were played. We hypothesised musical training to lead to more consistent mappings between pitch and height, loudness and distance/height, and tempo and speed of hand movement and muscular energy.Our results corroborate previously reported pitch vs. height (higher pitch leading to higher elevation in space and tempo vs. speed (increasing tempo leading to increasing speed of hand movement associations, but also reveal novel findings pertaining to musical training which influenced consistency of pitch mappings, annulling a commonly observed bias for convex (i.e. rising-falling pitch contours. Moreover, we reveal effects of interactions between musical parameters on cross-modal mappings (e.g., pitch and loudness on speed of hand movement, highlighting the importance of studying auditory stimuli concurrently varied in different musical parameters. Results are discussed in light of cross-modal cognition, with particular emphasis on studies within (embodied music cognition. Implications for theoretical refinements and potential clinical applications are provided.

  19. Concentrações salinas combinadas com tempos de hidratação: efeito no tempo de cocção em feijão Salts concentrations in combination with soaking time: effect in bean cooking time

    Directory of Open Access Journals (Sweden)

    Juliano Garcia Bertoldo

    2010-06-01

    Full Text Available Este trabalho teve como objetivo investigar o efeito da adição de diferentes doses de NaCl na água de hidratação, durante diferentes tempos, buscando uma redução no tempo de cocção. O Brasil, embora seja considerado um grande produtor e um dos maiores consumidores de feijão, está reduzindo gradativamente o consumo. Sendo assim, é necessário dispor de técnicas que facilitem o preparo do feijão, podendo dessa forma reverter a tendência de consumo e como consequência incentivar a produção. O experimento foi conduzido na área experimental do Instituto de Melhoramento e Genética Molecular da UDESC - IMEGEM, em Lages - SC. Foram avaliados os efeitos de três concentrações de NaCL (0, 50 e 125 g.L-1 em dois genótipos de feijão (Pérola e IPR Uirapuru hidratados durante três tempos (0,5, 9 e 18 horas. Os resultados revelaram um efeito significativo das doses de NaCl na redução do tempo de cocção. A adição de 56,50 g.L-1 de NaCl foi suficiente para reduzir significativamente o tempo de cocção. A hidratação dos grãos de feijão propiciou a redução no tempo de cocção, sendo necessárias 12,5 horas para a máxima hidratação, independente dos genótipos avaliados.This study aimed to investigate the effect of adding different doses of NaCl in hydration water, during different times, in order to reduce cooking time. Although considered a major producer and one of the largest bean consumers, Brazil has been experiencing a gradual decrease in consumption. Therefore, it is necessary to facilitate the preparation of beans to increase its consumption and production. This study was conducted at the experimental area of the Institute of Molecular Genetics and Plant Breeding at UDESC - IMEGEM, in the city of Lages, SC-Brazil. We evaluated the effect of three doses of NaCL (0, 50 e 125 g L-1 in two genotypes of beans (Pérola and IPR Uirapuru, hydrated at three different times (0.5, 9, and 18 hours. The results revealed a

  20. EPR spin trapping of protein radicals

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan; Hawkins, Clare Louise

    2004-01-01

    Electron paramagnetic resonance (EPR) spin trapping was originally developed to aid the detection of low-molecular-mass radicals formed in chemical systems. It has subsequently found widespread use in biology and medicine for the direct detection of radical species formed during oxidative stress...... 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...... examples of radical formation on proteins....

  1. The currency and tempo of extinction.

    Science.gov (United States)

    Regan, H M; Lupia, R; Drinnan, A N; Burgman, M A

    2001-01-01

    This study examines estimates of extinction rates for the current purported biotic crisis and from the fossil record. Studies that compare current and geological extinctions sometimes use metrics that confound different sources of error and reflect different features of extinction processes. The per taxon extinction rate is a standard measure in paleontology that avoids some of the pitfalls of alternative approaches. Extinction rates reported in the conservation literature are rarely accompanied by measures of uncertainty, despite many elements of the calculations being subject to considerable error. We quantify some of the most important sources of uncertainty and carry them through the arithmetic of extinction rate calculations using fuzzy numbers. The results emphasize that estimates of current and future rates rely heavily on assumptions about the tempo of extinction and on extrapolations among taxa. Available data are unlikely to be useful in measuring magnitudes or trends in current extinction rates.

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

    KAUST Repository

    Zhang, Tao

    2013-03-19

    A simple, nonhazardous, efficient and low energy-consuming process is desirable to generate powerful radicals from peroxymonosulfate (PMS) for recalcitrant pollutant removal. In this work, the production of radical species from PMS induced by a magnetic CuFe2O4 spinel was studied. Iopromide, a recalcitrant model pollutant, was used to investigate the efficiency of this process. CuFe2O4 showed higher activity and 30 times lower Cu2+ leaching (1.5 μg L-1 per 100 mg L-1) than a well-crystallized CuO at the same dosage. CuFe 2O4 maintained its activity and crystallinity during repeated batch experiments. In comparison, the activity of CuO declined significantly, which was ascribed to the deterioration in its degree of crystallinity. The efficiency of the PMS/CuFe2O4 was highest at neutral pH and decreased at acidic and alkaline pHs. Sulfate radical was the primary radical species responsible for the iopromide degradation. On the basis of the stoichiometry of oxalate degradation in the PMS/CuFe 2O4, the radical production yield from PMS was determined to be near 1 mol/mol. The PMS decomposition involved an inner-sphere complexation with the oxide\\'s surface Cu(II) sites. In situ characterization of the oxide surface with ATR-FTIR and Raman during the PMS decomposition suggested that surface Cu(II)-Cu(III)-Cu(II) redox cycle was responsible for the efficient sulfate radical generation from PMS. © 2013 American Chemical Society.

  3. Soil manganese redox cycling in suboxic zones: Effects on soil carbon stability

    Science.gov (United States)

    Suboxic soil environments contain a disproportionately higher concentration of highly reactive free radicals relative to the surrounding soil matrix, which may have significant implications for soil organic matter cycling and stabilization. This study investigated how Mn-ozidizin...

  4. A Free-Radical Pathway to Hydrogenated Phenanthrene in Molecular Clouds-Low Temperature Growth of Polycyclic Aromatic Hydrocarbons.

    Science.gov (United States)

    Thomas, Aaron M; Lucas, Michael; Yang, Tao; Kaiser, Ralf I; Fuentes, Luis; Belisario-Lara, Daniel; Mebel, Alexander M

    2017-08-05

    The hydrogen-abstraction/acetylene-addition mechanism has been fundamental to unravelling the synthesis of polycyclic aromatic hydrocarbons (PAHs) detected in combustion flames and carbonaceous meteorites like Orgueil and Murchison. However, the fundamental reaction pathways accounting for the synthesis of complex PAHs, such as the tricyclic anthracene and phenanthrene along with their dihydrogenated counterparts, remain elusive to date. By investigating the hitherto unknown chemistry of the 1-naphthyl radical with 1,3-butadiene, we reveal a facile barrierless synthesis of dihydrophenanthrene adaptable to low temperatures. These aryl-type radical additions to conjugated hydrocarbons via resonantly stabilized free-radical intermediates defy conventional wisdom that PAH growth is predominantly a high-temperature phenomenon and thus may represent an overlooked path to PAHs as complex as coronene and corannulene in cold regions of the interstellar medium like in the Taurus Molecular Cloud. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    Science.gov (United States)

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-03-01

    Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

  6. Reaction between protein radicals and other biomolecules

    DEFF Research Database (Denmark)

    Østdal, H.; Davies, M.J.; Andersen, Henrik Jørgen

    2002-01-01

    The present study investigates the reactivity of bovine serum albumin (BSA) radicals towards different biomolecules (urate, linoleic acid, and a polypeptide, poly(Glu-Ala-Tyr)). The BSA radical was formed at room temperature through a direct protein-to-protein radical transfer from H(2)O(2....... 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...

  7. Efetividade de um protocolo assistencial para redução do tempo porta-balão da angioplastia primária

    Directory of Open Access Journals (Sweden)

    Luis Cláudio Lemos Correia

    2013-07-01

    Full Text Available FUNDAMENTO: Tempo porta-balão adequado (< 120 minutos é a condição necessária para que a eficácia da angioplastia primária no infarto se traduza em efetividade. OBJETIVO: Descrever a efetividade de um protocolo de qualidade assistencial para redução do tempo porta-balão. MÉTODOS: Entre maio de 2010 e agosto de 2012, foram analisados todos os indivíduos que realizaram angioplastia primária em nosso hospital. O momento porta foi registrado eletronicamente, pela retirada de senha para atendimento na emergência, o que antecede o preenchimento da ficha e a triagem. O momento balão foi definido como o início da abertura da artéria (passagem do primeiro dispositivo. Os primeiros 5 meses de monitoramento corresponderam ao período pré-implementação do protocolo. O protocolo se constituiu de definição do fluxo de ações, desde a chegada do paciente ao hospital, a sensibilização da equipe quanto à priorização do tempo e a apresentação periódica de parecer dos resultados e de possíveis inadequações. RESULTADOS: Foram avaliados 50 indivíduos, divididos em cinco grupos de 10 pacientes sequenciais (um grupo pré e quatro grupos pós-protocolo. O tempo porta-balão referente aos 10 casos registrados antes da implementação do protocolo foi de 200 ± 77 minutos. Após a implementação do protocolo, houve progressiva melhora do tempo porta-balão, para 142 ± 78 minutos nos 10 primeiros pacientes, seguida de 150±50 minutos, 131±37 minutos e, finalmente, 116 ± 29 minutos no três grupos sequenciais de 10 pacientes, respectivamente. Regressão linear entre pacientes sequenciais e tempo porta-balão (r = - 0,41 evidenciou coeficiente de regressão de - 1,74 minutos. CONCLUSÃO: A implementação do protocolo se mostrou efetiva na redução do tempo porta-balão.

