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Sample records for radical experiencia con

  1. FACTORES SOCIO-ESTRUCTURALES Y EL ESTIGMA HACIA EL VIH/SIDA: EXPERIENCIAS DE PUERTORRIQUEÑOS/AS CON VIH/SIDA AL ACCEDER SERVICIOS DE SALUD

    PubMed Central

    RIVERA-DIAZ, MARINILDA; VARAS-DIAZ, NELSON; REYES-ESTRADA, MARCOS; SURO, BEATRIZ; CORIANO, DORALIS

    2013-01-01

    RESUMEN El estigma relacionado al VIH/SIDA continúa afectando la prestación de servicios de salud y el bienestar físico y mental de las personas con VIH/SIDA (PVS). Recientemente la literatura científica ha señalado la importancia de comprender las manifestaciones de estigma más allá de las interacciones individuales. Por tal razón, investigaciones recientes en y fuera de Puerto Rico enfatizan la importancia de entender cómo factores socio-estructurales (FSE) influyen en los procesos de estigmatización social. Con el propósito de examinar los FSE que influyen en las manifestaciones de estigma relacionado al VIH/SIDA, realizamos y analizamos nueve grupos focales compuestos por hombres y mujeres en tratamiento para el VIH/SIDA que habían tenido experiencias estigmatizantes. Los participantes identificaron FSE relacionados a las manifestaciones de estigma, tales como el uso de viviendas especializadas, descentralización de los servicios de salud y el desarrollo de protocolos administrativos excluyentes en los servicios de salud. Los resultados demuestran la importancia de considerar los FSE en el desarrollo e implementación de intervenciones dirigidas a la población. PMID:24639599

  2. Encefalitis por anticuerpos contra el receptor de NMDA: experiencia con seis pacientes pediátricos. Potencial eficacia del metotrexato

    PubMed Central

    Bravo-Oro, Antonio; Abud-Mendoza, Carlos; Quezada-Corona, Arturo; Dalmau, Josep; Campos-Guevara, Verónica

    2016-01-01

    Introducción La encefalitis por anticuerpos contra el receptor de N-metil-D-aspartato (NMDA) es una entidad cada vez más diagnosticada en edad pediátrica. A diferencia de los adultos, en muchos casos no se asocia a tumores y las manifestaciones iniciales en niños más frecuentes son crisis convulsivas y trastornos del movimiento, mientras que en los adultos predominan las alteraciones psiquiátricas. Casos clínicos Presentamos seis casos pediátricos confirmados con anticuerpos contra la subunidad NR1 del receptor de NMDA en suero y líquido cefalorraquídeo. Cinco de los casos comenzaron con crisis convulsivas como manifestación clínica inicial antes de desarrollar el cuadro clásico de esta entidad. En todos los casos se utilizaron esteroides como primera línea de tratamiento, con los que sólo se observó control de las manifestaciones en uno, por lo que el resto de los pacientes requirió inmunomoduladores de segunda línea. Todos los pacientes recibieron metotrexato como tratamiento inmunomodulador para evitar recaídas y la evolución fue a la mejoría en todos ellos. Conclusiones En nuestra serie de pacientes con encefalitis por anticuerpos contra el receptor de NMDA, ninguno se asoció a tumores. Todos los casos recibieron metotrexato por lo menos durante un año, no observamos eventos adversos clínicos ni por laboratorio, ni hubo secuelas neurológicas ni recaídas durante el tratamiento. Aunque es una serie pequeña y es deseable incrementar el número y tiempo de evolución, consideramos el metotrexato una excelente alternativa como tratamiento inmunomodulador para esta patología. PMID:24150952

  3. Expresiones de Desarrollo Profesional en Educadoras Principiantes y con Experiencia.

    ERIC Educational Resources Information Center

    Betsalel-Presser, Raquel

    1986-01-01

    Attempts to identify the conditions which affect the professional development of both experienced and inexperienced teachers. After presenting the theoretical and conceptual framework of the problem, discusses professional development needs identified by preschool and primary school teachers in an exploratory study done in Montreal, Quebec…

  4. Expresiones de Desarrollo Profesional en Educadoras Principiantes y con Experiencia.

    ERIC Educational Resources Information Center

    Betsalel-Presser, Raquel

    1986-01-01

    Attempts to identify the conditions which affect the professional development of both experienced and inexperienced teachers. After presenting the theoretical and conceptual framework of the problem, discusses professional development needs identified by preschool and primary school teachers in an exploratory study done in Montreal, Quebec…

  5. Osteoclast radicals.

    PubMed

    Silverton, S

    1994-11-01

    In biological research, new ideas arise and quickly spread to encompass the entire field. Thus, the evolution of molecular biology has significantly changed our methods of approaching our research. A similar far-reaching finding has been the advent of radical reactions into biology. Although radical chemistry has been utilized for many technological advances that affect our daily lives, the appreciation of this same process within our cells has opened an unexplored arena for research enquiry. As cellular messengers, radical molecules seem whimsically designed: they are evanescent, rapidly and apparently indiscriminately reactive, and barely detectable by most biological methods. Yet, our initial probing of these reactive agents in cells and organisms has led us to postulate a virtually undescribed system of communication within and among cells which may have significant effects in multiple organs. In bone, radical reactants have been attributed with an important role in the control of bone resorption.

  6. Religious Radicalism and Security in South Asia

    DTIC Science & Technology

    2004-01-01

    reputation con- tinued to take a beating. The radical Islamist cum terrorist brand clung to it like a tar baby —even more tightly, it seemed, when linked...of Bangladesh, reflecting her rabid anti- Islamic, pro-Indian and anti-male bias in her writings—both in literary works (often classified as soft porn

  7. Contemporary Radical Economics.

    ERIC Educational Resources Information Center

    Sherman, Howard J.

    1984-01-01

    The origins of contemporary radical economics are examined. Applications of radical economics to price and value theory, labor segmentation theory, business cycles, industrial organization, government and business, imperialism and development, and comparative systems are reviewed. (Author/RM)

  8. Contemporary Radical Economics.

    ERIC Educational Resources Information Center

    Sherman, Howard J.

    1984-01-01

    The origins of contemporary radical economics are examined. Applications of radical economics to price and value theory, labor segmentation theory, business cycles, industrial organization, government and business, imperialism and development, and comparative systems are reviewed. (Author/RM)

  9. Radical prostatectomy - discharge

    MedlinePlus

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

  10. The radical amplifier

    NASA Technical Reports Server (NTRS)

    Hastie, D. R.

    1994-01-01

    The radical amplifier as a method for measuring radical concentrations in the atmosphere has received renewed attention lately. In principle, it can measure the total concentration of HO(x) and RO(x) radicals by reacting ambient air with high concentrations of CO (3-10 percent) and NO (2-6 ppmv), and measuring the NO2 produced.

  11. [Lavoisier and radicals].

    PubMed

    Lafont, Olivier

    2007-01-01

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

  12. Forgotten Radicals in Biology

    PubMed Central

    Luc, Rochette; Vergely, Catherine

    2008-01-01

    Redox reactions play key roles in intra- and inter-cellular signaling, and in adaptative processes of tissues towards stress. Among the major free radicals with essential functions in cells are reactive oxygen species (ROS) including superoxide anion (O2•-), hydroxyl radical (•OH) and reactive nitrogen species (RNS) such as nitric oxide (•NO). In this article, we review the forgotten and new radicals with potential relevance to cardiovascular pathophysiology. Approximately 0.3% of O2•- present in cytosol exists in its protonated form: hydroperoxyl radical (HO2•). Water (H2O) can be split into two free radicals: •OH and hydrogen radical (H•). Several free radicals, including thiyl radicals (RS•) and nitrogen dioxide (NO2•) are known to isomerize double bonds. In the omega-6 series of poly-unsaturated fatty acids (PUFAs), cis-trans isomerization of γ-linolenate and arachidonate catalyzed by RS• has been investigated. Evidence is emerging that hydrogen disulphide (H2S) is a signaling molecule in vivo which can be a source of free radicals. The Cu-Zn superoxide dismutase (SOD) enzyme can oxidize the ionized form of H2S to hydro-sulphide radical: HS•. Recent studies suggest that H2S plays an important function in cardiovascular functions. Carbonate radical, which can be formed when •OH reacts with carbonate or bicarbonate ions, is also involved in the activity of Cu-Zn-SOD. Recently, it has been reported that carbonate anion were potentially relevant oxidants of nucleic acids in physiological environments. In conclusion, there is solid evidence supporting the formation of many free radicals by cells leading which may play an important role in their homeostasis. PMID:23675099

  13. Radical chemistry of artemisinin

    NASA Astrophysics Data System (ADS)

    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.

  14. Radical aminomethylation of imines.

    PubMed

    Fujii, Shintaro; Konishi, Takehito; Matsumoto, Yusuke; Yamaoka, Yousuke; Takasu, Kiyosei; Yamada, Ken-Ichi

    2014-09-05

    Taking advantage of the high level of performance of N-alkoxycarbonyl-imines, we achieved the first example of addition of the aminomethyl radical to imine. The reaction efficiency depended on the structure of the radical precursor, whether it is an iodide or a xanthate, and an electron-withdrawing group on the nitrogen atom of the radical. This reaction allows direct introduction of an N-substituted aminomethyl group onto imine to provide 1,2-diamine as well as the short-step synthesis of ICI-199,441.

  15. Online Radicalization: Bangladesh Perspective

    DTIC Science & Technology

    2017-06-09

    will work on developing a sustainable social awareness against radicalization. It will be responsible for coordinating and integrating all government...PAGE Form Approved OMB No. 0704-0188 Public reporting burden for this collection of information is estimated to average 1 hour per response , including...coordination among the counter-terrorism agencies, and lack of positive initiatives to grow enduring social resilience against radicalization. Bangladesh

  16. Free Radical Reactions in Food.

    ERIC Educational Resources Information Center

    Taub, Irwin A.

    1984-01-01

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

  17. Free Radical Reactions in Food.

    ERIC Educational Resources Information Center

    Taub, Irwin A.

    1984-01-01

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

  18. Chemistry of ascorbic acid radicals

    SciTech Connect

    Bielski, B.H.J.

    1982-01-01

    The chemistry of ascorbic acid free radicals is reviewed. Particular emphasis is placed on identification and characterization of ascorbate radicals by spectrophotometric and electron paramagnetic resonance techniques, the kinetics of formation and disappearance of ascorbate free radicals in enzymatic and nonenzymatic reactions, the effect of pH upon the spectral and kinetic properties of ascorbate anion radical, and chemical reactivity of ascorbate free radicals.

  19. Laparoscopic radical trachelectomy.

    PubMed

    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.

  20. Laparoscopic Radical Trachelectomy

    PubMed Central

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

    2012-01-01

    Introduction: The standard treatment for patients with early-stage cervical cancer has been radical hysterectomy. However, for women interested in future fertility, radical trachelectomy is now considered a safe and feasible option. The use of minimally invasive surgical techniques to perform this procedure has recently been reported. Case Description: We report the first case of a laparoscopic radical trachelectomy performed in a developing country. The patient is a nulligravid, 30-y-old 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. Conclusion: 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. PMID:23318085

  1. A fluorine 1,2-migration via aryl cation/radical/radical anion/radical sequence.

    PubMed

    Pretali, Luca; Dondi, Daniele; D'Angelantonio, Mila; Manet, Ilse; Fasani, Elisa; Monti, Sandra; Bovio, Bruna; Albini, Angelo

    2013-08-02

    Irradiation of a 7-piperazino-8-fluoroquinolone causes formal 1,2-fluorine migration, piperazine loss and reduction, or nucleophile addition in 8. Product study, laser flash photolysis, and computational modeling support F(-) detachment to yield a triplet 8-quinolyl cation that either inserts intramolecularly or is trapped by Cl(-), Br(-). However, iodide and pyrrole reduce it to the radical that continues the 'redox tour' (aryl cation→ radical→ radical anion→ radical and then again radical or radical anion) leading to the rearranged products.

  2. Radical dematerialization and degrowth.

    PubMed

    Kallis, Giorgos

    2017-06-13

    The emission targets agreed in Paris require a radical reduction of material extraction, use and disposal. The core claim of this article is that a radical dematerialization can only be part and parcel of degrowth. Given that capitalist economies are designed to grow, this raises the question of whether, and under what circumstances, the inevitable 'degrowth' can become socially sustainable. Three economic policies are discussed in this direction: work-sharing, green taxes and public money.This article is part of the themed issue 'Material demand reduction'. © 2017 The Author(s).

  3. Radical dematerialization and degrowth

    NASA Astrophysics Data System (ADS)

    Kallis, Giorgos

    2017-05-01

    The emission targets agreed in Paris require a radical reduction of material extraction, use and disposal. The core claim of this article is that a radical dematerialization can only be part and parcel of degrowth. Given that capitalist economies are designed to grow, this raises the question of whether, and under what circumstances, the inevitable `degrowth' can become socially sustainable. Three economic policies are discussed in this direction: work-sharing, green taxes and public money. This article is part of the themed issue 'Material demand reduction'.

  4. Beyond Radical Educational Cynicism.

    ERIC Educational Resources Information Center

    Wood, George H.

    1982-01-01

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

  5. Radical School Reform.

    ERIC Educational Resources Information Center

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

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

  6. Against Radical Multiculturalism.

    ERIC Educational Resources Information Center

    Zorn, Jeff

    This essay presents two strands of arguments against radical or critical emancipatory multiculturalism. In strand 1, "'Culture' is...whatever..." the looseness of the core concept of "culture," which can refer to anything at all concerning a social group that itself may exist only theoretically, is shown. In strand 2, "From ideology to leveling,…

  7. Beyond Radical Educational Cynicism.

    ERIC Educational Resources Information Center

    Wood, George H.

    1982-01-01

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

  8. Radically enhanced molecular recognition

    NASA Astrophysics Data System (ADS)

    Trabolsi, Ali; Khashab, Niveen; Fahrenbach, Albert C.; Friedman, Douglas C.; Colvin, Michael T.; Cotí, Karla K.; Benítez, Diego; Tkatchouk, Ekaterina; Olsen, John-Carl; Belowich, Matthew E.; Carmielli, Raanan; Khatib, Hussam A.; Goddard, William A.; Wasielewski, Michael R.; Stoddart, J. Fraser

    2010-01-01

    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.

  9. Radical Socioeducational Analysis.

    ERIC Educational Resources Information Center

    Sigmon, Scott B.

    This book describes an interactive-interdisciplinary way of looking at the social conditions which impinge upon schooling, and which impact upon the social facts of life. It examines current schooling problems from the perspective of radical social democratic thought. The book is organized into four major sections. Part 1 provides an overview and…

  10. The Oxonium Rydberg Radical

    NASA Astrophysics Data System (ADS)

    Lavín, C.; Martin, I.

    The Quantum Defect Orbital (QDO) method has been applied to the study of transition probabiUties in the oxonium Rydberg radical H3O. Absorption oscillator strengths and Einstein emission coefficients are reported and compared with the results of an earlier, simplified, molecular version of QDO method.

  11. Interrogating Hydrocarbon Radicals

    NASA Astrophysics Data System (ADS)

    Schmidt, Timothy W.

    2010-06-01

    Motivated by astrophysical problems (and a sense of fun) for some years my research group has been obtaining new spectra of hitherto unobserved hydrocarbon radicals. We employ the complementary techniques of resonant ionization and laser induced fluorescence to rigorously identify radicals by matching their ground state vibrational frequencies to those obtained using density functional theory (DFT). While some radicals were made to order in our pulsed electrical discharge source, others of particular chemical importance have been found lurking in the congested forest of dicarbon and tricarbon fluorescence. Using a 2-dimensional fluorescence (2df) map, we have extracted pure spectra, unpolluted by C_2 and C_3, from a benzene discharge. One spectrum was first presented at this symposium in 2006, but at that stage was not identified. Subsequent measurement of a matching resonant ionization spectrum revealed a mass of 115, much higher than the benzene precursor. With the aid of DFT calculations, the species was positively identified, giving clues to hydrocarbon-building chemistry of relevance to combustion; planetary atmospheres; and the interstellar and circumstellar space. Further experiments revealed other surprising additions to the radical zoo, also identified with the help of 2df. Along the way we have also identified two new band systems of C_2, the first involving the hidden c^3Σ_u^+ state, and have ventured into the world of larger molecules, such as hexabenzocoronene, C42H18.

  12. Tyrosyl Radicals in Dehaloperoxidase

    PubMed Central

    Dumarieh, Rania; D'Antonio, Jennifer; Deliz-Liang, Alexandria; Smirnova, Tatyana; Svistunenko, Dimitri A.; Ghiladi, Reza A.

    2013-01-01

    Dehaloperoxidase (DHP) from Amphitrite ornata, having been shown to catalyze the hydrogen peroxide-dependent oxidation of trihalophenols to dihaloquinones, is the first oxygen binding globin that possesses a biologically relevant peroxidase activity. The catalytically competent species in DHP appears to be Compound ES, a reactive intermediate that contains both a ferryl heme and a tyrosyl radical. By simulating the EPR spectra of DHP activated by H2O2, Thompson et al. (Thompson, M. K., Franzen, S., Ghiladi, R. A., Reeder, B. J., and Svistunenko, D. A. (2010) J. Am. Chem. Soc. 132, 17501–17510) proposed that two different radicals, depending on the pH, are formed, one located on either Tyr-34 or Tyr-28 and the other on Tyr-38. To provide additional support for these simulation-based assignments and to deduce the role(s) that tyrosyl radicals play in DHP, stopped-flow UV-visible and rapid-freeze-quench EPR spectroscopic methods were employed to study radical formation in DHP when three tyrosine residues, Tyr-28, Tyr-34, and Tyr-38, were replaced either individually or in combination with phenylalanines. The results indicate that radicals form on all three tyrosines in DHP. Evidence for the formation of DHP Compound I in several tyrosine mutants was obtained. Variants that formed Compound I showed an increase in the catalytic rate for substrate oxidation but also an increase in heme bleaching, suggesting that the tyrosines are necessary for protecting the enzyme from oxidizing itself. This protective role of tyrosines is likely an evolutionary adaptation allowing DHP to avoid self-inflicted damage in the oxidative environment. PMID:24100039

  13. Radicals in ionic liquids.

    PubMed

    Strehmel, Veronika

    2012-05-14

    Stable radicals and recombination of photogenerated lophyl radicals are investigated in ionic liquids. The 2,2,6,6-tetramethylpiperidine-1-yloxyl derivatives contain various substituents at the 4-position to the nitroxyl group, including hydrogen-bond-forming or ionic substituents that undergo additional interactions with the individual ions of the ionic liquids. Some of these spin probes contain similar ions to ionic liquids to avoid counter-ion exchange with the ionic liquid. Depending on the ionic liquid anion, the Stokes-Einstein theory or the Spernol-Gierer-Wirtz theory can be applied to describe the temperature dependence of the average rotational correlation time of the spin probe in the ionic liquids. Furthermore, the spin probes give information about the micropolarity of the ionic liquids. In this context the substituent at the 4-position to the nitroxyl group plays a significant role. Covalent bonding of a spin probe to the imidazolium ion results in bulky spin probes that are strongly immobilized in the ionic liquid. Furthermore, lophyl radical recombination in the dark, which is chosen to understand the dynamics of bimolecular reactions in ionic liquids, shows a slow process at longer timescale and a rise time at a shorter timescale. Although various reactions may contribute to the slower process during lophyl radical recombination, it follows a second-order kinetics that does not clearly show solvent viscosity dependence. However, the rise time, which may be attributed to radical pair formation, increases with increasing solvent viscosity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. A new stable perfluoroalkyl radical

    SciTech Connect

    Allayarov, S.R.; Barkalov, I.M.; Mikhailov, A.I.

    1986-01-01

    This paper uses ESR spectroscopy to study the radical formed upon the gamma-irradiation of liquid perfluoro-methyl-2-pentene (PMP). The ESR spectrum of this radical shows a well resolved doublet of triplets with splitting 6.2 and 1.5 mT with additional splitting of each component by 0.25 mT. This ESR corresponds to a radical formed upon the addition of a radical r, in particlular, CF/sub 3/ to PMP.

  15. Toward Radicalizing Community Service Learning

    ERIC Educational Resources Information Center

    Sheffield, Eric C.

    2015-01-01

    This article advocates a radicalized theoretical construction of community service learning. To accomplish this radicalization, I initially take up a discussion of traditional understandings of CSL rooted in pragmatic/progressive thought. I then suggest that this traditional structural foundation can be radicalized by incorporating Deborah…

  16. Toward Radicalizing Community Service Learning

    ERIC Educational Resources Information Center

    Sheffield, Eric C.

    2015-01-01

    This article advocates a radicalized theoretical construction of community service learning. To accomplish this radicalization, I initially take up a discussion of traditional understandings of CSL rooted in pragmatic/progressive thought. I then suggest that this traditional structural foundation can be radicalized by incorporating Deborah…

  17. Free radical explosive composition

    DOEpatents

    Walker, Franklin E.; Wasley, Richard J.

    1979-01-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a getter additive comprising a compound or mixture of compounds capable of capturing or deactivating free radicals or ions under mechanical or electrical shock conditions and which is not an explosive. Exemplary getter additives are isocyanates, olefins and iodine.

  18. Probability and radical behaviorism

    PubMed Central

    Espinosa, James M.

    1992-01-01

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

  19. Radicals in melanin biochemistry.

    PubMed

    Riley, P A

    1988-01-01

    Melanins are light-absorbant polymeric pigments found widely dispersed in nature. They possess many interesting physicochemical properties. One of these is the expression in the polymer of stable free radicals which appear to have a protective action in cells, probably by acting as a sink for diffusible free-radical species. Polymer formation is thought to occur by a free-radical process in which semiquinones are added to the chain. Semiquinones are formed by redox equilibration interactions between metabolic intermediates formed during the tyrosinase-catalyzed oxidation process. In the continued presence of substrate, steady-state concentrations of reactive species are predicted in the reaction system, and the melanogenic pathway may be considered as potentially hazardous for pigment-generating cells. This feature has been exploited by the use of analogue substrates to generate cytotoxic species as a possible rational approach to the treatment of malignant melanoma. One such substance is 4-hydroxyanisole, the oxidation of which gives rise to semiquinone radical species. The possibility that the anisyl semiquinone initiates a mechanism leading to cell damage has not been excluded. However, the current view is that the major cytotoxicity due to the oxidation products of this compound is the result of the action of the corresponding orthoquinone. A number of mechanisms exist for detoxifying quinones if they reach the cytosol such as O-methylation and the formation of thiol adducts with cysteine or glutathione, and these can be used as markers of melanogenesis. In general, however, only small amounts of reactive intermediates of melanogenesis escape from the confines of the melanosome, probably because of their limited lipid solubility. The selective toxic action of anisyl quinone in the treatment of melanoma may, in part, be due to membrane defects in the melanosomes of malignant melanocytes.

  20. THERMOCHEMISTRY OF HYDROCARBON RADICALS

    SciTech Connect

    Kent M. Ervin, Principal Investigator

    2004-08-17

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

  1. Diaryldichalcogenide radical cations.

    PubMed

    Mallow, Ole; Khanfar, Monther A; Malischewski, Moritz; Finke, Pamela; Hesse, Malte; Lork, Enno; Augenstein, Timo; Breher, Frank; Harmer, Jeffrey R; Vasilieva, Nadezhda V; Zibarev, Andrey; Bogomyakov, Artem S; Seppelt, Konrad; Beckmann, Jens

    2015-01-01

    One-electron oxidation of two series of diaryldichalcogenides (C6F5E)2 (13a-c) and (2,6-Mes2C6H3E)2 (16a-c) was studied (E = S, Se, Te). The reaction of 13a and 13b with AsF5 and SbF5 gave rise to the formation of thermally unstable radical cations [(C6F5S)2]˙(+) (14a) and [(C6F5Se)2]˙(+) (14b) that were isolated as [Sb2F11](-) and [As2F11](-) salts, respectively. The reaction of 13c with AsF5 afforded only the product of a Te-C bond cleavage, namely the previously known dication [Te4](2+) that was isolated as [AsF6](-) salt. The reaction of (2,6-Mes2C6H3E)2 (16a-c) with [NO][SbF6] provided the corresponding radical cations [(2,6-Mes2C6H3E)2]˙(+) (17a-c; E = S, Se, Te) in the form of thermally stable [SbF6](-) salts in nearly quantitative yields. The electronic and structural properties of these radical cations were probed by X-ray diffraction analysis, EPR spectroscopy, and density functional theory calculations and other methods.

  2. Types of radical hysterectomies

    PubMed Central

    Marin, F; Plesca, M; Bordea, CI; Moga, MA; Blidaru, A

    2014-01-01

    Abstract The treatment for cervical cancer is a complex, multidisciplinary issue, which applies according to the stage of the disease. The surgical elective treatment of cervical cancer is represented by the radical abdominal hysterectomy. In time, many surgeons perfected this surgical technique; the ones who stood up for this idea were Thoma Ionescu and Ernst Wertheim. There are many varieties of radical hysterectomies performed by using the abdominal method and some of them through vaginal and mixed way. Each method employed has advantages and disadvantages. At present, there are three classifications of radical hysterectomies which are used for the simplification of the surgical protocols: Piver-Rutledge-Smith classification which is the oldest, GCG-EORTC classification and Querlow and Morrow classification. The last is the most evolved and recent classification; its techniques can be adapted for conservative operations and for different types of surgical approaches: abdominal, vaginal, laparoscopic or robotic. Abbreviations: GCG-EORTC = Gynecologic Cancer Group of the European Organization of Research and Treatment of Cancer; LEEP = loop electrosurgical excision procedure; I.O.B. = Institute of Oncology Bucharest; PRS = Piver-Rutledge-Smith PMID:25408722

  3. [Radical prostatectomy - pro robotic].

    PubMed

    Gillitzer, R

    2012-05-01

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

  4. Free radical propulsion concept

    NASA Technical Reports Server (NTRS)

    Hawkins, C. E.; Nakanishi, S.

    1981-01-01

    The concept of a free radical propulsion system, utilizing the recombination energy of dissociated low molecular weight gases to produce thrust, is analyzed. The system, operating at a theoretical impulse with hydrogen, as high as 2200 seconds at high thrust to power ratio, is hypothesized to bridge the gap between chemical and electrostatic propulsion capabilities. A comparative methodology is outlined by which characteristics of chemical and electric propulsion for orbit raising mission can be investigated. It is noted that free radicals proposed in rockets previously met with difficulty and complexity in terms of storage requirements; the present study proposes to eliminate the storage requirements by using electric energy to achieve a continuous-flow product of free radicals which are recombined to produce a high velocity propellant. Microwave energy used to dissociate a continuously flowing gas is transferred to the propellant via three-body-recombination for conversion to propellant kinetic energy. Microwave plasma discharge was found in excess of 90 percent over a broad range of pressure in preliminary experiments, and microwave heating compared to electrothermal heating showed much higher temperatures in gasdynamic equations.

  5. 2.10 Titanium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  6. 1.35 Ruthenium-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  7. 2.33 Mercury-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  8. 2.32 Gold-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  9. 2.8 Potassium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  10. 2.28 Tantalum-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  11. 1.42 Iodine-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  12. 4.6.3 Vinyl radicals

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  13. 1.48 Gold-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  14. 2.7 Phosphorus-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  15. 1.46 Iridium-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  16. 2.16 Zinc-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  17. 1.38 Cadmium-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  18. 2.15 Copper-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  19. 2.4 Sodium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  20. 2.17 Gallium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  1. 2.31 Iridium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  2. 2.21 Niobium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  3. 1.36 Palladium-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  4. 2.3 Boron-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  5. 1.37 Silver-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  6. 2.24 Silver-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  7. 2.18 Rubidium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  8. 2.20 Zirconium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  9. 1.40 Tin-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  10. 1.41 Tellurium-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  11. 2.2 Lithium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  12. 2.5 Aluminum-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  13. 2.22 Molybdenum-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  14. 2.12 Chromium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  15. 2.14 Cobalt-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  16. 2.9 Scandium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  17. 2.6 Silicon-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  18. 2.19 Yttrium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  19. 2.27 Lanthanum-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  20. 2.23 Rhodium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  1. 2.13 Manganese-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  2. 4.6.2 Aryl radicals

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  3. 1.34 Molybdenum-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  4. 1.43 Lanthanum-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  5. 2.30 Osmium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  6. 2.29 Tungsten-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  7. 1.47 Platinum-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  8. 2.26 Cesium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  9. 1.45 Osmium-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  10. 1.44 Tantalum-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  11. 2.11 Vanadium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  12. 2.25 Cadmium-centered radicals

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  13. 1.49 Mercury-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  14. 1.39 Indium-centered radicals

    NASA Astrophysics Data System (ADS)

    Claridge, R. F. C.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

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

    PubMed

    Studer, Armido; Curran, Dennis P

    2016-01-04

    The area of catalysis of radical reactions has recently flourished. Various reaction conditions have been discovered and explained in terms of catalytic cycles. These cycles rarely stand alone as unique paths from substrates to products. Instead, most radical reactions have innate chains which form products without any catalyst. How do we know if a species added in "catalytic amounts" is a catalyst, an initiator, or something else? Herein we critically address both catalyst-free and catalytic radical reactions through the lens of radical chemistry. Basic principles of kinetics and thermodynamics are used to address problems of initiation, propagation, and inhibition of radical chains. The catalysis of radical reactions differs from other areas of catalysis. Whereas efficient innate chain reactions are difficult to catalyze because individual steps are fast, both inefficient chain processes and non-chain processes afford diverse opportunities for catalysis, as illustrated with selected examples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Radically innovative steelmaking technologies

    NASA Astrophysics Data System (ADS)

    Szekely, Julian

    1980-09-01

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

  17. Oligorotaxane Radicals under Orders.

    PubMed

    Wang, Yuping; Frasconi, Marco; Liu, Wei-Guang; Sun, Junling; Wu, Yilei; Nassar, Majed S; Botros, Youssry Y; Goddard, William A; Wasielewski, Michael R; Stoddart, J Fraser

    2016-02-24

    A strategy for creating foldameric oligorotaxanes composed of only positively charged components is reported. Threadlike components-namely oligoviologens-in which different numbers of 4,4'-bipyridinium (BIPY(2+)) subunits are linked by p-xylylene bridges, are shown to be capable of being threaded by cyclobis(paraquat-p-phenylene) (CBPQT(4+)) rings following the introduction of radical-pairing interactions under reducing conditions. UV/vis/NIR spectroscopic and electrochemical investigations suggest that the reduced oligopseudorotaxanes fold into highly ordered secondary structures as a result of the formation of BIPY(•+) radical cation pairs. Furthermore, by installing bulky stoppers at each end of the oligopseudorotaxanes by means of Cu-free alkyne-azide cycloadditions, their analogous oligorotaxanes, which retain the same stoichiometries as their progenitors, can be prepared. Solution-state studies of the oligorotaxanes indicate that their mechanically interlocked structures lead to the enforced interactions between the dumbbell and ring components, allowing them to fold (contract) in their reduced states and unfold (expand) in their fully oxidized states as a result of Coulombic repulsions. This electrochemically controlled reversible folding and unfolding process, during which the oligorotaxanes experience length contractions and expansions, is reminiscent of the mechanisms of actuation associated with muscle fibers.

  18. Oligorotaxane Radicals under Orders

    PubMed Central

    2016-01-01

    A strategy for creating foldameric oligorotaxanes composed of only positively charged components is reported. Threadlike components—namely oligoviologens—in which different numbers of 4,4′-bipyridinium (BIPY2+) subunits are linked by p-xylylene bridges, are shown to be capable of being threaded by cyclobis(paraquat-p-phenylene) (CBPQT4+) rings following the introduction of radical-pairing interactions under reducing conditions. UV/vis/NIR spectroscopic and electrochemical investigations suggest that the reduced oligopseudorotaxanes fold into highly ordered secondary structures as a result of the formation of BIPY•+ radical cation pairs. Furthermore, by installing bulky stoppers at each end of the oligopseudorotaxanes by means of Cu-free alkyne–azide cycloadditions, their analogous oligorotaxanes, which retain the same stoichiometries as their progenitors, can be prepared. Solution-state studies of the oligorotaxanes indicate that their mechanically interlocked structures lead to the enforced interactions between the dumbbell and ring components, allowing them to fold (contract) in their reduced states and unfold (expand) in their fully oxidized states as a result of Coulombic repulsions. This electrochemically controlled reversible folding and unfolding process, during which the oligorotaxanes experience length contractions and expansions, is reminiscent of the mechanisms of actuation associated with muscle fibers. PMID:27163033

  19. Confieso que Divulgo. Reflexiones y Experiencias de una Astrofísica

    NASA Astrophysics Data System (ADS)

    Rodríguez Hidalgo, I.

    Este artículo presenta algunas reflexiones en torno a la popularización de la Ciencia, desarrolladas a lo largo de mi trayectoria profesional, un camino inacabado desde la intuición al oficio. Tras revisar las señas de identidad de la divulgación científica, se exponen ideas, experiencias y recursos, cribados por la práctica y su posterior análisis crítico. Se destacan las actividades relacionadas con la Astronomía, que se cuentan entre las más espectaculares y gratificantes. Confessions of a popularizer: This paper presents some author's thoughts about scientific outreach, developed along her professional path, an unfinished way from intuition to trade. First, identity signs of outreach are revised; then, ideas, experiences and resources, sifted by practice and further critical analysis, are reviewed. Activities related to Astronomy, being one of the most spectacular and rewarding, are remarked 1

  20. Free radical propulsion concept

    NASA Technical Reports Server (NTRS)

    Hawkins, C. E.; Nakanishi, S.

    1981-01-01

    A free radical propulsion concept utilizing the recombination energy of dissociated low molecular weight gases to produce thrust was examined. The concept offered promise of a propulsion system operating at a theoretical impulse, with hydrogen, as high as 2200 seconds at high thrust to power ratio, thus filling the gas existing between chemical and electrostatic propulsion capabilities. Microwave energy used to dissociate a continuously flowing gas was transferred to the propellant via three body recombination for conversion to propellant kinetic energy. Power absorption by the microwave plasma discharge was in excess of 90 percent over a broad range of pressures. Gas temperatures inferred from gas dynamic equations showed much higher temperatures from microwave heating than from electrothermal heating. Spectroscopic analysis appeared to corroborate the inferred temperatures of one of the gases tested.