  8. Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons

    International Nuclear Information System (INIS)

    Bors, W.; Saran, M.; Michel, C.

    1982-01-01

    The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (radicalsOH) and hydrated electrons (e - sub(aq)), while superoxide anions (O 2 - ) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation. (author)

  9. Formation of long-lived radicals on proteins by radical transfer from heme enzymes--a common process?

    DEFF Research Database (Denmark)

    Ostdal, H; Andersen, H J; Davies, Michael Jonathan

    1999-01-01

    concentrations were observed after limited digestion, although this effect was less marked with the HRP/H2O2/BSA system than with Fe(III)Mb/H2O2/BSA, consistent with different modes of radical transfer. More extensive digestion of BSA decreased the radical concentration to levels below those detected with native...... investigated using horseradish peroxidase (HRP)/H2O2, in the presence and absence of added tyrosine. Incubation of HRP with H2O2 and bovine or human serum albumins, in the presence and absence of tyrosine, gave long-lived albumin-derived radicals as detected by EPR spectroscopy. Evidence has been obtained...... for these albumin radicals being located on buried tyrosine residues on the basis of blocking experiments. The effect of protein conformation on radical transfer has been investigated using partial proteolytic digestion prior to protein oxidation. With HRP/H2O2/BSA and Fe(III)Mb/H2O2/BSA increased radical...

  10. Injectable TEMPO-oxidized nanofibrillated cellulose/biphasic calcium phosphate hydrogel for bone regeneration.

    Science.gov (United States)

    Safwat, Engie; Hassan, Mohammad L; Saniour, Sayed; Zaki, Dalia Yehia; Eldeftar, Mervat; Saba, Dalia; Zazou, Mohamed

    2018-05-01

    Nanofibrillated cellulose, obtained from rice straw agricultural wastes was used as a substrate for the preparation of a new injectable and mineralized hydrogel for bone regeneration. Tetramethyl pyridine oxyl (TEMPO) oxidized nanofibrillated cellulose, was mineralized through the incorporation of a prepared and characterized biphasic calcium phosphate at a fixed ratio of 50 wt%. The TEMPO-oxidized rice straw nanofibrillated cellulose was characterized using transmission electron microscopy, Fourier transform infrared, and carboxylic content determination. The injectability and viscosity of the prepared hydrogel were evaluated using universal testing machine and rheometer testing, respectively. Cytotoxicity and alkaline phosphatase level tests on osteoblast like-cells for in vitro assessment of the biocompatibility were investigated. Results revealed that the isolated rice straw nanofibrillated cellulose is a nanocomposite of the cellulose nanofibers and silica nanoparticles. Rheological properties of the tested materials are suitable for use as injectable material and of nontoxic effect on osteoblast-like cells, as revealed by the positive alkaline phosphate assay. However, nanofibrillated cellulose/ biphasic calcium phosphate hydrogel showed higher cytotoxicity and lower bioactivity test results when compared to that of nanofibrillated cellulose.

  11. 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))

    1990-01-01

    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).

  12. Radical surgery compared with intracavitary cesium followed by radical surgery in cervical carcinoma stage IB

    International Nuclear Information System (INIS)

    Tinga, D.J.; Bouma, J.; Aalders, J.G.; Hollema, H.

    1990-01-01

    Forty-nine patients aged ≤ 45 years, with cervical carcinoma stage IB (≤ 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)

  13. Free radicals in an Adamantane matrix. XI. Electron paramagnetic resonance study of conformations in the β-halo-tert-butyl radicals

    International Nuclear Information System (INIS)

    Lloyd, R.V.; Wood, D.E.

    1975-01-01

    The β-halo-tert-butyl radicals were prepared by x-irradiation of the corresponding isobutyl halides in an adamantane matrix at 77 0 K and their conformations were determined by analysis of their EPR spectra. The radicals are nonplanar at the radical site, the fluoro and chloro radicals trans eclipsed and the bromo and iodo radicals gauche staggered with respect to the relative orientation of the carbon halogen bond and the direction of the singly occupied orbital. Vibration-rotation motions about the favored conformation are much larger for the fluoro radical than for the others. The rate of interconversion of the inequivalent methylene protons is approximately 1.5 x 10 9 sec -1 for the bromo radical at 202 0 K while it is too slow to measure for the iodo radical at the same temperature. The barrier to interconversion has a lower limit of 3 kcal/mol for the bromo radical and higher than that for the iodo radical. The halogen and proton hfsc in gauss and the g values for the XCH 2 C(CH 3 ) 2 radicals are: 19 F = 103.7, CH 2 = 10.4, CH 3 = 23.3, g = 2.0030 at 214 K; 35 Cl = 19.5, CH 2 = 6.3, CH 3 = 21.1, g = 2.0042 at 215 K; 81 Br = 6.7, CH 2 = 21.4, 42.7, CH 3 = 21.4, g = 2.0010 at 202 K; 127 I = 7.0, CH 2 = 21.9, 43.8, CH 3 = 21.9, g = 2.0009 at 208 K. The fluoro radical decays to nonradical products above 318 0 K, the chloro radical converts to 2-methyl allyl radical above 306 0 K, the bromo radical converts to tert-butyl radical by exchange with a matrix proton (or deuteron) at 209 0 K as does the iodo radical above 225 0 K. Photolysis with a Xe lamp converts the bromo and iodo radicals to nonradical products in less than the experimental time constant of 0.3 sec. The hypothesis is put forward that the nonplanarity and high barrier to rotation observed explain the retention of stereochemical configuration in reactions involving β-chloro, β-bromo, and β-iodo alkyl radicals. (auth)

  14. 17.9.3 Radical cations of diazo compounds

    Science.gov (United States)

    Davies, A. G.

    This document is part of Subvolume E2 `Phosphorus-Centered Radicals, Radicals Centered on Other Heteroatoms, Organic Radical Ions' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  15. Inhibition of radiation-induced DNA strand breaks by hoechst 33258: OH-radical scavenging and DNA radical quenching

    International Nuclear Information System (INIS)

    Adhikary, A.; Bothe, E.; Von Sonntag, C.; Adhikary, A.

    1997-01-01

    The minor-groove-binding dye Hoechst 33258 has been found to protect pBR322 DNA in aqueous solution against radiation-induced single-strand breaks (ssb). This protective effect has been assumed to be largely due to the scavenging of the strand-break-generating OH radicals by Hoechst. From D 37 values for ssb at different Hoechst concentrations the value of the OH radical scavenging constant of DNA-bound Hoechst has been estimated at k Ho/DNA = 2.7 * 10 11 dm 3 mol -1 . This unexpectedly high value has led us to study the reactions of OH radicals with Hoechst in the absence and in the presence of double-stranded calf thymus DNA (ds DNA) by pulse radiolysis, and the formation of radiation-induced ssb by low angle laser light scattering. The D 37 /D 37 0 values at different Hoechst concentrations agree with the values obtained by Martin and al. and demonstrate the protection. However, this protection cannot be explained on the basis of OH radical scavenging alone using the above rate constants. There must, in addition, be some quenching of DNA radicals. Hoechst radicals are formed in the later ms time range, i.e a long time after the disappearance of the OH radicals. This delayed Hoechst radical formation has been assigned to a a reaction of DNA radicals with Hoechst, thereby inhibiting strand breakage. In confirmation, pulse radiolysis of aqueous solution of nucleotides in the presence of Hoechst yields a similar delayed Hoechst radical formation. The data indicate that in DNA the cross-section of this quenching has a diameter of 3 to 4 base pairs per Hoechst molecule. (N.C.)

  16. Radical-Local Teaching and Learning

    DEFF Research Database (Denmark)

    Hedegaard, Mariane; Chaiklin, Seth

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

  17. Electronic structure of Co islands grown on the {radical}3 x {radical}3-Ag/Ge(111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Xiao-Lan; Chou, Chi-Hao; Lin, Chun-Liang; Tomaszewska, Agnieszka; Fu, Tsu-Yi, E-mail: phtifu@phy.ntnu.edu.tw

    2011-09-30

    By means of room temperature scanning tunneling spectroscopy (RT STS), we have studied the electronic structure of two different Ag/Ge(111) phases as well as Co islands grown on the {radical}3 x {radical}3-Ag/Ge (111) forming either {radical}13 x {radical}13 or 2 x 2 patterns. The spectrum obtained from 4 x 4-Ag/Ge(111) structure shows the existence of a shoulder at 0.7 V which is also present in the electronic structure of the Ge(111)-c2 x 8 and indicates donation of Ge electrons to electronic states of the Ag-driven phase. However, this fact is not supported by the electronic spectrum taken from the {radical}3 x {radical}3-Ag/Ge (111). The complexity of the Co-{radical}13 x {radical}13 islands bonding with the substrate is mirrored by a large number of peaks in their electronic spectra. The spectra obtained from the Co-2 x 2 islands which had grown on the step differ from those taken from Co-2 x 2 islands located along the edge of the terrace by a number of peaks at negative sample bias. This discrepancy is elucidated in terms of dissimilarities of Co-substrate interaction accompanying Co islands growth on different areas of the stepped surface.