  1. Radicals in Berkeley?

    PubMed Central

    Linn, Stuart

    2015-01-01

    In a previous autobiographical sketch for DNA Repair (Linn, S. (2012) Life in the serendipitous lane: excitement and gratification in studying DNA repair. DNA Repair 11, 595–605), I wrote about my involvement in research on mechanisms of DNA repair. In this Reflections, I look back at how I became interested in free radical chemistry and biology and outline some of our bizarre (at the time) observations. Of course, these studies could never have succeeded without the exceptional aid of my mentors: my teachers; the undergraduate and graduate students, postdoctoral fellows, and senior lab visitors in my laboratory; and my faculty and staff colleagues here at Berkeley. I am so indebted to each and every one of these individuals for their efforts to overcome my ignorance and set me on the straight and narrow path to success in research. I regret that I cannot mention and thank each of these mentors individually. PMID:25713083

  2. Radicals in Berkeley?

    PubMed

    Linn, Stuart

    2015-04-03

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

  3. Radical Change by Entrepreneurial Design

    DTIC Science & Technology

    1998-01-01

    This article offers a conceptual framework to understand radical change. It opens with a typology that defines change in terms of its pace and scope...known entrepreneurs who have been successful in molding and shaping the radical change process. The implications of this conceptual framework to

  4. Studies of radiation-produced radicals and radical ions

    SciTech Connect

    Williams, T.F.

    1991-01-01

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

  5. Free radicals and male reproduction.

    PubMed

    Agarwal, Ashok; Allamaneni, Shyam S R

    2011-03-01

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

  6. [Simultaneous radical retropubic prostatectomy, diverticulectomy].

    PubMed

    Loran, O B; Sokolov, A E; Guspanov, R I; Polegen'kiĭ, V V

    2014-01-01

    Presented clinical case demonstrates a combination of rare congenital abnormality - giant true diverticula of the bladder - and high-risk prostate cancer, as well as a successful result of simultaneous operation - a radical prostatectomy with diverticulectomy.

  7. Free radical inactivation of pepsin

    NASA Astrophysics Data System (ADS)

    Josimović, Lj; Ruvarac, I.; Janković, I.; Jovanović, S. V.

    1994-06-01

    Alkylperoxy radicals containing one, two or three chlorine atoms, CO -2, O 2 - were reacted with pepsin in aqueous solutions. It was found that only Cl 3COO and CO -2 inactive pepsin, attacking preferentially the disulfide bridge. Transient spectra obtained upon completion of the Cl 3COO + pepsin reaction at pH 5 indicate that 20% of initially produced Cl 3COO radicals oxidizes tryptophan residues, and 40% disulfide bridges. The inactivation induced by the Cl 3COO radical increases at lower pH, and the maximal inactivation, Gin = 5.8, was observed at pH 1.5. The inactivation of pepsin by CO -2 radicals depends on the absorbed dose. The maximal inactivation, Gin = 4.5, was determined in the dose range from 38 to 53 Gy.

  8. Redox Properties of Free Radicals.

    ERIC Educational Resources Information Center

    Neta, P.

    1981-01-01

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

  9. Redox Properties of Free Radicals.

    ERIC Educational Resources Information Center

    Neta, P.

    1981-01-01

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

  10. Peroxy radical oxidation of thymidine.

    PubMed

    Martini, M; Termini, J

    1997-02-01

    The peroxy radical (ROO) is unique among reactive oxygen species implicated in the production of DNA damage in that it possesses an extremely long half-life (order of seconds) and is predicted to have a relatively greater chemical selectivity in its reactions relative to other radical intermediates. Yet no product studies of the reactions of ROO with bases, nucleosides, or DNA have appeared, and thus no meaningful predictions can be made regarding its potential involvement in the production of DNA base damage and the mutagenic process. We report here on the reaction products formed by peroxy radical with thymidine, major target of oxidative base damage. ROO reacts with thymine to yield predominantly 5-Me oxidation products. The highly mutagenic 5-(hydroperoxymethyl)-2'-deoxyuridine, 5-formyl-2'-deoxyuridine, and 5-(hydroxymethyl)-2'-deoxyuridine are produced by peroxy radical oxidation. In contrast, 5Me oxidation products are minor products of thymidine oxidation by OH, which yields predominantly saturated derivatives via addition to the 5,6 double bound. A plausible mechanistic scheme for the formation of the base oxidation products of thymidine by peroxy radicals is presented. Attach at the deoxyribose moiety resulting in oxidative depyrimidination is also found to occur, as indicated by free base release. Phosphodiester backbone cleavage resulting in single and double strand breaks is also catalyzed by peroxy radical, as demonstrated using a plasmid nicking assay.

  11. Crystalline bipyridinium radical complexes and uses thereof

    DOEpatents

    Fahrenbach, Albert C.; Barnes, Jonathan C.; Li, Hao; Stoddart, J. Fraser; Basuray, Ashish Neil; Sampath, Srinivasan

    2015-09-01

    Described herein are methods of generating 4,4'-bipyridinium radical cations (BIPY.sup..cndot.+), and methods for utilizing the radical-radical interactions between two or more BIPY.sup..cndot.+ radical cations that ensue for the creation of novel materials for applications in nanotechnology. Synthetic methodologies, crystallographic engineering techniques, methods of physical characterization, and end uses are described.

  12. Entrenamiento con el traje espacial

    NASA Image and Video Library

    Después de 10 paseos espaciales, el astronauta de la NASA Michael López- Alegría sabe bastante de trajes espaciales. En este video, López Alegría comparte su experiencia acerca del uso y el entrena...

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

    SciTech Connect

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

    2015-12-01

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

  14. Planificación Neuroquirúrgica con Software Osirix

    PubMed Central

    Jaimovich, Sebastián Gastón; Guevara, Martin; Pampin, Sergio; Jaimovich, Roberto; Gardella, Javier Luis

    2014-01-01

    Introducción: La individualidad anatómica es clave para reducir el trauma quirúrgico y obtener un mejor resultado. Actualmente, el avance en las neuroimágenes ha permitido objetivar esa individualidad anatómica, permitiendo planificar la intervención quirúrgica. Con este objetivo, presentamos nuestra experiencia con el software Osirix. Descripción de la técnica: Se presentan 3 casos ejemplificadores de 40 realizados. Caso 1: Paciente con meningioma de la convexidad parasagital izquierda en área premotora; Caso 2: Paciente con macroadenoma hipofisario, operada previamente por vía transeptoesfenoidal en otra institución con una resección parcial; Caso 3: Paciente con lesiones en pedúnculo cerebeloso medio bilateral. Se realizó la planificación prequirúrgica con el software OsiriX, fusionando y reconstruyendo en 3D las imágenes de TC e IRM, para analizar relaciones anatómicas, medir distancias, coordenadas y trayectorias, entre otras funciones. Discusión: El software OsiriX de acceso libre y gratuito permite al cirujano, mediante la fusión y reconstrucción en 3D de imágenes, analizar la anatomía individual del paciente y planificar de forma rápida, simple, segura y económica cirugías de alta complejidad. En el Caso 1 se pudo analizar las relaciones del tumor con las estructuras adyacentes para minimizar el abordaje. En el Caso 2 permitió comprender la anatomía post-operatoria previa del paciente, para determinar la trayectoria del abordaje transnasal endoscópico y la necesidad de ampliar su exposición, logrando la resección tumoral completa. En el Caso 3 permitió obtener las coordenadas estereotáxicas y trayectoria de una lesión sin representación tomográfica. Conclusión: En casos de no contar con costosos sistemas de neuronavegación o estereotáxia el software OsiriX es una alternativa a la hora de planificar la cirugía, con el objetivo de disminuir el trauma y la morbilidad operatoria. PMID:25165617

  15. [Laparoscopic radical cystectomy: initial experience].

    PubMed

    Núñez Mora, C; García Mediero, J Ma; Cáceres Jiménez, F; Cabrera Castillo, P M

    2007-09-01

    To review our initial experience with laparoscopic radical cystectomy. Between September 2004 and June 2006 we performed 16 laparoscopic radical cystectomies (14 males and 2 females) with a median age of 63.8 y.o. (51-85). 12 ileal neobladder (with laparoscopic ileal-urethra anastomosis), 3 cutaneous ureteroileostomies and 1 cutaneous ureterostomy were performed as derivation techniques. Median follow up was 12.4 months Mean operation time was 340 minutes. Estimated blood loss was 350 ml. and 3 cases required intra-op blood transfusion. Mean hospitalization discharged was at 7.6 days. Median linph node dissection was 22.9 finding node metastasis in 6 cases. Most frequent complication was ileo in two cases. No local recurrentes in trocar placement was achieved. Laparoscopic Radical cystectomy is a challenged long-lasting procedure but with the advantage of a less transfusion rate and short hospital stay. Oncologycal outcomes are similar as tose from open surgery.

  16. Radical-Mediated Enzymatic Polymerizations

    PubMed Central

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  17. Epistemological barriers to radical behaviorism.

    PubMed

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

    1998-01-01

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

  18. Epistemological barriers to radical behaviorism

    PubMed Central

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

    1998-01-01

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

  19. Donor free radical explosive composition

    DOEpatents

    Walker, Franklin E. [15 Way Points Rd., Danville, CA 94526; Wasley, Richard J. [4290 Colgate Way, Livermore, CA 94550

    1980-04-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a donor additive comprising an organic compound or mixture of organic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and which is not an explosive, or an inorganic compound or mixture of inorganic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and selected from ammonium or alkali metal persulfates.

  20. Laparoscopic radical and partial cystectomy

    PubMed Central

    Challacombe, Ben J.; Rose, Kristen; Dasgupta, Prokar

    2005-01-01

    Radical cystectomy remains the standard treatment for muscle invasive organ confined bladder carcinoma. Laparoscopic radical cystoprostatectomy (LRC) is an advanced laparoscopic procedure that places significant demands on the patient and the surgeon alike. It is a prolonged procedure which includes several technical steps and requires highly developed laparoscopic skills including intra-corporeal suturing. Here we review the development of the technique, the indications, complications and outcomes. We also examine the potential benefits of robotic-assisted LRC and explore the indications and technique of laparoscopic partial cystectomy. PMID:21206662

  1. VUV Photoionisation of hydrocarbon radicals

    NASA Astrophysics Data System (ADS)

    Alcaraz, C.; Noller, Bastian; Hemberger, Patrick; Fischer, Ingo; Gans, Bérenger; Boyé-Peronne, Séverine; Douin, Stéphane; Gauyacq, Dolorès; Soldi-Lose, Héloïse; Garcia, Gustavo

    2008-09-01

    Hydrocarbon radicals CxHy are constituents of various planetary atmospheres, in particular Titan, as a result of the methane photochemistry induced by the solar radiation. They contribute to the neutral chemistry, but are also important for the ionosphere through their photoionisation leading to their cations CxHy +. These cations are also produced by ion-molecule reactions starting from the reaction of the primary ions CH4 + and CH3 + which are created in the non-dissociative and dissociative photoionisation of CH4. This work aims at caracterizing the VUV photoionisation of small hydrocarbon radicals as a function of photon energy. The objective is to provide laboratory data for modelers on the spectroscopy, the thermochemistry, and the reactivity of the radicals and their cations. The hydrocarbon radicals are much less caracterized than stable molecules since they have to be produced in situ in the laboratory experiment. We have adapted at Orsay [1-3] a pyrolysis source (Figure 1) well suited to produce cold beams of hydrocarbon radicals to our experimental setups. Available now at Orsay, we have two new sources of VUV radiation, complementary in terms of tunability and resolution, that can be used for these studies. The first one is the DESIRS beamline [4] at the new french synchrotron, SOLEIL. The second one is the VUV laser developped at the Centre Laser de l'Université Paris-Sud (CLUPS) [5]. At SOLEIL, a photoelectron-photoion coincidence spectrometer is used to monitor the photoionisation on a large photon energy range. At the CLUPS, a pulsedfield ionisation (PFI-ZEKE) spectrometer allows studies at higher resolution on selected photon energies. The first results obtained with these new setups will be presented. References [1] Fischer, I., Schussler, T., Deyerl, H.J., Elhanine, M. & Alcaraz, C., Photoionization and dissociative photoionization of the allyl radical, C3H5. Int. J. Mass Spectrom., 261 (2-3), 227-233 (2007) [2] Schüßler, T., Roth, W., Gerber

  2. Students' Ideas and Radical Constructivism

    ERIC Educational Resources Information Center

    Sánchez Gómez, Pedro J.

    2016-01-01

    In this article, I study, from the point of view of the analytic philosophy of mind, the compatibility of students' ideas studies (SIS) with radical constructivism (RC). I demonstrate that RC is based on a psychology of "narrow mental states"; that is, the idea that the mental content of an individual can be fully characterised without…

  3. The Other Women: Radicalizing Feminism.

    ERIC Educational Resources Information Center

    Puigvert, Lidia; Darder, Antonia; Merrill, Barbara; de los Reyes, Eileen; Stromquist, Nelly

    A recent international symposium on radicalizing feminism explored ways of developing a dialogic feminism that emphasizes working in different settings under the common goal of including women who have been invisible in the dominant feminist literature by furthering theories and practices based on the principles of dialogic feminism. The seminar…

  4. [Reprodcutive results of radical trachelectomy].

    PubMed

    Martínez-Chapa, Arnulfo; Alonso-Reyes, Nelly; Luna-Macías, Miguel

    2015-12-01

    Historically, cervical cancer in early stages has been treated with radical hysterectomy and radiotherapy with no option in keeping the uterine-ovarian function. Since two decades ago, evidence shows these cases are candidates for radical trachelectomy, a procedure capable of preserving the fertility without affecting the oncological outcome. To analyze reproductive results among patients treated with radical trachelectomy, in a reference center from the northeast of Mexico. Between March 1999 and December 2013, 27 cases with cervical cancer in early stages were treated with vaginal or abdominal radical trachelectomy in the ISSSTE Regional Hospital in Monterrey, NL (Mexico). We obtained the gynecological, medical and surgical clinical history. Plan of analysis consisted of descriptive statistics. Age range was 27-39 years. Main complications were cervical stenosis (n=1) and erosion of cerclaje (n=2). Eighteen patients tried to get pregnant, 8 of them got a spontaneous pregnancy; 1 more patient required assisted reproduction technics and did not succeed. All pregnancies were delivered by cesarean section and were preterm births; 3 underwent premature rupture of membranes. Two pregnancies ended in abortion, one at 10 weeks with severe hemorrhage that needed hysterectomy; the second one, at 1 7 weeks, received a fine uterine curettage. Only 6 cases (33%) got a live birth. Only one third of the attempted pregnancies got a live birth. Assisted reproduction technics play an important role and should be offer to all cases. Cerclaje is an important factor to carry a pregnancy up to the third trimester.

  5. Mitigating Radicalism in Northern Nigeria

    DTIC Science & Technology

    2013-08-01

    radicalization in northern Nigeria. u Active engagement of youth and communities in peacebuilding programs that facilitate interactions among individuals...leaders, sustained development investments in marginalized communities , promotion of values of inclusivity to mitigate the spread of extremist ideology...claiming to have repelled Boko Haram, the militants return, regroup, and seek revenge. As a result, social and economic activities in the northern

  6. Students' Ideas and Radical Constructivism

    ERIC Educational Resources Information Center

    Sánchez Gómez, Pedro J.

    2016-01-01

    In this article, I study, from the point of view of the analytic philosophy of mind, the compatibility of students' ideas studies (SIS) with radical constructivism (RC). I demonstrate that RC is based on a psychology of "narrow mental states"; that is, the idea that the mental content of an individual can be fully characterised without…

  7. ConSCRIPT

    PubMed Central

    Mottarella, Scott E.; Rosa, Mario; Bangura, Abdul; Bernstein, Herbert J.; Craig, Paul A.

    2011-01-01

    The aim of the Structural Biology Extensible Visualization Scripting Language (SBEVSL) project is to allow users who are experts in one scripting language to use that language in a second molecular visualization environment without requiring the user to learn a new scripting language. ConSCRIPT, the first SBEVSL release, is a plug-in for PyMOL that accepts RasMol scripting commands either as premade scripts or as line-by-line entries from PyMOL's own command line. The plug-in is available for download at http://sourceforge.net/projects/sbevsl/files in the ConSCRIPT folder. PMID:21567873

  8. REVERSIBILITY OF RADICAL-OLEFIN REACTIONS.

    DTIC Science & Technology

    ALKENES, *STYRENES, *POLYVINYL CHLORIDE, CHEMICAL EQUILIBRIUM, POLYMERIZATION, POLYMERIZATION, FREE RADICALS , MOLECULAR ISOMERISM, TRACER STUDIES, CHEMICAL REACTIONS, DECOMPOSITION, SYNTHESIS(CHEMISTRY).

  9. Free-radical chemistry of sulfite.

    PubMed Central

    Neta, P; Huie, R E

    1985-01-01

    The free-radical chemistry of sulfite oxidation is reviewed. Chemical transformations of organic and biological molecules induced by sulfite oxidation are summarized. The kinetics of the free-radical oxidations of sulfite are discussed, as are the kinetics of the reactions of the sulfite-derived radicals SO3 and the peroxy derivative SO5 with organic compounds. PMID:3830699

  10. REACTIONS OF FREE RADICALS CONTAINING NITROGEN.

    DTIC Science & Technology

    deduced. The reactions of methyl and ethyl radicals with a variety of amino compounds were studied. The reactions of difluoroamino radicals in the...Hydrazines, Anilines and Cyanides were pyrolysed and the heats of formation of the resultant radicals and the strengths of the bonds formed by them

  11. The Radical Axis: A Motion Study

    ERIC Educational Resources Information Center

    McGivney, Ray; McKim, Jim

    2006-01-01

    Interesting problems sometimes have surprising sources. In this paper we take an innocent looking problem from a calculus book and rediscover the radical axis of classical geometry. For intersecting circles the radical axis is the line through the two points of intersection. For nonintersecting, nonconcentric circles, the radical axis still…

  12. Highly durable photochromic radical complexes having no steric protections of radicals.

    PubMed

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

    2017-04-21

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

  13. Mutagenicity of Oxygen Free Radicals

    NASA Astrophysics Data System (ADS)

    Moody, Carmella S.; Hassan, Hosni M.

    1982-05-01

    Paraquat 1,1'-dimethyl-4,4'-bipyridinium dichloride) was used as an intracellular generator of oxygen free radicals and was found to be highly mutagenic for Salmonella typhimurium. It caused both base-pair substitution and frameshift mutations. Paraquat was much more toxic and mutagenic in a simple nutritionally restricted medium than in a rich complex medium. The mutagenicity of paraquat was dependent upon the presence of a supply of both electrons and oxygen. Cells containing high levels of superoxide dismutase (superoxide:superoxide oxidoreductase, EC 1.15.1.1) were more resistant to the toxicity and the mutagenicity of paraquat than were cells containing normal levels of this enzyme. The mutagenicity of paraquat thus appears to be due to its ability to exacerbate the intracellular production of superoxide radicals.

  14. Geoscientists and the Radical Middle

    NASA Astrophysics Data System (ADS)

    Tinker, S. W.

    2015-12-01

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

  15. Radical Islam in East Africa

    DTIC Science & Technology

    2009-01-01

    carrying out operations. The documents paint a portrait of al-Qaeda cells operating freely in Kenya without concern about being monitored or detained...against Ethiopian Christians.80 For the United States, the Ethiopian occupation has removed the immediate problem of a radical ICU faction sheltering...the U.S. decision to support the Ethiopian invasion and occupation of 8 William Reno, review of monograph. 9 International Crisis Group, Counter

  16. [Waist-hip ratio and perioperative bleeding in patients who underwent radical prostatectomy].

    PubMed

    León-Ramírez, Víctor; Santiago-López, Janaí; Reyes-Rivera, Juan Gabriel; Miguel-Soto, Edgar

    2016-01-01

    Introducción: la prostatectomía radical se asocia con sangrado perioperatorio y múltiples transfusiones. La obesidad abdominal representa un factor de riesgo perioperatorio. Sugerimos un efecto protector del adipocito en pacientes oncológicos sometidos a prostatectomía radical. El objetivo fue evaluar el efecto del índice cintura-cadera (ICC) sobre la magnitud del sangrado y los requerimientos perioperatorios de transfusiones en pacientes oncológicos sometidos a prostatectomía radical. Métodos: estudio de cohorte en 156 pacientes. Se integraron dos grupos: el control (ICC < 0.95) y el problema (ICC > 0.95); se registraron la magnitud del sangrado y las fracciones transfundidas durante la cirugía y en el postoperatorio. Se utilizaron medidas de tendencia central y dispersión, así como chi cuadrada, t de Student, U de Mann-Whitney y ANOVA. Una p < 0.05 fue significativa. Resultados: encontramos diferencias significativas en el peso, índice de masa corporal, cintura, índice cintura-cadera, sangrado perioperatorio, fracciones transfundidas, permanencia de la sonda y días de hospitalización. Conclusión: los pacientes sometidos a prostatectomía radical con ICC ≥ 0.95 tuvieron un sangrado y requerimientos transfusionales perioperatorios menores que aquellos con un ICC < 0.95.

  17. Hydroxyl radical detection in vivo

    SciTech Connect

    Chevion, M.; Floyd, R.A.

    1986-05-01

    Hydroxyl radicals have been implicated as the actual species responsible for the deleterious effects of active oxygen in biology. However, in most cases, its presence has only been inferred by circumstantial evidence. Using electrochemical detection coupled to HPLC separation technique the authors can identify and quantitate (at sub-picomole level) the hydroxylated products of 3 aromatic compounds (phenol, salicylate, and 2-deoxy-guanosine) as a direct measure of hydroxyl radical formation. Firstly, the authors showed that mixing ascorbate with copper ions (in the absence of presence of a protein) yields catechols, dihydroxybenzoic acids and 8-OH-deoxy-guanosine (8-OHdG). This approach has been used to study the formation of OH in vivo. Human granulocytes stimulated with TPA showed that 8-OHdG was formed in the cellular DNA at high levels (one 8-OHdG/800 DNA bases). Unstimulated granulocytes contained 8-OHdG below detection level. Formation of 8-OHdG in the TPA-stimulated granulocytes DNA was decreased by the addition of SOD and catalase. Using salicylate as an in vivo scavenger of hydroxyl radicals the authors showed that the level of trapped-dihydroxybenzoic acids is increased approx.8 and approx.3 fold in the lungs and liver of paraquat-poisoned mice, respectively, as compared to normal animals. Similarly, the detected level of dihydroxybenzoic acids in the hearts of adriamycin-treated rats was increased over 100-fold as compared to the hearts of control animals.

  18. A radical way to burn

    SciTech Connect

    Ashley, S.

    1996-08-01

    By manipulating chamber geometries as well as engine cycle pressures and timing, engineers are exploiting a long-obscure technology known as activated radical combustion. Piston-driven internal combustion engines generally come in two varieties: compression-ignited diesels and spark-ignited gasoline power plants. There, is however, a third way to initiate burning of the fuel-air mixture. The technique--variously called radical ignition (RI), activated radical (AR) combustion, Toyota-Soken combustion, and active thermo-atmosphere combustion--is not exactly new, but only recently have engineers begun to exploit the process in practical power plants. These new units include a lightweight two-stroke racing-motorcycle engine, truck diesels with reduced soot output, and lean-burn spark-ignited car engines. This long-obscure combustion process is based on a range of specialized chemical kinetic and physical acoustic techniques developed over decades. Engineers manipulate fundamental combustion parameter such as chamber geometries, valving and porting configurations, and engine cycle pressures and timing to foster the formation of certain highly reactive chemical species that lower the fuel-air mixture`s flash point so that even modest compression make sit self-ignite. These chemical initiators are then retained into the next cycle to start combustion, allowing the engineer to run stably with no spark.

  19. Radical scavengers from heavy hydrocarbons

    SciTech Connect

    Kubo, Junichi

    1996-10-01

    The hydrogen-donating properties of some hydrocarbons form the basis for processes such as coal liquefaction and heavy oil upgrading. However, these hydrocarbons have seldom been used for other purposes, because their potential applications have not been well recognized. Research has indicated that these hydrogen-donating hydrocarbons can be used in important reactions as radical scavengers and have properties particular to those of pure hydrocarbons without functional groups containing heteroatoms. Over years of study researchers have found that pure hydrocarbons with radical-scavenging effects nearly as high as those in conventional hindered phenolic antioxidants can be produced from petroleum, and these hydrogen-donating hydrocarbons exhibit such effects even in oxidative atmospheres (i.e., they function as antioxidants). He has also shown that these mixtures have some properties particular to pure hydrocarbons without functional groups containing heteroatoms, and they`ve seen that a mechanism based on the steric effects appears when these hydrocarbons are used in heavy oil hydroprocessing. Hydrogen-donating hydrocarbons should be a viable resource in many applications. In this article, he presents radical-scavenging abilities, characteristics as pure hydrocarbons, and applications on the basis of the studies.

  20. Chemistry of The Oio Radical

    NASA Astrophysics Data System (ADS)

    Joseph, M.; Ashworth, S. H.; Plane, J. M. C.

    This paper will describe a laboratory study of the chemistry that the OIO radical under- goes in the marine boundary layer. The radical was produced by the pulsed photolysis at 193 nm of a N2O/CF3I mixture. The resulting OIO radicals, formed by the self- reaction of IO, were then observed by time-resolved cavity ringdown spectroscopy, using the vibrational bands between 540 and 620 nm. A high resoluting spectral scan found no rotational structure in these bands, indicating that the upper state of this electronic transition is predissociative (lifetime = 150 fs). Ab initio quantum calcula- tions indicate that I + O2 is formed, and this was confirmed by adding a third laser to photolyse OIO as a function of wavelength, with detection of atomic I by resonance fluorescence at 178 nm. This system was also used to measure the absolute absorption cross-section of OIO (1.6 x 10(-17) cm2 at 568 nm). The photodissociation lifetime of OIO is about 0.5 s at midday. Although of minor atmospheric importance, the reac- tions of OIO with NO and OH will also be discussed.

  1. 4.6.1 Acyl and related radicals

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  2. 4.5.2.2 Radicals from bridged rings

    NASA Astrophysics Data System (ADS)

    Howard, J. A.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  3. Free-radical-mediated DNA binding.

    PubMed Central

    O'Brien, P J

    1985-01-01

    Free-radical metabolites can be generated metabolically by a one-electron reductase-catalyzed reaction or a "peroxidase" catalyzed oxidation or by photoactivation of a wide variety of aromatic xenobiotics. Radicals may also be generated during lipid peroxidation. Some radicals can react with DNA or bind covalently or noncovalently as a dismutation product or as a dimer, trimer or polymeric product. Modification to the DNA can result in single-strand breaks, loss of template activity, and crosslinking. The binding can prevent enzymic digestion. In some cases, the radicals react with oxygen, resulting before conversion to DNA reactive oxygen species. Most radicals probably do not interact with DNA. PMID:3007090

  4. Oxidative stress, free radicals and protein peroxides.

    PubMed

    Gebicki, Janusz M

    2016-04-01

    Primary free radicals generated under oxidative stress in cells and tissues produce a cascade of reactive secondary radicals, which attack biomolecules with efficiency determined by the reaction rate constants and target concentration. Proteins are prominent targets because they constitute the bulk of the organic content of cells and tissues and react readily with many of the secondary radicals. The reactions commonly lead to the formation of carbon-centered radicals, which generally convert in vivo to peroxyl radicals and finally to semistable hydroperoxides. All of these intermediates can initiate biological damage. This article outlines the advantages of the application of ionizing radiations to studies of radicals, with particular reference to the generation of desired radicals, studies of the kinetics of their reactions and correlating the results with events in biological systems. In one such application, formation of protein hydroperoxides in irradiated cells was inhibited by the intracellular ascorbate and glutathione. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. The Con Test

    ERIC Educational Resources Information Center

    Fletcher, Michael

    2009-01-01

    In this article, the author describes the format of the Con Test, an Australian television game show which followed the same general rules and game play as the UK show PokerFace. At the end of each round a contestant needs to decide whether or not he or she should fold. A contestant needs to know how likely it is that he or she is in last place.…

  6. Urinary incontinence following radical vulvectomy.

    PubMed

    Reid, G C; DeLancey, J O; Hopkins, M P; Roberts, J A; Morley, G W

    1990-05-01

    Although incontinence has been reported after radical vulvectomy, its relationship to operative technique, anatomy, and treatment has not been defined. Twenty-one patients having vulvectomies for vulvar cancer were prospectively evaluated preoperatively and postoperatively with urodynamic function studies. A portion of the urethra was removed in four patients undergoing radical vulvectomy, and 14 had a vulvectomy excision that came within 1 cm of the distal urethra. Six patients (28%) developed a change of continence, with three developing total incontinence, two stress incontinence, and one urge incontinence. All four patients who had a portion of the urethra excised developed stress or total incontinence. The other two patients with incontinence (one total, one urge) had the vulvectomy excision that came close to the urethra. No patient had a change in continence when surgery did not involve or come close to the urethra. When the four patients with a distal urethral resection were compared with patients in whom the urethra was not excised, there was a significant decrease postoperatively in functional urethral length (P less than .0001), anatomical urethral length (P less than .0001), and distal urethral pressure transmission ratios in Q3 (P = .004), Q4 (P = .02), and Q5 (P = .005); but no difference in urethral support (Q-tip test), flow rates, residual urine, bladder capacity, maximal urethral pressure, resting closure pressure, or squeeze pressure. Histologic examination of urethral specimens demonstrated that a portion of the compressor urethrae muscle was often excised. Radical vulvectomy by itself does not cause incontinence, but it would appear that removal of a portion of the urethra increases the chance of incontinence.(ABSTRACT TRUNCATED AT 250 WORDS)

  7. Iron and iron derived radicals

    SciTech Connect

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

    1987-04-01

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

  8. Aromatic-radical oxidation chemistry

    SciTech Connect

    Glassman, I.; Brezinsky, K.

    1993-12-01

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

  9. Laser spectroscopy of hydrocarbon radicals

    SciTech Connect

    Chen, P.

    1993-12-01

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

  10. Neuroprotective strategies in radical prostatectomy.

    PubMed

    Schiff, Jonathan D; Mulhall, John P

    2005-01-01

    In this section, authors from New York give their views on the various neuroprotective strategies for patients having a radical prostatectomy, such as the use of nerve grafts and other approaches. A joint study from Korea, the USA, Canada and the UK is presented in a paper on the importance of patient perception in the clinical assessment and management of BPH. There is also a review of robotic urological surgery. Finally, authors from New York give a review on the life of Isaac Newton. This is a new historical review in the journal, but one that will be of general interest.

  11. Bioinspired terpene synthesis: a radical approach.

    PubMed

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

    2011-07-01

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

  12. Emergence of oxyl radicals as selective oxidants.

    PubMed

    Ramasarma, T

    2012-10-01

    Hydroxyl radicals (HO*) are derived in Fenton reaction with ferrous salt and H2O2 in acid medium, and at neutral pH, metal-oxyl radicals (M-O*) predominate. Evidence is accumulating that M-O* radicals are also active in oxidation reactions, in addition to metal-oxo (M=O) now shown in many publications. Reactivity of these radicals gives selective oxidized products useful in cellular activities, in contrast to purported indiscriminate cell damage by hydroxyl radicals. Reactions with vanadium compounds, such as diperoxovanadate, peroxo-bridged mixed valency divanadate, vanadium-oxyl radical, tetravalent vanadyl and decavanadate illustrates selective gain in oxidative capacity of oxo- and oxyl- species. Occurrence of ESR signals typical of hydroxyl radicals is demonstrated in cell homogenates and tissue perfusates treated with spin trap agents. It is known for a long time lipid peroxides are formed in tissue microsomal systems exclusively in presence of salts of iron, among many metals tested. Oxygen and a reducing agent, ascorbate (non-enzymic) or NADPH (enzymic) are required to produce 'ferryl', the chelated Fe=O active form (possibly Fe-O* and Fe-O-O-Fe ?) for the crucial step of H-atom abstraction. Yet literature is replete with unsupported affirmations that hydroxyl radicals initiate lipid peroxidation, an unexplained fixation of mindset. The best-known *OH generator, a mixture of ferrous salt and H2O2, does not promote lipid peroxidation, nor do the many hydroxyl radical quenching agents stop it. The availability of oxo and oxyl-radical forms with transition metals, and also with non metals, P, S, N and V, calls for expansion of vision beyond superoxide and hydroxyl radicals and explore functions of multiple oxygen radicals for their biological relevance.

  13. Quantitative determination of atmospheric hydroperoxyl radical

    DOEpatents

    Springston, Stephen R.; Lloyd, Judith; Zheng, Jun

    2007-10-23

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

  14. Laser induced photoluminescence spectroscopy of cometary radicals

    NASA Technical Reports Server (NTRS)

    Jackson, W. M.; Cody, R. J.; Sabety-Dzvonik, M.

    1976-01-01

    Flash photolysis together with laser excitation of the product fragments was used in laboratory studies of cometary radicals. The LIPS method has been applied to the CN radical to determine: (1) Radiative lifetimes of individual rotational levels in the zeroth vibrational level of the B state; (2) energy partitioning during photodissociation of C2N2; and (3) vibrational and rotational excitation during formation of CN radicals in the photodissociation of dicyanoacetylene.

  15. The tyrosyl free radical in ribonucleotide reductase.

    PubMed Central

    Gräslund, A; Sahlin, M; Sjöberg, B M

    1985-01-01

    The enzyme, ribonucleotide reductase, catalyses the formation of deoxyribonucleotides from ribonucleotides, a reaction essential for DNA synthesis in all living cells. The Escherichia coli ribonucleotide reductase, which is the prototype of all known eukaryotic and virus-coded enzymes, consists of two nonidentical subunits, proteins B1 and B2. The B2 subunit contains an antiferromagnetically coupled pair of ferric ions and a stable tyrosyl free radical. EPR studies show that the tyrosyl radical, formed by loss of ferric ions and a stable tyrosyl free radical. EPR studies show that the tyrosyl radical, formed by loss of an electron, has its unpaired spin density delocalized in the aromatic ring of tyrosine. Effects of iron-radical interaction indicate a relatively close proximity between the iron center and the radical. The EPR signal of the radical can be studied directly in frozen packed cells of E. coli or mammalian origin, if the cells are made to overproduce ribonucleotide reductase. The hypothetic role of the tyrosyl free radical in the enzymatic reaction is not yet elucidated, except in the reaction with the inhibiting substrate analogue 2'-azido-CDP. In this case, the normal tyrosyl radical is destroyed with concomitant appearance of a 2'-azido-CDP-localized radical intermediate. Attempts at spin trapping of radical reaction intermediates have turned out negative. In E. coli the activity of ribonucleotide reductase may be regulated by enzymatic activities that interconvert a nonradical containing form and the fully active protein B2. In synchronized mammalian cells, however, the cell cycle variation of ribonucleotide reductase, studied by EPR, was shown to be due to de novo protein synthesis. Inhibitors of ribonucleotide reductase are of medical interest because of their ability to control DNA synthesis. One example is hydroxyurea, used in cancer therapy, which selectively destroys the tyrosyl free radical. PMID:3007085

  16. Nam Con Son Basin

    SciTech Connect

    Tin, N.T.; Ty, N.D.; Hung, L.T.