  18. Understanding political radicalization: The two-pyramids model.

    Science.gov (United States)

    McCauley, Clark; Moskalenko, Sophia

    2017-04-01

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

  19. 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

  20. O Behaviorismo Radical como filosofia da mente Radical Behaviorism as philosophy of mind

    Directory of Open Access Journals (Sweden)

    Carlos Eduardo Lopes

    2003-01-01

    Full Text Available O Behaviorismo Radical de B. F. Skinner é constantemente acusado de eliminar a mente de sua explicação do comportamento humano. Uma análise do livro The Concept of Mind, de Gilbert Ryle, sugere a possibilidade de defender a existência de uma mente relacional, diferente da categoria de existência da mente defendida em interpretações cartesianas (mente substancial. A análise de alguns textos de Skinner sugere que o conceito de uma mente relacional também pode ser defendido no Behaviorismo Radical. Esse fato, culminaria na possibilidade de que, além de filosofia da Ciência do Comportamento, o Behaviorismo Radical, também pode ser uma filosofia da mente, o que traria conseqüências ao estudo e à aplicação da Análise do Comportamento.B. F. Skinner's Radical Behaviorism has been repeatedly accused of eliminating the mind from its explanation of human behavior. An analysis of Gilbert Ryle's book, The Concept of Mind, suggests the possibility of defending the existence of a relational mind, different from the category of existence of mind defended in Cartesian interpretations (substantial mind. The analysis of some texts of Skinner suggests that the concept of a relational mind can also be defended in Radical Behaviorism. This fact would lead to the possibility that, beyond a philosophy of Behavior Science, Radical Behaviorism may also be a philosophy of mind, which would bring consequences to the study and application of Analysis of Behavior.

  1. Muonium radicals in benzene-styrene mixtures

    International Nuclear Information System (INIS)

    Ng, B.W.; Stadlbauer, J.W.; Walker, D.C.

    1984-01-01

    Muonium radicals were observed through their μ + SR precession frequencies in high transverse magnetic fields in pure benzene, pure styrene and their mixtures, all as liquids at room temperature. In benzene-styrene mixtures, the radicals obtained in each pure liquid are both present, so no slow (10 -9 -10 -5 s) intermolecular exchange occurs; but strong selectivity was found with the formation of the radical from styrene being about eight-times more probable than the radical from benzene. (Auth.)

  2. The tempo and mode of barnacle evolution

    DEFF Research Database (Denmark)

    Pérez-Losada, Marcos; Harp, Margaret; Høeg, Jens T

    2008-01-01

    (outgroup) species representing almost all the Thoracica families to assess the tempo and mode of barnacle evolution. Using phylogenetic methods of maximum parsimony, maximum likelihood, and Bayesian inference and 14 fossil calibrations, we found that: (1) Iblomorpha form a monophyletic group; (2......) pedunculated barnacles without shell plates (Heteralepadomorpha) are not ancestral, but have evolved, at least twice, from plated forms; (3) the ontogenetic pattern with 5-->6-->8-->12+ plates does not reflect Thoracica shell evolution; (4) the traditional asymmetric barnacles (Verrucidae) and the Balanomorpha......) the Thoracica suborders evolved since the Early Carboniferous (340mya) with the final radiation of the Sessilia in the Upper Jurassic (147mya). These results, therefore, reject many of the underlying hypotheses about character evolution in the Cirripedia Thoracica, stimulate a variety of new thoughts...

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

    KAUST Repository

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

    2013-01-01

    of the PMS/CuFe2O4 was highest at neutral pH and decreased at acidic and alkaline pHs. Sulfate radical was the primary radical species responsible for the iopromide degradation. On the basis of the stoichiometry of oxalate degradation in the PMS/CuFe 2O4

  4. Laparoscopic radical cystectomy: key points

    Directory of Open Access Journals (Sweden)

    D. V. Perlin

    2018-01-01

    Full Text Available Background. Radical cystectomy remains the golden standard for treatment of muscle invasive bladder cancer. Objective: to duplicate with highest accuracy the open radical cystectomy procedure, which we successfully utilized earlier in our clinic, in the of laparoscopic conditions in order to preserve the advantages of minimally invasive procedures and retain the reliability of the tried and tested open surgery.Materials and methods. In the report were included 35 patients (27 men and 8 women with bladder cancer, who underwent laparoscopic radical cystectomy in Volgograd Regional Center of Urology and Nephrology between April 2013 and March 2016. Only the patients who had been submitted to full intracorporal ileal conduits were included.Results. The mean operative time was 378 minutes, the mean blood loss was 285 millilitres, the mean length of hospital stay was 12.4 days, only 20 % of patients required the narcotic anesthetics. The postoperative complication rate was 11.4 %. However, the majority of the patients were successfully treated with minimally invasive procedures. Generally, our results were similar to other reported studies.Conclusion. Laparoscopic radical cystectomy is a safe and efficient modality of treatment of bladder cancer. However, it needs more procedures and longer observation period to establish laparoscopic radical cystectomy as an alternative to open radical cystectomy.

  5. Relationship Between Exercise Heart Rate and Music\\ud Tempo Preference

    OpenAIRE

    Karageorghis, C. I; Jones, Leighton; Low, D. C

    2006-01-01

    The present study examined the predicted positive and linear relationship (Iwanaga, 1995a, 1995b) between exercise heart rate and music tempo preference. Initially, 128 undergraduate students (M age = 20.0 years, SD = 0.9) were surveyed to establish their three favorite music artists. A separate experimental group of 29 undergraduates (M age = 20.3 years, SD = 1.2) selected the music of a single artist from the three highest-rated artists from the earlier survey. They reported their\\ud prefer...

  6. Effects of Molecular Iodine and 4-tert-Butylcatechol Radical Inhibitor on the Radical Polymerization of Styrene

    Directory of Open Access Journals (Sweden)

    Mojtaba Bozorg

    2017-05-01

    Full Text Available The presence of molecular iodine was studied in relation the molecular weight and molecular weight distribution of polystyrene, produced by radical poly merization. Radical polymerization of styrene initiated by 2,2׳-azobisisobutyronitrile (AIBN was performed at 70°C in the presence of molecular iodine. The synthesized polymers were characterized by gel permeation chromatography (GPC and proton- nuclear magnetic resonance (1H NMR techniques. The results of these reactions including conversion data, number-average molecular weight and molecular weight distribution were compared with those obtained for styrene radical polymerization initiated by AIBN at the same temperature in the absence of molecular iodine. It was found that the presence of iodine had a profound effect on the molecular weight and its distribution in the produced polystyrene. This was attributed to the ability of iodine to control the polymerization of styrene initiated by AIBN via reverse iodine transfer polymerization (RITP mechanism. The polymer produced by this method had a molecular weight of 10600 g/mol with a molecular weight polydispersity index of 1.3. Due to the importance of induction period in reverse iodine transfer radical polymerization, increasing the temperature to 120°C during the induction period resulted in shorter induction periods and the produced species led to better control of the molecular weight. Also, due to the role of iodine molecules as a radical inhibitor, the presence of a secondary radical inhibitor, i.e. 4-tert-butylcatechol, along with the iodine was investigated in radical polymerization of polystyrene initiated by AIBN. It was observed that the secondary radical inhibitor prevented the consumption of the iodine molecules by the radicals produced from decomposition of the AIBN initiator; therefore, alkyl halides were not produced during the induction period.

  7. 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)

    2011-12-29

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

  8. Radical chemistry of artemisinin

    Science.gov (United States)

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

    2010-12-01

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

  9. Radical chemistry of artemisinin

    International Nuclear Information System (INIS)

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

    2010-01-01

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

  10. Radical chemistry of artemisinin

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-12-29

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

  11. Oxygen free radicals in rheumatoid arthritis

    NARCIS (Netherlands)

    P. Biemond (Pieter)

    1986-01-01

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

  12. Free radicals in health and disease

    International Nuclear Information System (INIS)

    Gonet, B.

    1993-01-01

    Free radicals appear in the cells as the result of exogenic factors (ionizing radiation, UV) or reactions naturally occurring in the cell. Free radical reactions may cause destruction of macromolecules (DNA, lipids, proteins). Free radical pathology is important in many diseases and aging processes in organisms

  13. Study of Radiation Induced Radicals in HAP and β-TCP Based Bone Graft Materials by ERP Spectroscopy

    International Nuclear Information System (INIS)

    Maltar-Strmecki, N.; Matkovic, I.

    2013-01-01

    Calcium phosphates such as beta-tricalcium phosphate (β-TCP) and hydroxyapatite (HAP) are frequently used as dental implants due to proven excellent biocompatibility. Because of their resorption in the body and direct contact with tissues, in order to inactivate bacteria, fungal spores and viruses, they are usually sterilized by γ-irradiation. However, literature provides little information about effects of γ-irradiation on the formation and stability of the free radicals in the bone graft materials during and after sterilization procedure. In this study EPR (electron paramagnetic resonance) spectroscopy was used to investigate HAP and β-TCP based dental implants present on the market. Eight dental graft materials present on the market were investigated: Bioresorb R Macropore, Poresorb R -TCP, Easy-Graft T M and Cerasorb R synthetic β-tricalcium phosphates, Easy-Graft T M crystal and Ossceram R two phase synthetic CaP consisting of 60 % HAP and 40 % β-TCP, and Dexabone R and Bio-Oss R bone graft material of bovine origin. EPR study shows that this is the only technique for characterization of free radicals that can simultaneously determine not only the presence and content, but also the position and the structure of free radicals formed by γ-sterilization in the investigated materials, as well as the paramagnetic substitutions incorporated in the materials during the synthesis (such as Mn 2+ , Fe 3+ or Cr 2+ ). Additionally, EPR provides information on stability of irradiation-induced radicals (CO 2 - , trapped H-atoms, NO 3 2 etc.) and processes for reducing them. Results show that EPR should be considered as a valuable technique in improving the quality of bone graft materials, which must be sterile, and to offer the high quality, efficacy and reliable materials to the patients.(author)

  14. Does Metal Ion Complexation Make Radical Clocks Run Fast? An Experimental Perspective.

    Science.gov (United States)

    Abdel Latif, Marwa K; Spencer, Jared N; Paradzinsky, Mark; Tanko, James M

    2017-12-28

    The rate constant for the β-scission of the cumyloxyl radical (k β ) was measured in the presence of various added electrolytes in acetonitrile and DMSO solvent. The results show that in CH 3 CN, k β increases in the presence of added electrolyte, roughly paralleling the size of the cation: Li + > Mg 2+ ≈ Na + > n Bu 4 N + > no added electrolyte. As suggested by Bietti et al. earlier, this effect is attributable to stabilizing ion-dipole interactions in the transition state of the developing carbonyl group, a conclusion further amplified by MO calculations (gas phase) reported herein. Compared to the gas phase predictions, however, this effect is seriously attenuated in solution because complexation of the cation to the electrophilic alkoxyl radical (relative to the solvent, CH 3 CN) is very weak. Because the interaction of Li + and Na + is much stronger with DMSO than with CH 3 CN, addition of these ions has no effect on the rate of β-scission.

  15. BREVES CONSIDERAÇÕES SOBRE A ABORDAGEM DE CHARLES GUIGNON DO MÉTODO FENOMENOLÓGICO EM SER E TEMPO

    Directory of Open Access Journals (Sweden)

    Rogério Tolfo

    2011-05-01

    Full Text Available Este artigo apresenta os estágios do método filosófico em Ser e Tempo, deacordo com a obra Heidegger e o Problema do Conhecimento de Charles Guignon.Segundo Guignon, Heidegger realiza em Ser e Tempo um processo em etapas: 1.Descritivo; 2. Hermenêutico; 3. Processo Dialético; 4. Diagnóstico do Senso Comum. Oobjetivo principal deste artigo é divulgar a proposta de Guignon. No entanto, faremosbreves considerações sobre esta proposta.

  16. Stabilization of sulfide cations: mechanisms relevant to oxidation of peptides and proteins containing methionine

    International Nuclear Information System (INIS)

    Bobrowski, K.; Hug, G.L.; Pogocki, D.; Horner, G.; Marciniak, B.; Schoneich, C.

    2006-01-01

    Sulfide radical cations (R 2 S +. ) have recently attracted considerable attention. In particular they are implicated in assorted biological electron transfers where they are likely intermediates in biological redox-processes. There is unambigous theoretical and experimental evidence that R 2 S +. can be stabilized through intramolecular complexation with nucleophiles that are present in neighboring groups. Reactions of this type are of special interest to biology when stabilization of sulfide radical cations derived from methionine, Met(>S +. ) occurs in peptides and proteins. The methionine (Met) residues in these biopolymers are susceptible to attack by Reactive Oxygen Species (ROS) during oxidative stress and biological aging. Moreover, the pathogenesis of some neurodegenerative diseases (Alzheimer's, Jacob-Creutzfeld's, and Parkinson's) seems to be strongly linked to the presence in brain tissue of β-amyloid peptide (βAP), human prion protein (hPrP), and an aggregated form of α-synuclein, respectively. These macro- molecules contain methionine(s) with βAP having a Met 35 residue in its C-terminal α-helical domain, hPrP having three out of nine Met-residues (namely Met 205 , Met 206 , and Met 213 ) located within its α-helical segments, and α-synuclein having four Met-residues. The effective neighboring-group interactions would likely involve nucleophilic functionalities in the side chain of amino acids residues. However, very often heteroatoms in peptide bonds are the only nucleophiles present in the vicinity of Met(>S +. ). In this regard, it was recently shown that such interactions play an important role in N-acetylmethione amide and in oligopeptides of the form N-Ac-Gly-Met-Gly and N-Ac-Gly-(Gly) 2 -Met-(Gly) 3 . Intramolecularly bonded sulfide radical cations, Met(>S +. ), were directly observed in these systems with the bonding partner being either the carbonyl oxygen or the amide nitrogen of a peptide bond. Cyclic dipeptides are suitable model

  17. Free radicals in wood induced by γ-radiation

    International Nuclear Information System (INIS)

    Xu Honglin; Zhang Wenhui

    1994-01-01

    The free radicals in wood induced by γ-radiation were studied by electron spin resonance. The fine structure of the ESR signal from sawdust samples irradiated could be resolved into various radicals. These free radicals have a very long lifetime. The major spectrum for the free radicals will exponentially increased along with the radiation dose according to Y 1-Exp(-α a D). The intensity of radiation radicals is dependent on tree species. The stronger the intensity of mechanic free radicals is, the stronger the intensity of radiation free radicals

  18. A psicologia social nos tempos de S. Freud

    Directory of Open Access Journals (Sweden)

    Gustavo Adolfo Ramos Mello Neto

    Full Text Available Trata-se de uma revisão dos textos psicossociais citados por Freud em Psicologia de massas e análise do eu. O objetivo é propor ao leitor algum conhecimento desses textos que já se perdem no tempo. São referidos textos de Wilfred Trotter, William MacDougall, Gustave Le Bon e Gabriel Tarde. Alude-se também a Durkheim, autor não citado por Freud, mas cuja referência permite contrastar uma visão psicologizante do fenômeno social, que é a de Freud e dos autores que ele cita, com um aporte em que o social é visto como independente do psicológico.

  19. A psicologia social nos tempos de S. Freud

    Directory of Open Access Journals (Sweden)

    Mello Neto Gustavo Adolfo Ramos

    2000-01-01

    Full Text Available Trata-se de uma revisão dos textos psicossociais citados por Freud em Psicologia de massas e análise do eu. O objetivo é propor ao leitor algum conhecimento desses textos que já se perdem no tempo. São referidos textos de Wilfred Trotter, William MacDougall, Gustave Le Bon e Gabriel Tarde. Alude-se também a Durkheim, autor não citado por Freud, mas cuja referência permite contrastar uma visão psicologizante do fenômeno social, que é a de Freud e dos autores que ele cita, com um aporte em que o social é visto como independente do psicológico.

  20. TEMPO functionalized C{sub 60} fullerene deposited on gold surface for catalytic oxidation of selected alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Piotrowski, Piotr; Pawłowska, Joanna [University of Warsaw, Department of Chemistry (Poland); Sadło, Jarosław Grzegorz [Institute of Nuclear Chemistry and Technology (Poland); Bilewicz, Renata; Kaim, Andrzej, E-mail: akaim@chem.uw.edu.pl [University of Warsaw, Department of Chemistry (Poland)

    2017-05-15

    C{sub 60}TEMPO{sub 10} catalytic system linked to a microspherical gold support through a covalent S-Au bond was developed. The C{sub 60}TEMPO{sub 10}@Au composite catalyst had a particle size of 0.5–0.8 μm and was covered with the fullerenes derivative of 2.3 nm diameter bearing ten nitroxyl groups; the organic film showed up to 50 nm thickness. The catalytic composite allowed for the oxidation under mild conditions of various primary and secondary alcohols to the corresponding aldehyde and ketone analogues with efficiencies as high as 79–98%, thus giving values typical for homogeneous catalysis, while retaining at the same time all the advantages of heterogeneous catalysis, e.g., easy separation by filtration from the reaction mixture. The catalytic activity of the resulting system was studied by means of high pressure liquid chromatography. A redox mechanism was proposed for the process. In the catalytic cycle of the oxidation process, the TEMPO moiety was continuously regenerated in situ with an applied primary oxidant, for example, O{sub 2}/Fe{sup 3+} system. The new intermediate composite components and the final catalyst were characterized by various spectroscopic methods and thermogravimetry.

  1. Nucleo multiprocessado para aplicações em tempo-real

    OpenAIRE

    Roberto Andre Hexsel

    1988-01-01

    Resumo: Esta Dissertação descreve o nucleo de tempo-real do Multiprocessador para Sistemas de Controle (MSC). O MSC foi desenvolvido no Instituto de Automação do Centro Tecnológico para Informática e possui características que o tornam adequado a aplicações em controle de processos e automação industrial. Estas aplicações exigem respostas rápidas a eventos externos e grande capacidade de processamento. O MSC pode ser configurado para satisfazer as mais diversas aplicações e diferentes níveis ...