    1994-07-01

    The Nam Con Son basin is the largest oil and gas bearing basin in Vietnam, and has a number of producing fields. The history of studies in the basin can be divided into four periods: Pre-1975, 1976-1980, 1981-1989, and 1990-present. A number of oil companies have carried out geological and geophysical studies and conducted drilling activities in the basin. These include ONGC, Enterprise Oil, BP, Shell, Petro-Canada, IPL, Lasmo, etc. Pre-Tertiary formations comprise quartz diorites, granodiorites, and metamorphic rocks of Mesozoic age. Cenozoic rocks include those of the Cau Formation (Oligocene and older), Dua Formation (lower Miocene), Thong-Mang Cau Formation (middle Miocene), Nam Con Son Formation (upper Miocene) and Bien Dong Formation (Pliocene-Quaternary). The basement is composed of pre-Cenozoic formations. Three fault systems are evident in the basin: north-south fault system, northeast-southwest fault system, and east-west fault system. Four tectonic zones can also be distinguished: western differentiated zone, northern differentiated zone, Dua-Natuna high zone, and eastern trough zone.

  17. Formation of free radicals during phacoemulsification.

    PubMed

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

    1993-04-01

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

  18. Physiological aspects of free-radical reactions.

    PubMed Central

    Yamazaki, I; Tamura, M; Nakajima, R; Nakamura, M

    1985-01-01

    Enzymes which catalyze the formation of free radicals in vitro will catalyze similar reactions in vivo. We believe that the formation of some kinds of free radicals has definite physiological meanings in metabolism. In this sense, the enzymes forming such free radicals are concluded to be in evolutionally advanced states. Elaborated structure and function of enzymes such as horseradish peroxidase and microsomal flavoproteins support the idea. Deleterious and side reactions caused by free radicals are assumed to be minimized in vivo by localizing the reactions, but this assumption should be verified by future studies. PMID:3007098

  19. Dynamics of Radical-Mediated Enzyme Catalyses

    NASA Astrophysics Data System (ADS)

    Warncke, Kurt

    1997-11-01

    An emergent class of enzymes harnesses the extreme reactivity of electron-deficient free radical species to perform some of the most difficult reactions in biology. The regio- and stereo-selectivity achieved by these enzymes defies long-held ideas that radical reactions are non-specific. The common primary step in these catalyses is metal- or metallocenter-assisted generation of an electron-deficient organic "initiator radical". The initiator radical abstracts a hydrogen atom from the substrate, opening a new reaction channel for rearrangement to the product. Our aim is to elucidate the detailed molecular mechanisms of the radical pair separation and radical rearrangement steps. Radical pair separation and substrate radical rearrangement are tracked by using time-resolved (10-7 to 10-3 s) techniques of pulsed-electron paramagnetic resonance spectroscopy (FT-EPR, ESEEM). Synchronous time-evolution of the reactions is attained by triggering with a visible laser pulse. Transient non-Boltzmann population of the states of the spin-coupled systems, and resultant electron spin polarization, facilitates study at or near room temperature under conditions where the enzymes are operative. The systems examined include ethanolamine deaminase, a vitamin B12 coenzyme-dependent enzyme, ribonucleotide reductase and photosynthetic reaction centers. The electronic and nuclear structural and kinetic information obtained from the pulsed-EPR studies is used to address how the initiator radicals are stabilized against deleterious recombination with the metal, and to distinguish the participation of concerted versus sequential rearrangement pathways.

  20. Kinetics Studies of Radical-Radical Reactions: The NO2 + N2H3 System

    DTIC Science & Technology

    2013-10-01

    investigating the kinetics of this elementary reaction . 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT 18. NUMBER OF PAGES...Viewgraph 3. DATES COVERED (From - To) September 2013- October 2013 4. TITLE AND SUBTITLE Kinetics Studies of Radical-Radical Reactions (I): The NO2...characteristics in relevant operating environments. Here we report theoretical results obtained on the prototypical radical- radical reaction : NO2 + N2H3

  1. Peroxy radical measurements with NCAR's chemical amplifier

    NASA Technical Reports Server (NTRS)

    Cantrell, Christopher; Shetter, Richard; Calvert, Jack G.

    1994-01-01

    The present NCAR instrument for HO2/RO2 measurements has been described previously. It is based on the reactions involving HO2, RO2, and HO radicals with CO and NO. Since (HO2) + (RO2) + (HO) is much greater than (HO) for most atmospheres, it is useful as a peroxy radical detector. Operation of the instrument depends on the creation of a chemical chain reaction which is initiated as HO2 and RO2 radicals in ambient air encounter added NO gas; this forms an NO2 molecule and an HO or RO radical: HO2(RO2) + NO yields HO(RO) + NO2. RO radicals react relatively efficiently with O2 to form an HO2 radical, and subsequently an HO-radical, by reaction with NO. CO gas added to the reaction chamber during part of the operating cycle, recycles the HO to HO2; HO + CO (+O2) yields HO2 + CO2. The reaction sequence may form several hundred NO2 molecules per HO2 (RO2) originally present, before chain termination occurs. The added CO is replaced by N2 addition periodically so that the chain reaction is suppressed, and a 'blank' signal resulting from NO2, O3 and possibly other NO2-forming species (non-chain processes) in ambient air is recorded. The difference between the signal with and without CO is proportional to the peroxy radical concentration. The NO2 produced is monitored using a sensitive luminol chemiluminescence detector system. In the NCAR instrument the length of the amplification chain is determined using a stable source of HO2 radicals (H2O2 thermal decomposition); the ratio of the signal seen with CO present to that with N2 present gives the sensitivity of the instrument to HO2 (molecules of NO2 formed/peroxy radical). The instrument is automated to carry out in hourly repeated cycles: (1) chain length determination; (2) NO2 calibration; and (3) linearity check on the response of signals. One minute averages of signals are normally recorded. The sensitivity of the instrument to detect peroxy radicals is in the pptv range. The present instrument has operated

  2. Peroxy radical measurements with NCAR's chemical amplifier

    NASA Technical Reports Server (NTRS)

    Cantrell, Christopher; Shetter, Richard; Calvert, Jack G.

    1994-01-01

    The present NCAR instrument for HO2/RO2 measurements has been described previously. It is based on the reactions involving HO2, RO2, and HO radicals with CO and NO. Since (HO2) + (RO2) + (HO) is much greater than (HO) for most atmospheres, it is useful as a peroxy radical detector. Operation of the instrument depends on the creation of a chemical chain reaction which is initiated as HO2 and RO2 radicals in ambient air encounter added NO gas; this forms an NO2 molecule and an HO or RO radical: HO2(RO2) + NO yields HO(RO) + NO2. RO radicals react relatively efficiently with O2 to form an HO2 radical, and subsequently an HO-radical, by reaction with NO. CO gas added to the reaction chamber during part of the operating cycle, recycles the HO to HO2; HO + CO (+O2) yields HO2 + CO2. The reaction sequence may form several hundred NO2 molecules per HO2 (RO2) originally present, before chain termination occurs. The added CO is replaced by N2 addition periodically so that the chain reaction is suppressed, and a 'blank' signal resulting from NO2, O3 and possibly other NO2-forming species (non-chain processes) in ambient air is recorded. The difference between the signal with and without CO is proportional to the peroxy radical concentration. The NO2 produced is monitored using a sensitive luminol chemiluminescence detector system. In the NCAR instrument the length of the amplification chain is determined using a stable source of HO2 radicals (H2O2 thermal decomposition); the ratio of the signal seen with CO present to that with N2 present gives the sensitivity of the instrument to HO2 (molecules of NO2 formed/peroxy radical). The instrument is automated to carry out in hourly repeated cycles: (1) chain length determination; (2) NO2 calibration; and (3) linearity check on the response of signals. One minute averages of signals are normally recorded. The sensitivity of the instrument to detect peroxy radicals is in the pptv range. The present instrument has operated

  3. Fourier Transform Infrared Spectroscopy of Radicals

    NASA Astrophysics Data System (ADS)

    Rohrs, Henry William

    Radicals occur in many areas of chemistry as they are intermediates in reactions. They arise in combustion processes and several atmospheric phenomena and they have been located in interstellar space. In order to elucidate these areas of chemistry it is important to understand radicals. This is no easy task as these species are short -lived. This work focuses on determining the structure and bonding of these species using experimental measurements. Since it is specifically aimed at gas phase radicals, spectroscopy is the tool of choice for probing the radicals. This work developed a general technique for taking the rotation-vibration spectra of jet-cooled radicals. The work was based in the infrared since the desired structural information can be obtained in this region of the spectrum. The jet-cooling simplifies the enormous task of spectral assignment. A BOMEM FTIR was optically coupled to a supersonic expansion of radicals streaming from a homemade silicon carbide pyrolysis nozzle. This nozzle was heated to wall temperatures of 1500 K. A suitable organic precursor was entrained in an inert carrier gas, usually helium. Conditions were adjusted such that this precursor was nearly completely decomposed to produce high number densities of the radical of choice. The gas flows were adjusted such that the time for recombination and other radical destroying reactions were minimized. The first radical species observed was nitric oxide, NO, made from the pyrolysis of alkyl nitrites. Spectra with rotational temperatures from 20 K to 80 K were observed. This proved the viability of the method. It also demonstrated that fluid dynamics modeling and a separate photoionization mass spectrometry experiment would be invaluable aids in maximizing radical concentrations since the best chance of recording the spectra is when the most radicals are present.

  4. Photoionisation of the tropyl radical

    PubMed Central

    Fischer, Kathrin H; Bodi, Andras

    2013-01-01

    Summary We present a study on the photoionisation of the cycloheptatrienyl (tropyl) radical, C7H7, using tunable vacuum ultraviolet synchrotron radiation. Tropyl is generated by flash pyrolysis from bitropyl. Ions and electrons are detected in coincidence, permitting us to record mass-selected photoelectron spectra. The threshold photoelectron spectrum of tropyl, corresponding to the X + 1A1’ ← X 2E2” transition, reveals an ionisation energy of 6.23 ± 0.02 eV, in good agreement with Rydberg extrapolations, but slightly lower than the value derived from earlier photoelectron spectra. Several vibrations can be resolved and are reassigned to the C–C stretch mode ν16 + and to a combination of ν16 + with the ring breathing mode ν2 +. Above 10.55 eV dissociative photoionisation of tropyl is observed, leading to the formation of C5H5 + and C2H2. PMID:23616813

  5. Students' Ideas and Radical Constructivism

    NASA Astrophysics Data System (ADS)

    Sánchez Gómez, Pedro J.

    2016-08-01

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

  6. DNA Binding Hydroxyl Radical Probes.

    PubMed

    Tang, Vicky J; Konigsfeld, Katie M; Aguilera, Joe A; Milligan, Jamie R

    2012-01-01

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

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

    PubMed

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

    2012-06-21

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

  8. Free Radical Mechanisms in Autoxidation Processes.

    ERIC Educational Resources Information Center

    Simic, Michael G.

    1981-01-01

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

  9. Radical Constructivism: Between Realism and Solipsism.

    ERIC Educational Resources Information Center

    Martinez-Delgado, Alberto

    2002-01-01

    Criticizes radical constructivism of the Glasersfeld type, pointing out some contradictions between the declared radical principles and their theoretical and practical development. Suggests the possibility of an ideological substratum in the construction and hegemonic success of subjective constructivism, and briefly advances an alternative…

  10. THE RADICAL OF A JORDAN ALGEBRA

    PubMed Central

    McCrimmon, Kevin

    1969-01-01

    In this paper we define a Jacobson radical for Jordan algebras analogous to that for associative algebras and show that it enjoys many of the properties of the associative radical. We then relate the corresponding notion of “semisimplicity” to the previously defined notion of “nondegeneracy” (Jacobson, N., these Proceedings, 55, 243-251 (1966)). PMID:16591736

  11. Rearrangement of sulfonamidyl radicals with hydrogen migration

    SciTech Connect

    Troyanskii, E.I.; Lazareva, M.I.; Nikishin, G.I.

    1987-01-20

    One-step outlying oxidative chlorination of alkanesulfonamides by the action of the Na/sub 2/S/sub 2/O/sub 8/-CuCl/sub 2/ system via intermediate sulfonamidyl radicals gives 3- and 4-chloroalkanesulfonamides. Rearrangements of sulfonamidyl radicals with H atom migration from the sulfonyl segment predominates over rearrangement with H atom migration from the amide segment.

  12. Radical Puppets and the Language of Art

    ERIC Educational Resources Information Center

    Asher, Rikki

    2009-01-01

    Radical puppets are puppets with a social message. Radical puppets encourage creative ideas that lead toward understanding global and environmental aspects of society through the "art of the puppet," a phrase coined by American puppeteer Bill Baird (1965). There is a blending of performance and visual art in puppetry. Through radical…

  13. Ideals Adrift: An Educational Approach to Radicalization

    ERIC Educational Resources Information Center

    van San, Marion; Sieckelinck, Stijn; de Winter, Micha

    2013-01-01

    These days, the radicalization of young people is above all viewed as a security risk. Almost all research into this phenomenon has been carried out from a legal, criminological or socio-psychological perspective with a focus on detecting and containing the risks posed by radicalization. In the light of the political developments since September…

  14. Free Radical Mechanisms in Autoxidation Processes.

    ERIC Educational Resources Information Center

    Simic, Michael G.

    1981-01-01

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

  15. Victimology: A Consideration of the Radical Critique.

    ERIC Educational Resources Information Center

    Friedrichs, David O.

    1983-01-01

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

  16. Alex Bloom, Pioneer of Radical State Education

    ERIC Educational Resources Information Center

    Fielding, Michael

    2005-01-01

    Alex Bloom is one of the greatest figures of radical state education in England. His approach to "personalised learning" and the development of a negotiated curriculum was immeasurably more profound and more inspiring than anything to emerge thus far from the current DfES. His approach to student voice was much more radical than anything…

  17. Victimology: A Consideration of the Radical Critique.

    ERIC Educational Resources Information Center

    Friedrichs, David O.

    1983-01-01

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

  18. Ideals Adrift: An Educational Approach to Radicalization

    ERIC Educational Resources Information Center

    van San, Marion; Sieckelinck, Stijn; de Winter, Micha

    2013-01-01

    These days, the radicalization of young people is above all viewed as a security risk. Almost all research into this phenomenon has been carried out from a legal, criminological or socio-psychological perspective with a focus on detecting and containing the risks posed by radicalization. In the light of the political developments since September…

  19. Radical Behaviorism and Buddhism: Complementarities and Conflicts

    ERIC Educational Resources Information Center

    Diller, James W.; Lattal, Kennon A.

    2008-01-01

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

  20. Radical Behaviorism and Buddhism: Complementarities and Conflicts

    ERIC Educational Resources Information Center

    Diller, James W.; Lattal, Kennon A.

    2008-01-01

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

  1. Organic chemistry: A radical step forward

    NASA Astrophysics Data System (ADS)

    Zhang, Wenhao; Li, Ang

    2017-02-01

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

  2. Radical Voices; A Film Course Study Guide.

    ERIC Educational Resources Information Center

    Kernan, Margot

    The leftist radical ideas current in the 1960s and 1970s are expressed in the films discussed in this cinema study guide. The radical film takes extreme and avant-garde approaches to the somewhat publicly taboo topics of sex, social issues, and religion. Among the films discussed, I AM CURIOUS (YELLOW) and SOMETHING DIFFERENT show women in their…

  3. Catalytic Radical Domino Reactions in Organic Synthesis.

    PubMed

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

    2014-02-07

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

  4. Roaming radical pathways for the decomposition of alkanes.

    SciTech Connect

    Harding, L. B.; Klippenstein, S. J.

    2010-01-01

    CASPT2 calculations predict the existence of roaming radical pathways for the decomposition of propane, n-butane, isobutane and neopentane. The roaming radical paths lead to the formation of an alkane and an alkene instead of the expected radical products. The predicted barriers for the roaming radical paths lie {approx}1 kcal/mol below the corresponding radical asymptotes.

  5. Measurement of atmospheric radicals by chemical amplification

    NASA Astrophysics Data System (ADS)

    Arias, Maria Corina

    1998-11-01

    In this work, atmospheric radicals were measured using the chemical amplification technique. To calibrate the chemical amplifier, an UV water photolysis radical source was built and tested. This source proved to be reliable and portable, and capable of delivering radical concentrations within the range of values found in the troposphere. We tested the performance of our instrument at the Peroxy Radical InterComparison Exercise II (PRICE II). In this intercomparison seven chemical amplifiers participated measuring several HO2 and CH3O2 concentrations. Results from this campaign indicate that all of the chemical amplifiers are equally capable of measuring HO2 and CH3O2 radicals from two different radical sources (ICG-HO2 source and UEA- CH3O2 source). The average response towards the ICG and UEA sources were 70% and 45%, respectively. Losses in the delivery system are thought to be responsible for these low responses. Radical measurements were taken at 4 contrasting sites: Atlantic '96 (clean continental), SONTOS '92 and '93 (rural), Calabozo '93 (tropical clean continental), and Pacific '93 (predominantly urban), where maximum ROx concentrations ranged from 17 to 52 pptv. These values are consistent with those found in the literature for similar regions. The measured radical concentrations reflect the interaction between the main production and loss processes at the different sites, as for example ozone photolysis and HNO3 formation. At Calabozo, the combination of moderate O3, low NOx and small Zenith angles resulted in the highest ROx measured. At the Pacific '93 site, O3 is higher, but NOx concentrations are also very high, enhancing the radical loss processes, and explaining the moderate radical concentrations observed. At Atlantic '96 the very low NOx concentration might account for the radical concentrations observed, even in the presence of low O3 concentrations. At SONTOS, the highest ozone concentrations were observed, so we would expect the radical

  6. Polymers based on stable phenoxyl radicals for the use in organic radical batteries.

    PubMed

    Jähnert, Thomas; Häupler, Bernhard; Janoschka, Tobias; Hager, Martin D; Schubert, Ulrich S

    2014-05-01

    Polymers with pendant phenoxyl radicals are synthesized and the electrochemical properties are investigated in detail. The monomers are polymerized using ring-opening metathesis polymerization (ROMP) or free-radical polymerization methods. The monomers and polymers, respectively, are oxidized to the radical either before or after the polymerization. These phenoxyl radicals containing polymers reveal a reversible redox behavior at a potential of -0.6 V (vs Ag/AgCl). Such materials can be used as anode-active material in organic radical batteries (ORBs).

  7. Synchrotron threshold photoelectron photoion coincidence spectroscopy of radicals produced in a pyrolysis source: The methyl radical

    NASA Astrophysics Data System (ADS)

    Zhu, Yupeng; Wu, Xiangkun; Tang, Xiaofeng; Wen, Zuoying; Liu, Fuyi; Zhou, Xiaoguo; Zhang, Weijun

    2016-11-01

    We present here a flash pyrolysis source coupled with a threshold photoelectron photoion coincidence (TPEPICO) spectrometer and vacuum ultraviolet synchrotron radiation to investigate the spectroscopy and photochemistry of free radicals. The radicals are produced from pyrolysis in a heated silicon carbide tube, and the TPEPICO scheme provides a strategy to obtain pure spectra of the radicals without contamination from other byproducts. As a representative example, the methyl radical was studied, and its threshold photoelectron spectrum shows a series of umbrella vibrational transitions. The adiabatic ionization energy of the methyl radical was determined to be 9.84 ± 0.01 eV.

  8. Characteristics of Radical Reactions, Spin Rules, and a Suggestion for the Consistent Use of a Dot on Radical Species

    ERIC Educational Resources Information Center

    Wojnarovits, Laszlo

    2011-01-01

    In many chemical reactions, reactive radicals have been shown to be transient intermediates. The free radical character of a chemical species is often, but not always, indicated by adding a superscript dot to the chemical formula. A consistent use of this radical symbol on all species that have radical character is suggested. Free radicals have a…

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

    SciTech Connect

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

    1988-03-16

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

  10. Characteristics of Radical Reactions, Spin Rules, and a Suggestion for the Consistent Use of a Dot on Radical Species

    ERIC Educational Resources Information Center

    Wojnarovits, Laszlo

    2011-01-01

    In many chemical reactions, reactive radicals have been shown to be transient intermediates. The free radical character of a chemical species is often, but not always, indicated by adding a superscript dot to the chemical formula. A consistent use of this radical symbol on all species that have radical character is suggested. Free radicals have a…

  11. Structural effects on the reactivity 1,4-dihydropyridines with alkylperoxyl radicals and ABTS radical cation.

    PubMed

    Yáñez, C; López-Alarcón, C; Camargo, C; Valenzuela, V; Squella, J A; Núñez-Vergara, L J

    2004-05-01

    A series of eight commercial C-4 substituted 1,4-dihydropyridines and other synthesized related compounds were tested for direct potential scavenger effect towards alkylperoxyl radicals and ABTS radical cation in aqueous Britton-Robinson buffer pH7.4. A direct quenching radical species was established. The tested 1,4-dihydropyridines were 8.3-fold more reactive towards alkylperoxyl radicals than ABTS cation radical, expressed by their corresponding kinetic rate constants. Furthermore, NPD a photolyte of nifedipine and the C-4 unsubstituted 1,4-DHP were the most reactive derivatives towards alkylperoxyl radicals. The pyridine derivative was confirmed by GC/MS technique as the final product of reaction. In consequence, the reduction of alkylperoxyl and ABTS radicals by 1,4-dihydropyridines involved an electron transfer process. Also, the participation of the hydrogen of the 1-position appears as relevant on the reactivity. Results of reactivity were compared with Trolox.

  12. Halogenated silanes, radicals, and cations

    NASA Astrophysics Data System (ADS)

    Wang, Liming; He, Yi-Liang

    2008-09-01

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

  13. Involvement of free radicals in breast cancer.

    PubMed

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

    2013-08-27

    Researchers have recently shown an increased interest in free radicals and their role in the tumor microenvironment. Free radicals are molecules with high instability and reactivity due to the presence of an odd number of electrons in the outermost orbit of their atoms. Free radicals include reactive oxygen and nitrogen species, which are key players in the initiation and progression of tumor cells and enhance their metastatic potential. In fact, they are now considered a hallmark of cancer. However, both reactive species may contribute to improve the outcomes of radiotherapy in cancer patients. Besides, high levels of reactive oxygen species may be indicators of genotoxic damage in non-irradiated normal tissues. The purpose of this article is to review recent research on free radicals and carcinogenesis in order to understand the pathways that contribute to tumor malignancy. This review outlines the involvement of free radicals in relevant cellular events, including their effects on genetic instability through (growth factors and tumor suppressor genes, their enhancement of mitogenic signals, and their participation in cell remodeling, proliferation, senescence, apoptosis, and autophagy processes; the possible relationship between free radicals and inflammation is also explored. This knowledge is crucial for evaluating the relevance of free radicals as therapeutic targets in cancer.

  14. Magnetic fields, radicals and cellular activity.

    PubMed

    Montoya, Ryan D

    2017-01-01

    Some effects of low-intensity magnetic fields on the concentration of radicals and their influence on cellular functions are reviewed. These fields have been implicated as a potential modulator of radical recombination rates. Experimental evidence has revealed a tight coupling between cellular function and radical pair chemistry from signaling pathways to damaging oxidative processes. The effects of externally applied magnetic fields on biological systems have been extensively studied, and the observed effects lack sufficient mechanistic understanding. Radical pair chemistry offers a reasonable explanation for some of the molecular effects of low-intensity magnetic fields, and changes in radical concentrations have been observed to modulate specific cellular functions. Applied external magnetic fields have been shown to induce observable cellular changes such as both inhibiting and accelerating cell growth. These and other mechanisms, such as cell membrane potential modulation, are of great interest in cancer research due to the variations between healthy and deleterious cells. Radical concentrations demonstrate similar variations and are indicative of a possible causal relationship. Radicals, therefore, present a possible mechanism for the modulation of cellular functions such as growth or regression by means of applied external magnetic fields.

  15. Kinetics of Propargyl Radical Dissociation.

    PubMed

    Klippenstein, Stephen J; Miller, James A; Jasper, Ahren W

    2015-07-16

    Due to the prominent role of the propargyl radical for hydrocarbon growth within combustion environments, it is important to understand the kinetics of its formation and loss. The ab initio transition state theory-based master equation method is used to obtain theoretical kinetic predictions for the temperature and pressure dependence of the thermal decomposition of propargyl, which may be its primary loss channel under some conditions. The potential energy surface for the decomposition of propargyl is first mapped at a high level of theory with a combination of coupled cluster and multireference perturbation calculations. Variational transition state theory is then used to predict the microcanonical rate coefficients, which are subsequently implemented within the multiple-well multiple-channel master equation. A variety of energy transfer parameters are considered, and the sensitivity of the thermal rate predictions to these parameters is explored. The predictions for the thermal decomposition rate coefficient are found to be in good agreement with the limited experimental data. Modified Arrhenius representations of the rate constants are reported for utility in combustion modeling.

  16. Orgasmic Dysfunction after Radical Prostatectomy

    PubMed Central

    Ventimiglia, Eugenio; Cazzaniga, Walter; Montorsi, Francesco; Salonia, Andrea

    2017-01-01

    In addition to urinary incontinence and erectile dysfunction, several other impairments of sexual function potentially occurring after radical prostatectomy (RP) have been described; as a whole, these less frequently assessed disorders are referred to as neglected side effects. In particular, orgasmic dysfunctions (ODs) have been reported in a non-negligible number of cases, with detrimental impacts on patients' overall sexual life. This review aimed to comprehensively discuss the prevalence and physiopathology of post-RP ODs, as well as potential treatment options. Orgasm-associated incontinence (climacturia) has been reported to occur in between 20% and 93% of patients after RP. Similarly, up to 19% of patients complain of postoperative orgasm-associated pain, mainly referred pain at the level of the penis. Moreover, impairment in the sensation of orgasm or even complete anorgasmia has been reported in 33% to 77% of patients after surgery. Clinical and surgical factors including age, the use of a nerve-sparing technique, and robotic surgery have been variably associated with the risk of ODs after RP, although robust and reliable data allowing for a proper estimation of the risk of postoperative orgasmic function impairment are still lacking. Likewise, little evidence regarding the management of postoperative ODs is currently available. In general, physicians should be aware of the prevalence of ODs after RP, in order to properly counsel all patients both preoperatively and immediately post-RP about the potential occurrence of bothersome and distressful changes in their overall sexual function. PMID:28459142

  17. Consciousness: the radical plasticity thesis.

    PubMed

    Cleeremans, Axel

    2008-01-01

    In this chapter, I sketch a conceptual framework which takes it as a starting point that conscious and unconscious cognition are rooted in the same set of interacting learning mechanisms and representational systems. On this view, the extent to which a representation is conscious depends in a graded manner on properties such as its stability in time or its strength. Crucially, these properties are accrued as a result of learning, which is in turn viewed as a mandatory process that always accompanies information processing. From this perspective, consciousness is best characterized as involving (1) a graded continuum defined over "quality of representation", such that availability to consciousness and to cognitive control correlates with quality, and (2) the implication of systems of metarepresentations. A first implication of these ideas is that the main function of consciousness is to make flexible, adaptive control over behavior possible. A second, much more speculative implication, is that we learn to be conscious. This I call the "radical plasticity thesis"--the hypothesis that consciousness emerges in systems capable not only of learning about their environment, but also about their own internal representations of it.

  18. Erectile preservation following radical prostatectomy

    PubMed Central

    Segal, Robert; Burnett, Arthur L.

    2011-01-01

    Prostate cancer is the most common cancer among men, representing approximately 25% of all new cancer diagnoses in the USA. For clinically localized prostate cancer, the gold standard for therapy remains radical prostatectomy. One of the main adverse effects of this procedure is erectile dysfunction, which can have a significant impact on the patient’s quality of life. There are several mechanisms of erectile dysfunction postprostatectomy, including arteriogenic, venogenic and neurogenic types, as well as the potentially heightened risk of postprostatectomy patients to develop Peyronie’s disease. The purpose of this review is to explain the various treatment options available, including phosphodiesterase type 5 inhibitors, intracavernosal injections, intraurethral alprostadil suppositories, vacuum erection devices, and penile prostheses. The role of these therapies in an erectile-dysfunction-treatment function, as well as in penile rehabilitation, will be discussed. Finally, a review of research on novel therapies will also be presented. A comprehensive literature review was performed using the PubMed database. Articles were chosen based on topical relevance and assessed for methodology and major findings. There are data to support the use of each of the therapeutic options in both treatment and rehabilitative roles. More study is needed, however, specifically in regard to penile rehabilitation, to confirm its benefits, as well as to determine optimal rehabilitation protocols. PMID:21789097

  19. Erectile preservation following radical prostatectomy.

    PubMed

    Segal, Robert; Burnett, Arthur L

    2011-02-01

    Prostate cancer is the most common cancer among men, representing approximately 25% of all new cancer diagnoses in the USA. For clinically localized prostate cancer, the gold standard for therapy remains radical prostatectomy. One of the main adverse effects of this procedure is erectile dysfunction, which can have a significant impact on the patient's quality of life. There are several mechanisms of erectile dysfunction postprostatectomy, including arteriogenic, venogenic and neurogenic types, as well as the potentially heightened risk of postprostatectomy patients to develop Peyronie's disease. The purpose of this review is to explain the various treatment options available, including phosphodiesterase type 5 inhibitors, intracavernosal injections, intraurethral alprostadil suppositories, vacuum erection devices, and penile prostheses. The role of these therapies in an erectile-dysfunction-treatment function, as well as in penile rehabilitation, will be discussed. Finally, a review of research on novel therapies will also be presented. A comprehensive literature review was performed using the PubMed database. Articles were chosen based on topical relevance and assessed for methodology and major findings. There are data to support the use of each of the therapeutic options in both treatment and rehabilitative roles. More study is needed, however, specifically in regard to penile rehabilitation, to confirm its benefits, as well as to determine optimal rehabilitation protocols.

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

    PubMed

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

    2008-02-01

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

  1. Expanding Radical SAM Chemistry by Using Radical Addition Reactions and SAM Analogues.

    PubMed

    Ji, Xinjian; Li, Yongzhen; Xie, Liqi; Lu, Haojie; Ding, Wei; Zhang, Qi

    2016-09-19

    Radical S-adenosyl-l-methionine (SAM) enzymes utilize a [4Fe-4S] cluster to bind SAM and reductively cleave its carbon-sulfur bond to produce a highly reactive 5'-deoxyadenosyl (dAdo) radical. In almost all cases, the dAdo radical abstracts a hydrogen atom from the substrates or from enzymes, thereby initiating a highly diverse array of reactions. Herein, we report a change of the dAdo radical-based chemistry from hydrogen abstraction to radical addition in the reaction of the radical SAM enzyme NosL. This change was achieved by using a substrate analogue containing an olefin moiety. We also showed that two SAM analogues containing different nucleoside functionalities initiate the radical-based reactions with high efficiencies. The radical adduct with the olefin produced in the reaction was found to undergo two divergent reactions, and the mechanistic insights into this process were investigated in detail. Our study demonstrates a promising strategy in expanding radical SAM chemistry, providing an effective way to access nucleoside-containing compounds by using radical SAM-dependent reactions.

  2. Competition of charge- versus radical-directed fragmentation of gas-phase protonated cysteine sulfinyl radicals.

    PubMed

    Love, Chasity B; Tan, Lei; Francisco, Joseph S; Xia, Yu

    2013-04-24

    The fragmentation behavior of various cysteine sulfinyl ions (intact, N-acetylated, and O-methylated), new members of the gas-phase amino acid radical ion family, was investigated by low-energy collision-induced dissociation (CID). The dominant fragmentation channel for the protonated cysteine sulfinyl radicals ((SO•)Cys) was the radical-directed Cα-Cβ homolytic cleavage, resulting in the formation of glycyl radical ions and loss of CH2SO. This channel, however, was not observed for protonated N-acetylated cysteine sulfinyl radicals (Ac-(SO•)Cys); instead, charge-directed H2O loss followed immediately by SH loss prevailed. Counterintuitively, the H2O loss did not derive from the carboxyl group but involved the sulfinyl oxygen, a proton, and a Cβ hydrogen atom. Theoretical calculations suggested that N-acetylation significantly increases the barrier (~14 kcal mol(-1)) for the radical-directed fragmentation channel because of its reduced capability to stabilize the thus-formed glycyl radical ions via the captodative effect. N-Acetylation also assists in moving the proton to the sulfinyl site, which reduces the barrier for H2O loss. Our studies demonstrate that for cysteine sulfinyl radical ions, the stability of the product ions (glycyl radical ions) and the location of the charge (proton) can significantly modulate the competition between radical- and charge-directed fragmentation.

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

    PubMed

    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.

  4. Iodine(III) Reagents in Radical Chemistry

    PubMed Central

    2017-01-01

    Conspectus The chemistry of hypervalent iodine(III) compounds has gained great interest over the past 30 years. Hypervalent iodine(III) compounds show valuable ionic reactivity due to their high electrophilicity but also express radical reactivity as single electron oxidants for carbon and heteroatom radical generation. Looking at ionic chemistry, these iodine(III) reagents can act as electrophiles to efficiently construct C–CF3, X–CF3 (X = heteroatom), C–Rf (Rf = perfluoroalkyl), X–Rf, C–N3, C–CN, S–CN, and C–X bonds. In some cases, a Lewis or a Bronsted acid is necessary to increase their electrophilicity. In these transformations, the iodine(III) compounds react as formal “CF3+”, “Rf+”, “N3+”, “Ar+”, “CN+”, and “X+” equivalents. On the other hand, one electron reduction of the I(III) reagents opens the door to the radical world, which is the topic of this Account that focuses on radical reactivity of hypervalent iodine(III) compounds such as the Togni reagent, Zhdankin reagent, diaryliodonium salts, aryliodonium ylides, aryl(cyano)iodonium triflates, and aryl(perfluoroalkyl)iodonium triflates. Radical generation starting with I(III) reagents can also occur via thermal or light mediated homolysis of the weak hypervalent bond in such reagents. This reactivity can be used for alkane C–H functionalization. We will address important pioneering work in the area but will mainly focus on studies that have been conducted by our group over the last 5 years. We entered the field by investigating transition metal free single electron reduction of Togni type reagents using the readily available sodium 2,2,6,6-tetramethylpiperidine-1-oxyl salt (TEMPONa) as an organic one electron reductant for clean generation of the trifluoromethyl radical and perfluoroalkyl radicals. That valuable approach was later successfully also applied to the generation of azidyl and aryl radicals starting with the corresponding benziodoxole (Zhdankin reagent

  5. Produccion Gaseosa del Cometa Halley: Erupciones Y Fotodisociacion del Radical OH

    NASA Astrophysics Data System (ADS)

    Silva, A. M.; Mirabel, I. F.

    1990-11-01

    RESUMEN:En este trabajo informamos la detecci6n de 20 erupciones en la li'nea de =18cm (1667MHz) del radical OH en el Cometa Halley.Las observaciones incluyen todos los monitoreos existentes y se extienden desde 120 dias antes del perihelio hasta 90 dias despues.Se detectan bruscos crecimientos en el flujo medido,hasta un factor 1O,seguidos por decaimientos lentos asociados con la fotodisociaci6n del OH. Se obtuvieron valores para el tiempo de vida fotoquimico del OH y del H2O basandose en el modelo desarrollado previamente por Silva(1988). Esos tiempos de vida estan de acuerdo con predicciones teoricas y con las observaciones en el Ultravioleta, y los resultados, los que son fuertemente dependientes de la velocidad heliocentrica del Coineta (variando hasta un factor 6), han sido calculados para varios rangos de velocidad entre +28 y -28 km/seg. Key wo'L :

  6. Day case laparoscopic radical prostatectomy.

    PubMed

    Abboudi, Hamid; Doyle, Patrick; Winkler, Mathias

    2017-10-03

    To evaluate the feasibility of performing laparoscopic radical prostatectomy (LRP) as a day case procedure while maintaining patient satisfaction and safety. Herein we report our experience, selection criteria, and discharge criteria for day case LRP. We performed a prospective study with 32 patients undergoing extraperitoneal LRP. These patients were counselled before the procedure that they would go home the same evening of the procedure. Pain scores and quality of life data were recorded day 1 postoperatively via a telephone consultation. The patients underwent routine blood tests on day 2 and an outpatient review on day 7 and regularly thereafter via an assigned key worker. Socio-demographic data, comorbidities, and outcomes were collected for analysis. All patients were successfully discharged the same day of surgery. Mean patient age was 62 years with a mean body mass index of 25. Mean operative time was 147 minutes, and estimated blood loss was 101 ml. Three patients were treated for post operative urinary tract infections; two patients developed infected lymphoceles which required percutaneous drainage and one patient required re-catheterisation due to a burst catheter balloon. Of these six complications four patients required re-admission. Post-operative pain, nausea and vomiting were low whilst patient satisfaction scores were unanimously high in all patients surveyed. The early experience with extraperitoneal LRP as a same day surgery is promising although patients who are at high risk of lymphocele should be excluded. Preoperative patient counselling and selection is paramount. Patient satisfaction is not adversely affected by the shortened stay. Surgeon experience, a well-motivated patient, meticulous attention to detail through an integrated pathway, a multidisciplinary team and adequate postoperative assessment are essential.

  7. Magnetic Trapping of Cold Methyl Radicals

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

    We have demonstrated that a supersonic beam of methyl radicals (CH3 ) in the ground rotational state of both para and ortho species has been slowed down to standstill with a magnetic molecular decelerator, and successfully captured spatially in an anti-Helmholtz magnetic trap for >1 s . The trapped CH3 radicals have a mean translational temperature of about 200 mK with an estimated density of >5.0 ×1 07 cm-3 . The methyl radical is an ideal system for the study of cold molecules not only because of its high reactivities at low temperatures, but also because further cooling below 1 mK is plausible via sympathetic cooling with ultracold atoms. The demonstrated trapping capability of methyl radicals opens up various possibilities for realizing ultracold ensembles of molecules towards Bose-Einstein condensation of polyatomic molecules and investigations of reactions governed by quantum statistics.

  8. A Mechanochemical Switch to Control Radical Intermediates

    PubMed Central

    2015-01-01

    B12-dependent enzymes employ radical species with exceptional prowess to catalyze some of the most chemically challenging, thermodynamically unfavorable reactions. However, dealing with highly reactive intermediates is an extremely demanding task, requiring sophisticated control strategies to prevent unwanted side reactions. Using hybrid quantum mechanical/molecular mechanical simulations, we follow the full catalytic cycle of an AdoB12-dependent enzyme and present the details of a mechanism that utilizes a highly effective mechanochemical switch. When the switch is “off”, the 5′-deoxyadenosyl radical moiety is stabilized by releasing the internal strain of an enzyme-imposed conformation. Turning the switch “on,” the enzyme environment becomes the driving force to impose a distinct conformation of the 5′-deoxyadenosyl radical to avoid deleterious radical transfer. This mechanochemical switch illustrates the elaborate way in which enzymes attain selectivity of extremely chemically challenging reactions. PMID:24846280

  9. A mechanochemical switch to control radical intermediates.

    PubMed

    Brunk, Elizabeth; Kellett, Whitney F; Richards, Nigel G J; Rothlisberger, Ursula

    2014-06-17

    B₁₂-dependent enzymes employ radical species with exceptional prowess to catalyze some of the most chemically challenging, thermodynamically unfavorable reactions. However, dealing with highly reactive intermediates is an extremely demanding task, requiring sophisticated control strategies to prevent unwanted side reactions. Using hybrid quantum mechanical/molecular mechanical simulations, we follow the full catalytic cycle of an AdoB₁₂-dependent enzyme and present the details of a mechanism that utilizes a highly effective mechanochemical switch. When the switch is "off", the 5'-deoxyadenosyl radical moiety is stabilized by releasing the internal strain of an enzyme-imposed conformation. Turning the switch "on," the enzyme environment becomes the driving force to impose a distinct conformation of the 5'-deoxyadenosyl radical to avoid deleterious radical transfer. This mechanochemical switch illustrates the elaborate way in which enzymes attain selectivity of extremely chemically challenging reactions.

  10. Fast beam studies of free radical photodissociation

    SciTech Connect

    Neumark, D.M.

    1993-12-01

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

  11. RADICALLY CONTESTED ASSERTIONS IN ECOSYSTEM MANAGEMENT

    EPA Science Inventory

    Ecosystem management is a magnet for controversy, in part because some of its formulations rest on questionable assertions that are radically contested. These assertions are important to understanding much of the conflict surrounding ecosystem management and, therrefore, deserve...

  12. RADICALLY CONTESTED ASSERTIONS IN ECOSYSTEM MANAGEMENT

    EPA Science Inventory

    Ecosystem management is a magnet for controversy, in part because some of its formulations rest on questionable assertions that are radically contested. These assertions are important to understanding much of the conflict surrounding ecosystem management and, therrefore, deserve...

  13. Neutral radical deposition from silane discharges

    NASA Astrophysics Data System (ADS)

    Gallagher, Alan

    1988-04-01

    The fractional contributions of the various SiHn radicals (n=0-3) to deposition are calculated for low-power, pure-silane rf and dc discharges. This is done using a radical diffusion plus reaction equation, combined with current knowledge of SiH4 dissociation fractionation, of SiHn+SiH4 reactions, and of the distributed source of radicals. The conclusion reached is that more than 98% of neutral radical deposition is by SiH3 for typical deposition pressures (>100 mT at 240 °C). The effect of SiH3+SiH3 reactions at higher power is also evaluated using an estimated reaction rate coefficient (k3). The resulting loss in deposition rate is given as a function of film growth rate and of k3.

  14. Vertical Electron Transitions in Rydberg Radicals

    NASA Astrophysics Data System (ADS)

    Martin, I.; Lavín, C.; Pérez-Delgado, Y.; Karwowski, J.; Diercksen, G. H. F.

    Oscillator strengths and Einstein emission coefficients for several Rydberg radicals are reported. The Quantum Defect Orbital (QDO) method has been employed, and comparison is made with the results of more complex theorical procedures.

  15. Psychopathology according to behaviorism: a radical restatement.

    PubMed

    Pérez-Alvarez, Marino

    2004-11-01

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

  16. Radical formation in cytochrome c oxidase☆

    PubMed Central

    Yu, Michelle A.; Egawa, Tsuyoshi; Shinzawa-Itoh, Kyoko; Yoshikawa, Shinya; Yeh, Syun-Ru; Rousseau, Denis L.; Gerfen, Gary J.

    2015-01-01

    The formation of radicals in bovine cytochrome c oxidase (bCcO), during the O2 redox chemistry and proton translocation, is an unresolved controversial issue. To determine if radicals are formed in the catalytic reaction of bCcO under single turnover conditions, the reaction of O2 with the enzyme, reduced by either ascorbate or dithionite, was initiated in a custom-built rapid freeze quenching (RFQ) device and the products were trapped at 77 K at reaction times ranging from 50 µs to 6 ms. Additional samples were hand mixed to attain multiple turnover conditions and quenched with a reaction time of minutes. X-band (9 GHz) continuous wave electron paramagnetic resonance (CW-EPR) spectra of the reaction products revealed the formation of a narrow radical with both reductants. D-band (130 GHz) pulsed EPR spectra allowed for the determination of the g-tensor principal values and revealed that when ascorbate was used as the reductant the dominant radical species was localized on the ascorbyl moiety, and when dithionite was used as the reductant the radical was the SO2•− ion. When the contributions from the reductants are subtracted from the spectra, no evidence for a protein-based radical could be found in the reaction of O2 with reduced bCcO. As a surrogate for radicals formed on reaction intermediates, the reaction of hydrogen peroxide (H2O2) with oxidized bCcO was studied at pH 6 and pH 8 by trapping the products at 50 µs with the RFQ device to determine the initial reaction events. For comparison, radicals formed after several minutes of incubation were also examined, and X-band and D-band analysis led to the identification of radicals on Tyr-244 and Tyr-129. In the RFQ measurements, a peroxyl (R – O – O•) species was formed, presumably by the reaction between O2 and an amino acid-based radical. It is postulated that Tyr-129 may play a central role as a proton loading site during proton translocation by ejecting a proton upon formation of the radical

  17. Hydroxyl radical generation by red tide algae.

    PubMed

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

    1992-04-01

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

  18. Mechanism of disproportionation of ascorbate radicals

    SciTech Connect

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

    1981-06-17

    Existing data on the kinetics of ascorbate radical decay, together with some new data on the effects of temperature, ionic strength, and presence of phosphate buffers, suggest a mechanism in which the ascorbate radical ion is in equilibrium with a dimer. This dimer reacts with hydrogen ion, or with other proton donors present including water and buffers (at rates depending upon their acid strengths), to form the disproportionation products ascorbate ion and dehydroascorbate acid.

  19. The stabilization energies of polyenyl radicals

    NASA Astrophysics Data System (ADS)

    Luo, Yu-Ran; Holmes, John L.

    1994-10-01

    The resonance stabilization energies, Es, of polyenyl radicals can be estimated by the equation Es( N)=-13.2+[3.95-15.8(2) -2/ n] kcal mol -1, where N is the number of C, C-π bonds in the polyenyl radicals. This correlation has been extended for predicting the weakest HC, CC and COH bond dissociation energies in vitamin A and similar compounds.

  20. Radicals: Reactive Intermediates with Translational Potential

    PubMed Central

    2016-01-01

    This Perspective illustrates the defining characteristics of free radical chemistry, beginning with its rich and storied history. Studies from our laboratory are discussed along with recent developments emanating from others in this burgeoning area. The practicality and chemoselectivity of radical reactions enable rapid access to molecules of relevance to drug discovery, agrochemistry, material science, and other disciplines. Thus, these reactive intermediates possess inherent translational potential, as they can be widely used to expedite scientific endeavors for the betterment of humankind. PMID:27631602

  1. Radical behaviorism and buddhism: complementarities and conflicts.

    PubMed

    Diller, James W; Lattal, Kennon A

    2008-01-01

    Comparisons have been made between Buddhism and the philosophy of science in general, but there have been only a few attempts to draw comparisons directly with the philosophy of radical behaviorism. The present review therefore considers heretofore unconsidered points of comparison between Buddhism and radical behaviorism in terms of their respective goals, conceptualization of human beings, and the outcomes of following either philosophy. From these comparisons it is concluded that the commonalities discerned between these two philosophies may enhance both philosophical systems.

  2. Laser Studies of Gas Phase Radical Reactions.

    DTIC Science & Technology

    1989-01-01

    Acremonium chrysogenum , was prepared according to the published procedure [6]. This fungal enzyme had a specific activity of 0.023 IUmg1, and was estimated to...Dist-lbitionj Avdielbiity Codes jAvail atidjor Dist 6a A-I . p -1- Laser Studies of Gas Phase Radical Reactions G. Hancock Physical Chemistry...some additional experiments concerning the formation of carbene radicals in liquid phase enzyme cleavage studies are described. Keywords Laser

  3. Radical-water complexes in Earth's atmosphere.

    PubMed

    Aloisio, S; Francisco, J S

    2000-12-01

    In the atmosphere, many chemical processes are controlled by open-shell radical species. While these species are present in relatively small number densities, they initiate many of the cycles that control the chemistry of the atmosphere. The purpose of this Account is to examine recent studies of radical-water complexes that are composed of atmospherically important species. We hope this Account will provide a report on the status of this topical field, while encouraging new research directions.

  4. Hydroxyl radical scavengers inhibit lymphocyte mitogenesis.

    PubMed Central

    Novogrodsky, A; Ravid, A; Rubin, A L; Stenzel, K H

    1982-01-01

    Agents that are known to be scavengers of hydroxyl radicals inhibit lymphocyte mitogenesis induced by phorbol myristate acetate (PMA) to a greater extent than they inhibit mitogenesis induced by concanavalin A or phytohemagglutinin. These agents include dimethyl sulfoxide, benzoate, thiourea, dimethylurea, tetramethylurea, L-tryptophan, mannitol, and several other alcohols. Their inhibitory effect is not associated with cytotoxicity. The hydroxyl radical scavengers do not inhibit PMA-dependent amino acid transport in T cells or PMA-induced superoxide production by monocytes. Thus, they do not inhibit the primary interaction of PMA with responding cells. Treatment of peripheral blood mononuclear cells with PMA increased cellular guanylate cyclase in most experiments, and dimethyl sulfoxide tended to inhibit this increase. In addition to inhibition of PMA-induced mitogenesis, hydroxyl radical scavengers markedly inhibited the activity of lymphocyte activating factor (interleukin 1). The differential inhibition of lymphocyte mitogenesis induced by different mitogens appears to be related to the differential macrophage requirements of the mitogens. The data suggest that hydroxyl radicals may be involved in mediating the triggering signal for lymphocyte activation. Some of the hydroxyl radical scavengers are inducers of cellular differentiation,. nd it is possible that their differentiating activity is related to their ability to scavenge free radicals. PMID:6122209

  5. Inactivation of Bacillus atrophaeus by OH radicals

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  6. Hydroxyl radical oxidation of feruloylated arabinoxylan.

    PubMed

    Bagdi, Attila; Tömösközi, Sándor; Nyström, Laura

    2016-11-05

    Feruloylated arabinoxylan (AX) has a unique capacity to form covalent gels in the presence of certain oxidizing agents. The present study demonstrates that hydroxyl radical oxidation does not provoke ferulic acid dimerization and thus oxidative gelation. We studied the hydroxyl radical mediated oxidation of an alkali-extracted AX preparation (purity: 92g/100g dry matter) that showed gel-forming capability upon peroxidase/hydrogen peroxide treatment. Hydroxyl radicals were produced with ascorbate-driven Fenton reaction and the radical formation was monitored with electron paramagnetic resonance, using a POBN/EtOH spin trapping system. Oxidation was carried out at different catalytic concentrations of iron (50 and 100μM) and at different temperatures (20°C, 50°C, and 80°C). It was demonstrated that hydroxyl radical oxidation does not provoke gel formation, but viscosity decrease in AX solution, which suggests polymer degradation. Furthermore, it was demonstrated that hydroxyl radical formation in AX solution can be initiated merely by increasing temperature. Copyright © 2016. Published by Elsevier Ltd.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

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

    PubMed Central

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

    2016-01-01

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

  9. Ferromagnetic behavior of formyl-group-carrying stable thioaminyl radicals.

    PubMed

    Miura, Yozo; Nakamura, Shogo; Teki, Yoshio

    2003-10-17

    Four formyl-group-carrying thioaminyl radicals were generated, and one radical could be isolated as radical crystals. Magnetic susceptibility measurements of the isolated radical showed a ferromagnetic regular linear-chain interaction of 2J/k(B) = 3.2 K, which was explained in terms of the X-ray crystallographic results.

  10. Practicing Radical Pedagogy: Balancing Ideals with Institutional Constraints.

    ERIC Educational Resources Information Center

    Sweet, Stephen

    1998-01-01

    Describes radical pedagogy and observes that an overview of "Teaching Sociology" suggests that few teachers fully practice it. Argues that while professors are free to teach radical theory, radical pedagogy is hindered by institutional constraints. Concludes that radical teachers may benefit from remaining more within the confines imposed by their…

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

    PubMed Central

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

    2015-01-01

    Highly selective radical/radical cross-coupling is paid more attention in bond formations. However, due to their intrinsic active properties, radical species are apt to achieve homo-coupling instead of cross-coupling, which makes the selective cross-coupling as a great challenge and almost untouched. Herein a notable strategy to accomplish direct radical/radical oxidative cross-coupling has been demonstrated, that is metal tuning a transient radical to a persistent radical intermediate followed by coupling with another transient radical. Here, a transient nitrogen-centered radical is tuned to a persistent radical complex by copper catalyst, followed by coupling with a transient allylic carbon-centered radical. Firstly, nitrogen-centered radical generated from N-methoxybenzamide stabilized by copper catalyst was successfully observed by EPR. Then DFT calculations revealed that a triplet diradical Cu(II) complex formed from the chelation N-methoxybenzamide nitrogen-centered radical to Cu(II) is a persistent radical species. Moreover, conceivable nitrogen-centered radical Cu(II) complex was observed by high-resolution electrospray ionization mass spectrometry (ESI-MS). Ultimately, various allylic amides derivatives were obtained in good yields by adopting this strategy, which might inspire a novel and promising landscape in radical chemistry. PMID:26525888

  12. Formation and reactivity of phenylperoxyl radicals in aqueous solutions

    SciTech Connect

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

    1994-08-18

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

  13. Evidence for hydroxyl radical generation during lipid (linoleate) peroxidation.

    PubMed

    Frenette, Mathieu; Scaiano, Juan C

    2008-07-30

    The autoxidation of methyl linoleate in benzene at 37 degrees C by peroxyl radicals was found to generate hydroxyl radicals (.OH) from a secondary oxidation mechanism. The yield of hydroxyl radicals (approximately 2%) was determined by trapping these reactive radicals with benzene to give phenol. We propose that alphaC-H hydrogen abstraction from lipid hydroperoxides, the main autoxidation products, is the source of hydroxyl radicals.

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

    PubMed

    Khachatryan, Lavrent; Dellinger, Barry

    2011-11-01

    A chemical spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), in conjunction with electron paramagnetic resonance (EPR) spectroscopy was employed to measure the production of hydroxyl radical (·OH) in aqueous suspensions of 5% Cu(II)O/silica (3.9% Cu) particles containing environmentally persistent free radicals (EPFRs) of 2-monochlorophenol (2-MCP). The results indicate: (1) a significant differences in accumulated DMPO-OH adducts between EPFR containing particles and non-EPFR control samples, (2) a strong correlation between the concentration of DMPO-OH adducts and EPFRs per gram of particles, and (3) a slow, constant growth of DMPO-OH concentration over a period of days in solution containing 50 μg/mL EPFRs particles + DMPO (150 mM) + reagent balanced by 200 μL phosphate buffered (pH = 7.4) saline. However, failure to form secondary radicals using standard scavengers, such as ethanol, dimethylsulfoxide, sodium formate, and sodium azide, suggests free hydroxyl radicals may not have been generated in solution. This suggests surface-bound, rather than free, hydroxyl radicals were generated by a surface catalyzed-redox cycle involving both the EPFRs and Cu(II)O. Toxicological studies clearly indicate these bound free radicals promote various types of cardiovascular and pulmonary disease normally attributed to unbound free radicals; however, the exact chemical mechanism deserves further study in light of the implication of formation of bound, rather than free, hydroxyl radicals.

  15. The inclusive jet cross section at {radical}s = 630 GeV at D0

    SciTech Connect

    Krane, J.; D0 Collaboration

    1996-09-01

    The authors present a preliminary measurement of the cross section for central inclusive jet production at {radical}s = 630 GeV using {approximately} 400 nb{sup {minus}1} of data collected during the December 1995 Fermilab collider run at D0. These results are compared to NLO QCD predictions.

  16. Salud mental en desastres naturales: estrategias interventivas con adultos mayores en sectores rurales de Chile.

    PubMed

    Osorio-Parraguez, Paulina; Espinoza, Adriana

    2016-06-01

    En el presente artículo se da a conocer una estrategia de intervención llevada a cabo con adultos mayores en la comuna de Paredones, sexta región de Chile, con posterioridad al terremoto y tsunami del 27 de febrero 2010 en Chile, en el contexto de una investigación sobre fortalezas y vulnerabilidades desplegadas por este grupo etario, con posterioridad a un desastre natural. Se presenta una descripción del desarrollo metodológico de la intervención y de los sustentos teóricos y conceptuales en los que se basa. Como resultado de este proceso, se propone una estrategia que trabaje a través de la identificación de las propias experiencias y fortalezas de los sujetos. De tal forma se minimizan los efectos negativos de los determinantes sociales de la salud (como la edad y el lugar de residencia) en contexto de crisis; permitiendo a los adultos mayores fortalecer sus recursos individuales y colectivos, en pro de su bienestar psicosocial.

  17. [Lower urinary tract dysfunction following radical hysterectomy].

    PubMed

    Aoun, F; Roumeguère, T

    2015-12-01

    Radical hysterectomy is associated with a significant amount of urinary functional complications and a negative impact on quality of life. The aim of this review is to provide a comprehensive overview of the neurological etiology of lower urinary tract dysfunction following radical hysterectomy and to establish an optimal postoperative management strategy. We performed a comprehensive overview using the following terms: "radical hysterectomy" and "urologic diseases etiology" or "urologic disease prevention and control". The reported incidence of lower urinary tract dysfunction after radical hysterectomy varies from 12 to 85%. Several animal and clinical urodynamic studies corroborate the neurologic etiology of the dysfunction. Lower urinary tract dysfunction is a common postoperative finding (70-85%) but spontaneous recovery is to be expected within 6-12 months after surgery. The most frequent long term sequela is stress urinary incontinence (40% of cases) and its management is complex and challenging. Postoperative refractory overactive bladder and bladder underactivity can be treated by neuromodulation of sacral roots and superior hypogastric plexus, respectively. In the absence of good clinical predictors, preoperative urodynamic examinations could have a role in understanding the pathophysiology of the dysfunction before such interventions. The pathophysiology of lower urinary tract dysfunction following radical hysterectomy is multifactorial. Its management is complex and should be multidisciplinary. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  18. Introducing Stable Radicals into Molecular Machines.

    PubMed

    Wang, Yuping; Frasconi, Marco; Stoddart, J Fraser

    2017-09-27

    Ever since their discovery, stable organic radicals have received considerable attention from chemists because of their unique optical, electronic, and magnetic properties. Currently, one of the most appealing challenges for the chemical community is to develop sophisticated artificial molecular machines that can do work by consuming external energy, after the manner of motor proteins. In this context, radical-pairing interactions are important in addressing the challenge: they not only provide supramolecular assistance in the synthesis of molecular machines but also open the door to developing multifunctional systems relying on the various properties of the radical species. In this Outlook, by taking the radical cationic state of 1,1'-dialkyl-4,4'-bipyridinium (BIPY(•+)) as an example, we highlight our research on the art and science of introducing radical-pairing interactions into functional systems, from prototypical molecular switches to complex molecular machines, followed by a discussion of the (i) limitations of the current systems and (ii) future research directions for designing BIPY(•+)-based molecular machines with useful functions.

  19. Introducing Stable Radicals into Molecular Machines

    PubMed Central

    2017-01-01

    Ever since their discovery, stable organic radicals have received considerable attention from chemists because of their unique optical, electronic, and magnetic properties. Currently, one of the most appealing challenges for the chemical community is to develop sophisticated artificial molecular machines that can do work by consuming external energy, after the manner of motor proteins. In this context, radical-pairing interactions are important in addressing the challenge: they not only provide supramolecular assistance in the synthesis of molecular machines but also open the door to developing multifunctional systems relying on the various properties of the radical species. In this Outlook, by taking the radical cationic state of 1,1′-dialkyl-4,4′-bipyridinium (BIPY•+) as an example, we highlight our research on the art and science of introducing radical-pairing interactions into functional systems, from prototypical molecular switches to complex molecular machines, followed by a discussion of the (i) limitations of the current systems and (ii) future research directions for designing BIPY•+-based molecular machines with useful functions. PMID:28979933

  20. Electrochemistry and spectroelectrochemistry of nitroxyl free radicals

    SciTech Connect

    Fish, J.R.; Swarts, S.G.; Sevilla, M.D.; Malinski, T.

    1988-06-30

    This work reports electrochemical and spectroelectrochemical studies of the two nitroxyl radicals 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-yloxy (3-carbamoyl-PROXYL). Oxidation and reduction reactions have been observed in aqueous media over the pH range 2-12 in the potential range -0.8 to +0.8 V by differential pulse voltammetry, cyclic voltammetry, and thin-layer UV-visible spectroelectrochemistry, and the reaction products have been characterized by IR, NMR, and ESR spectrometry. At pH values less than 10, characteristic electrochemical behavior is observed to be analogous for both radicals, and the products from electron transfer compare quite favorably with those found by pulse radiolysis of aqueous solutions of nitroxyl radicals. At pH 2-9, a stable cation from a reversible oxidation and hydroxylamine following an irreversible reduction, as well as hydroxylated cation at pH higher than 9, are the same as those obtained in pulse radiolysis experiments. Spectroscopic evidence indicates that behavior following reduction at high pH differs for the two radicals. At pH 12, reduced TEMPO may undergo structural changes leading to the formation of a new radical consisting of a seven-membered ring.

  1. Vibronic Spectroscopy of the Phenylcyanomethyl Radical

    NASA Astrophysics Data System (ADS)

    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.

  2. Modeling Radicalization Phenomena in Heterogeneous Populations

    PubMed Central

    2016-01-01

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

  3. Improving postoperative radiotherapy following radical prostatectomy.

    PubMed

    Lipman, D; Pieters, B R; De Reijke, Theo M

    2017-10-01

    Prostate cancer has one of the highest incidences in the world, with good curative treatment options like radiotherapy and radical prostatectomy. Unfortunately, about 30% of the patients initially treated with curative intent will develop a recurrence and need adjuvant treatment. Five randomized trials covered the role of postoperative radiotherapy after radical prostatectomy, but there is still a lot of debate about which patients should receive postoperative radiotherapy. Areas covered: This review will give an overview on the available literature concerning post-operative radiotherapy following radical prostatectomy with an emphasis on the five randomized trials. Also, new imaging techniques like prostate-specific membrane antigen positron emission tomography (PSMA-PET) and multiparametric magnetic resonance imaging (mp-MRI) and the development of biomarkers like genomic classifiers will be discussed in the search for an improved selection of patients who will benefit from postoperative radiotherapy following radical prostatectomy. With new treatment techniques like Intensity Modulated Radiotherapy, toxicity profiles will be kept low. Expert commentary: Patients with biochemical recurrence following radical prostatectomy with an early rise in prostate-specific antigen (PSA) will benefit most from postoperative radiotherapy. In this way, patients with only high risk pathological features can avoid unnecessary treatment and toxicity, and early intervention in progressing patients would not compromise the outcome.

  4. Substrate radical intermediates in soluble methane monooxygenase.

    PubMed

    Liu, Aimin; Jin, Yi; Zhang, Jingyan; Brazeau, Brian J; Lipscomb, John D

    2005-12-09

    EPR spin-trapping experiments were carried out using the three-component soluble methane monooxygenase (MMO). Spin-traps 5,5-dimethyl-1-pyrroline N-oxide (DMPO), alpha-4-pyridyl-1-oxide N-tert-butylnitrone (POBN), and nitrosobenzene (NOB) were used to investigate the possible formation of substrate radical intermediates during catalysis. In contrast to a previous report, the NADH-coupled oxidations of various substrates did not produce any trapped radical species when DMPO or POBN was present. However, radicals were detected by these traps when only the MMO reductase component and NADH were present. DMPO and POBN were found to be weak inhibitors of the MMO reaction. In contrast, NOB is a strong inhibitor for the MMO-catalyzed nitrobenzene oxidation reaction. When NOB was used as a spin-trap in the complete MMO system with or without substrate, EPR signals from an NOB radical were detected. We propose that a molecule of NOB acts simultaneously as a substrate and a spin-trap for MMO, yielding the long-lived radical and supporting a stepwise mechanism for MMO.

  5. Modeling Radicalization Phenomena in Heterogeneous Populations.

    PubMed

    Galam, Serge; Javarone, Marco Alberto

    2016-01-01

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

  6. Reactivity of 1,4-dihydropyridines toward alkyl, alkylperoxyl radicals, and ABTS radical cation.

    PubMed

    López-Alarcón, C; Navarrete, P; Camargo, C; Squella, J A; Núñez-Vergara, L J

    2003-02-01

    A series of C4-substituted 1,4-dihydropyridines (DHP) with either secondary or tertiary nitrogen in the dihydropyridine ring were synthesized. All of these compounds together with some commercial DHP derivatives were tested for potential scavenger effects toward alkyl, alkylperoxyl radicals, and ABTS radical cation in aqueous media at pH 7.4. Kinetic rate constants were assessed either by UV/vis spectroscopy or GC/MS techniques. Tested compounds reacted faster toward alkylperoxyl radicals and ABTS radical cation than alkyl ones. N-Ethyl-substituted DHPs showed the lowest reactivity. Kinetic results were compared with either trolox or nisoldipine. Using deuterium kinetic isotope effect studies, we have proved that the hydrogen of the 1-position of the DHP ring is involved in the proposed mechanism. This fact is mostly noticeable in the case of alkyl radicals. In all cases, the respective pyridine derivative was detected as the main product of the reaction.

  7. Bimolecular self-reactions of ketyl radicals of acetophenone and diphenylaminyl radicals

    NASA Astrophysics Data System (ADS)

    Khudyakov, I. V.; Koroli, L. L.

    1984-01-01

    The rate constants of self-reactions of ketyl radicals of acetophenone in n-heptane [2 k = (3.2 ± 0.5) × 10 9 M -1 s -1] and diphenylaminyl radicals in toluene [2 k = (3.3 ± 0.5) × 10 7 M -1 s -1] have been determined at 298 K using the flash photolysis technique. The rate constant of ketyl radicals is equal to the calculated diffusion constant and, therefore, this reaction is diffusion-controlled. The aminyl radical recombination rate is independent of the viscosity of the toluene/vaseline oil binary mixture (0.55 ⩽ η ⩽ 12 cP) and this reaction is activation-controlled. Reactivity anisotropy averaging due to the cage effect has been considered for ketyl and some other radicals. On the basis of the analysis it has been proposed that ketyl recombination involves formation of not only pinacol, but also iso-pinacols.

  8. A Radically Configurable Six-State Compound

    SciTech Connect

    Barnes, J.C.; Fahrenbach, Albert C.; Cao, Dennis; Dyar, Scott M.; Frasconi, M.; Giesener, M. A.; Benítez, D.; Tkatchouk, E.; Li, H.; Stern, Charlotte L.; Sarjeant, Amy A.; Hartlieb, K.J.; Liu, Z.; Carmieli, Raanan; Botros, Y.Y.; Wasielewski, M. R.; Goddard III, W.A.; Stoddart, J. Fraser

    2013-01-24

    Most organic radicals possess short lifetimes and quickly undergo dimerization or oxidation. Here, we report on the synthesis by radical templation of a class of air- and water-stable organic radicals, trapped within a homo[2]catenane composed of two rigid and fixed cyclobis(paraquat-p-phenylene) rings. The highly energetic octacationic homo[2]catenane, which is capable of accepting up to eight electrons, can be configured reversibly, both chemically and electrochemically, between each one of six experimentally accessible redox states (0, 2+, 4+, 6+, 7+, and 8+) from within the total of nine states evaluated by quantum mechanical methods. All six of the observable redox states have been identified by electrochemical techniques, three (4+, 6+, and 7+) have been characterized by x-ray crystallography, four (4+, 6+, 7+, and 8+) by electron paramagnetic resonance spectroscopy, one (7+) by superconducting quantum interference device magnetometry, and one (8+) by nuclear magnetic resonance spectroscopy.

  9. Resveratrol products resulting by free radical attack

    NASA Astrophysics Data System (ADS)

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

    2008-06-01

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

  10. Mechanically controlled radical polymerization initiated by ultrasound

    NASA Astrophysics Data System (ADS)

    Mohapatra, Hemakesh; Kleiman, Maya; Esser-Kahn, Aaron Palmer

    2017-02-01

    In polymer chemistry, mechanical energy degrades polymeric chains. In contrast, in nature, mechanical energy is often used to create new polymers. This mechanically stimulated growth is a key component of the robustness of biological materials. A synthetic system in which mechanical force initiates polymerization will provide similar robustness in polymeric materials. Here we show a polymerization of acrylate monomers initiated and controlled by mechanical energy provided by ultrasonic agitation. The activator for an atom-transfer radical polymerization is generated using piezochemical reduction of a Cu(II) precursor complex, which thus converts a mechanical activation of piezoelectric particles to the synthesis of a new material. This polymerization reaction has some characteristics of controlled radical polymerization, such as narrow molecular-weight distribution and linear dependence of the polymeric chain length on the time of mechanical activation. This new method of controlled radical polymerization complements the existing methods to synthesize commercially useful well-defined polymers.

  11. Radicality of surgical treatment for cervical cancer.

    PubMed

    Mirković, L; Petković, S; Mirković, D; Jeremić, K; Milenković, V; Maksimović, M

    2009-01-01

    Analyses were carried out on 545 Wertheim-Meigs radical hysterectomies performed at the Institute of Gynecology and Obstetrics of the Clinical Center of Serbia during a four-year period from 2002 to 2006. More than ten lymphatic glands in 84.4% of patients were removed. The apical part of the vagina was removed in 77.8% of cases, and 77.6% of patients had the right part of the vagina removed. Distribution of surgical radicality according to FIGO stage of disease has been demonstrated. Comparison of research results in the period from 1996 to 2000 shows a significantly more radical approach concerning the number of lymphatic glands removed during this period.

  12. High-Power-Density Organic Radical Batteries.

    PubMed

    Friebe, Christian; Schubert, Ulrich S

    2017-02-01

    Batteries that are based on organic radical compounds possess superior charging times and discharging power capability in comparison to established electrochemical energy-storage technologies. They do not rely on metals and, hence, feature a favorable environmental impact. They furthermore offer the possibility of roll-to-roll processing through the use of different printing techniques, which enables the cost-efficient fabrication of mechanically flexible devices. In this review, organic radical batteries are presented with the focus on the hitherto developed materials and the key properties thereof, e.g., voltage, capacity, and cycle life. Furthermore, basic information, such as significant characteristics, housing approaches, and applied additives, are presented and discussed in the context of organic radical batteries.

  13. Free radicals, antioxidant defense systems, and schizophrenia.

    PubMed

    Wu, Jing Qin; Kosten, Thomas R; Zhang, Xiang Yang

    2013-10-01

    The etiopathogenic mechanisms of schizophrenia are to date unknown, although several hypotheses have been suggested. Accumulating evidence suggests that excessive free radical production or oxidative stress may be involved in the pathophysiology of schizophrenia as evidenced by increased production of reactive oxygen or decreased antioxidant protection in schizophrenic patients. This review aims to summarize the basic molecular mechanisms of free radical metabolism, the impaired antioxidant defense system and membrane pathology in schizophrenia, their interrelationships with the characteristic clinical symptoms and the implications for antipsychotic treatments. In schizophrenia, there is accumulating evidence of altered antioxidant enzyme activities and increased levels of lipid peroxidation, as well as altered levels of plasma antioxidants. Moreover, free radical-mediated abnormalities may contribute to specific aspects of schizophrenic symptomatology and complications of its treatment with antipsychotic drugs, as well as the development of tardive dyskinesia (TD). Finally, the potential therapeutic strategies implicated by the accumulating data on oxidative stress mechanisms for the treatment of schizophrenia are discussed.