  2. 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......, and Aidarova. The second half of the book addresses the central concern of radical-local teaching and learning - how to relate educational practices to children's specific historical and cultural conditions. The experiment was conducted for an academic year in an afterschool programme in the East Harlem......Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded...

  3. What is Radical Behaviorism? A Review of Jay Moore's Conceptual Foundations of Radical Behaviorism

    Science.gov (United States)

    Baum, William M

    2011-01-01

    B. F. Skinner founded both radical behaviorism and behavior analysis. His founding innovations included: a versatile preparation for studying behavior; explicating the generic nature of stimulus and response; a pragmatic criterion for defining behavioral units; response rate as a datum; the concept of stimulus control; the concept of verbal behavior; and explicating the explanatory power of contingencies. Besides these achievements, however, Skinner also made some mistakes. Subsequent developments in radical behaviorist thought have attempted to remedy these mistakes. Moore's book presents a “party line” version of radical behaviorism. It focuses narrowly on a few of Skinner's concepts (mostly mentalism and verbal behavior) and contains no criticism of his mistakes. In fact, Moore adds a few mistakes of his own manufacture; for example, he insists that the mental realm does not exist—an unprovable and distracting assertion. The book's portrayal of behavior analysis would have been current around 1960; it mentions almost none of the developments since then. It also includes almost no developments in radical behaviorism since Skinner. Moore's book would give an unwary reader a highly distorted picture of contemporary behavior analysis and radical behaviorism.

  4. Development of ionization effects on oxidative stability of spices and its enhancement in the detection of irradiated foods

    International Nuclear Information System (INIS)

    Mekni, Mouna

    2010-01-01

    Physico-chemical properties and anti oxidative stability were released on extracts from untreated (non irradiated) caraway (carum carvi) and oregano leaves (origanum vulgare) samples, as well as from those γ irradiated by Co 6 0 source at doses from 0,5 to 15 kGy were studied by EPR and UV-Vis Spectroscopy, and expressed as DPPH radical scavenging ability, antioxidant index which was determined by β carotene/linoleic acid co-oxidation and total phenolic compounds content (TPC) of each extract were characterized. Respecting the fact that the application of γ radiation on spices leads to the production of paramagnetic species, character of radicals formed upon γ irradiation in solid phase was studied by mean of EPR spectroscopy and the stability of the obtained EPR signal of irradiated samples was studied over a storage period of 3 months. Irradiation was found to nonsignificantly increase and/or maintain all antioxidant parameters, TPC and the EPR signal intensity was found to be increased in studied spices with the radiation doses. The EPR measurements performed during storage period after radiation process showed a significant decrease of free radicals signal intensity until their stability.

  5. Doença e Tempo

    Directory of Open Access Journals (Sweden)

    Fernando S. P. Telles

    Full Text Available Trata-se de um ensaio que procura estabelecer a propriedade da questão: "Faz sentido conceber a doença como um fenômeno que transcende as categorias da representação?" Destaca-se uma correspondência entre os fenômenos da representação e da espacialização. Representar passa a ser a atividade de definir uma trajetória que admite uma cronologia temporal de referência, onde um certo fenômeno é apresentado. O paradigma que define a "Anátomo-Clínica" e a Epidemiologia é considerado por nós como uma forma de representação ou espacialização da doença. Conclui-se ser possível o acesso a algo que se denomina "adoecer", que transcende a representação "Anátomo-Clínica" e epidemiológica, desde que, para tal, se admita a possibilidade de o conhecimento poder ser, também, construído fora do espaço, isto é, no tempo não-cronológico.

  6. Analysis of cerium-composite polymer-electrolyte membranes during and after accelerated oxidative-stability test

    Science.gov (United States)

    Shin, Dongwon; Han, Myungseong; Shul, Yong-Gun; Lee, Hyejin; Bae, Byungchan

    2018-02-01

    The oxidative stability of membranes constructed from a composite of pristine sulfonated poly(arylene ether sulfone) and cerium was investigated by conducting an accelerated oxidative-stability test at the open-circuit voltage (OCV). The membranes were analyzed in situ through OCV and impedance measurements, cyclic voltammetry, and linear-sweep voltammetry to monitor the electrochemical properties during the stability test. Although the high-frequency resistance of a composite membrane was slightly higher than that of a pristine membrane because of the exchange of protons from the sulfonic acid with cerium ions, the composite membrane maintained its potential for much longer than the pristine membrane. The effect of the cerium ions as radical scavengers was confirmed by analyzing the drain water and chemical structure after operation. These post-operation analyses confirmed that cerium ions improved the oxidative stability of the hydrocarbon-based polymer during fuel-cell operation. It is clear that the cerium-based radical scavengers prevented chemical degradation of the polymer membrane as well as the electrode in terms of hydrogen cross-over, polymer-chain scission, and the electrochemical surface area, while they rarely diffused outward from the membrane.

  7. Orthographic Skills Important to Chinese Literacy Development: The Role of Radical Representation and Orthographic Memory of Radicals

    Science.gov (United States)

    Yeung, Pui-sze; Ho, Connie Suk-han; Chan, David Wai-ock; Chung, Kevin Kien-hoa

    2016-01-01

    A 3-year longitudinal study among 239 Chinese students in Grades 2-4 was conducted to investigate the relationships between orthographic skills (including positional and functional knowledge of semantic radicals and phonetic radicals, and orthographic memory of radicals) and Chinese literacy skills (word reading, word spelling, reading…

  8. EEG alpha desynchronization in musicians and nonmusicians in response to changes in melody, tempo, and key in classical music.

    Science.gov (United States)

    Overman, Amy A; Hoge, Jessica; Dale, J Alexander; Cross, Jeffrey D; Chien, Alec

    2003-10-01

    Two experiments were performed to examine musicians' and nonmusicians' electroencephalographic (EEG) responses to changes in major dimensions (tempo, melody, and key) of classical music. In Exp. 1, 12 nonmusicians' and 12 musicians' EEGs during melody and tempo changes in classical music showed more alpha desynchronization in the left hemisphere (F3) for changes in tempo than in the right. For melody, the nonmusicians were more right-sided (F4) than left in activation, and musicians showed no left-right differences. In Exp. 2, 18 musicians' and 18 nonmusicians' EEG after a key change in classical music showed that distant key changes elicited more right frontal (F4) alpha desynchronization than left. Musicians showed more reaction to key changes than nonmusicians and instructions to attend to key changes had no significant effect. Classical music, given its well-defined structure, offers a unique set of stimuli to study the brain. Results support the concept of hierarchical modularity in music processing that may be automatic.

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

    Directory of Open Access Journals (Sweden)

    John C. Walton

    2015-02-01

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

  10. Modulation of oxidative damage by nitroxide free radicals.

    Science.gov (United States)

    Dragutan, Ileana; Mehlhorn, Rolf J

    2007-03-01

    Piperidine nitroxides like 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) are persistent free radicals in non-acidic aqueous solutions and organic solvents that may have value as therapeutic agents in medicine. In biological environments, they undergo mostly reduction to stable hydroxylamines but can also undergo oxidation to reactive oxoammonium compounds. Reactions of the oxoammonium derivatives could have adverse consequences including chemical modification of vital macromolecules and deleterious effects on cell signaling. An examination of their reactivity in aqueous solution has shown that oxoammonium compounds can oxidize almost any organic as well as many inorganic molecules found in biological systems. Many of these reactions appear to be one-electron transfers that reduce the oxoammonium to the corresponding nitroxide species, in contrast to a prevalence of two-electron reductions of oxoammonium in organic solvents. Amino acids, alcohols, aldehydes, phospholipids, hydrogen peroxide, other nitroxides, hydroxylamines, phenols and certain transition metal ions and their complexes are among reductants of oxoammonium, causing conversion of this species to the paramagnetic nitroxide. On the other hand, thiols and oxoammonium yield products that cannot be detected by ESR even under conditions that would oxidize hydroxylamines to nitroxides. These products may include hindered secondary amines, sulfoxamides and sulfonamides. Thiol oxidation products other than disulfides cannot be restored to thiols by common enzymatic reduction pathways. Such products may also play a role in cell signaling events related to oxidative stress. Adverse consequences of the reactions of oxoammonium compounds may partially offset the putative beneficial effects of nitroxides in some therapeutic settings.