  14. Mechanically controlled radical polymerization initiated by ultrasound

    NASA Astrophysics Data System (ADS)

    Mohapatra, Hemakesh; Kleiman, Maya; Esser-Kahn, Aaron Palmer

    2016-10-01

    In polymer chemistry, mechanical energy degrades polymeric chains. In contrast, in nature, mechanical energy is often used to create new polymers. This mechanically stimulated growth is a key component of the robustness of biological materials. A synthetic system in which mechanical force initiates polymerization will provide similar robustness in polymeric materials. Here we show a polymerization of acrylate monomers initiated and controlled by mechanical energy provided by ultrasonic agitation. The activator for an atom-transfer radical polymerization is generated using piezochemical reduction of a Cu(II) precursor complex, which thus converts a mechanical activation of piezoelectric particles to the synthesis of a new material. This polymerization reaction has some characteristics of controlled radical polymerization, such as narrow molecular-weight distribution and linear dependence of the polymeric chain length on the time of mechanical activation. This new method of controlled radical polymerization complements the existing methods to synthesize commercially useful well-defined polymers.

  15. Antioxidant and radical scavenging properties of curcumin.

    PubMed

    Ak, Tuba; Gülçin, Ilhami

    2008-07-10

    Curcumin (diferuoyl methane) is a phenolic compound and a major component of Curcuma longa L. In the present paper, we determined the antioxidant activity of curcumin by employing various in vitro antioxidant assays such as 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH*) scavenging, 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical scavenging activity, N,N-dimethyl-p-phenylenediamine dihydrochloride (DMPD) radical scavenging activity, total antioxidant activity determination by ferric thiocyanate, total reducing ability determination by the Fe(3+)-Fe(2+) transformation method, superoxide anion radical scavenging by the riboflavin/methionine/illuminate system, hydrogen peroxide scavenging and ferrous ions (Fe(2+)) chelating activities. Curcumin inhibited 97.3% lipid peroxidation of linoleic acid emulsion at 15 microg/mL concentration (20 mM). On the other hand, butylated hydroxyanisole (BHA, 123 mM), butylated hydroxytoluene (BHT, 102 mM), alpha-tocopherol (51 mM) and trolox (90 mM) as standard antioxidants indicated inhibition of 95.4, 99.7, 84.6 and 95.6% on peroxidation of linoleic acid emulsion at 45 microg/mL concentration, respectively. In addition, curcumin had an effective DPPH* scavenging, ABTS*(+) scavenging, DMPD*(+) scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging, ferric ions (Fe(3+)) reducing power and ferrous ions (Fe(2+)) chelating activities. Also, BHA, BHT, alpha-tocopherol and trolox, were used as the reference antioxidant and radical scavenger compounds. According to the present study, curcumin can be used in the pharmacological and food industry because of these properties.

  16. Nitrene Radical Intermediates in Catalytic Synthesis.

    PubMed

    Kuijpers, Petrus; van der Vlugt, Jarl Ivar; Schneider, Sven; de Bruin, Bas

    2017-07-04

    Nitrene radical complexes are reactive intermediates with discrete spin density at the nitrogen-atom of the nitrene moiety. These species have become important intermediates for organic synthesis, being invoked in a broad range of C-H functionalization and aziridination reactions. Nitrene radical complexes have intriguing electronic structures, and are best described as one-electron reduced Fischer-type nitrenes. They can be generated by intramolecular single electron transfer to the 'redox non-innocent' nitrene moiety at the metal. Nitrene radicals generated at open-shell cobalt(II) have thus far received most attention in terms of spectroscopic characterization, reactivity screening, catalytic application and (computational and experimental) mechanistic studies, but some interesting iron and precious metal catalysts have also been employed in related reactions involving nitrene radicals. In some cases, redox-active ligands are used to facilitate intramolecular single electron transfer from the complex to the nitrene moiety. Organic azides are among the most attractive nitrene precursors in this field, typically requiring pre-activated organic azides (e.g. RSO2N3, (RO)2P(=O)N3, ROC(=O)N3 and alike) to achieve efficient and selective catalysis. Challenging, non-activated aliphatic organic azides were recently added to the palette of synthetically useful reactions proceeding via nitrene radical intermediates. This concept article describes the electronic structure of nitrene radical complexes, emphasizes on their usefulness in the catalytic synthesis of various organic products, and highlights the important developments in the field. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Resonance ionization detection of combustion radicals

    SciTech Connect

    Cool, T.A.

    1993-12-01

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

  18. Radical Behaviorism and Buddhism: Complementarities and Conflicts

    PubMed Central

    Diller, James W; Lattal, Kennon A

    2008-01-01

    Comparisons have been made between Buddhism and the philosophy of science in general, but there have been only a few attempts to draw comparisons directly with the philosophy of radical behaviorism. The present review therefore considers heretofore unconsidered points of comparison between Buddhism and radical behaviorism in terms of their respective goals, conceptualization of human beings, and the outcomes of following either philosophy. From these comparisons it is concluded that the commonalities discerned between these two philosophies may enhance both philosophical systems. PMID:22478509

  19. Evolution of radical mastectomy for breast cancer

    PubMed Central

    Plesca, M; Bordea, C; El Houcheimi, B; Ichim, E; Blidaru, A

    2016-01-01

    Surgical treatment of breast cancer has been marked by a constant evolution since the Halsted radical mastectomy described in the late 19th century has become the current standard Madden radical mastectomy, a breast surgery that involves the ablation of tissue with the axillary lymphatic preserving both pectoral muscles. The purpose of this paper was to present the stages that have marked the evolution of this intervention and to provide an overview of the way breast cancer has been understood and treated in the last century. PMID:27453752

  20. Carbon nanotubes: promising agents against free radicals.

    PubMed

    Galano, Annia

    2010-03-01

    The potential role of carbon nanotubes (CNTs) as free-radical scavengers is still an emerging area of research. So far some promising results have been reported strongly suggesting that CNTs can be very efficient for that task. The implications of such a valuable property for applications aimed at biomedical and environmental uses are encouraging. There are still abundant open questions related to the possible use of CNTs for scavenging free radicals. Thus much more work needs to be devoted to this fascinating topic. In this mini review the progress made so far is reviewed and some future perspectives are provided.

  1. Trisphenalenyl-based neutral radical molecular conductor.

    PubMed

    Pal, Sushanta K; Itkis, Mikhail E; Tham, Fook S; Reed, Robert W; Oakley, Richard T; Haddon, Robert C

    2008-03-26

    We report the preparation, crystallization, and solid-state characterization of the first member of a new family of tris(1,9-disubstituted phenalenyl)silicon neutral radicals. In the solid state, the radical packs as weak partial pi-dimers with intermolecular carbon...carbon contacts that fall at the van der Waals atomic separation. Magnetic susceptibility measurements indicate approximately 0.7 Curie spins per molecule from room temperature down to 50 K, below which antiferromagnetic coupling becomes apparent; the compound has a room-temperature single-crystal conductivity of sigmaRT = 2.4 x 10(-6) S cm(-1).

  2. Resonant cavity spectroscopy of radical species

    NASA Astrophysics Data System (ADS)

    Ritchie, Grant

    2015-04-01

    Photo-oxidation in the troposphere is highly complex, being initiated by short lived radical species, in the daytime dominated by the hydroxyl radical, OH, with contributions from Cl atoms, and at night by either NO3 radicals or ozone. Chemical oxidation cycles, which couple OH, HO2 and peroxy (RO2) radical species, remove primary emitted trace species which are harmful to humans or to the wider environment. However, many of the secondary products produced by atmospheric photo-oxidation are also directly harmful, for example O3, NO2, acidic and multifunctional species, many of which are of low volatility and are able to partition effectively to the condensed phase, creating secondary organic aerosol (SOA), which contributes a significant fraction of tropospheric aerosol, with associated impacts on climate and human health. The accuracy of atmospheric models to predict these impacts necessarily requires accurate knowledge of the chemical oxidative cycling. Two of the simplest intermediates are the hydroperoxy radical, HO2, and the smallest and dominant organic peroxy radical, CH3O2, formed directly by the reactions of OH with CO/O2 and CH4/O2, respectively, and indirectly following the oxidation of larger VOCs. OH, HO2 and RO2 (collectively known as ROx) are rapidly cycled, being at the centre of tropospheric oxidation, and hence are some of the best targets for models to compare with field data. The reaction of HO2 and RO2 with NO constitutes the only tropospheric in-situ source of O3. Despite their importance, neither HO2 nor CH3O2 is measured directly in the atmosphere. HO2 is only measured indirectly following its conversion to OH and CH3O2 is not measured at all. Typically only the sum of RO2 radicals is measured, making no distinction between different organic peroxy radicals. This contribution will detail recent studies using (i) optical feedback cavity enhanced absorption spectroscopy with both quantum and inter-band cascade lasers in the mid-IR, and (ii

  3. Free-radical kinetics of coal liquefaction

    SciTech Connect

    Wang, M.; Smith, J.M.; McCoy, B.J.

    1994-07-16

    A rate expression with first- and second-order terms in the concentration of extractable compounds in solid coal particles is derived from a fundamental free-radical mechanism. The expression was suggested empirically by prior experiments for coal liquefaction in the presence of a hydrogen-donor solvent. Radical reactions are considered to occur in both coal and in solvent. The long-chain approximation justifies the neglect of initiation, hydrogen abstraction, and termination rates as quantitatively insignificant relative to propagation reaction rates.

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

    SciTech Connect

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

    1981-11-01

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

  5. Peroxy Radical Chemistry and Partitioning under a Ponderosa Pine Canopy

    NASA Astrophysics Data System (ADS)

    Wolfe, G. M.; Cantrell, C. A.; Mauldin, L.; Kim, S.; Henry, S. B.; Boyle, E. S.; Karl, T.; Harley, P. C.; Turnipseed, A.; Zheng, W.; Flocke, F. M.; Apel, E. C.; Hornbrook, R. S.; Hall, S. R.; Ullmann, K.; Guenther, A. B.; DiGangi, J. P.; Kaser, L.; Schnitzhofer, R.; Hansel, A.; Graus, M.; Nakashima, Y.; Kajii, Y. J.; Keutsch, F. N.

    2012-12-01

    As the first intermediates in the OH-initiated oxidation of hydrocarbons, peroxy radicals are central to the photochemistry of the lower atmosphere. Peroxy radical abundance and partitioning controls relative rates of radical propagation and termination in low-NOx regimes, and the coupled cycling of these molecules lies at the heart of recently-highlighted deficiencies in traditional chemical mechanisms. Using observations of hydroperoxy (HO2) and total peroxy (HO2 + RO2) radicals acquired during the summer 2010 BEACHON-ROCs campaign, we explore the processes affecting radical-mediated chemistry within a rural Ponderosa pine forest in central Colorado. Steady-state and fully-coupled 0-D modeling studies are used to provide complementary perspectives on our understanding of the radical budget in this environment. Analysis will focus on the nature and impact of unidentified radical sources and sinks and on how the composition of the peroxy radical pool modulates radical regeneration.

  6. The sensitivity of a radical pair compass magnetoreceptor can be significantly amplified by radical scavengers.

    PubMed

    Kattnig, Daniel R; Hore, P J

    2017-09-14

    Birds have a remarkable ability to obtain navigational information from the Earth's magnetic field. The primary detection mechanism of this compass sense is uncertain but appears to involve the quantum spin dynamics of radical pairs formed transiently in cryptochrome proteins. We propose here a new version of the current model in which spin-selective recombination of the radical pair is not essential. One of the two radicals is imagined to react with a paramagnetic scavenger via spin-selective electron transfer. By means of simulations of the spin dynamics of cryptochrome-inspired radical pairs, we show that the new scheme offers two clear and important benefits. The sensitivity to a 50 μT magnetic field is greatly enhanced and, unlike the current model, the radicals can be more than 2 nm apart in the magnetoreceptor protein. The latter means that animal cryptochromes that have a tetrad (rather than a triad) of tryptophan electron donors can still be expected to be viable as magnetic compass sensors. Lifting the restriction on the rate of the spin-selective recombination reaction also means that the detrimental effects of inter-radical exchange and dipolar interactions can be minimised by placing the radicals much further apart than in the current model.

  7. Glutathione – Hydroxyl Radical Interaction: A Theoretical Study on Radical Recognition Process

    PubMed Central

    Fiser, Béla; Jójárt, Balázs; Csizmadia, Imre G.; Viskolcz, Béla

    2013-01-01

    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. PMID:24040010

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

    PubMed

    Fiser, Béla; Jójárt, Balázs; Csizmadia, Imre G; Viskolcz, Béla

    2013-01-01

    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.

  9. Direct assembly of multiply oxygenated carbon chains by decarbonylative radical-radical coupling reactions.

    PubMed

    Masuda, Kengo; Nagatomo, Masanori; Inoue, Masayuki

    2017-03-01

    Pentoses and hexoses contain more than three oxygen-bearing stereocentres and are ideal starting materials for the synthesis of multiply oxygenated natural products such as sagittamide D, maitotoxin and hikizimycin. Here we demonstrate new radical-radical homocoupling reactions of sugar derivatives with minimal perturbation of their chiral centres. The radical exchange procedure using Et3B/O2 converted sugar-derived α-alkoxyacyl tellurides into α-alkoxy radicals via decarbonylation and rapidly dimerized the monomeric radicals. The robustness of this process was demonstrated by a single-step preparation of 12 stereochemically diverse dimers with 6-10 secondary hydroxy groups, including the C5-C10 stereohexad of sagittamide D and the enantiomer of the C51-C60 stereodecad of maitotoxin. Furthermore, the optimally convergent radical-radical cross-coupling reaction achieved a one-step assembly of the protected C1-C11 oxygenated carbon chain of the anthelmintic hikizimycin. These exceptionally efficient homo- and heterocoupling methods together provide a powerful strategy for the expedited total synthesis of contiguously hydroxylated natural products.

  10. Direct assembly of multiply oxygenated carbon chains by decarbonylative radical-radical coupling reactions

    NASA Astrophysics Data System (ADS)

    Masuda, Kengo; Nagatomo, Masanori; Inoue, Masayuki

    2016-10-01

    Pentoses and hexoses contain more than three oxygen-bearing stereocentres and are ideal starting materials for the synthesis of multiply oxygenated natural products such as sagittamide D, maitotoxin and hikizimycin. Here we demonstrate new radical-radical homocoupling reactions of sugar derivatives with minimal perturbation of their chiral centres. The radical exchange procedure using Et3B/O2 converted sugar-derived α-alkoxyacyl tellurides into α-alkoxy radicals via decarbonylation and rapidly dimerized the monomeric radicals. The robustness of this process was demonstrated by a single-step preparation of 12 stereochemically diverse dimers with 6-10 secondary hydroxy groups, including the C5-C10 stereohexad of sagittamide D and the enantiomer of the C51-C60 stereodecad of maitotoxin. Furthermore, the optimally convergent radical-radical cross-coupling reaction achieved a one-step assembly of the protected C1-C11 oxygenated carbon chain of the anthelmintic hikizimycin. These exceptionally efficient homo- and heterocoupling methods together provide a powerful strategy for the expedited total synthesis of contiguously hydroxylated natural products.

  11. COST Action CM1201 "Biomimetic Radical Chemistry": free radical chemistry successfully meets many disciplines.

    PubMed

    Ferreri, Carla; Golding, Bernard T; Jahn, Ullrich; Ravanat, Jean-Luc

    2016-11-01

    The COST Action CM1201 "Biomimetic Radical Chemistry" has been active since December 2012 for 4 years, developing research topics organized into four working groups: WG1 - Radical Enzymes, WG2 - Models of DNA damage and consequences, WG3 - Membrane stress, signalling and defenses, and WG4 - Bio-inspired synthetic strategies. International collaborations have been established among the participating 80 research groups with brilliant interdisciplinary achievements. Free radical research with a biomimetic approach has been realized in the COST Action and are summarized in this overview by the four WG leaders.

  12. Tropospheric aqueous-phase free-radical chemistry: radical sources, spectra, reaction kinetics and prediction tools.

    PubMed

    Herrmann, Hartmut; Hoffmann, Dirk; Schaefer, Thomas; Bräuer, Peter; Tilgner, Andreas

    2010-12-17

    The most important radicals which need to be considered for the description of chemical conversion processes in tropospheric aqueous systems are the hydroxyl radical (OH), the nitrate radical (NO(3)) and sulphur-containing radicals such as the sulphate radical (SO(4)(-)). For each of the three radicals their generation and their properties are discussed first in the corresponding sections. The main focus herein is to summarize newly published aqueous-phase kinetic data on OH, NO(3) and SO(4)(-) radical reactions relevant for the description of multiphase tropospheric chemistry. The data compilation builds up on earlier datasets published in the literature. Since the last review in 2003 (H. Herrmann, Chem. Rev. 2003, 103, 4691-4716) more than hundred new rate constants are available from literature. In case of larger discrepancies between novel and already published rate constants the available kinetic data for these reactions are discussed and recommendations are provided when possible. As many OH kinetic data are obtained by means of the thiocyanate (SCN(-)) system in competition kinetic measurements of OH radical reactions this system is reviewed in a subchapter of this review. Available rate constants for the reaction sequence following the reaction of OH+SCN(-) are summarized. Newly published data since 2003 have been considered and averaged rate constants are calculated. Applying competition kinetics measurements usually the formation of the radical anion (SCN)(2)(-) is monitored directly by absorption measurements. Within this subchapter available absorption spectra of the (SCN)(2)(-) radical anion from the last five decades are presented. Based on these spectra an averaged (SCN)(2)(-) spectrum was calculated. In the last years different estimation methods for aqueous phase kinetic data of radical reactions have been developed and published. Such methods are often essential to estimate kinetic data which are not accessible from the literature. Approaches for

  13. Rate constants of the reaction of C2-C4 peroxy radicals with OH radicals

    NASA Astrophysics Data System (ADS)

    Assaf, Emmanuel; Tanaka, Shisei; Kajii, Yoshizumi; Schoemaecker, Coralie; Fittschen, Christa

    2017-09-01

    The rate constants for the reaction of three peroxy radicals with OH have been measured using different precursors. Peroxy radicals have been prepared by either the reaction of Cl-atoms with C2H6, C3H8 and n-C4H10 or through photolysis of the corresponding alkyliodide. Using Cl-atoms, the following rate constants have been measured: Experiments using 248 nm photolysis of the corresponding alkyliodides as precursor enhances the rate constants by a factor of two, bringing up the suspicion of a fast reaction between I-atoms and OH radicals.

  14. Understanding political radicalization: The two-pyramids model.

    PubMed

    McCauley, Clark; Moskalenko, Sophia

    2017-04-01

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

  15. Hydroxyl Radical Dosimetry for High Flux Hydroxyl Radical Protein Footprinting Applications Using a Simple Optical Detection Method

    PubMed Central

    Xie, Boer; Sharp, Joshua S.

    2015-01-01

    Hydroxyl radical protein footprinting (HRPF) by Fast Photochemical Oxidation of Proteins (FPOP) is a powerful benchtop tool used to probe protein structure, interactions, and conformational changes in solution. However, the reproducibility of all HRPF techniques is limited by the ability to deliver a defined concentration of hydroxyl radicals to the protein. This ability is impacted by both the amount of radical generated and the presence of radical scavengers in solution. In order to compare HRPF data from sample to sample, a hydroxyl radical dosimeter is needed that can measure the effective concentration of radical that is delivered to the protein, after accounting for both differences in hydroxyl radical generation and non-analyte radical consumption. Here, we test three radical dosimeters (Alexa Fluor 488, terepthalic acid, and adenine) for their ability to quantitatively measure the effective radical dose under the high radical concentration conditions of FPOP. Adenine has a quantitative relationship between UV spectrophotometric response, effective hydroxyl radical dose delivered, and peptide and protein oxidation levels over the range of radical concentrations typically encountered in FPOP. The simplicity of an adenine-based dosimeter allows for convenient and flexible incorporation into FPOP applications, and the ability to accurately measure the delivered radical dose will enable reproducible and reliable FPOP across a variety of platforms and applications. PMID:26455423

  16. Hydroxyl Radical Dosimetry for High Flux Hydroxyl Radical Protein Footprinting Applications Using a Simple Optical Detection Method.

    PubMed

    Xie, Boer; Sharp, Joshua S

    2015-11-03

    Hydroxyl radical protein footprinting (HRPF) by fast photochemical oxidation of proteins (FPOP) is a powerful benchtop tool used to probe protein structure, interactions, and conformational changes in solution. However, the reproducibility of all HRPF techniques is limited by the ability to deliver a defined concentration of hydroxyl radicals to the protein. This ability is impacted by both the amount of radical generated and the presence of radical scavengers in solution. In order to compare HRPF data from sample to sample, a hydroxyl radical dosimeter is needed that can measure the effective concentration of radical that is delivered to the protein, after accounting for both differences in hydroxyl radical generation and nonanalyte radical consumption. Here, we test three radical dosimeters (Alexa Fluor 488, terepthalic acid, and adenine) for their ability to quantitatively measure the effective radical dose under the high radical concentration conditions of FPOP. Adenine has a quantitative relationship between UV spectrophotometric response, effective hydroxyl radical dose delivered, and peptide and protein oxidation levels over the range of radical concentrations typically encountered in FPOP. The simplicity of an adenine-based dosimeter allows for convenient and flexible incorporation into FPOP applications, and the ability to accurately measure the delivered radical dose will enable reproducible and reliable FPOP across a variety of platforms and applications.

  17. Praxis: Implication for "Really" Radical Education.

    ERIC Educational Resources Information Center

    Allman, Paula; Wallis, John

    1990-01-01

    Explicates the concept of praxis in Marx's dialectical analysis of capitalism and relates it to radical education: issues of access to educational opportunities, the challenge to the status quo through curriculum change, the role of the intellectual, and the relationship between knowledge and action. (SK)

  18. Radical Negativity: Music Education for Social Justice

    ERIC Educational Resources Information Center

    McLaren, Peter

    2011-01-01

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

  19. Cold and intense OH radical beam sources

    SciTech Connect

    Ploenes, Ludger; Meerakker, Sebastiaan Y. T. van de; Haas, Dominik; Zhang, Dongdong E-mail: stefan.willitsch@unibas.ch; Willitsch, Stefan E-mail: stefan.willitsch@unibas.ch

    2016-05-15

    We present the design and performance of two supersonic radical beam sources: a conventional pinhole-discharge source and a dielectric barrier discharge (DBD) source, both based on the Nijmegen pulsed valve. Both designs have been characterized by discharging water molecules seeded in the rare gases Ar, Kr, or Xe. The resulting OH radicals have been detected by laser-induced fluorescence. The measured OH densities are (3.0 ± 0.6) × 10{sup 11} cm{sup -3} and (1.0 ± 0.5) × 10{sup 11} cm{sup -3} for the pinhole-discharge and DBD sources, respectively. The beam profiles for both radical sources show a relative longitudinal velocity spread of about 10%. The absolute rotational ground state population of the OH beam generated from the pinhole-discharge source has been determined to be more than 98%. The DBD source even produces a rotationally colder OH beam with a population of the ground state exceeding 99%. For the DBD source, addition of O{sub 2} molecules to the gas mixture increases the OH beam density by a factor of about 2.5, improves the DBD valve stability, and allows to tune the mean velocity of the radical beam.

  20. Radical Negativity: Music Education for Social Justice

    ERIC Educational Resources Information Center

    McLaren, Peter

    2011-01-01

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

  1. Globins Scavenge Sulfur Trioxide Anion Radical.

    PubMed

    Gardner, Paul R; Gardner, Daniel P; Gardner, Alexander P

    2015-11-06

    Ferrous myoglobin was oxidized by sulfur trioxide anion radical (STAR) during the free radical chain oxidation of sulfite. Oxidation was inhibited by the STAR scavenger GSH and by the heme ligand CO. Bimolecular rate constants for the reaction of STAR with several ferrous globins and biomolecules were determined by kinetic competition. Reaction rate constants for myoglobin, hemoglobin, neuroglobin, and flavohemoglobin are large at 38, 120, 2,600, and ≥ 7,500 × 10(6) m(-1) s(-1), respectively, and correlate with redox potentials. Measured rate constants for O2, GSH, ascorbate, and NAD(P)H are also large at ∼100, 10, 130, and 30 × 10(6) m(-1) s(-1), respectively, but nevertheless allow for favorable competition by globins and a capacity for STAR scavenging in vivo. Saccharomyces cerevisiae lacking sulfite oxidase and deleted of flavohemoglobin showed an O2-dependent growth impairment with nonfermentable substrates that was exacerbated by sulfide, a precursor to mitochondrial sulfite formation. Higher O2 exposures inactivated the superoxide-sensitive mitochondrial aconitase in cells, and hypoxia elicited both aconitase and NADP(+)-isocitrate dehydrogenase activity losses. Roles for STAR-derived peroxysulfate radical, superoxide radical, and sulfo-NAD(P) in the mechanism of STAR toxicity and flavohemoglobin protection in yeast are suggested.

  2. DNP with Trityl Radicals in Deuterated Polyethylene

    NASA Astrophysics Data System (ADS)

    Wang, Li; Meyer, W.; Berlin, A.; Herick, J.; Hess, C.; Reicherz, G.

    2016-02-01

    Chemically doping with trityl radicals was performed in fully deuterated polyethylene. The behavior of paramagnetic centers has been investigated by ESR X-band spectrometer. The highest deuteron polarization was 8% at 2.5 T and 1 K with a spin concentration of 3 × 1019 spins/g.

  3. Radical Constructivism, and the Sin of Relativism

    ERIC Educational Resources Information Center

    Quale, Andreas

    2007-01-01

    The epistemology of "relativism" that is featured by the theory of radical constructivism is addressed. In particular, I examine several objections, all based on this epistemic position of relativism, that are often raised by critics of the theory: the charge of "reality denial" (which, it is often claimed, must lead ultimately to the…

  4. Albert Einstein: Radical Pacifist and Democrat

    NASA Astrophysics Data System (ADS)

    Jayaraman, T.

    We draw attention here to the radical political grounding of Einstein's pacifism. We also drescribe some less commonly known aspects of his commitment to civil liberties, particularly in the context of the anti-l hysteria and anti-racism current in the United States of the late 1940s and 1950s. We also examine briefly his views on socialism.

  5. Prophetic Movements: A Study in Conservative Radicalism.

    ERIC Educational Resources Information Center

    Anderson, Ruth D.

    Dorothy Day and the American Catholic Worker Movement are paradoxical in that they are at the same time conservative and radical, liturgical and rebellious, holy and subversive. These apparently paradoxical qualities become clear when translated through the components of the prophetic movement model. Within this model, prophetic movements are…

  6. Combined radical retropubic prostatectomy and rectal resection.

    PubMed

    Klee, L W; Grmoljez, P

    1999-10-01

    To present our experience with a small series of men who underwent simultaneous radical retropubic prostatectomy and rectal resection. Three men with newly diagnosed prostate cancer were found to have concurrent rectal tumors requiring resection. All three men underwent non-nerve-sparing radical retropubic prostatectomy and abdominoperineal resection (APR) or low anterior resection (LAR) of the rectum at the same operation. In the 2 patients undergoing APR, the levators were approximated posterior to the urethra, and the bladder was secured to the pubis. The patient undergoing LAR had urinary diversion stents placed and a diverting transverse loop colostomy. All 3 patients had excellent return of urinary continence. One patient required reoperation in the early postoperative period for small bowel adhesiolysis and stoma revision. Another patient had a mild rectal anastomotic stricture and a bladder neck stricture; both were successfully treated with a single dilation. No other significant complications occurred in these patients. Radical retropubic prostatectomy can safely be performed with partial or complete rectal resection in a single operation. A few minor modifications of the standard radical retropubic prostatectomy in this setting are suggested.

  7. The Radical Faculty -- What Are Its Goals?

    ERIC Educational Resources Information Center

    Kampf, Louis

    According to radical faculty members and students, universities have been contradicting their humanistic educational ideals by concentrating on competitive professionalism and non-academic research in a struggle for institutional power in a preponderantly capitalistic society. It is their belief that meaningful education provides intellectual…

  8. Globins Scavenge Sulfur Trioxide Anion Radical*

    PubMed Central

    Gardner, Paul R.; Gardner, Daniel P.; Gardner, Alexander P.

    2015-01-01

    Ferrous myoglobin was oxidized by sulfur trioxide anion radical (STAR) during the free radical chain oxidation of sulfite. Oxidation was inhibited by the STAR scavenger GSH and by the heme ligand CO. Bimolecular rate constants for the reaction of STAR with several ferrous globins and biomolecules were determined by kinetic competition. Reaction rate constants for myoglobin, hemoglobin, neuroglobin, and flavohemoglobin are large at 38, 120, 2,600, and ≥ 7,500 × 106 m−1 s−1, respectively, and correlate with redox potentials. Measured rate constants for O2, GSH, ascorbate, and NAD(P)H are also large at ∼100, 10, 130, and 30 × 106 m−1 s−1, respectively, but nevertheless allow for favorable competition by globins and a capacity for STAR scavenging in vivo. Saccharomyces cerevisiae lacking sulfite oxidase and deleted of flavohemoglobin showed an O2-dependent growth impairment with nonfermentable substrates that was exacerbated by sulfide, a precursor to mitochondrial sulfite formation. Higher O2 exposures inactivated the superoxide-sensitive mitochondrial aconitase in cells, and hypoxia elicited both aconitase and NADP+-isocitrate dehydrogenase activity losses. Roles for STAR-derived peroxysulfate radical, superoxide radical, and sulfo-NAD(P) in the mechanism of STAR toxicity and flavohemoglobin protection in yeast are suggested. PMID:26381408

  9. Rydberg electron transitions in the methyl radical

    NASA Astrophysics Data System (ADS)

    Velasco, A. M.; Martin, I.; Lavín, C.

    1997-01-01

    Transition probabilities corresponding to one-photon transitions to Rydberg states of the methyl radical have been calculated with a molecular-adapted version of the quantum defect orbital (QDO) method. The results appear to be in accord with those of an analysis of the experimental spectrum by Herzberg.

  10. Serendipitous Findings While Researching Oxygen Free Radicals

    PubMed Central

    Floyd, Robert A.

    2009-01-01

    This review is based on the honor of receiving the Discovery Award from the Society of Free Radical Biology and Medicine. The review is reflective and presents our thinking which led to experiments that yielded novel observations. Critical questioning of our understanding of oxygen free radicals in biomedical problems led us to use and develop more direct and extremely sensitive methods. This included nitrone free radical spin-trapping and HPLC-electrochemical detection. This technology led to the pioneering use of salicylate to trap hydroxyl free radicals and show increased flux in ischemia/reperfused brain regions and to also first sensitively detect 8-hydroxy-droxyguanosine (8-OHdG) in oxidative-damaged DNA and help assess its role in cancer development. We demonstrated that Methylene Blue (MB) photo-induced formation of 8-hydroxy-guanine in DNA and RNA and discovered that MB sensitively photo-inactivated RNA viruses including HIV and the West Nile Virus. Studies in experimental stroke led us to serendipitously discover that α-phenyl-tert-butylnitrone (PBN) was neuroprotective if given after the stroke. This led to extensive commercial development of NXY-059, a PBN derivative, for the treatment of stroke. More recently we discovered that PBN-nitrones have potent anti-cancer activity and are active in preventing hearing loss caused by acute acoustical trauma. PMID:19439210

  11. Serendipitous findings while researching oxygen free radicals.

    PubMed

    Floyd, Robert A

    2009-04-15

    This review is based on the honor of receiving the Discovery Award from the Society of Free Radical Biology and Medicine. The review is reflective and presents our thinking that led to experiments that yielded novel observations. Critical questioning of our understanding of oxygen free radicals in biomedical problems led us to use and develop more direct and extremely sensitive methods. This included nitrone free radical spin trapping and HPLC-electrochemical detection. This technology led to the pioneering use of salicylate to trap hydroxyl free radicals and show increased flux in ischemia/reperfused brain regions and also to first sensitively detect 8-hydroxyl-2-deoxyguanosine in oxidatively damaged DNA and help assess its role in cancer development. We demonstrated that methylene blue (MB) photoinduces formation of 8-hydroxyguanine in DNA and RNA and discovered that MB sensitively photoinactivates RNA viruses, including HIV and the West Nile virus. Studies in experimental stroke led us serendipitously to discover that alpha-phenyl-tert-butylnitrone (PBN) was neuroprotective if given after the stroke. This led to extensive commercial development of NXY-059, a PBN derivative, for the treatment of stroke. More recently we discovered that PBN nitrones have potent anti-cancer activity and are active in preventing hearing loss caused by acute acoustical trauma.

  12. Radical Constructivism, and the Sin of Relativism

    ERIC Educational Resources Information Center

    Quale, Andreas

    2007-01-01

    The epistemology of "relativism" that is featured by the theory of radical constructivism is addressed. In particular, I examine several objections, all based on this epistemic position of relativism, that are often raised by critics of the theory: the charge of "reality denial" (which, it is often claimed, must lead ultimately to the…

  13. Radical Change: Digital Age Literature and Learning.

    ERIC Educational Resources Information Center

    Dresang, Eliza T.; McClelland, Kathryn

    1999-01-01

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

  14. Free radicals in adolescent varicocele testis.

    PubMed

    Romeo, Carmelo; Santoro, Giuseppe

    2014-01-01

    We examine the relationship between the structure and function of the testis and the oxidative and nitrosative stress, determined by an excessive production of free radicals and/or decreased availability of antioxidant defenses, which occur in the testis of adolescents affected by varicocele. Moreover, the effects of surgical treatment on oxidative stress were provided. We conducted a PubMed and Medline search between 1980 and 2014 using "adolescent," "varicocele," "free radicals," "oxidative and nitrosative stress," "testis," and "seminiferous tubules" as keywords. Cross-references were checked in each of the studies, and relevant articles were retrieved. We conclude that increased concentration of free radicals, generated by conditions of hypoxia, hyperthermia, and hormonal dysfunction observed in adolescent affected by varicocele, can harm germ cells directly or indirectly by influencing nonspermatogenic cells and basal lamina. With regard to few available data in current literature, further clinical trials on the pre- and postoperative ROS and RNS levels together with morphological studies of the cellular component of the testis are fundamental for complete comprehension of the role played by free radicals in the pathogenesis of adolescent varicocele and could justify its pharmacological treatment with antioxidants.