  11. Novel hydrazones – antioxidant potential and stabilization via polysaccharide particles

    International Nuclear Information System (INIS)

    Hristova-Avakumova, N; Hadjimitova, V; Nikolova-Mladenova, B; Yoncheva, K

    2017-01-01

    In this study, we aimed to: i) determine the impact of three new isonicotinoyl hydrazones derivatives in in vitro systems used to investigate free radical processes - radical scavenging approach (ABTS and DPPH) and iron induced peroxidation in lipid containing model systems and ii) evaluate the potential of polysaccharide-based particles to act as protective carriers preserving the antioxidant activity (AOA) of the tested compounds. The tested compounds revealed excellent antioxidant effectiveness in the ABTS system. In the DPPH radical scavenging assay the compounds exhibited very weak or absence of AOA. The data from the iron induced peroxidation methods disclosed better antioxidant properties of the derivatives in the system containing egg yolk homogenate which is more plausible compared to the lecithin containing one. The incorporation of a bromine atom on 5 th position in salicylaldehyde moiety is associated with diminishment of the radical scavenging activity in the systems containing stable free radicals but its AOA reduction after encapsulation during the storage was only 9.17%. The obtained data indicate that compounds have proven themselves as promising candidates for further evaluation as antioxidant agents. Their encapsulation in chitosan-alginate particles could be a useful approach for improving the stability of their antioxidant properties. (paper)

  12. Radical-pair based avian magnetoreception

    Science.gov (United States)

    Procopio, Maria; Ritz, Thorsten

    2014-03-01

    Behavioural experiments suggest that migratory birds possess a magnetic compass sensor able to detect the direction of the geomagnetic. One hypothesis for the basis of this remarkable sensory ability is that the coherent quantum spin dynamics of photoinduced radical pair reactions transduces directional magnetic information from the geomagnetic field into changes of reaction yields, possibly involving the photoreceptor cryptochrome in the birds retina. The suggested radical-pair based avian magnetoreception has attracted attention in the field of quantum biology as an example of a biological sensor which might exploit quantum coherences for its biological function. Investigations on such a spin-based sensor have focussed on uncovering the design features for the design of a biomimetic magnetic field sensor. We study the effects of slow fluctuations in the nuclear spin environment on the directional signal. We quantitatively evaluate the robustness of signals under fluctuations on a timescale longer than the lifetime of a radical pair, utilizing two models of radical pairs. Our results suggest design principles for building a radical-pair based compass sensor that is both robust and highly directional sensitive.

  13. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali

    2009-12-17

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

  14. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali; Khashab, Niveen M.; Fahrenbach, Albert C.; Friedman, Douglas C.; Colvin, Michael T.; Coti, Karla K.; Bení tez, Diego S.; Tkatchouk, Ekaterina; Olsen, John Carl; Belowich, Matthew E.; Carmieli, Raanan; Khatib, Hussam A.; Goddard, William Andrew III; Wasielewski, Michael R.; Stoddart, Fraser Fraser Raser

    2009-01-01

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

  15. Thermal Behavior and Free-Radical-Scavenging Activity of Phytic Acid Alone and Incorporated in Cosmetic Emulsions

    Directory of Open Access Journals (Sweden)

    André Luis Máximo Daneluti

    2015-07-01

    Full Text Available Phytic acid is a natural compound widely used as depigmenting agent in cosmetic emulsions. Few studies are available in the literature covering the stability and the antioxidating property of this substance, used alone or into emulsions. Therefore, the purpose of this work was to investigate the thermal behavior and antioxidant properties of phytic acid alone and into cosmetic emulsions. The thermal behavior of this substance was evaluated by thermogravimetry (TG/derivative thermogravimetry (DTG and differential scanning calorimetry (DSC and the free-radical-scavenging activity by 1,1-diphenyl-2-picrylhydrazyl (DPPH. TG/DTG and DSC curves allowed evaluation of the thermal behavior of phytic acid. These results showed that the substance presented four stages of mass loss. Thermal decomposition of the material initiated at 150 °C. Thermal behavior of the cosmetic emulsions detected that the addition of phytic acid decreased the thermal stability of the system. DPPH free-radical-scavenging activity showed that phytic acid incorporated into emulsion had no antioxidant capacity compared to BHT. In summary, we concluded that the thermoanalytical techniques (TG and DSC were efficient and reliable in the characterization of phytic acid alone and incorporated into cosmetic emulsions.

  16. Effects of Movement, Tempo, and Gender on Steady Beat Performance of Kindergarten Children

    Science.gov (United States)

    Rose, Paige

    2016-01-01

    The purposes of this research were to discover the effects of manual (hand) and pedal (foot) movements, tempo, and gender on steady beat accuracy. Participants (N = 119) consisted of male (n = 63) and female (n = 56) kindergarten students randomly divided into two groups, counterbalanced with regard to school, homeroom, and gender. Participants…

  17. Formation and spectroscopy of {alpha}-muoniated radicals

    Energy Technology Data Exchange (ETDEWEB)

    McKenzie, I.; Brodovitch, J.C.; Ghandi, K.; Kecman, S.; Percival, P.W

    2003-02-01

    Several novel {alpha}-muoniated radicals have been produced by the reaction of muonium with compounds containing diazo, isocyanate or carbene functional groups. In {alpha}-muoniated radicals the muon is attached directly to the radical centre; they can be formed either directly or indirectly via a {beta}-muoniated radical intermediate. The hyperfine coupling constants of the resulting radicals have been measured by transverse field muon spin rotation and muon avoided level-crossing resonance. The effect of muonium substitution was investigated for cases where ESR data are available for comparison.

  18. Formation and spectroscopy of α-muoniated radicals

    International Nuclear Information System (INIS)

    McKenzie, I.; Brodovitch, J.C.; Ghandi, K.; Kecman, S.; Percival, P.W.

    2003-01-01

    Several novel α-muoniated radicals have been produced by the reaction of muonium with compounds containing diazo, isocyanate or carbene functional groups. In α-muoniated radicals the muon is attached directly to the radical centre; they can be formed either directly or indirectly via a β-muoniated radical intermediate. The hyperfine coupling constants of the resulting radicals have been measured by transverse field muon spin rotation and muon avoided level-crossing resonance. The effect of muonium substitution was investigated for cases where ESR data are available for comparison

  19. Efficacy of rasagiline in early Parkinson's disease: a meta-analysis of data from the TEMPO and ADAGIO studies.

    Science.gov (United States)

    Hauser, Robert A; Abler, Victor; Eyal, Eli; Eliaz, Rom E

    2016-10-01

    To evaluate the efficacy of rasagiline versus placebo in a pooled population of patients with early Parkinson's disease (PD). TEMPO and ADAGIO were Phase III studies that evaluated the symptomatic efficacy of rasagiline versus placebo in patients with early PD. This meta-analysis included Unified Parkinson's Disease Rating Scale (UPDRS) observations from weeks 12, 24 and 36 in ADAGIO and from weeks 14 and 26 in TEMPO; TEMPO visits were recoded to weeks 12 and 24, respectively. The present analysis includes all patients who received rasagiline 1 mg/day, 2 mg/day or placebo, and had ≥1 post-baseline observations and a subgroup of patients whose baseline UPDRS Total scores were ≥27 (Upper Quartile population). Change from baseline in UPDRS scores were evaluated using mixed models repeated measures analyses. Of the 1578 patients randomized to the two studies, 1546 patients met criteria for inclusion in the meta-analysis. Effects on UPDRS Total, motor and activities of daily living scores were significantly better for both doses of rasagiline compared with placebo at all time periods. The Upper Quartile population included 402 patients with a UPDRS Total score ≥27 at baseline. These patients generally demonstrated a larger magnitude of treatment effect than was seen in the full population. This meta-analysis confirms the efficacy of rasagiline monotherapy over 36 weeks. Although TEMPO and ADAGIO are considered studies of "very early" PD, both contained a sizeable pool of patients with more severe disease. In addition, the meta-analysis showed a larger magnitude of effect in patients with more severe baseline disease.

  20. Avaliação do impacto da transferência precoce de informação no tempo e no custo de desenvolvimento de projetos

    OpenAIRE

    Daniel Drumond Campos e Silva

    2010-01-01

    O tempo de desenvolvimento de projetos é um fator de vantagem competitiva para as empresas responderem de forma rápida às exigências do mercado. A pressão pela agilização no repasse de informação entre tarefas, visando diminuir o tempo de projeto, pode impactar em retrabalho, considerando que esse repasse apresenta uma carga de incerteza quanto à assertividade do dado. Torna-se pertinente uma análise comparativa entre o tempo de finalização de um projeto e o custo associado a sua execução, co...

  1. Semantic Radicals Contribute More Than Phonetic Radicals to the Recognition of Chinese Phonograms: Behavioral and ERP Evidence in a Factorial Study

    Directory of Open Access Journals (Sweden)

    Xieshun Wang

    2017-12-01

    Full Text Available The Chinese phonograms consist of a semantic radical and a phonetic radical. The two types of radicals have different functional contributions to their host phonogram. The semantic radical typically signifies the meaning of the phonogram, while the phonetic radical usually contains a phonological clue to the phonogram’s pronunciation. However, it is still unclear how they interplay with each other when we attempt to recognize a phonogram because previous studies rarely manipulated the functionality of the two types of radicals in a single design. Using a full factorial design, the present study aimed to probe this issue by directly manipulating the functional validity of the two types of radicals in a lexical decision task with both behavioral and event-related potential (ERP measurements. The results showed that recognition of phonograms which were related to their semantic radicals in meaning took a shorter reaction time, showed a lower error rate, and elicited a smaller P200 and a larger N400 than did recognition of those which had no semantic relation with their semantic radicals. However, the validity of phonetic radicals did not show any main effect or interaction with that of semantic radicals on either behavioral or ERP measurements. These results indicated that semantic radicals played a dominant role in the recognition of phonograms. Transparent semantic radicals, which provide valid semantic cues to phonograms, can facilitate the recognition of phonograms.

  2. Pyrimidine nucleobase radical reactivity in DNA and RNA

    Science.gov (United States)

    Greenberg, Marc M.