  15. Free Radicals in Adolescent Varicocele Testis

    PubMed Central

    Romeo, Carmelo; Santoro, Giuseppe

    2014-01-01

    We examine the relationship between the structure and function of the testis and the oxidative and nitrosative stress, determined by an excessive production of free radicals and/or decreased availability of antioxidant defenses, which occur in the testis of adolescents affected by varicocele. Moreover, the effects of surgical treatment on oxidative stress were provided. We conducted a PubMed and Medline search between 1980 and 2014 using “adolescent,” “varicocele,” “free radicals,” “oxidative and nitrosative stress,” “testis,” and “seminiferous tubules” as keywords. Cross-references were checked in each of the studies, and relevant articles were retrieved. We conclude that increased concentration of free radicals, generated by conditions of hypoxia, hyperthermia, and hormonal dysfunction observed in adolescent affected by varicocele, can harm germ cells directly or indirectly by influencing nonspermatogenic cells and basal lamina. With regard to few available data in current literature, further clinical trials on the pre- and postoperative ROS and RNS levels together with morphological studies of the cellular component of the testis are fundamental for complete comprehension of the role played by free radicals in the pathogenesis of adolescent varicocele and could justify its pharmacological treatment with antioxidants. PMID:25580183

  16. Radical Change: Digital Age Literature and Learning.

    ERIC Educational Resources Information Center

    Dresang, Eliza T.; McClelland, Kathryn

    1999-01-01

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

  17. Neurotoxins: Free Radical Mechanisms and Melatonin Protection

    PubMed Central

    Reiter, Russel J.; Manchester, Lucien C.; Tan, Dun-Xian

    2010-01-01

    Toxins that pass through the blood-brain barrier put neurons and glia in peril. The damage inflicted is usually a consequence of the ability of these toxic agents to induce free radical generation within cells but especially at the level of the mitochondria. The elevated production of oxygen and nitrogen-based radicals and related non-radical products leads to the oxidation of essential macromolecules including lipids, proteins and DNA. The resultant damage is referred to as oxidative and nitrosative stress and, when the molecular destruction is sufficiently severe, it causes apoptosis or necrosis of neurons and glia. Loss of brain cells compromises the functions of the central nervous system expressed as motor, sensory and cognitive deficits and psychological alterations. In this survey we summarize the publications related to the following neurotoxins and the protective actions of melatonin: aminolevulinic acid, cyanide, domoic acid, kainic acid, metals, methamphetamine, polychlorinated biphenyls, rotenone, toluene and 6-hydroxydopamine. Given the potent direct free radical scavenging activities of melatonin and its metabolites, their ability to indirectly stimulate antioxidative enzymes and their efficacy in reducing electron leakage from mitochondria, it would be expected that these molecules would protect the brain from oxidative and nitrosative molecular mutilation. The studies summarized in this review indicate that this is indeed the case, an action that is obviously assisted by the fact that melatonin readily crosses the blood brain barrier. PMID:21358970

  18. Designed metalloprotein stabilizes a semiquinone radical

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  19. The Radical Challenge of Family Learning

    ERIC Educational Resources Information Center

    West, Linden

    2005-01-01

    This article focuses on the nature of "family learning" programmes in marginalised communities. Such programmes present a series of radical challenges (in the sense of getting to the root of things) to policy makers and professionals alike: about, for instance, the kinds of "learning" on offer and the neglect, perhaps…

  20. Radicals derived from acetaldehyde and vinyl alcohol.

    PubMed

    Estep, Marissa L; Morgan, W James; Winkles, Alexander T; Abbott, Adam S; Villegas-Escobar, Nery; Mullinax, J Wayne; Turner, Walter E; Wang, Xiao; Turney, Justin M; Schaefer, Henry F

    2017-09-04

    Vinyl alcohol and acetaldehyde are isoelectronic products of incomplete butanol combustion. Along with the radicals resulting from the removal of atomic hydrogen or the hydroxyl radical, these species are studied here using ab initio methods as complete as coupled cluster theory with single, double, triple, and perturbative quadruple excitations [CCSDT(Q)], with basis sets as large as cc-pV5Z. The relative energies provided herein are further refined by including corrections for relativistic effects, the frozen core approximation, and the Born-Oppenheimer approximation. The effects of anharmonic zero-point vibrational energies are also treated. The syn conformer of vinyl alcohol is predicted to be lower in energy than the anti conformer by 1.1 kcal mol(-1). The alcoholic hydrogen of syn-vinyl alcohol is found to be the easiest to remove, requiring 84.4 kcal mol(-1). Five other radicals are also carefully considered, with four conformers investigated for the 1-hydroxyvinyl radical. Beyond energetics, we have conducted an overhaul of the spectroscopic literature for these species. Our results also provide predictions for fundamental modes yet to be reported experimentally. To our knowledge, the ν3 (3076 cm(-1)) and ν4 (2999 cm(-1)) C-H stretches for syn-vinyl alcohol and all but one of the vibrational modes for anti-vinyl alcohol (ν1-ν14) are yet to be observed experimentally. For the acetyl radical, ν6 (1035 cm(-1)), ν11 (944 cm(-1)), ν12 (97 cm(-1)), and accounting for our changes to the assignment of the 1419.9 cm(-1) experimental mode, ν10 (1441 cm(-1)), are yet to be observed. We have predicted these unobserved fundamentals and reassigned the experimental 1419.9 cm(-1) frequency in the acetyl radical to ν4 rather than to ν10. Our work also strongly supports reassignment of the ν10 and ν11 fundamentals of the vinoxy radical. We suggest that the bands assigned to the overtones of these fundamentals were in fact combination bands. Our findings may be

  1. [Radical prostatectomy--100 years of evolution].

    PubMed

    Gofrit, Ofer N; Shalhav, Arieh L

    2008-07-01

    Prostate cancer is the most common malignant disease in men. The incidence of prostate cancer has been rising since the early 1990s. Not all men inflicted by prostate cancer will develop clinical disease. Therefore, sorting these cases is a great clinical challenge. Radical prostatectomy has undergone evolution in the last 100 years. Better understanding of the pelvic anatomy has led to a decrease in the blood loss during surgery and in the rate of urinary incontinence and erectile dysfunction following surgery. The introduction of laparoscopy in the late 1990s to this surgery provided the surgeon with a magnified multi-angle field of view and facilitated accurate dissection and suturing. Decreased damage to neighboring tissue made recovery hastier. Nevertheless, laparoscopic radical prostatectomy is a technically challenging surgery and did not become popular. The last step in the evolution of radical prostatectomy is the introduction of robotic systems for assistance in laparoscopic radical prostatectomy. A master-slave robotic system is composed of console and mechanical arms. The surgeon is provided with a magnified three dimensional view of the operative field and with two mechanical arms that accurately replicate its fingers movements. The initial results of robotic-assisted laparoscopic prostatectomy seem promising, however, long-term follow-up and comparison to open surgeries are lacking. Robotic systems were rapidly implemented in the American market and in the year 2006, 40% of all radical prostatectomies were robotic assisted. Future systems may reveal deep structures to the visualized surface by superimposing MRI images on the surgical field.

  2. Cu, Zn-Superoxide Dismutase-driven Free Radical Modifications: Copper- and Carbonate Radical Anion-initiated Protein Radical Chemistry

    PubMed Central

    Ramirez, Dario C.; Gomez-Mejiba, Sandra E.; Corbett, Jean T.; Deterding, Leesa J.; Tomer, Kenneth B.; Mason, Ronald P.

    2009-01-01

    SYNOPSIS The understanding of the mechanism, oxidant(s) involved, and how/what protein radicals are produced during the reaction of wild type Cu, Zn-superoxide dismutase (SOD1) with H2O2 and their fate is incomplete, but a better understanding of the role of this reaction is needed. We used immuno-spin trapping and mass spectrometry analysis to study the protein oxidations driven by human (h) and bovine (b) SOD1 when reacting with H2O2 using human serum albumin (HSA) and mouse brain homogenate (mBH) as target models. In order to gain mechanistic information about this reaction, we considered both copper- and carbonate radical anion-initiated protein oxidation. We chose experimental conditions that clearly separated SOD1-driven oxidation via CO3 •− from that initiated by copper released from the SOD1 active site. In the absence of (bi)carbonate, site-specific radical-mediated fragmentation is produced by SOD1 active-site copper. In the presence of (bi)carbonate and DTPA (to suppress copper chemistry), CO3 •− radical produced distinct radical sites in both SOD1 and HSA, which caused protein aggregation without causing protein fragmentation. The CO3 •− produced by reaction of hSOD1 with H2O2 also produced distinctive DMPO nitrone adduct positive protein bands in the mBH. Finally, we propose a biochemical mechanism to explain CO3 •− production from carbon dioxide, enhanced protein radical formation, and protection by (bi)carbonate against H2O2-induced fragmentation of the SOD1 active site. Our study is important for establishing experimental conditions for studying the molecular mechanism and targets of oxidation during the reverse reaction of SOD1 with H2O2; these results are the first step in analyzing the critical targets of SOD1-driven oxidation during such pathological processes as neuroinflammation. PMID:18764780

  3. Cytochrome c catalyses the formation of pentyl radical and octanoic acid radical from linoleic acid hydroperoxide.

    PubMed Central

    Iwahashi, Hideo; Nishizaki, Koji; Takagi, Ichiro

    2002-01-01

    A reaction of 13-hydroperoxide octadecadienoic acid (13-HPODE) with cytochrome c was analysed using ESR, HPLC-ESR and HPLC-ESR-MS by the combined use of the spin-trapping technique. The ESR, HPLC-ESR and HPLC-ESR-MS analyses showed that cytochrome c catalyses formation of pentyl and octanoic acid radicals from 13-HPODE. On the other hand, only the alpha-(4-pyridyl-1-oxide)-N-t-butylnitrone/octanoic acid radical adduct was detected in the elution profile of HPLC-ESR for a mixture of 13-HPODE with haematin, indicating that haematin catalyses the formation of octanoic acid radical. In addition, the reaction of 13-HPODE with cytochrome c was inhibited by chlorogenic acid, caffeic acid and ferulic acid via two possible mechanisms, i.e. reducing cytochrome c (chlorogenic acid and caffeic acid) and scavenging the radical intermediates (chlorogenic acid, caffeic acid and ferulic acid). PMID:11742529

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

    NASA Technical Reports Server (NTRS)

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

    2002-01-01

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

  5. Understanding the microsolvation of radicals: Infrared spectroscopy of benzyl radical water clusters

    NASA Astrophysics Data System (ADS)

    Leicht, Daniel; Kaufmann, Matin; Schwan, Raffael; Schäfer, Jan; Schwaab, Gerhard; Havenith, Martina

    2016-11-01

    The IR spectrum of benzyl radical:water clusters was recorded. Benzyl radicals were produced by vacuum flash pyrolysis and trapped in superfluid helium nanodroplets. The infrared spectrum of benzyl radical water aggregates in the range 2585-2820 cm-1 was recorded by subsequent addition of deuterated water. A total of seven peaks are observed at 2766, 2750, 2656, 2638, 2633, 2598, and 2593 cm-1. Based on pressure dependent measurements and comparison to accompanying ab initio calculations, five of these bands are assigned to distinct O-D stretch vibrations of benzyl:water clusters with one and two water molecules. In line with previous experiments on benzene:water clusters, we observe the formation of a water dimer-like motif that is attached to one face of the benzyl radical.

  6. Radical scavenging activity of antioxidants evaluated by means of electrogenerated HO radical.

    PubMed

    Oliveira, Raquel; Geraldo, Dulce; Bento, Fátima

    2014-11-01

    A method is proposed and tested concerning the characterization of antioxidants by means of their reaction with electrogenerated HO radicals in galvanostatic assays with simultaneous O2 evolution, using a Pt anode fairly oxidized. The consumption of a set of species with antioxidant activity, ascorbic acid (AA), caffeic acid (CA), gallic acid (GA) and trolox (T), is described by a first order kinetics. The rate of the processes is limited by the kinetics of reaction with HO radicals and by the kinetics of charge transfer. Information regarding the scavenger activity of antioxidants is obtained by the relative value of the rate constant of the reaction between antioxidants and HO radicals, k(AO,HO)/k(O2). The number of HO radicals scavenged per molecule of antioxidant is also estimated and ranged from 260 (ascorbic acid) to 500 (gallic acid). The method is applied successfully in the characterization of the scavenger activity of ascorbic acid in a green-tea based beverage.

  7. Pressure effects on the radical-radical recombination reaction of photochromic bridged imidazole dimers.

    PubMed

    Mutoh, Katsuya; Abe, Jiro

    2014-09-07

    The bridged imidazole dimers are some of the attractive fast photochromic compounds which have potential applications to the ophthalmic lenses, real-time hologram and molecular machines. The strategy for expanding their photochromic properties such as the colour variation and tuning the decolouration rates has been vigorously investigated, but the insight into the structural changes along the photochromic reactions has not been demonstrated in detail. Here, we demonstrated the pressure dependence of the radical-radical recombination reaction of the bridged imidazole dimers. The radical-radical interaction can be controlled by applying high pressure. Our results give fundamental information about the molecular dynamics of the bridged imidazole dimers, leading to the development of new functional photochromic machines and pressure-sensitive photochromic materials.

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

    NASA Technical Reports Server (NTRS)

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

    2002-01-01

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

  9. TRANSITION METAL CATALYSIS IN CONTROLLED RADICAL POLYMERIZATION: ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    EPA Science Inventory

    Novel and diversified macromolecular structures, which include polymers with designed topologies (top), compostions (middle), and functionalities (bottom), can be prepared by atom transfer radical polymerization processes. These polymers can be synthesized from a large variety of...

  10. Carbon radicals. Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH).

    PubMed

    Savee, John D; Papajak, Ewa; Rotavera, Brandon; Huang, Haifeng; Eskola, Arkke J; Welz, Oliver; Sheps, Leonid; Taatjes, Craig A; Zádor, Judit; Osborn, David L

    2015-02-06

    Oxidation of organic compounds in combustion and in Earth's troposphere is mediated by reactive species formed by the addition of molecular oxygen (O2) to organic radicals. Among the most crucial and elusive of these intermediates are hydroperoxyalkyl radicals, often denoted "QOOH." These species and their reactions with O2 are responsible for the radical chain branching that sustains autoignition and are implicated in tropospheric autoxidation that can form low-volatility, highly oxygenated organic aerosol precursors. We report direct observation and kinetics measurements of a QOOH intermediate in the oxidation of 1,3-cycloheptadiene, a molecule that offers insight into both resonance-stabilized and nonstabilized radical intermediates. The results establish that resonance stabilization dramatically changes QOOH reactivity and, hence, that oxidation of unsaturated organics can produce exceptionally long-lived QOOH intermediates.

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

    NASA Astrophysics Data System (ADS)

    Manoj, P.; Mohan, H.; Mittal, J. P.; Manoj, V. M.; Aravindakumar, C. T.

    2007-01-01

    Pulse radiolysis study has been carried out to investigate the properties of the radical cation of 2-aminopurine (2AP) and the probable charge transfer from the radical cation and radical anion of 2AP to natural nucleobases in aqueous medium. The radical cation of 2AP was produced by the reaction of sulfate radical anion ( SO4rad -). The time resolved absorption spectra obtained by the reaction of SO4rad - with 2AP at neutral pH have two distinct maxima at 380 and 470 nm and is assigned to the formation of a neutral radical of the form 2AP-N 2(-H) rad ( k2 = 4.7 × 10 9 dm 3 mol -1 s -1 at pH 7). This neutral radical is formed from the deprotonation reaction of a very short-lived radical cation of 2AP. The transient absorption spectra recorded at pH 10.2 have two distinct maxima at 400 and 480 nm and is assigned to the formation of a nitrogen centered radical (2AP-N(9) rad ). As the hole transport from 2AP to guanine is a highly probable process, the reaction of SO4rad - is carried out in the presence of guanosine, adenosine and inosine. The spectrum obtained in the presence of guanosine was significantly different from that in the absence and it showed prominent absorption maxima at 380 and 470 nm, and a weak broad maximum centered around 625 nm which match well with the reported spectrum of a neutral guanine radical (G(-H) rad ). The electron transfer reaction from the radical anion of 2AP to thymine (T), cytidine (Cyd) and uridine (Urd) was also investigated at neutral pH. Among the three pyrimidines, only the transient spectrum in the presence of T gave a significant difference from the spectral features of the electron adduct of 2AP, which showed a prominent absorption maximum at 340 nm and this spectrum is similar to the electron adduct spectrum of T. The preferential reduction of thymine by 2AP rad - and the oxidation of guanosine by 2AP rad + clearly follow the oxidation/reduction potentials of the purines and pyrimidines.

  12. Free radical metabolism of ethanol by deermouse microsomes

    SciTech Connect

    Knecht, K.T.; Thurman, R.G.; Mason, R.P. NIEHS, Research Triangle Park, NC )

    1991-03-15

    One-electron oxidation of ethanol to the {alpha}-hydroxyethyl radical by rat liver microsomes was previously found to be cytochrome P-450-dependent in the presence of Desferal. With deermouse microsomes, the formation of {alpha}-hydroxyethyl radical from ethanol was demonstrated with the electron paramagnetic resonance (EPR) technique of spin trapping. Free radical formation was enhanced by pretreatment of the animals with ethanol. Boiling of the microsomes, omission of NADPH, or addition of superoxide dismutase abolished free radical formation, but addition of catalase or azide had no affect. Free radicals from the hydroxyl radical scavenger formate were detected when ethanol in the incubation medium was replaced by formate. When equal concentrations of ethanol and formate were added to microsomes, the intensity of each radical adduct signal was decreased by half. Thus, it is concluded that free radical formation in deermouse microsomes is mediated by a P-450-derived, superoxide-dependent oxidizing species.

  13. Pyrimidine nucleobase radical reactivity in DNA and RNA

    NASA Astrophysics Data System (ADS)

    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.

  14. Some Pluses and Minuses of Radical Constructivism in Mathematics Education.

    ERIC Educational Resources Information Center

    Ellerton, Nerida; Clements, M. A.

    1992-01-01

    Reviews the radical constructivism movement in mathematics education. Benefits identified include learner ownership of mathematical learning; importance of social interaction; and identification of principles for improving mathematics teaching and learning. Weaknesses identified include overzealousness of some radical constructivists; downplaying…

  15. Pyrimidine Nucleobase Radical Reactivity in DNA and RNA.

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2009-10-01

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

  17. Spectroscopic Identification of New Benzyl-Type Radicals in Corona Excitation: CHLORO-α-METHYLBENZYL Radicals

    NASA Astrophysics Data System (ADS)

    Yoon, Young Wook; Lee, Seung Woon; Lee, Sang Kuk; Lee, Gi Woo

    2010-06-01

    Using a pinhole-type glass nozzle coupled with corona excited supersonic expansion (CESE), precursors o- and p-chloro-ethylbenzenes seeded in a large amount of inert carrier gas helium were corona discharged to produce jet-cooled benzyl-type radicals. The vibronic emission spectra were recorded with a long path monochromator to observe vibronic bands of benzyl-type radicals in the visible region. The analysis of the spectra shows the evidence of the o- and p-chlorobenzyl radicals as typical products in corona excitation as well as the o- and p-chloro-α-methylbenzyl radicals as unexpected species. After subtracting the bands belonging to chlorobenzyl radicals, we could construct the vibronic emission spectra of the o- and p-chloro-α-methylbenzyl radical in the D_1 → D_0 electronic transition at the gas phase. By comparing with those of ab initio calculation and of the known vibrational mode frequencies with similar structures, we could obtain the electronic transition and assign the vibrational modes to the bands observed. H. G. Ahn, G. W. Lee, and S. K. Lee J. Phys. Chem. A, 112 (51), 13427 (2008).

  18. Radical production from photosensitization of imidazoles

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  19. Education Research Will Not Profit from Radical Constructionism.

    ERIC Educational Resources Information Center

    Cobern, William W.

    This paper examines the historical roots of critical realism in western thought, highlights the dramatic nature of the shift in thought that the radical constructivists are seeking, and critically considers the relevance of radical constructivism in science teacher education. Radical constructivism is an epistemological philosophy that divorces…

  20. Hybrid radical energy storage device and method of making

    DOEpatents

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

    2016-04-26

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

  1. Hybrid radical energy storage device and method of making

    DOEpatents

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

    2015-01-27

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

  2. Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

    PubMed

    Liao, Zhixiong; Yi, Hong; Li, Zheng; Fan, Chao; Zhang, Xu; Liu, Jie; Deng, Zixin; Lei, Aiwen

    2015-01-01

    A simple copper-catalyzed direct radical carbooxygenation of styrenes is developed utilizing alkyl bromides as radical resources. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of styrenes in one pot. A broad range of styrenes and alcohols are well tolerated in this transformation. The EPR experiment shows that alkyl halides could oxidize Cu(I) to Cu(II) in this transformation.

  3. Primary radical yields in pulse irradiated alkaline aqueous solution

    NASA Technical Reports Server (NTRS)

    Fielden, E. M.; Hart, E. J.

    1969-01-01

    Primary radical yields of hydrated electrons, H atoms, and OH radicals are determined by measuring hydrated electron formation following a 4 microsecond pulse of X rays. The pH dependence of free radical yields beyond pH 12 is determined by observation of the hydrated electrons.

  4. Radical-Radical Cyclization Cascades of Barbiturates Triggered by Electron-Transfer Reduction of Amide-Type Carbonyls.

    PubMed

    Huang, Huan-Ming; Procter, David J

    2016-06-22

    Radical-radical cyclization cascades, triggered by single-electron transfer to amide-type carbonyls by SmI2-H2O, convert simple achiral barbiturates in one step to hemiaminal- or enamine-containing tricyclic scaffolds containing up to five contiguous stereocenters (including quaternary stereocenters). Furthermore, we describe the surprising beneficial effect of LiBr on the most challenging of the radical-radical cyclization cascades. An alternative fragmentation-radical cyclization sequence of related substrates allows access to bicyclic uracil derivatives. The radical-radical cyclization process constitutes the first example of a radical cascade involving ET reduction of the amide carbonyl. Products of the cascade can be readily manipulated to give highly unusual and medicinally relevant bi- and tricyclic barbiturates.

  5. Polarized absorption spectra of aromatic radicals in stretched polymer film. 3. Radical ions of acridine and phenazine

    SciTech Connect

    Sekigucki, K.; Hiratsuka, H.; Tanizaki, Y.; Hatano, Y.

    1980-02-21

    Radical anions and cations of acridine and phenazine have been prepared in polymer film by ..gamma..-ray irradiation at 77 K. For the preparation of radical anions the sample was incorporated into polyethylene film by sec-butylamine, while for radical cations poly(vinyl chloride) film and sec-butyl chloride were used. Polarized absorption spectra of these radical ions have been measured in stretched polymer film and analyzed qualitatively in terms of molecular orbital calculations.

  6. Coming to Grips with Radical Social Constructivisms

    NASA Astrophysics Data System (ADS)

    Phillips, D. C.

    This essay distinguishes two broad groups - psychological constructivists and social constructivists - but focusses upon the second of these, although it is stressed that there is great within group variation. More than half of the paper is devoted to general clearing of the ground, during which the reasons for the growing acrimony in the debates between social constructivists and their opponents are assessed, an important consequence of these debates for education is discussed, and an examination is carried out of the radical social constructivist tendency to make strong and exciting but untenable claims which are then backed away from (a tendency which is documented by a close reading of the early pages in Bloors classic book). The last portion of the essay focuses upon social constructivist accounts of the causes of belief in science - the more radical of which denegrate the role of warranting reasons, and which give an exalted place to quasi-anthropological or sociological studies of scientific communities.

  7. Chemiluminescent detection of neutral gaseous radicals.

    PubMed

    Grankin, V P; Styrov, V V; Karpov, E G

    2007-10-07

    This paper presents a systematic approach to the development of novel solid-state chemical sensors on the basis of heterogeneous chemiluminescence. The method is applicable for the identification and measurements of concentration of H, O, and other gaseous chemical radicals, where utilization of standard techniques is difficult. The luminescence is invoked during Eley-Rideal recombination of the radicals in question on the surface of the sensor core. A technique is discussed to separate the contributions of Eley-Rideal and Langmuir-Hinshelwood mechanisms, and to select appropriate materials for the sensor emitter fabrication. Typical sensor characteristics include sensitivity of 10(5) cm(-3), working gas pressures of 10(-8) - 10(1) Torr, and measurement time approximately 1 s.

  8. Spreading out spin density in polyphenalenyl radicals.

    PubMed

    Trinquier, Georges; Malrieu, Jean-Paul

    2017-10-05

    As suggested by simple topological arguments, monoradical arrangements of properly-oriented polycondensed phenalenyl units can produce highly-delocalized spin distributions. This work examines under which geometrical conditions and to which extent these flat distributions take place. UDFT calculations performed on various instances gathering up to 19 such fused phenalene units confirm the spin-density spreading over entire conjugated skeletons. This occurs, however, with more or less uniformity depending on the compacity of the arrangement, and simple linear stretches do not actually support the delocalized picture. Thermodynamic stability of the radicals is assessed, which follows their delocalization degree. Monocations and monoanions derived from these delocalized radicals are expected to support likewise delocalized charges, as checked by various calculations on corresponding closed-shell ions. Altogether, these attributes might lead to possible applications in organic design, electronic devices, and spintronics.

  9. Lipid modification processes induced by thiyl radicals

    NASA Astrophysics Data System (ADS)

    Mihaljević, Branka; Bujak, Ivana Tartaro

    2016-07-01

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

  10. EPR study of free radicals in bread

    NASA Astrophysics Data System (ADS)

    Yordanov, Nicola D.; Mladenova, Ralitsa

    2004-05-01

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

  11. Electronic spectrum of 9-methylanthracenium radical cation

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  12. Activist emotions: gay radicalism and melancholic attachments.

    PubMed

    Reynolds, Robert

    2010-01-01

    It has been argued recently that Australian historians have overlooked histories of emotion. In this article, through the life-history analysis of two long-standing Sydney gay activists, I trace the emotional currents of radical gay activism and suggest these histories point to a wider story of Left melancholy in the closing decades of the twentieth century. I argue that their melancholia is not a trauma-like despair but surprisingly is tinged with a sustaining hope.

  13. Chemical Studies of Free Radical Relocalization

    DTIC Science & Technology

    2015-01-13

    and wavefunctions on a 3D tonal, coupled cluster isomerization potential energy surface of cyclooctatetraenyl radical Gerardo Soriano, Peter Zajac...the alkyne-vinylidene isomerization on a heterocyclic ruthenium catalyst Babgen Manookian, Vy Le, Gerardo Soriano, Douglas B. Grotjahn, Andrew L...the presence of CH3I, rather than any of its isomers . This compound, while the first to be prepared, was also the least promising with regards to these

  14. Radical-free biology of oxidative stress

    PubMed Central

    Jones, Dean P.

    2008-01-01

    Free radical-induced macromolecular damage has been studied extensively as a mechanism of oxidative stress, but large-scale intervention trials with free radical scavenging antioxidant supplements show little benefit in humans. The present review summarizes data supporting a complementary hypothesis for oxidative stress in disease that can occur without free radicals. This hypothesis, which is termed the “redox hypothesis,” is that oxidative stress occurs as a consequence of disruption of thiol redox circuits, which normally function in cell signaling and physiological regulation. The redox states of thiol systems are sensitive to two-electron oxidants and controlled by the thioredoxins (Trx), glutathione (GSH), and cysteine (Cys). Trx and GSH systems are maintained under stable, but nonequilibrium conditions, due to a continuous oxidation of cell thiols at a rate of about 0.5% of the total thiol pool per minute. Redox-sensitive thiols are critical for signal transduction (e.g., H-Ras, PTP-1B), transcription factor binding to DNA (e.g., Nrf-2, nuclear factor-κB), receptor activation (e.g., αIIbβ3 integrin in platelet activation), and other processes. Nonradical oxidants, including peroxides, aldehydes, quinones, and epoxides, are generated enzymatically from both endogenous and exogenous precursors and do not require free radicals as intermediates to oxidize or modify these thiols. Because of the nonequilibrium conditions in the thiol pathways, aberrant generation of nonradical oxidants at rates comparable to normal oxidation may be sufficient to disrupt function. Considerable opportunity exists to elucidate specific thiol control pathways and develop interventional strategies to restore normal redox control and protect against oxidative stress in aging and age-related disease. PMID:18684987

  15. Quenching Dynamics of Electronically Excited Hydroxyl Radicals

    DTIC Science & Technology

    2008-05-19

    the research of graduate students Margaret Greenslade , Erika Derro, Ilana Pollack, Logan Dempsey, and Eunice Li. In addition, postdoctoral...acknowledging AFOSR support 1) M. E. Greenslade , M. 1. Lester, D. C. Radenovi6, A. J. A. van Roij, and D. H. Parker, "(2+1) Resonance Enhanced Ionization...Spectroscopy of a State Selected Beam of OH Radicals", J. Chem. Phys. 123, 074309 (2005). 4 2) E. L. Derro, I. B. Pollack, L. Dempsey, M. E. Greenslade , Y

  16. Prison Radicalization: The New Extremist Training Grounds?

    DTIC Science & Technology

    2007-09-01

    Virginia (Washington, D.C.: The George Washington University, September 2006), 8, at http://www.heathsystem.virginia.edu/ internet /ciag/publications...www.heathsystem.virginia.edu/ internet /ciag/publications/out_of_the_shadows.pdf (Accessed September 19, 2006), 1. 32 Rex A. Hudson, The Sociology and Psychology of...information, as was Media (publications/ print)(37%), Internet (31%), Books/academic journals (47%) and Informants (29%). Radical group publications were

  17. Addressing Free Radical Oxidation in Acne Vulgaris

    PubMed Central

    Criscito, Maressa C.; Schlesinger, Todd E.; Verdicchio, Robert; Szoke, Ernest

    2016-01-01

    Objective: Comparatively little attention has been paid to the role of free radical oxidation in acne vulgaris. Here, using the traditional abnormalities cited for acne, the authors address the role of free radical oxidation throughout the pathogenesis by detailing the chemistry that may contribute to clinical changes. To probe the effects of free radical oxidation and test an antioxidant, they conducted a preliminary study of topically applied vitamin E. Methods: Seventeen patients with mild-to-moderate acne vulgaris were evaluated over an eight-week period in two private dermatology practices in this open-label study. All patients enrolled were on the same baseline regimen of salicylic acid and benzoyl peroxide. This regimen was then supplemented with topical vitamin E in sunflower seed oil. Results: At the end of the eight-week period, all patients demonstrated clinical improvement, as indicated by a reduction in the number of lesions and global mean difference. A statistically significant reduction was noted as early as Week 2. Enrolled patients also expressed a positive experience due to good tolerability and easy application. Conclusion: Although the exact pathogenesis of acne vulgaris remains unknown, the presence of excessive reactive oxygen species can be implicated in each of the major abnormalities involved. This presence, along with the positive results of the authors’ preliminary study, demonstrates the need for more exploration on the use of topical antioxidants in limiting free radical oxidation in the acne model. This paper is designed to stimulate academic discussion regarding a new way of thinking about the disease state of acne. PMID:26962389

  18. Chromatin changes predict recurrence after radical prostatectomy

    PubMed Central

    Hveem, Tarjei S; Kleppe, Andreas; Vlatkovic, Ljiljana; Ersvær, Elin; Wæhre, Håkon; Nielsen, Birgitte; Kjær, Marte Avranden; Pradhan, Manohar; Syvertsen, Rolf Anders; Nesheim, John Arne; Liestøl, Knut; Albregtsen, Fritz; Danielsen, Håvard E

    2016-01-01

    Background: Pathological evaluations give the best prognostic markers for prostate cancer patients after radical prostatectomy, but the observer variance is substantial. These risk assessments should be supported and supplemented by objective methods for identifying patients at increased risk of recurrence. Markers of epigenetic aberrations have shown promising results in several cancer types and can be assessed by automatic analysis of chromatin organisation in tumour cell nuclei. Methods: A consecutive series of 317 prostate cancer patients treated with radical prostatectomy at a national hospital between 1987 and 2005 were followed for a median of 10 years (interquartile range, 7–14). On average three tumour block samples from each patient were included to account for tumour heterogeneity. We developed a novel marker, termed Nucleotyping, based on automatic assessment of disordered chromatin organisation, and validated its ability to predict recurrence after radical prostatectomy. Results: Nucleotyping predicted recurrence with a hazard ratio (HR) of 3.3 (95% confidence interval (CI), 2.1–5.1). With adjustment for clinical and pathological characteristics, the HR was 2.5 (95% CI, 1.5–4.1). An updated stratification into three risk groups significantly improved the concordance with patient outcome compared with a state-of-the-art risk-stratification tool (P<0.001). The prognostic impact was most evident for the patients who were high-risk by clinical and pathological characteristics and for patients with Gleason score 7. Conclusion: A novel assessment of epigenetic aberrations was capable of improving risk stratification after radical prostatectomy. PMID:27124335

  19. Free Radical Mechanisms of Xenobiotic Mammalian Cytotoxicities

    DTIC Science & Technology

    1991-06-30

    of iron increase the toxicity of halogenated hydrocarbons, while probu- col (an lipid-lowering drug with anti-oxidant properties, a- tocopherol , and...toluene or other solvents which do not assist in conversion of hydroperoxides to alkoxyl radicals. Page #5 F. HPLC Separation of Phospholipids from IRP...different tested agents could be detected in the usual phospholipid composition, the phospholipid HPLC profiles showed the occurrence of a new lipid peak

  20. Ultraviolet photodissociation dynamics of the phenyl radical

    SciTech Connect

    Song Yu; Lucas, Michael; Alcaraz, Maria; Zhang Jingsong; Brazier, Christopher

    2012-01-28

    Ultraviolet (UV) photodissociation dynamics of jet-cooled phenyl radicals (C{sub 6}H{sub 5} and C{sub 6}D{sub 5}) are studied in the photolysis wavelength region of 215-268 nm using high-n Rydberg atom time-of-flight and resonance enhanced multiphoton ionization techniques. The phenyl radicals are produced from 193-nm photolysis of chlorobenzene and bromobenzene precursors. The H-atom photofragment yield spectra have a broad peak centered around 235 nm and are in good agreement with the UV absorption spectra of phenyl. The H + C{sub 6}H{sub 4} product translational energy distributions, P(E{sub T})'s, peak near {approx}7 kcal/mol, and the fraction of average translational energy in the total excess energy, , is in the range of 0.20-0.35 from 215 to 268 nm. The H-atom product angular distribution is isotropic. The dissociation rates are in the range of 10{sup 7}-10{sup 8} s{sup -1} with internal energy from 30 to 46 kcal/mol above the threshold of the lowest energy channel H +o-C{sub 6}H{sub 4} (ortho-benzyne), comparable with the rates from the Rice-Ramsperger-Kassel-Marcus theory. The results from the fully deuterated phenyl radical are identical. The dissociation mechanism is consistent with production of H +o-C{sub 6}H{sub 4}, as the main channel from unimolecular decomposition of the ground electronic state phenyl radical following internal conversion of the electronically excited state.