    2016-11-01

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

  3. Quantification of hydroxyl radical produced during phacoemulsification.

    Science.gov (United States)

    Gardner, Jonathan M; Aust, Steven D

    2009-12-01

    To quantitate hydroxyl radicals produced during phacoemulsification with various irrigating solutions and conditions used in cataract surgery. Chemistry and Biochemistry Department, Utah State University, Logan, Utah, USA. All experiments were performed using an Infiniti Vision System phacoemulsifier with irrigation and aspiration. Hydroxyl radicals were quantitated using electron spin resonance spectroscopy and a spectrophotometric assay for malondialdehyde, which is formed by the oxidation of deoxyribose by the hydroxyl radical. Hydroxyl radical production increased during longitudinal-stroking phacoemulsification as power levels were increased in a nonlinear, nonexponential fashion. The detection of hydroxyl radical was reduced in irrigating solutions containing organic molecules (eg, citrate, acetate, glutathione, dextrose) and further reduced in Navstel, an irrigating solution containing a viscosity-modifying agent, hydroxypropyl methylcellulose. Hydroxyl radicals produced in settings representative of those used in phacoemulsification cataract surgery were quantitated using the deoxyribose method. Hydroxyl radical production was dependent on the level of ultrasound power applied and the irrigating solution used. Oxidative stress on the eye during phacoemulsification may be minimized by using irrigating solutions that contain organic molecules, including the viscosity-modifying agent hydroxypropyl methylcellulose, that can compete for reaction with hydroxyl radicals.

  4. Free radicals in biology. Volume II

    International Nuclear Information System (INIS)

    Pryor, W.A.

    1976-01-01

    This volume continues the treatment of topics in free radical biology and free radical pathology from Volume I. In the first chapter, pyridinyl radicals, radicals which are models for those derived from NAD, are discussed. Pyridinyl radicals can be synthesized and isolated and directly studied in a number of chemical systems. The next chapter treats the role of glutathione in the cell. It is becoming even more apparent that this vital thiol controls a large number of important cellular functions. The GSH/GSSG balance has recently been implicated as a control for cellular development; this balance also may be important in relaying the effects of oxidants from one site to another in the body. The next chapter outlines the reactions of singlet oxygen; some of these involve free radicals and some do not. This reactive intermediate appears to be important both in photochemical smog and in cellular chemistry where singlet oxygen is produced by nonphotochemical processes. The production of free radicals from dry tissues, a controversial area with conflicting claims is reviewed. The next chapter outlines the current status of the studies of photochemical smog. The next two chapters treat specific reactive materials which are present in smog. The first discusses the chemistry of nitrogen oxides and ozone. The second chapter treats the chemistry of the peroxyacyl nitrites. These compounds, although present in only small concentration, are among the most toxic components of smog. The last two chapters treat radiation damage to proteins and radiation protection and radical reactions produced by radiation in nucleic acids

  5. O conceito de mal radical The concept of radical evil

    Directory of Open Access Journals (Sweden)

    Adriano Correia

    2005-01-01

    Full Text Available A noção de mal radical aparece em Kant no contexto da discussão da religião nos limites da simples razão e busca dar conta da complexa relação entre o respeito pela lei moral e o amor-próprio na definição do móbil para a ação. Na busca por identificar o fundamento da propensão para o mal no homem, Kant se vê diante da dificuldade de ter de articular natureza e liberdade, e ainda que a noção de mal radical possa conservar algumas ambigüidades, permite conceber uma noção de responsabilidade compatível com uma inata propensão para o mal. Neste texto busco explicitar alguns passos fundamentais na construção do conceito por Kant.The concept of radical evil appears in Kant's theory when he discusses the religion in the limits of the mere reason and aims explain the complex relationship between respect for the moral law and the self-love, for establish the motive of the action. By aiming identify the basis of human inclination to evil, Kant is faced with the trouble of have to put nature and freedom in connection. Despite of the concept of radical evil retain some ambiguity, it allows conceive a notion of responsibility suitable to an inherent inclination to evil. In this paper is my purpose to explain some basic moments of Kantian formulation of that notion.

  6. HPLC-ESR techniques for detection of complex trapped radicals

    International Nuclear Information System (INIS)

    Tu Tiecheng; Dong Jirong; Lin Nianyun; Xie Leidong; Liu Rengzhong

    1992-01-01

    High performance liquid chromatography (HPLC) and ESR combined examination of radical species is an advanced techniques for separation and identification of complex radical species. At SRCL, Waters 990 HPLC has been used to separate the complex trapped radicals and Varian E-112 ESR spectrometer to record the spectra of single trapped radicals after HPLC separation. The advantages of the combined techniques are described as bellow: HPLC is used to separate the long-lived complex trapped radicals derived from reaction of short-lived radicals with spin trap. ESR spectra from single trapped radicals, obtained following HPLC separation of complex trapped radicals, are recorded one by one and well resolved. The structures of short-lived radicals can be inferred from the ESR spectra of the long-lived trapped radicals

  7. Scavenging of free-radical metabolites of aniline xenobiotics and drugs by amino acid derivatives: toxicological implications of radical-transfer reactions.

    Science.gov (United States)

    Michail, Karim; Baghdasarian, Argishti; Narwaley, Malyaj; Aljuhani, Naif; Siraki, Arno G

    2013-12-16

    We investigated a novel scavenging mechanism of arylamine free radicals by poly- and monoaminocarboxylates. Free radicals of arylamine xenobiotics and drugs did not react with oxygen in peroxidase-catalyzed reactions; however, they showed marked oxygen uptake in the presence of an aminocarboxylate. These free-radical intermediates were identified using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and electron paramagnetic resonance (EPR) spectrometry. Diethylenetriaminepentaacetic acid (DTPA), a polyaminocarboxylate, caused a concentration-dependent attenuation of N-centered radicals produced by the peroxidative metabolism of arylamines with the subsequent formation of secondary aliphatic carbon-centered radicals stemming from the cosubstrate molecule. Analogously, N,N-dimethylglycine (DMG) and N-methyliminodiacetate (MIDA), but not iminodiacetic acid (IDA), demonstrated a similar scavenging effect of arylamine-derived free radicals in a horseradish peroxidase/H2O2 system. Using human promyelocytic leukemia (HL-60) cell lysate as a model of human neutrophils, DTPA, MIDA, and DMG readily reduced anilinium cation radicals derived from the arylamines and gave rise to the corresponding carbon radicals. The rate of peroxidase-triggered polymerization of aniline was studied as a measure of nitrogen-radical scavenging. Although, IDA had no effect on the rate of aniline polymerization, this was almost nullified in the presence of DTPA and MIDA at half of the molar concentration of the aniline substrate, whereas a 20 molar excess of DMPO caused only a partial inhibition. Furthermore, the yield of formaldehyde, a specific reaction endproduct of the oxidation of aminocarboxylates by aniline free-radical metabolites, was quantitatively determined. Azobenzene, a specific reaction product of peroxidase-catalyzed free-radical dimerization of aniline, was fully abrogated in the presence of DTPA, as confirmed by GC/MS. Under aerobic conditions, a radical-transfer reaction

  8. Carmen Covito’s ‘Tempo parziale’ : Mothering and Work in Italy in a Nutshell

    NARCIS (Netherlands)

    Jansen, M.M.

    2016-01-01

    Carmen Covito’s short story ‘Tempo parziale’ (2009) [‘Part Time’] can be read as a comment on the peculiarities of female employment and defective social policies in contemporary Italy. Originally written in 2007 for the INAIL campaign Diritti senza rovesci [Rights without flip side] against

  9. Tempo do conhecimento interativo: reflexões sobre a inteligência coletiva e o pensamento complexo

    Directory of Open Access Journals (Sweden)

    Angela Halen Claro Bembem

    2014-06-01

    Full Text Available A predominância das tecnologias da informação e comunicação na atualidade tem encaminhado a Ciência da Informação a diferentes contextos de tempo e espaço. O tempo do conhecimento interativo e o Espaço do saber trazem novas perspectivas quanto à concepção e o uso das tecnologias. Utilizando como procedimento metodológico a análise exploratória e descritiva, e tomando como referencial teórico consolidados autores da área, pretende-se discorrer sobre essas alterações e refletir como a Ciência da Informação tem se posicionado frente a esses desafios. Observou-se que o pensamento crítico torna-se alternativa para a compreensão das tecnologias longe de uma prerrogativa determinista.

  10. Previsão de tempos de internamento num hospital português: aplicação da metodologia CRISP-DM

    OpenAIRE

    Laureano, R. M. S.; Caetano, N.; Cortez, P.

    2014-01-01

    Com base nos dados disponíveis num hospital português relativos aos processos de internamento, ocorridos no período de 2000 a 2013, e seguindo a metodologia de data mining CRISP-DM, obteve-se um modelo de previsão dos tempos de internamento baseado no algoritmo random forest que apresentou uma elevada qualidade, e superior à obtida com outras técnicas de data mining, e que permitiu identificar os atributos clínicos do paciente como os mais importantes para a explicação dos tempos de ...

  11. Reactions of carbonate radical with cobalt(II) aminopolycarboxylates

    International Nuclear Information System (INIS)

    Mandal, P.C.; Bardhan, D.K.; Bhattacharyya, S.N.