  1. How Hume's Philosophy Informed Radical Behaviorism.

    PubMed

    Nuzzolilli, Andrew E; Diller, James W

    2015-05-01

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

  2. Orthographic Skills Important to Chinese Literacy Development: The Role of Radical Representation and Orthographic Memory of Radicals

    ERIC Educational Resources Information Center

    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…

  3. Orthographic Skills Important to Chinese Literacy Development: The Role of Radical Representation and Orthographic Memory of Radicals

    ERIC Educational Resources Information Center

    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…

  4. The photodissociation dynamics of alkyl radicals

    SciTech Connect

    Giegerich, Jens; Fischer, Ingo

    2015-01-28

    The photodisscociation dynamics of the alkyl radicals i-propyl (CH(CH{sub 3}){sub 2}) and t-butyl (C(CH{sub 3}){sub 3}) are investigated by H-atom photofragment imaging. While i-propyl is excited at 250 nm, the photodynamics of t-butyl are explored over a large energy range using excitation wavelengths between 347 nm and 233 nm. The results are compared to those obtained previously for ethyl, CH{sub 3}CH{sub 2}, and to those reported for t-butyl using 248 nm excitation. The translational energy (E{sub T}) distribution of the H-atom photofragments is bimodal and appears rather similar for all three radicals. The low E{sub T} part of the distribution shows an isotropic photofragment angular distribution, while the high E{sub T} part is associated with a considerable anisotropy. Thus, for t-butyl, two H-atom loss channels of roughly equal importance have been identified in addition to the CH{sub 3}-loss channel reported previously. A mechanism for the photodissociation of alkyl radicals is suggested that is based on interactions between Rydberg- and valence states.

  5. The Spectroscopy of the Formyl Radical.

    NASA Astrophysics Data System (ADS)

    Adamson, George William

    Fluorescence-excitation and stimulated emission pumping (SEP) spectroscopies were used to study the properties of photolytically generated, gas phase, formyl radical (HCO). This work focused on the ground doublet electronic state, between 4000-11 200cm^{-1} of energy, and the second excited doublet electronic state, between 38 590-38 750cm^{-1 } of energy. From the fluorescence-excitation spectrum the rotational, centrifugal distortion, and spin -rotational constants were determined for the vibrationless level of the second excited doublet electronic state. From the stimulated emission pumping spectrum vibrational term values, rotational constants, spin-rotational constants, and rotational linewidths were determined for ground electronic state vibrational levels--both above and below the dissociation limit for formyl radical dissociating to hydrogen atom and carbon monoxide. The systematics of the dissociation lifetimes, inferred from the observed rotational linewidths, for rovibrational levels of the ground electronic state were studied. The dissociating lifetimes were found to be strongly correlated with bending vibrational excitation and the amount of angular momentum about the minimum inertial axis of formyl radical. The observed dissociation lifetimes indicates the need for an upward adjustment of the currently accepted dissociation limit and barrier height. (Copies available exclusively from MIT Libraries, Rm. 14-0951, Cambridge, MA 02139-4307. Ph. 617-253-5668; Fax 617-253 -1690.).

  6. Gastric carcinoma: is radical gastrectomy worth while?

    PubMed Central

    Longmire, William P

    1980-01-01

    Total gastrectomy as the treatment of choice for gastric carcinoma was evaluated by a number of centres during the decade 1945-55. The operative mortality was found to be higher, the 5-year survival rate was lower, and the undesirable digestive side effects were greater than those following subtotal resection. The very radical subtotal resections with miniature gastric remnants were also found to result in postgastrectomy symptoms quite similar to those of total gastrectomy. Technical refinements of oesophagojejunal anastomoses and the use of nutritional supplements and antianaemic therapy have reduced but have not eliminated the sequelae of radical gastrectomy. A review of 15 reports of gastric cancer treatment from 8 countries suggests that in recent years total gastrectomy has been utilised in 25.4% of resections, with an average operative mortality of 21.7% and a 5-year survival of 12.3%. Radical resection or total gastrectomy is recommended for certain specific conditions, but for the usual antral gastric cancer subtotal resection distal to the vasa brevia with preservation of the gastric fundus and spleen is recommended PMID:7362184

  7. Free radical biology of the cardiovascular system.

    PubMed

    Chen, Alex F; Chen, Dan-Dan; Daiber, Andreas; Faraci, Frank M; Li, Huige; Rembold, Christopher M; Laher, Ismail

    2012-07-01

    Most cardiovascular diseases (CVDs), as well as age-related cardiovascular alterations, are accompanied by increases in oxidative stress, usually due to increased generation and/or decreased metabolism of ROS (reactive oxygen species; for example superoxide radicals) and RNS (reactive nitrogen species; for example peroxynitrite). The superoxide anion is generated by several enzymatic reactions, including a variety of NADPH oxidases and uncoupled eNOS (endothelial NO synthase). To relieve the burden caused by this generation of free radicals, which also occurs as part of normal physiological processes, such as mitochondrial respiratory chain activity, mammalian systems have developed endogenous antioxidant enzymes. There is an increased usage of exogenous antioxidants such as vitamins C and E by many patients and the general public, ostensibly in an attempt to supplement intrinsic antioxidant activity. Unfortunately, the results of large-scale trails do not generate much enthusiasm for the continued use of antioxidants to mitigate free-radical-induced changes in the cardiovascular system. In the present paper, we review the clinical use of antioxidants by providing the rationale for their use and describe the outcomes of several large-scale trails that largely display negative outcomes. We also describe the emerging understanding of the detailed regulation of superoxide generation by an uncoupled eNOS and efforts to reverse eNOS uncoupling. SIRT1 (sirtuin 1), which regulates the expression and activity of multiple pro- and anti-oxidant enzymes, could be considered a candidate molecule for a 'molecular switch'.

  8. Accurate Theoretical Thermochemistry for Fluoroethyl Radicals.

    PubMed

    Ganyecz, Ádám; Kállay, Mihály; Csontos, József

    2017-02-09

    An accurate coupled-cluster (CC) based model chemistry was applied to calculate reliable thermochemical quantities for hydrofluorocarbon derivatives including radicals 1-fluoroethyl (CH3-CHF), 1,1-difluoroethyl (CH3-CF2), 2-fluoroethyl (CH2F-CH2), 1,2-difluoroethyl (CH2F-CHF), 2,2-difluoroethyl (CHF2-CH2), 2,2,2-trifluoroethyl (CF3-CH2), 1,2,2,2-tetrafluoroethyl (CF3-CHF), and pentafluoroethyl (CF3-CF2). The model chemistry used contains iterative triple and perturbative quadruple excitations in CC theory, as well as scalar relativistic and diagonal Born-Oppenheimer corrections. To obtain heat of formation values with better than chemical accuracy perturbative quadruple excitations and scalar relativistic corrections were inevitable. Their contributions to the heats of formation steadily increase with the number of fluorine atoms in the radical reaching 10 kJ/mol for CF3-CF2. When discrepancies were found between the experimental and our values it was always possible to resolve the issue by recalculating the experimental result with currently recommended auxiliary data. For each radical studied here this study delivers the best heat of formation as well as entropy data.

  9. Retroperitoneal hematoma following radical orchiectomy: Two cases

    PubMed Central

    Glicksman, Rachel; Hamilton, Robert J.; Chung, Peter

    2017-01-01

    Treatment of testicular cancer is dependent on the stage of disease at presentation. Stage 1 testicular cancer is treated with radical orchiectomy, followed by active surveillance, radiotherapy, or chemotherapy. Occasionally, unusual and unexpected postoperative changes can be seen on computed tomography (CT), and may raise concern for metastatic disease. Here, we present two cases of testicular cancer patients who developed retroperitoneal hematomas post-radical orchiectomy, one as a classical clinical presentation, and the other as an atypical radiological entity only. The first is a case of a 38-year-old male with a non-seminoma testicular cancer, who developed severe flank pain, hemodynamic instability, and progressive anemia from a retroperitoneal hematoma in the immediate (<24 hours) postoperative period, requiring urgent surgical evacuation. The second is a case of a 33-year-old male with a testicular seminoma who had a large, suspicious retroperitoneal mass on a staging CT scan concerning for metastatic disease, which was later diagnosed as a retroperitoneal hematoma. These cases reveal the clinical variability with which a retroperitoneal hematoma post-radical orchiectomy may present. In addition, the second case demonstrates the importance of recognizing radiological postoperative changes and ensuring that these findings are not mistaken for and treated as metastatic disease. PMID:28163811

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

    PubMed

    Szijártó, Attila

    2015-11-22

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

  11. Probing RNA folding by hydroxyl radical footprinting.

    PubMed

    Costa, Maria; Monachello, Dario

    2014-01-01

    In recent years RNA molecules have emerged as central players in the regulation of gene expression. Many of these noncoding RNAs possess well-defined, complex, three-dimensional structures which are essential for their biological function. In this context, much effort has been devoted to develop computational and experimental techniques for RNA structure determination. Among available experimental tools to investigate the higher-order folding of structured RNAs, hydroxyl radical probing stands as one of the most informative and reliable ones. Hydroxyl radicals are oxidative species that cleave the nucleic acid backbone solely according to the solvent accessibility of individual phosphodiester bonds, with no sequence or secondary structure specificity. Therefore, the cleavage pattern obtained directly reflects the degree of protection/exposure to the solvent of each section of the molecule under inspection, providing valuable information about how these different sections interact together to form the final three-dimensional architecture. In this chapter we describe a robust, accurate and very sensitive hydroxyl radical probing method that can be applied to any structured RNA molecule and is suitable to investigate RNA folding and RNA conformational changes induced by binding of a ligand.

  12. Chemical Nonlinearities and Radical Pair Lifetime Estimation

    NASA Astrophysics Data System (ADS)

    Robinson, Gregory

    2013-03-01

    Much attention has recently developed around chemical reactions that depend on applied static magnetic fields as weak as earth's. This interest is largely motivated by experiments that implicate the role of spin-selective radical pair recombination in biological magnetic sensing. Existing literature uses a straightforward calculation to approximate the expected lifetime of coherent radical pairs as a function of the minimum RF amplitude that is observed to disrupt magnetic navigation, apparently by decohering the radical pair via electronic Zeeman excitations. But we show that chemical nonlinearities can preclude direct computation of coherent pair lifetime without considering the cellular signalling mechanisms involved, and discuss whether it can explain the surprising fragility of some animals' compass sense. In particular, we demonstrate that an autocatalytic cycle can introduce threshold effects on the disruption sensitivity to applied oscillatory magnetic fields. We will show examples in the mean-field limit and consider the consequences of noise and fluctuations in the Freidlin-Wentzell picture of perturbed dynamical systems.

  13. Free radical generation by selenium compounds

    SciTech Connect

    Yan, L.; Spallholz, J.E. )

    1991-03-11

    Sodium selenite, sodium selenate, selenocystine (SeCys) and selenomethionine (SeMet) were tested for their ability to generate free radicals in the absence and presence of glutathione (GSH) and in the presence of cells of the human mammary tumor cell line HTB123/DU4475. Free radical generation was measured by lucigenin or luminol enhanced chemiluminescence (CL). Lucigenin CL was observed form the reaction of selenite with GSH, 2-mercaptoethanol and L-cysteine. Catalase (CT), glutathione peroxidase (GSHPx) and superoxide dismutase (SOD) suppressed CL. Heat inactivated enzymes had no suppressive inhibition of CL. Luminol CL from the reaction of selenite with GSH was much less than that observed from lucigenin CL. In the presence of the human mammary tumor cells, lucigenin CL increased 5 times the CL produced by selenite or SeCys alone and GSH in the absence of tumor cells. The enhanced CL from these reactions in the presence of tumor cells was also suppressed by CT, GSHPx and SOD. These data suggest that free radicals, mainly superoxide (O{sub 2}{sup {minus}}) anion are produced by the reaction of selenite or SeCys with GSH. In the presence of tumor cells CL was enhanced which may account for selenite and Se Cys toxicity in vitro in comparison to the lesser toxicity of selenate or SeMet.

  14. 4.2.2 Primary alkyl radicals, type R2CH-CH2•

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  15. 4.3.6 Secondary alkyl radicals, type R1-ĊH-CHR2 2

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  16. 4.5.1.5 Alkyl radicals from 7- and higher membered rings

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  17. 4.5.2.1 Radicals from fused rings and spiro compounds

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  18. 4.2.4 Primary alkyl radicals, type R-CH2•

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  19. 4.2.1 Primary alkyl radicals, type R-CH2-CH2•

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  20. 4.5.1.3 Alkyl radicals from 5-membered rings

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  1. 4.3.7 Secondary alkyl radicals, type R1-ĊH-CR2 3

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  2. 4.5.1.2 Alkyl radicals from 4-membered rings

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  3. 4.3.8 Secondary alkyl radicals, type R1-ĊH-R2

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  4. 4.5.1.4 Alkyl radicals from 6-membered rings

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  5. 4.5.1.1 Alkyl radicals from 3-membered rings

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  6. 4.2.3 Primary alkyl radicals, type R3C-CH2•

    NASA Astrophysics Data System (ADS)

    Beckwith, A. L. J.

    This document is part of Subvolume A1 `Inorganic Radicals, Metal Complexes and Nonconjugated Carbon Centered Radicals' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  7. The reaction of formyl radical with chlorine atom

    NASA Astrophysics Data System (ADS)

    Qu, Zhang-Wang; Dong, Feng; Zhang, Qiyuan; Kong, Fanao

    2004-03-01

    The radical-radical reaction of formyl radical with chlorine atom has been investigated by the time-resolved infrared emission spectroscopy and by the theoretical calculations at the UB3LYP/6-31++G(d,p) and single-point UCCSD(T)/6-311++G(d,p) levels. The products have been verified as the vibrationally excited CO ( v⩽4) and HCl. The reaction is initiated by radical-radical recombination forming an intermediate of formaldehyde chloride, which further dissociates into the products of HCl and CO.

  8. Formation of stable radicals in the radiolysis of hexafluoropropylene

    SciTech Connect

    Allayarov, S.R.; Barkalov, I.M.; Lebedeva, M.Yu.; Loginova, N.N.; Mikhailov, A.I.

    1986-08-20

    The radiolysis of the dimer (perfluoro-4-methyl-2-pentene) and trimer (perfluoro-2,4-dimethyl-3-ethyl-2-pentene) of hexafluoropropylene (HFP) gives thermally stable perfluoroalkyl radicals. The stability of these radicals is apparently related to the steric isolation of the unpaired electron. The formation of a growing oligomer chain perfluoroalkyl radical which is stable in the liquid phase is observed upon the radiolysis of hexafluoropropylene. The radio-chemical yield of such a radical G approx. 0.05 x 10/sup -2/ eV. The low capacity of hexafluoropropylene to undergo homopolymerization is related to the formation of similar inactive radicals.

  9. Radicals contributing to preirradiation graft polymerization onto porous polyethylene

    NASA Astrophysics Data System (ADS)

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

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

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

    NASA Technical Reports Server (NTRS)

    Jackson, William M.

    1992-01-01

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

  11. Substituent effect on electronic transition energy of dichlorobenzyl radicals

    NASA Astrophysics Data System (ADS)

    Yoon, Young Wook; Chae, Sang Youl; Lee, Sang Kuk

    2016-01-01

    Ring-substituted benzyl radicals exhibit electronic energies of the D1 ⿿ D0 transition being shifted to red region with respect to the benzyl radical. The red-shifts of disubstituted benzyl radicals are highly dependent on the substitution positions irrespective of substituents. By analyzing the red-shifts of dichlorobenzyl radicals observed, we found that the substituent effect on electronic transition energy is attributed to the molecular plane shape of delocalized Ͽ electrons. We will discuss the influences of locations of Cl substituents on the D1 ⿿ D0 transition energies of dichlorobenzyl radicals using Hückel's molecular orbital theory.

  12. Radicals Are Required for Thiol Etching of Gold Particles.

    PubMed

    Dreier, Timothy A; Ackerson, Christopher J

    2015-08-03

    Etching of gold with an excess of thiol ligand is used in both synthesis and analysis of gold particles. Mechanistically, the process of etching gold with excess thiol is unclear. Previous studies have obliquely considered the role of oxygen in thiolate etching of gold. Herein, we show that oxygen or a radical initiator is a necessary component for efficient etching of gold by thiolates. Attenuation of the etching process by radical scavengers in the presence of oxygen, and the restoration of activity by radical initiators under inert atmosphere, strongly implicate the oxygen radical. These data led us to propose an atomistic mechanism in which the oxygen radical initiates the etching process.

  13. What is Radical Behaviorism? A Review of Jay Moore's Conceptual Foundations of Radical Behaviorism

    PubMed Central

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  15. The Reaction of Acetyl Peroxy Radical with Aldehyde: Impact on the OH Radical Model Simulation

    NASA Astrophysics Data System (ADS)

    Huang, D.; Chen, Z.

    2014-12-01

    Understanding the budget of OH (hydroxyl radical) is very important for investigating the atmospheric oxidation capacity, aerosol formation and climate change. Recent studies indicate that there may be a great gap between the modeled and measured OH concentrations in some rural forest areas. This gap may result from our incomplete knowledge about the oxidation mechanism of volatile organic compounds (VOCs). Here, we suggest that acetyl peroxy radical (CH3C(O)OO•), the OH-initiated oxidation intermediate of most VOCs, can take the H-atom from the aldehyde group to form corresponding peroxy carboxylic acids. This reaction has not been concerned in the atmosphere. The acetyl peroxy radical may share the "oxidation responsibility" of OH, and help saving OH from being consumed by aldehyde. Using a box model coupled with the isoprene-OH reaction mechanism selected from MCM v3.2, we get OH saving ratio (SROH) when we compare the modeled OH levels in the presence and absence of the reaction of acetyl peroxy radical with aldehyde. We find that SROH is not a constant but a function of OH production rate, reaction time, isoprene concentration and the ratio of aldehyde to isoprene. It is expected that CH3C(O)OO• radical, a non-OH oxidant, plays an important role in maintaining the oxidation capacity of the troposphere.

  16. Hydroxyl radical reactions and the radical scavenging activity of β-carboline alkaloids.

    PubMed

    Herraiz, Tomás; Galisteo, Juan

    2015-04-01

    β-Carbolines are bioactive pyridoindole alkaloids occurring in foods, plants and the human body. Their activity as hydroxyl radical (OH) scavengers is reported here by using three different methods: deoxyribose degradation, hydroxylation of benzoate and hydroxylation of 2'-deoxyguanosine to give 8-hydroxy-2'-deoxyguanosine (8-OHdG) as assessed by RP-HPLC (MS). Fenton reactions (Fe(2+)/Fe(3+) plus H2O2) were used for OH generation, and the radical increased in the presence of ascorbic acid or 6-hydroxydopamine as pro-oxidants. β-Carbolines were scavengers of OH in the three assays and in the presence of pro-oxidants. Tetrahydro-β-carboline-3-carboxylic acids were active against the hydroxylation of 2'-deoxyguanosine. β-Carbolines reacted with hydroxyl radicals (OH) affording hydroxy-β-carbolines, whereas tetrahydro-β-carbolines gave oxidative and degradation products. On the basis of IC50 and reaction rates (k), β-carbolines (norharman and harman), and tetrahydro-β-carbolines (tetrahydro-β-carboline, 1-methyltetrahydro-β-carboline and pinoline) were good OH radical scavengers and their activity was comparable to that of the indole, melatonin, which is an effective hydroxyl radical scavenger and antioxidant.

  17. Free radical scavenging activity of red ginseng aqueous extracts.

    PubMed

    Kim, Yoo K; Guo, Qiong; Packer, Lester

    2002-03-20

    This study was performed to investigate the free radical scavenging activity of Panax red ginseng C.A. Meyer aqueous extract on 1,1-dipheny-2-picrylhydrazyl (DPPH), carbon-centered radical, hydroxyl and superoxide radicals using Electron Spin Resonance (ESR) spectrometer and spin-trapping techniques. Two different Red ginseng aqueous extracts prepared by boiling water or room temperature extraction exhibited no significant difference in free radical scavenging activity. Ginseng extracts completely eliminated DPPH radical at 2 mg/ml. About 0.5 mg/ml ginseng extracts quenched 80% carbon-centered free radicals generated from 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH). Hydroxyl radical and superoxide radical were generated by UV irradiation and trapped by 5,5-dimethyl-l-pyrroline-N oxide (DMPO). Ginseng extracts scavenged 40% of hydroxyl radical at 0.1 mg/ml. Two mg/ml ginseng extracts completely scavenged superoxide radical. Ginseng extracts did not scavenge nitric oxide. The ESR data demonstrate that red ginseng aqueous extract is not a strong free radical scavenger.

  18. Total free radical species and oxidation equivalent in polluted air.

    PubMed

    Wang, Guoying; Jia, Shiming; Niu, Xiuli; Tian, Haoqi; Liu, Yanrong; Chen, Xuefu; Li, Lan; Zhang, Yuanhang; Shi, Gaofeng

    2017-12-31

    Free radicals are the most important chemical intermediate or agent of the atmosphere and influenced by thousands of reactants. The free radicals determine the oxidizing power of the polluted air. Various gases present in smog or haze are oxidants and induce organ and cellular damage via generation of free radical species. At present, however, the high variability of total free radicals in polluted air has prevented the detection of possible trends or distributions in the concentration of those species. The total free radicals are a kind of contaminants with colorless, tasteless characteristics, and almost imperceptible by human body. Here we present total free radical detection and distribution characteristics, and analyze the effects of total free radicals in polluted air on human health. We find that the total free radical values can be described by not only a linear dependence on ozone at higher temperature period, but also a linear delay dependence on particulate matter at lower temperature period throughout the measurement period. The total free radical species distribution is decrease from west to east in Lanzhou, which closely related to the distribution of the air pollutants. The total free radical oxidation capacity in polluted air roughly matches the effects of tobacco smoke produced by the incomplete combustion of a controlled amount of tobacco in a smoke chamber. A relatively unsophisticated chromatographic fingerprint similarity is used for indicating preliminarily the effect of total free radicals in polluted air on human health. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Covalently Bound Nitroxyl Radicals in an Organic Framework

    SciTech Connect

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

    2016-09-15

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

  20. Free radicals, exercise and antioxidant supplementation.

    PubMed

    Kanter, M

    1998-02-01

    Although conflicting data exist, the preponderance of available information suggests that physical exercise promotes an increase in free-radical generation. However, few studies have actually measured exercise-induced free radicals directly, primarily because of a lack of sophisticated methodologies to measure this phenomenon. Instead, researchers have relied heavily on the measurement of lipid peroxidation as the principal indicator of exercise-induced free radicals. It should be noted that free radicals can also alter and inactivate enzyme complexes, damage DNA and RNA, and promote mutations and cancer, among other activities. However, there have been few reported studies dealing with exercise and oxidant stress which have measured these outcomes. It should also be noted that free-radical species are continuously produced in the human body, and that some have beneficial effects (Arouma, 1994), notably as a part of the body's natural immune system. It is not presently known if long-term ingestion of antioxidant compounds will affect these positive aspects of free-radical generation. The preponderance of available evidence suggests that antioxidant supplementation, particularly with the vitamins C and E, has favourable effects on markers of lipid peroxidation following exercise. Although the physiological implications of these effects remain to be elucidated, the prudent use of an antioxidant supplement can provide insurance against a suboptimal diet and/or the elevated demands of physical activity. Future research may uncover additional nutritional antioxidants that can benefit the physically-active individual. Numerous additional questions regarding the antioxidant needs for physical activity remain to be answered. Little is known about the needs of physically-active women, particularly those who habitually consume an energy-restricted diet, or the effects of monthly menstrual blood loss (coupled with exercise) on antioxidant requirements. The needs of the

  1. Electron spin resonance spectroscopic studies of radical cation reactions

    SciTech Connect

    Dai, S.

    1990-01-01

    A spin Hamiltonian suitable for theoretical analyses of ESR spectra is derived using the general effective Hamiltonian theory in the usual Schroedinger representation. The Permutation Indices method is extended to obtain the dynamic exchange equations used in ESR lineshape simulation. The correlation between [beta]-hydrogen coupling constants and their geometric orientations are derived using a perturbation method. The three electron bond model is extended to rationalize unimolecular rearrangements of radical cations. The ring-closed radical cations of 9,10-octalin oxide and synsesquinorbornene oxide have been characterized by ESR spectroscopy in the CFCl[sub 3] matrix at low temperature. The self-electron-transfer rate constants between the methyl viologen dication and cation have been determined by dynamic ESR lineshape simulations at room temperature in allyl alcohol, water, methanol and propargyl alcohol solvents. The radical cation formed by the radiolytic oxidation of allylamine in Freon matrices at 77 K is the 3-iminiopropyl distonic species(3-iminium-1-propyl radical). The nucleophilic endocylization of the but-3-en-1-ol radical cation to the protonated tetrahydrofuran-3-yl radical was observed in the radiolytic oxidation of but-3-en-1-ol in Freon matrices. ESR studies of the radiolytic oxidation of 1,5-hexdiyne have resulted in characterization the 1,5-hexadiyne radical cation isomerizing to the 1,2,4,5-hexatetraene radical cation. The symmetric (C[sub 2v]) bicyclo[3.3.0]-octa-2,6-diene-4,8-diyl(a bridged 1,4-bishomobenzene species) radical cation is produced by the radiolytic oxidation of semibullvalene in Freon matrices. The ring-opening 3,4-dimethylenecyclobutene radical cation to 1,2,4,5-hexatetraene radical cation was observed in the photolysis of 3,4-dimethylenecyclobutene radical cation. The cyclooctatetraene radical cation generated by radiolytic oxidation photoisomerizes to bicyclo[3.3.0]octa-2,6-diene-4,8-diyl radical cation.

  2. Radical cyclizations of cyclic ene sulfonamides occur with β-elimination of sulfonyl radicals to form polycyclic imines

    PubMed Central

    Zhang, Hanmo; Hay, E. Ben; Geib, Steven J.; Curran, Dennis P.

    2013-01-01

    Radical cyclizations of cyclic ene sulfonamides provide stable bicyclic and tricyclic aldimines and ketimines in good yields. Depending on the structure of the precursor, the cyclizations occur to provide fused and spirocyclic imines with five-, six-, and seven-membered rings. The initial radical cyclization produces an α-sulfonamidoyl radical that undergoes elimination to form the imine and a phenylsulfonyl radical. In a related method, 3,4-dihydroquinolines can also be produced by radical translocation reactions of N-(2-iodophenylsulfonyl)tetrahydroisoquinolines. In either case, very stable sulfonamides are cleaved to form imines (rather than amines) under mild reductive conditions. PMID:24111991

  3. Radical cyclizations of cyclic ene sulfonamides occur with β-elimination of sulfonyl radicals to form polycyclic imines.

    PubMed

    Zhang, Hanmo; Hay, E Ben; Geib, Steven J; Curran, Dennis P

    2013-11-06

    Radical cyclizations of cyclic ene sulfonamides provide stable bicyclic and tricyclic aldimines and ketimines in good yields. Depending on the structure of the precursor, the cyclizations occur to provide fused and spirocyclic imines with five-, six-, and seven-membered rings. The initial radical cyclization produces an α-sulfonamidoyl radical that undergoes elimination to form the imine and a phenylsulfonyl radical. In a related method, 3,4-dihydroquinolines can also be produced by radical translocation reactions of N-(2-iodophenylsulfonyl)tetrahydroiso-quinolines. In either case, very stable sulfonamides are cleaved to form imines (rather than amines) under mild reductive conditions.

  4. Experiencia Pedagogica con Adolescentes Paraliticos Cerebrales: La Musica, Un Elemento Rehabilitador (A Pedagogical Experience with Teenage Cerebral Paralytics Using Music as a Rehabilitating Element).

    ERIC Educational Resources Information Center

    Colomer, Marta; And Others

    The monograph describes efforts carried out in the Department of Work Therapy of a center for cerebral paralysis in Barcelona, Spain. The rehabilitation program incorporated music and movement in an attempt to develop the musical ear, sensitivity, and a sensorial education. The program stresses rhythm, melody, harmony, voice, musical audition, and…

  5. Experiencia Pedagogica con Adolescentes Paraliticos Cerebrales: La Musica, Un Elemento Rehabilitador (A Pedagogical Experience with Teenage Cerebral Paralytics Using Music as a Rehabilitating Element).

    ERIC Educational Resources Information Center

    Colomer, Marta; And Others

    The monograph describes efforts carried out in the Department of Work Therapy of a center for cerebral paralysis in Barcelona, Spain. The rehabilitation program incorporated music and movement in an attempt to develop the musical ear, sensitivity, and a sensorial education. The program stresses rhythm, melody, harmony, voice, musical audition, and…

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

    PubMed

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

    2015-01-01

    Free radicals and oxidants are now implicated in physiological responses and in several diseases. Given the wide range of expertise of free radical researchers, application of the greater understanding of chemistry has not been uniformly applied to biological studies. We suggest that some widely used methodologies and terminologies hamper progress and need to be addressed. We make the case for abandonment and judicious use of several methods and terms and suggest practical and viable alternatives. These changes are suggested in four areas: use of fluorescent dyes to identify and quantify reactive species, methods for measurement of lipid peroxidation in complex biological systems, claims of antioxidants as radical scavengers, and use of the terms for reactive species. Copyright © 2014 Elsevier Inc. All rights reserved.

  7. Mobile protons versus mobile radicals: gas-phase unimolecular chemistry of radical cations of cysteine-containing peptides.

    PubMed

    Lam, Adrian K Y; Ryzhov, Victor; O'Hair, Richard A J

    2010-08-01

    A combination of electrospray ionization (ESI), multistage, and high-resolution mass spectrometry experiments are used to examine the gas-phase fragmentation reactions of radical cations of cysteine containing di- and tripeptides. Two different chemical methods were used to form initial populations of radical cations in which the radical sites were located at different positions: (1) sulfur-centered cysteinyl radicals via bond homolysis of protonated S-nitrosocysteine containing peptides; and (2) alpha-carbon backbone-centered radicals via Siu's sequence of reactions (J. Am. Chem. Soc.2008, 130, 7862). Comparison of the fragmentation reactions of these regiospecifically generated radicals suggests that hydrogen atom transfer (HAT) between the alpha C-H of adjacent residues and the cysteinyl radical can occur. In addition, using accurate mass measurements, deuterium labeling, and comparison with an authentic sample, a novel loss of part of the N-terminal cysteine residue was shown to give rise to the protonated, truncated N-formyl peptide (an even-electron x(n) ion). DFT calculations were performed on the radical cation [GCG]*(+) to examine: the relative stabilities of isomers with different radical and protonation sites; the barriers associated with radical migration between four possible radical sites, [G*CG](+), [GC*G](+), [GCG*](+), and [GC(S*)G](+); and for dissociation from these sites to yield b(2)-type ions. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2011-10-01

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

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

    PubMed Central

    2014-01-01

    Background The goal of this study was to compare treatment outcomes for Federation of Gynecology and Obstetrics (FIGO) stage IIB cervical carcinoma patients receiving radical surgery followed by adjuvant postoperative radiotherapy versus radical radiotherapy. Methods Medical records of FIGO stage IIB cervical cancer patients treated between July 2008 and December 2011 were retrospectively reviewed. A total of 148 patients underwent radical hysterectomy with pelvic lymph node dissection followed by adjuvant radiotherapy (surgery-based group). These patients were compared with 290 patients that received radical radiotherapy alone (RT-based group). Recurrence rates, progression-free survival (PFS), overall survival (OS), local control rates, and treatment-related complications were compared for these two groups. Results Similar rates of recurrence (16.89% vs. 12.41%, p = 0.200), PFS (log-rank, p = 0.211), OS (log-rank, p = 0.347), and local control rates (log-rank, p = 0.668) were observed for the surgery-based group and the RT-based group, respectively. Moreover, the incidence of acute grade 3–4 gastrointestinal reactions and late grade 3–4 lower limb lymphedema were significantly higher for the surgery-based group versus the RT-based group. Cox multivariate analyses found no significant difference in survival outcome between the two groups, and tumor diameter and histopathology were identified as significant prognostic factors for OS. Conclusions Radical radiotherapy was associated with fewer treatment-related complications and achieved comparable survival outcomes for patients with FIGO stage IIB cervical cancer compared to radical hysterectomy followed by postoperative radiotherapy. PMID:24495453

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  11. Standard electrode potentials involving radicals in aqueous solution: inorganic radicals (IUPAC Technical Report)

    DOE PAGES

    Armstrong, David A.; Huie, Robert E.; Koppenol, Willem H.; ...

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1990-07-01

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

  13. Spectroscopic identification of dichlorobenzyl radicals: Jet-cooled 2,3-dichlorobenzyl radical

    NASA Astrophysics Data System (ADS)

    Chae, Sang Youl; Yoon, Young Wook; Lee, Sang Kuk

    2015-07-01

    The vibronically excited but jet-cooled 2,3-dichlorobenzyl radical was generated from the corona discharge of precursor 2,3-dichlorotoluene seeded in a large amount of carrier gas He using a pinhole-type glass nozzle. From an analysis of the visible vibronic emission spectrum observed, we obtained the electronic energy of the D1 → D0 transition and vibrational mode frequencies in the D0 state of the 2,3-dichlorobenzyl radical by comparing the observation with the results of ab initio calculations. In addition, we discussed substituent effect of Cls on electronic transition energy in terms of substituent orientation for the first time.

  14. Taking a Radical Position: Evidence for Position-Specific Radical Representations in Chinese Character Recognition Using Masked Priming ERP

    PubMed Central

    Su, I.-Fan; Mak, Sin-Ching Cassie; Cheung, Lai-Ying Milly; Law, Sam-Po

    2012-01-01

    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 et al., 2004; Tsang and 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 96 ms 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 event-related potential (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. PMID:23024634

  15. Taking a Radical Position: Evidence for Position-Specific Radical Representations in Chinese Character Recognition Using Masked Priming ERP.

    PubMed

    Su, I-Fan; Mak, Sin-Ching Cassie; Cheung, Lai-Ying Milly; Law, Sam-Po

    2012-01-01

    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 et al., 2004; Tsang and 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 96 ms 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 event-related potential (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.

  16. Free Radical Scavenging Activity of Leaves of Alocasia indica (Linn).

    PubMed

    Mulla, W A; Salunkhe, V R; Kuchekar, S B; Qureshi, M N

    2009-05-01

    The free radical scavenging potential of the plant Alocasia indica(Linn.) was studied by using different antioxidant models of screening like scavenging of 1,1-diphenyl-2-picryl hydrazyl radical, nitric oxide radical, superoxide anion radical, hydroxyl radical, iron chelating activity, total antioxidant capacity, non-enzymatic glycosylation of haemoglobin, rapid screening for antioxidant compounds by thin layer chromatography. The hydroalcoholic extract at 1000 mug/ml showed maximum scavenging of superoxide radical (87.17) by riboflavin-NBT-system, followed by scavenging of stable radical 1,1-diphenyl-2-picryl hydrazyl radical (83.48%), nitric oxide radical (74.09%) hydroxyl radical (60.96%) at the same concentration. However the extract showed only moderate activity by iron chelation (68.26%). That could be due to higher phenolic content in the extract. This finding suggests that hydro alcoholic extract of A. indica possess potent in vitro antioxidant activity as compared to the standard ascorbic acid. The results justify the therapeutic applications of the plant in the indigenous system of medicine, augmenting its therapeutic value.