    1992-01-01

    Reactions of carbonate (CO 3 - radical) and bicarbonate (HCO 3 radical) radicals generated by photolysis of a carbonate or bicarbonate solution at pH 11.2 and 8.5, respectively, with Co(II) complexes of iminodiacetic acid (IDA) and ethylenediaminetetraacetic acid (EDTA) have been studied. The rate constants for the reactions were in the order of 10 6 -10 7 dm 3 mol -1 s -1 . From the time-resolved spectroscopy of the products formed after reaction of CO 3 - radical or HCO 3 radical, it is observed that CO 3 - radical or HCO 3 radical oxidize the metal center to its higher oxidation state. (author) 26 refs.; 2 figs.; 1 tab

  12. Estabilização química do subleito de estradas: influência do tempo decorrido entre a mistura e a compactação na resistência mecânica de misturas solo-RBI Grade 81 Chemical stabilization of road subgrade: influence of elapsed time between mixture and compaction on mechanical strength of soil-RBI Grade 81 mixtures

    Directory of Open Access Journals (Sweden)

    Tiago Pinto da Trindade

    2005-06-01

    Full Text Available Este artigo aborda o estudo da influência do tempo decorrido entre mistura e compactação na resistência mecânica de três solos da Zona da Mata Norte de Minas Gerais, Brasil, quando estabilizados com 4% de RBI Grade 81, em relação ao peso de solo seco. Um solo residual maduro (solo 1 e dois solos residuais jovens (solos 2 e 3 de gnáisse foram utilizados no presente estudo. O programa de ensaios de laboratório englobou: (i tempos decorridos entre mistura e compactação: 0, 4, 8 e 24 horas; (ii energia de compactação: Proctor Modificado; (iii período de cura das misturas: 7 dias; e (iv determinação da resistência mecânica: média de três determinações da resistência à compressão não-confinada. Os resultados desta pesquisa indicam que: (i o tempo decorrido entre mistura e compactação dos corpos-de-prova influenciou significativamente o parâmetro resistência à compressão não confinada das misturas; (ii 4 horas foi o tempo ótimo entre mistura e compactação para as misturas dos solos 1 e 2 com RBI Grade 81; e (iii no solo 3, foi observado um melhor resultado para a compactação imediatamente após a mistura.This paper describes the study of the influence of time between mixture and compaction in the mechanical strength of three soils from ";Zona da Mata Norte";, Minas Gerais, Brazil, stabilized with 4% of RBI Grade 81. One mature (soil 1 and two young (soils 2 and 3 gneiss residual soils were used throughout the study. The laboratory testing program consisted of the following steps: (i elapsed times between mixture and compaction: 0, 4, 8 and 24 hours; (ii mixture specimen compaction effort: Modified Proctor; (iii mixture specimen curing time: 7 days in acclimatized room; (iv determination of mechanical strength: average of three determinations of unconfined compression strength. The testing data supported that: (i the elapsed time between mixture and specimen compaction affected significantly the mixture mechanical

  13. Objeto e desejo em tempos de superexposição Object and desire in times of super exposure

    Directory of Open Access Journals (Sweden)

    Marcus André Vieira

    2005-01-01

    Full Text Available Interroga-se a tristeza a partir da retomada lacaniana da teorização do luto por Freud. Delimitam-se, a seguir, as bases de uma teoria lacaniana da perda, localizando a importância do objeto a e destacando-se sua função de causa do desejo. Situa-se a dor da perda em relação com a perda da função do objeto, causa do desejo, necessariamente vinculada à inacessibilidade do objeto. Aborda-se a contemporaneidade com a seguinte questão: é possível que o objeto tenha se tornado visível/acessível? Isto não implicaria em instabilidades radicais na estruturação do imaginário do corpo? Objeto e desejo em tempos de superexposição.It is questioned the sadness from the Lacanian resume of the mourning theorization by Freud. It is determined, afterwards, the bases of a Lacanian theory of loss, pin pointing the importance of the object a, and setting apart its function of desire motive. It is found the pain of the loss in relation to the loss of function of the object motive of the desire. The contemporarily is approached in the following questions: Is it possible for the object to have become visible/accessible? Wouldn't that implicate in radical instability in the building of the imaginary body? Object and desire in times of super exposure.

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

    Science.gov (United States)

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

    2011-01-01

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

  15. Programação de operações em sistemas com tempo de processamento variável

    Directory of Open Access Journals (Sweden)

    José Manuel Valério de Carvalho

    2002-07-01

    Full Text Available Neste artigo analisa-se um problema de planeamento de operações com tempos de processamento variável. Em particular, este projecto está relacionado com o planeamento de operações de carga de camiões em armazéns automáticos. As operações podem ser vistas como tarefas executadas em paralelo, com tempos de disponibilidade (data de chegada dos camiões e datas de entrega (data de cut off. Os tempos de processamento das tarefas são variáveis e dependem do número de tarefas a serem processadas simultaneamente; para garantir a taxa de expedição nominal de funcionamento do armazém, é necessário impor um número mínimo de tarefas em execução simultânea. Apresenta-se um procedimento baseado em programação dinâmica com os tempos de expedição dos camiões ordenados pela regra EDD. A eficiência do algoritmo é também discutida.In this work a scheduling operation problem with variable processing times is analysed. In particular this project is concerned with the scheduling of the truck load operations in an automatic warehouse. The truck load operations can be assumed as processing tasks in parallel, with ready times (availability of the trucks and due dates (trip cut off time. Processing time is variable and depends upon the number of tasks simultaneously in progress; a minimum number of simultaneous tasks is imposed to guarantee the nominal rate of expedition of the warehouse. A procedure based on Dynamic Programming with truck expedition times ordered by EDD rule is presented. The algorithm efficiency is also discussed.

  16. Self-Terminating, Oxidative Radical Cyclizations

    Directory of Open Access Journals (Sweden)

    Uta Wille

    2004-05-01

    Full Text Available The recently discovered novel concept of self-terminating, oxidative radical cyclizations, through which alkynes can be converted into carbonyl compounds under very mild reaction conditions using O-centered inorganic and organic radicals as oxidants, is described

  17. Tempo 1 méthode de français

    CERN Document Server

    Bérard, Evelyne; Lavenne, Christian

    1996-01-01

    Tempo c'est : une méthode qui s'adresse aux adolescents et adultes, vrais débutants, des objectifs précis, définis par l'observation fine d'échanges authentiques, une progression rigoureuse où les acquis sont constamment repris et élargis, l'acquisition de compétences complètes dans un délai très bref (acquisitions par paliers), des techniques de classe dynamiques : apprentissage par tâches, une mise en scène active de la civilisation, de nombreux exercices, une évaluation régulière, une totale adéquation aux épreuves du DELF.

  18. O tempo do luto e o discurso do Outro

    OpenAIRE

    Maesso, Márcia Cristina

    2017-01-01

    Resumo: Trata-se de uma leitura pelo método psicanalítico sobre o tempo de trabalho do luto, através do filme Sede de viver, da biografia de Van Gogh escrita por Forrester, e das concepções sobre o luto no campo da psicanálise, formuladas por Lacan e Allouch, visando abordar a travessia do luto como uma experiência que exige um trabalho não determinado exclusivamente pela relação entre o enlutado e o objeto perdido, mas contando com a função dos ritos e com a linguagem para concluir o luto co...

  19. Recent advances in ambit stochastics with a view towards tempo-spatial stochastic volatility/intermittency

    DEFF Research Database (Denmark)

    Barndorff-Nielsen, Ole E.; Benth, Fred Espen; Veraart, Almut

    Ambit stochastics is the name for the theory and applications of ambit fields and ambit processes and constitutes a new research area in stochastics for tempo-spatial phenomena. This paper gives an overview of the main findings in ambit stochastics up to date and establishes new results on genera...

  20. Efeito do tempo de conservação de polimorfonucleares do sangue de bezerros sobre o metabolismo oxidativo e a atividade de fagocitose de Escherichia coli

    Directory of Open Access Journals (Sweden)

    Elizabeth Bohland

    2008-02-01

    Full Text Available Foram avaliados os efeitos do tempo sobre o metabolismo oxidativo e a fagocitose de Escherichia coli, em amostras de polimorfonucleares (PMN do sangue, de cinco bezerros hígidos, conservadas em banho de gelo por duas (t2, quatro (t4, seis (t6, 12 (t12 e 24 (t24 horas. O metabolismo oxidativo foi avaliado utilizando o Diacetato 2' 7' Diclorofluoresceína (DCFH-DA e a E. coli, como estímulo. Para a fagocitose a mesma bactéria foi utilizada. As amostras foram analisadas por citometria de fluxo. O metabolismo oxidativo basal dos PMN do sangue de bezerros foi maior nos tempos t4, t6 e t12, do que em t2 (p<0,05. A intensidade de fluorescência do metabolismo oxidativo induzido pela bactéria foi maior nos tempos t4 e t6 do que em t2 (p<0,05. A comparação entre o metabolismo basal e induzido pela bactéria, em cada um dos tempos, mostrou que a maior diferença ocorreu em t2, com valores da média geométrica e desvios padrão respectivos de 18,3 ± 4,4 e 26,7 ± 1,8 (p< 0,05. A atividade de fagocitose, medida pela intensidade de fluorescência, foi maior para as amostras mantidas em gelo por 6 horas do que para t2, t4 e t12 (p<0,05. O percentual de fagocitose não diferiu entre os tempos. O tempo ideal para análise do metabolismo oxidativo foi o de duas horas. Maiores estudos são necessários para se verificar a influência do tempo de conservação na fagocitose de E. coli por PMN do sangue de bovinos.