  17. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    PubMed Central

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-01-01

    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. PMID:26960916

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

    NASA Astrophysics Data System (ADS)

    Hu, Na; Green, Sarah A.

    2014-10-01

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

  19. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    NASA Astrophysics Data System (ADS)

    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.

  20. Free Radical Scavenging Activity of Leaves of Alocasia indica (Linn)

    PubMed Central

    Mulla, W. A.; Salunkhe, V. R.; Kuchekar, S. B.; Qureshi, M. N.

    2009-01-01

    The free radical scavenging potential of the plant Alocasia indica(Linn.) was studied by using different antioxidant models of screening like scavenging of 1,1-diphenyl-2-picryl hydrazyl radical, nitric oxide radical, superoxide anion radical, hydroxyl radical, iron chelating activity, total antioxidant capacity, non-enzymatic glycosylation of haemoglobin, rapid screening for antioxidant compounds by thin layer chromatography. The hydroalcoholic extract at 1000 μg/ml showed maximum scavenging of superoxide radical (87.17) by riboflavin-NBT-system, followed by scavenging of stable radical 1,1-diphenyl-2-picryl hydrazyl radical (83.48%), nitric oxide radical (74.09%) hydroxyl radical (60.96%) at the same concentration. However the extract showed only moderate activity by iron chelation (68.26%). That could be due to higher phenolic content in the extract. This finding suggests that hydro alcoholic extract of A. indica possess potent in vitro antioxidant activity as compared to the standard ascorbic acid. The results justify the therapeutic applications of the plant in the indigenous system of medicine, augmenting its therapeutic value. PMID:20490298

  1. Acetyl Radical Generation in Cigarette Smoke: Quantification and Simulations

    PubMed Central

    Hu, Na; Green, Sarah A.

    2014-01-01

    Free radicals are present in cigarette smoke and can have a negative effect on human health. However, little is known about their formation mechanisms. Acetyl radicals were quantified in tobacco smoke and mechanisms for their generation were investigated by computer simulations. Acetyl radicals were trapped from the gas phase using 3-amino-2, 2, 5, 5-tetramethyl-proxyl (3AP) on solid support to form stable 3AP adducts for later analysis by high performance liquid chromatography (HPLC), mass spectrometry/tandem mass spectrometry (MS-MS/MS) and liquid chromatography–mass spectrometry (LC-MS). Simulations were performed using the Master Chemical Mechanism (MCM). A range of 10–150 nmol/cigarette of acetyl radical was measured from gas phase tobacco smoke of both commerial and research cigarettes under several different smoking conditions. More radicals were detected from the puff smoking method compared to continuous flow sampling. Approximately twice as many acetyl radicals were trapped when a glass filber particle filter (GF/F specifications) was placed before the trapping zone. Simulations showed that NO/NO2 reacts with isoprene, initiating chain reactions to produce hydroxyl radical, which abstracts hydrogen from acealdehyde to generate acetyl radical. These mechanisms can account for the full amount of acetyl radical detected experimentally from cigarette smoke. Similar mechanisms may generate radicals in second hand smoke. PMID:25253993

  2. Experimental evidence for efficient hydroxyl radical regeneration in isoprene oxidation

    NASA Astrophysics Data System (ADS)

    Fuchs, H.; Hofzumahaus, A.; Rohrer, F.; Bohn, B.; Brauers, T.; Dorn, H.-P.; Häseler, R.; Holland, F.; Kaminski, M.; Li, X.; Lu, K.; Nehr, S.; Tillmann, R.; Wegener, R.; Wahner, A.

    2013-12-01

    Most pollutants in the Earth's atmosphere are removed by oxidation with highly reactive hydroxyl radicals. Field measurements have revealed much higher concentrations of hydroxyl radicals than expected in regions with high loads of the biogenic volatile organic compound isoprene. Different isoprene degradation mechanisms have been proposed to explain the high levels of hydroxyl radicals observed. Whether one or more of these mechanisms actually operates in the natural environment, and the potential impact on climate and air quality, has remained uncertain. Here, we present a complete set of measurements of hydroxyl and peroxy radicals collected during isoprene-oxidation experiments carried out in an atmospheric simulation chamber, under controlled atmospheric conditions. We detected significantly higher concentrations of hydroxyl radicals than expected based on model calculations, providing direct evidence for a strong hydroxyl radical enhancement due to the additional recycling of radicals in the presence of isoprene. Specifically, our findings are consistent with the unimolecular reactions of isoprene-derived peroxy radicals postulated by quantum chemical calculations. Our experiments suggest that more than half of the hydroxyl radicals consumed in isoprene-rich regions, such as forests, are recycled by these unimolecular reactions with isoprene. Although such recycling is not sufficient to explain the high concentrations of hydroxyl radicals observed in the field, we conclude that it contributes significantly to the oxidizing capacity of the atmosphere in isoprene-rich regions.

  3. Ab initio studies of hydrocarbon peroxyl radicals

    SciTech Connect

    Besler, B.H.; Sevilla, M.D.; MacNeille, P.

    1986-11-20

    Extensive ab initio molecular orbital calculations have been performed for the importance series of peroxyl radicals (O/sub 2//sup .-/), HO/sub 2//sup ./, CH/sub 3/O/sub 2//sup ./, (CH/sub 3/)/sub 2/CHO/sub 2//sup ./, and (CH/sub 3/CH/sub 2/)/sub 2/CHO/sub 2//sup ./. Parameters calculated include equilibrium geometries, harmonic vibrational frequencies, dipole moments, and isotropic and anisotropic hyperfine couplings. Equilibrium geometries were of primary interest. In the two large hydrocarbon peroxyl radicals the carbon atoms and appropriate hydrogen atoms were constrained to be coplanar and the O-O group was forced to be perpendicular to the carbon chain in order to stimulate the presence of a peroxyl radical site in a polyethylene chain. Calculations were performed with large Gaussian basis sets (up to 6-311 ++G(d,p)). Calculations for HO/sub 2//sup ./ including electron correlation utilizing Moeller-Plesset perturbation theory were performed at the following levels: MP2(6-31G(d)) and 6-311G(d,p), MP3(6-311G(d,p)) and MP4SDTQ(6-311(d,p)). Calculated values are compared against the highly accurate experimental data for HO/sub 2//sup ./ known from microwave, laser magnetic resonance, and diode laser studies in order to determine the level of calculation necessary for accurate predictions. Comparison of the various calculations shows that MP2(6-31G(d)) compares favorably with MP4SDTQ(6-311G(d,p)) at a considerable savings in computation time.

  4. Isoprene, sulphoxy radical-anions and acidity

    NASA Astrophysics Data System (ADS)

    Rudziński, K. J.; Gmachowski, L.; Kuznietsova, I.

    2008-12-01

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

  5. Kinetics and Near-Infrared Spectroscopy of Organic Peroxy Radicals

    NASA Astrophysics Data System (ADS)

    Smarte, M. D.; Okumura, M.

    2016-12-01

    Organic peroxy radicals are important intermediates in atmospheric chemistry with fates that control the rate of radical propagation in an oxidation mechanism. Laboratory methods for detecting peroxy radicals are essential to measuring precise rate constants that constrain these fates. In this work, we discuss the use of near-infrared cavity ringdown spectroscopy to detect organic peroxy radicals for the purpose of laboratory kinetics measurements. We focus on chlorine-substituted peroxy radicals generated in the oxidation of alkenes by chlorine, a minor tropospheric oxidant found in marine and coastal regions. Previous kinetics experiments on peroxy radicals have largely used UV absorption spectroscopy via the dissociative B-X transition. However, the spectra produced are featureless and exhibit substantial overlap; determining the concentration profile of an individual peroxy radical can be an arduous task. In our work, we probe the forbidden peroxy radical A-X transition in the near-infrared. While this approach requires overcoming small cross sections ( 10-21 cm2), the A state is bound and leads to structured absorption spectra that may be useful in constraining the kinetics of mixtures of organic peroxy radicals formed in the oxidation of complex hydrocarbons. Only a few kinetics studies utilizing the A-X transition exist in the literature and they are focused on small, unsubstituted species. This presentation explores the ability of the A-X transition to unravel the kinetics of more complex peroxy radicals in laboratory experiments using several example systems: (1) Determining rate constants for the self and cross reactions of β-chloroethylperoxy and HO2. (2) Detecting the second generation of peroxy radicals formed from alkoxy radical decomposition in the chlorine-initiated oxidation of 2-butene. (3) Observing different rates of reactivity with NO across the pool of peroxy radical isomers formed in the chlorine-initiated oxidation of isoprene.

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

    NASA Astrophysics Data System (ADS)

    Tobin, Kenneth

    2007-07-01

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

  7. Radical Nature of C-Lignin

    SciTech Connect

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

    2016-05-17

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

  8. [Detrusor underactivity following laparoscopic radical prostatectomy].

    PubMed

    Ishida, Yoko; Matsukawa, Yoshihisa; Komatsu, Tomonori; Yoshikawa, Yoko; Hattori, Ryohei; Goton, Momokazu

    2008-04-01

    Strain voiding has been reported to be a frequent symptom following radical prostatectomy. However, pathophysiology of vesicourethral function underlying voiding difficulty has not been well studied. In the present study, we investigated detrusor underactivity following radical prostatectomy. The records on urodynamic study (pressure-flow study, urethral pressure profile) were retrospectively investigated in 80 patients undergoing laparoscopic radical prostatectomy and all urodynamic studies pre- and post-operatively. We extracted the cases with detrusor underactivity according to the criteria of overt strain voiding pattern on post-operative pressure flow study; detrusor pressure at the maximum flow rate (Pdet Q(max)) of less than 10 cmH2O in conjunction with an increase of abdominal pressure. Of the 80 patients, 6 (7.5%) were found to have detrusor underactivity. In all patients, good detrusor contraction was confirmed on the pre-operative urodynamic study performed before surgery. On the voiding phase of pressure-flow study in these patients, mean Pdet Q(max) showed a significant decrease postoperatively from 58.5 cmH2O to 3.0 cmH2O (p < 0.01), although mean abdominal pressure at Q(max) significantly increased from 24.2 cmH2O to 105.8 cmH2O (p < 0.05). Mean Q(max) on free uroflowmetry showed a significant increase from 12.8 ml/sec to 22.1 ml/sec (p < 0.05). No patient had significant post-void residual urine. On the storage phase of the study, however, maximum cystometric capacity, maximum urethral closing pressure showed no significant change between pre- and post-operative studies. Five patients acquired continence and one had mild urinary incontinence using one pad a day. The present study showed that detrusor contaractility could be impaired during radical prostatectomy, but, no apparent operative procedure related to detrusor dysfunction could be identified in the present patients.

  9. Fragmentation Pathways in the Uracil Radical Cation

    SciTech Connect

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

    2012-08-24

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

  10. Radical Nature of C-Lignin

    DOE PAGES

    Berstis, Laura; Elder, Thomas; Crowley, Michael; ...

    2016-05-17

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

  11. From Living Carbocationic to Living Radical Polymerization.

    DTIC Science & Technology

    1994-06-30

    C 1 -OFFICE OF NAVAL RESEARCH CONTRACT N00014-94-1-0101 R&T Code 31321075 Technical Report No. 18 FROM " LIVING " CARBOCATIONIC TO " LIVING " RADICAL...NUMBERS "From Living " Carbocationic to " Living " ’jical Polymerization N00014-94-1-01I01 6. AUTHOR(S) Krzysztof Matyjaszewski 7. PERFORMING ORGANIZATION NAME...1994) 1Za. DISTRIBUTION I AVAILABILITY STATEMENT 12b. DISTRIBUTION CODE 13. ABSTRACT (Maximum 200 words) " Living " carbocationic polymerization is

  12. Laser Studies of Gas Phase Radical Reaction.

    DTIC Science & Technology

    1985-11-30

    1nai Irvest-aator Or.G. Hancock gn; FILE CO, Contr3ctor : Oxford University . Physical Chemistry Laboratory. South Parks Road.AD-A 193 689 Oxfor o~d...HIF spectrum and study of reaction of this and the CCI radical with atoms vi) sea;rchtrr; f(r FC) ’ndlict of the 0 *CF, reaction. OXFORD UNIVERSITY -. - SOUTH...0 Awtilability Codes I Avail ’and/or Dis Spcal0 Spoo OXFORD UNIVERSITY Tt SOUTH PARKS ROAD OXFCRD OXFORD � X3Z U.S. Army Contract DAJA45-85-C-0034

  13. Radical Nature of C-Lignin

    SciTech Connect

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

    2016-05-17

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

  14. Free radical kinetics on irradiated fennel

    NASA Astrophysics Data System (ADS)

    Yamaoki, Rumi; Kimura, Shojiro; Ohta, Masatoshi

    2008-09-01

    Herein, an electron spin resonance study on the behavior of organic radicals in fennel before and after irradiation is reported. The spectrum of irradiated fennel composed of the spectrum component derived from the un-irradiated sample (near g=2.005) and the spectra components derived from carbohydrates. The time decay of intensity spectral components was well explained by first-order kinetics with a variety of rate constants. Especially, the signal at near g=2.02 ascribed to stable cellulose-derivative components is expected to be a good indicator in the identification of irradiated plant samples.

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

    PubMed

    El-Agamey, Ali; McGarvey, David J

    2016-01-01

    The reactions of acetylperoxyl radicals with different carotenoids (7,7'-dihydro-β-carotene and ζ-carotene) in SDS and CTAC microemulsions of different compositions were investigated using laser flash photolysis (LFP) coupled with kinetic absorption spectroscopy. The primary objective of this study was to explore the influence of microemulsion composition and the type of surfactant used on the yields and kinetics of various transients formed from the reaction of acetylperoxyl radicals with carotenoids. Also, the influence of the site (hydrocarbon phases or aqueous phase) of generation of the peroxyl radical precursor was examined by using 4-acetyl-4-phenylpiperidine hydrochloride (APPHCl) and 1,1-diphenylacetone (11DPA) as water-soluble and lipid-soluble peroxyl radical precursors, respectively. LFP of peroxyl radical precursors with 7,7'-dihydro-β-carotene (77DH) in different microemulsions gives rise to the formation of three distinct transients namely addition radical (λmax=460 nm), near infrared transient1 (NIR, λmax=700 nm) and 7,7'-dihydro-β-carotene radical cation (77DH(•+), λmax=770 nm). In addition, for ζ-carotene (ZETA) two transients (near infrared transient1 (NIR1, λmax=660 nm) and ζ-carotene radical cation (ZETA(•+), λmax=730-740 nm)) are generated following LFP of peroxyl radical precursors in the presence of ζ-carotene (ZETA) in different microemulsions. The results show that the composition of the microemulsion strongly influences the observed yield and kinetics of the transients formed from the reactions of peroxyl radicals (acetylperoxyl radicals) with carotenoids (77DH and ZETA). Also, the type of surfactant used in the microemulsions influences the yield of the transients formed. The dependence of the transient yields and kinetics on microemulsion composition (or the type of surfactant used in the microemulsion) can be attributed to the change of the polarity of the microenvironment of the carotenoid. Furthermore, the nature of

  16. On the mechanism of reaction of radicals with tirapazamine.

    PubMed

    Shi, Xiaofeng; Mandel, Sarah M; Platz, Matthew S

    2007-04-18

    Ketyl radicals produced by photolysis of ketones or di-tert-butyl peroxide (DTBP) in alcohol solvents react rapidly with tirapazamine (TPZ). The acetone ketyl radical (ACOH) reacts with TPZ with an absolute second-order rate constant of (9.7 +/- 0.4) x 108 M-1 s-1. The reaction kinetics can be followed by monitoring the bleaching of TPZ absorption at 475 nm or the formation of a reaction product which absorbs at 320 and 410 nm. The ACOD radical reacts with TPZ in 2-propanol-OD with an absolute rate constant of (6.7 +/- 0.5) x 108 M-1 s-1, corresponding to a kinetic isotope effect (KIE) of 1.4. Deuteration of the radical on carbon (ACOH-d6) retards the reaction of the radical with TPZ even further (absolute rate constant = (4.8 +/- 0.04) x 108 M-1 s-1). This result corresponds to a KIE of 2.0. Radicals derived from dioxane and diisopropyl ether by flash photolysis of DTBP in ethereal solvent react with TPZ more slowly than do ketyl radicals. It is concluded that ketyl radicals react, in part, with TPZ in organic solvents by transfer of a hydrogen atom from the OH and CH3 groups of the ketyl radical to the oxygen atom at the N4 position of TPZ to form acetone or acetone enol and a radical derivative of TPZ (TPZH). The latter species absorbs at 320 and 405 nm, has a lifetime of hundreds of microseconds in alcohol solvents, and decays by disproportionation to form TPZ and a reduced heterocycle. The reduced heterocycle eventually forms a desoxytirapazamine by a polar mechanism. The results are supported by density functional theory calculations. It is proposed that dioxanyl radical will also react, in part, with TPZ by transfer of a hydrogen atom from the carbon adjacent to the radical center to the oxygen atom at the N4 position of TPZ. This produces the enol ether and the previously mentioned TPZH radical. It is further posited that ether radicals react a bit more slowly than ketyl radicals because they lack the second mode of hydrogen transfer (from the OH group

  17. Carbohydrate radicals: from ethylene glycol to DNA strand breakage.

    PubMed

    von Sonntag, Clemens

    2014-06-01

    Radiation-induced DNA strand breakage results from the reactions of radicals formed at the sugar moiety of DNA. In order to elucidate the mechanism of this reaction investigations were first performed on low molecular weight model systems. Results from studies on deoxygenated aqueous solutions of ethylene glycol, 2-deoxy-d-ribose and other carbohydrates and, more relevantly, of d-ribose-5-phosphate have shown that substituents can be eliminated from the β-position of the radical site either proton and base-assisted (as in the case of the OH substituent), or spontaneously (as in the case of the phosphate substituent). In DNA the C(4') radical undergoes strand breakage via this type of reaction. In the presence of oxygen the carbon-centred radicals are rapidly converted into the corresponding peroxyl radicals. Again, low molecular weights models have been investigated to elucidate the key reactions. A typical reaction of DNA peroxyl radicals is the fragmentation of the C(4')-C(S') bond, a reaction not observed in the absence of oxygen. Although OH radicals may be the important direct precursors of the sugar radicals of DNA, results obtained with poly(U) indicate that base radicals may well be of even greater importance. The base radicals, formed by addition of the water radicals (H and OH) to the bases would in their turn attack the sugar moiety to produce sugar radicals which then give rise to strand breakage and base release. For a better understanding of strand break formation it is therefore necessary to investigate in more detail the reactions of the base radicals. For a start, the radiolysis of uracil in oxygenated solutions has been reinvestigated, and it has been shown that the major peroxyl radical in this system undergoes base-catalysed elimination of [Formula: see text], a reaction that involves the proton at N(l). In the nucleic acids the pyrimidines are bound at N(l) to the sugar moiety and this type of reaction can no longer occur. Therefore, with

  18. Radical Reform Within a Liberal and Democratic Framework? Rawls and the Radical Critique of Schooling.

    ERIC Educational Resources Information Center

    Claus, John F.

    1981-01-01

    The radical critique of American education portrays the schools as perpetuators of ethnic, social, and racial inequalities because they do not alter existing class relations. John Rawls' theory of social justice is discussed as an alternative approach to this situation that remains firmly grounded in the liberal tradition. (PP)

  19. Bromine radical-mediated sequential radical rearrangement and addition reaction of alkylidenecyclopropanes.

    PubMed

    Kippo, Takashi; Hamaoka, Kanako; Ryu, Ilhyong

    2013-01-16

    Bromine radical-mediated cyclopropylcarbinyl-homoallyl rearrangement of alkylidenecyclopropanes was effectively accomplished by C-C bond formation with allylic bromides, which led to the syntheses of 2-bromo-1,6-dienes. A three-component coupling reaction comprising alkylidenecyclopropanes, allylic bromides, and carbon monoxide also proceeded well to give 2-bromo-1,7-dien-5-ones in good yield.

  20. Antioxidant capacity of betacyanins as radical scavengers for peroxyl radical and nitric oxide.

    PubMed

    Taira, Junsei; Tsuchida, Eito; Katoh, Megumi C; Uehara, Masatsugu; Ogi, Takayuki

    2015-01-01

    This study was designed to assess the antioxidant capacity of betacyanins as indole derived plant pigments, such as betanin, phyllocactin and betanidin. The antioxidant capacity of the betacyanins was evaluated as an index of radical scavenging ability using the peroxyl radical generating system in the presence of AAPH and NO generating system using NOR3 as an NO donor. The peroxyl radical scavenging capacity was dose-dependent in the low concentration range (25-100 nM). The mol-Trolox equivalent activity/mol compound (mol-TEA/mol-compound) as an index of the antioxidant capacity indicated the following order at 10.70 ± 0.01, 3.31 ± 0.14 and 2.83 ± 0.01 mol-TEA/mol-compound for betanidin, betanin and phyllocactin, respectively. In addition, betacyanins reduced the nitrite-level in the low concentration range of 2.5-20 μM. The IC₅₀ values (μM) of nitrogen radical scavenging activity were 24.48, 17.51 and 6.81 for betanin, phyllocactin and betanidin. ESR studies provided evidence that the compounds directly scavenged NO. These results indicated that betacyanins have a strong antioxidant capacity, particularly betanidin with a catechol group had higher activity than those of the glycoside of betacyanins. This study demonstrated that the betacyanins will be useful as natural pigments to provide defence against oxidative stress.

  1. Environmentally Persistent Free Radicals (EPFRs). 3. Free versus Bound Hydroxyl Radicals in EPFR Aqueous Solutions

    PubMed Central

    2015-01-01

    Additional experimental evidence is presented for in vitro generation of hydroxyl radicals because of redox cycling of environmentally persistent free radicals (EPFRs) produced after adsorption of 2-monochlorophenol at 230 °C (2-MCP-230) on copper oxide supported by silica, 5% Cu(II)O/silica (3.9% Cu). A chemical spin trapping agent, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), in conjunction with electron paramagnetic resonance (EPR) spectroscopy was employed. Experiments in spiked O17 water have shown that ∼15% of hydroxyl radicals formed as a result of redox cycling. This amount of hydroxyl radicals arises from an exogenous Fenton reaction and may stay either partially trapped on the surface of particulate matter (physisorbed or chemisorbed) or transferred into solution as free OH. Computational work confirms the highly stable nature of the DMPO–OH adduct, as an intermediate produced by interaction of DMPO with physisorbed/chemisorbed OH (at the interface of solid catalyst/solution). All reaction pathways have been supported by ab initio calculations. PMID:25036238

  2. E.s.r. of spin-trapped radicals in aqueous solutions of peptides. Reactions of the hydroxyl radical.

    PubMed

    Joshi, A; Rustgi, S; Moss, H; Riesz, P

    1978-03-01

    The reactions of hydroxyl radicals with 30 dipeptides and several larger peptides were studied in aqueous solutions. The OH radicals were generated by U.V. photolysis of H2O2. The short-lived peptide radicals were spin-trapped using t-nitrosobutane and identified by e.s.r. For dipeptides containing the amino terminal residues glycine, alanine and phenylalanine, abstraction of the hydrogen from the carbon adjacent to the peptide nitrogen was the major process leading to the spin-adducts. Such radicals will be referred to as backbone radicals. Dipeptides with a carbonyl terminal serine residue and also glycylglutamic acid form both backbone and side-chain radicals, with the latter being formed in larger quantities. For dipeptides, side-chain radicals were detected on either the carboxyl or amino terminal residues of both. The effect of pD on the e.s.r. sectrum of the spin-adducts of glycylglycine was studied and the pK of the carboxyl group of this radical was determined to be 2.5. For (Ala)3 and (Ala)n, with an average value of n = 1800, backbone and minor side-chain radicals were observed. For ribonucleases-S-peptide, containing 20 amino acid residues, both backbone and side-chain radicals were detected.

  3. Analysis of radicals, radical precursors and chemical transformations for Houston/Texas

    NASA Astrophysics Data System (ADS)

    Rappenglück, Bernhard; Czader, Beata; Li, Xiangshang

    2015-04-01

    Air quality simulations were performed for the Houston-Galveston-Brazoria area for springtime conditions in May and June of 2009. Meteorological parameters predicted by Weather Research and Forecasting (WRF) model, for which data assimilation with recursive objective analysis was performed, are well simulated most of the time. The Community Multiscale Air Quality (CMAQ) model driven by meteorology from WRF simulates ozone and many other trace species, including radical precursors such as HCHO and HONO, with a satisfactory agreement with observations. While CMAQ satisfactorily captures the daily variations of the OH radical, it sometimes underestimates its high daytime values. Concentrations of HO2 are often underpredicted in polluted air masses and persistently severely underpredicted at low NOx conditions, when the Houston air is affected bymarine air masses. In contrast, concentrations of H2O2 and CH3OOHare almost always overpredicted by the model, the overprediction occurs frequently in the polluted air and occurs always when marine air is encountered. Those mispredictions are consistent despite day-to-day variations in meteorological conditions and emissions and bring into question current representation of radical-related chemistry in the model as radical production and recirculation in the model is overtaken by termination processes and creation ofmore stable compounds, such asH2O2 and CH3OOH. Smaller model biases of H2O2 and peroxides are associated with lower humidity. The relative importance of various photolysis processes as radical sources in the Houston atmosphere was also elucidated. Morning HOx formation is dominated by HONO while ozone contributes the most during midday. HONO contribution to HOx formation is more pronounced at the surface layer where most of it is formed, radical production from ozone is more important at elevated levels where higher concentrations of ozone are observed. Formaldehyde contributes up to 40% and also peaks during midday

  4. CMAQ modeling and analysis of radicals, radical precursors, and chemical transformations

    NASA Astrophysics Data System (ADS)

    Czader, Beata H.; Li, Xiangshang; Rappenglueck, Bernhard

    2013-10-01

    quality simulations were performed for the Houston-Galveston-Brazoria area for springtime conditions in May and June of 2009. Meteorological parameters predicted by Weather Research and Forecasting (WRF) model, for which data assimilation with recursive objective analysis was performed, are well simulated most of the time. The Community Multiscale Air Quality (CMAQ) model driven by meteorology from WRF simulates ozone and many other trace species, including radical precursors such as HCHO and HONO, with a satisfactory agreement with observations. While CMAQ satisfactorily captures the daily variations of the OH radical, it sometimes underestimates its high daytime values. Concentrations of HO2 are often underpredicted in polluted air masses and persistently severely underpredicted at low NOx conditions, when the Houston air is affected by marine air masses. In contrast, concentrations of H2O2 and CH3OOH are almost always overpredicted by the model, the overprediction occurs frequently in the polluted air and occurs always when marine air is encountered. Those mispredictions are consistent despite day-to-day variations in meteorological conditions and emissions and bring into question current representation of radical-related chemistry in the model as radical production and recirculation in the model is overtaken by termination processes and creation of more stable compounds, such as H2O2 and CH3OOH. Smaller model biases of H2O2 and peroxides are associated with lower humidity. The relative importance of various photolysis processes as radical sources in the Houston atmosphere was also elucidated. Morning HOx formation is dominated by HONO while ozone contributes the most during midday. HONO contribution to HOx formation is more pronounced at the surface layer where most of it is formed, radical production from ozone is more important at elevated levels where higher concentrations of ozone are observed. Formaldehyde contributes up to 40% and also peaks during midday

  5. Spin polarization transfer by the radical pair mechanism

    SciTech Connect

    Zarea, Mehdi Ratner, Mark A.; Wasielewski, Michael R.

    2015-08-07

    In a three-site representation, we study a spin polarization transfer from radical pair spins to a nearby electron or nuclear spin. The quantum dynamics of the radical pair spins is governed by a constant exchange interaction between the radical pair spins which have different Zeeman frequencies. Radical pair spins can recombine to the singlet ground state or to lower energy triplet states. It is then shown that the coherent dynamics of the radical pair induces spin polarization on the nearby third spin in the presence of a magnetic field. The spin polarization transfer depends on the difference between Zeeman frequencies, the singlet and triplet recombination rates, and on the exchange and dipole-dipole interactions between the different spins. In particular, the sign of the polarization depends on the exchange coupling between radical pair spins and also on the difference between singlet and triplet recombination rate constants.

  6. The pi-Cation Radical of Chlorophyll a.

    PubMed

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

    1970-10-01

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

  7. Spin polarization transfer by the radical pair mechanism.

    PubMed

    Zarea, Mehdi; Ratner, Mark A; Wasielewski, Michael R

    2015-08-07

    In a three-site representation, we study a spin polarization transfer from radical pair spins to a nearby electron or nuclear spin. The quantum dynamics of the radical pair spins is governed by a constant exchange interaction between the radical pair spins which have different Zeeman frequencies. Radical pair spins can recombine to the singlet ground state or to lower energy triplet states. It is then shown that the coherent dynamics of the radical pair induces spin polarization on the nearby third spin in the presence of a magnetic field. The spin polarization transfer depends on the difference between Zeeman frequencies, the singlet and triplet recombination rates, and on the exchange and dipole-dipole interactions between the different spins. In particular, the sign of the polarization depends on the exchange coupling between radical pair spins and also on the difference between singlet and triplet recombination rate constants.

  8. Glycyl radical activating enzymes: structure, mechanism, and substrate interactions.

    PubMed

    Shisler, Krista A; Broderick, Joan B

    2014-03-15

    The glycyl radical enzyme activating enzymes (GRE-AEs) are a group of enzymes that belong to the radical S-adenosylmethionine (SAM) superfamily and utilize a [4Fe-4S] cluster and SAM to catalyze H-atom abstraction from their substrate proteins. GRE-AEs activate homodimeric proteins known as glycyl radical enzymes (GREs) through the production of a glycyl radical. After activation, these GREs catalyze diverse reactions through the production of their own substrate radicals. The GRE-AE pyruvate formate lyase activating enzyme (PFL-AE) is extensively characterized and has provided insights into the active site structure of radical SAM enzymes including GRE-AEs, illustrating the nature of the interactions with their corresponding substrate GREs and external electron donors. This review will highlight research on PFL-AE and will also discuss a few GREs and their respective activating enzymes.

  9. How solvent modulates hydroxyl radical reactivity in hydrogen atom abstractions.

    PubMed

    Mitroka, Susan; Zimmeck, Stephanie; Troya, Diego; Tanko, James M

    2010-03-10

    The hydroxyl radical (HO*) is a highly reactive oxygen-centered radical whose bimolecular rate constants for reaction with organic compounds (hydrogen atom abstraction) approach the diffusion-controlled limit in aqueous solution. The results reported herein show that hydroxyl radical is considerably less reactive in dipolar, aprotic solvents such as acetonitrile. This diminished reactivity is explained on the basis of a polarized transition state for hydrogen abstraction, in which the oxygen of the hydroxyl radical becomes highly negative and can serve as a hydrogen bond acceptor. Because acetonitrile cannot participate as a hydrogen bond donor, the transition state cannot be stabilized by hydrogen bonding, and the reaction rate is lower; the opposite is true when water is the solvent. This hypothesis explains hydroxyl radical reactivity both in solution and in the gas phase and may be the basis for a "containment strategy" used by Nature when hydroxyl radical is produced endogenously.

  10. Modeling the free radical polymerization of acrylates

    NASA Astrophysics Data System (ADS)

    Günaydin, Hakan; Salman, Seyhan; Tüzün, Nurcan Şenyurt; Avci, Duygu; Aviyente, Viktorya

    Acrylates have gained importance because of their ease of conversion to high-molecular-weight polymers and their broad industrial use. Methyl methacrylate (MMA) is a well-known monomer for free radical polymerization, but its α-methyl substituent restricts the chemical modification of the monomer and therefore the properties of the resulting polymer. The presence of a heteroatom in the methyl group is known to increase the polymerizability of MMA. Methyl α-hydroxymethylacrylate (MHMA), methyl α-methoxymethylacrylate (MC1MA), methyl α-acetoxymethylacrylate (MAcMA) show even better conversions to high-molecular-weight polymers than MMA. In contrast, the polymerization rate is known to decrease as the methyl group is replaced by ethyl in ethyl α-hydroxymethylacrylate (EHMA) and t-butyl in t-butyl α-hydroxymethylacrylate (TBHMA). In this study, quantum mechanical tools (B3LYP/6-31G*) have been used in order to understand the mechanistic behavior of the free radical polymerization reactions of acrylates. The polymerization rates of MMA, MHMA, MC1MA, MAcMA, EHMA, TBHMA, MC1AN (α-methoxymethyl acrylonitrile), and MC1AA (α-methoxymethyl acrylic acid) have been evaluated and rationalized. Simple monomers such as allyl alcohol (AA) and allyl chloride (AC) have also been modeled for comparative purposes.

  11. Single port radical prostatectomy: current status.

    PubMed

    Martín, Oscar Darío; Azhar, Raed A; Clavijo, Rafael; Gidelman, Camilo; Medina, Luis; Troche, Nelson Ramirez; Brunacci, Leonardo; Sotelo, René

    2016-06-01

    The aim of this study is to analyze the current literature on single port radical prostatectomy (LESS-RP). Single port radical prostatectomy laparoendoscopic (LESS-RP) has established itself as a challenge for urological community, starting with the proposal of different approaches: extraperitoneal, transperitoneal and transvesical, initially described for laparoscopy and then laparoscopy robot-assisted. In order to improve the LESS-RP, new instruments, optical devices, trocars and retraction mechanisms have been developed. Advantages and disadvantages of LESS-RP are controversial, while some claim that it is a non-trustable approach, regarding the low cases number and technical difficulties, others acclaim that despite this facts some advantages have been shown and that previous described difficulties are being overcome, proving this is novel proposal of robotics platform, the Da Vinci SP, integrating the system into "Y". The LESS-RP approach gives us a new horizon and opens the door for rapid standardization of this technique. The few studies and short series available can be result of a low interest in the application of LESS-RP in prostate, probably because of the technical complexity that it requires. The new robotic platform, the da Vinci SP, shows that it is clear that the long awaited evolution of robotic technologies for laparoscopy has begun, and we must not lose this momentum.

  12. Fast beam studies of free radical photodissociation

    SciTech Connect

    Cyr, Douglas Robert

    1993-11-01

    The photodissociation of free radicals is studied in order to characterize the spectroscopy and dissociation dynamics of the dissociative electronic states in these species. To accomplish this, a novel method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with a highly complementary form of photofragment translational spectroscopy. The optical spectroscopy of transitions to dissociative states is determined by monitoring the total photofragment yield as a function of dissociation photon energy. Branching ratios to various product channels, internal energy distributions of the fragments, bond dissociation energies, and the translational energy-dependent photofragment recoil angular distributions are then determined at selected excitation energies. A detailed picture of the dissociation dynamics can then be formulated, allowing insight concerning the interactions of potential energy surfaces involved in the dissociation. After an introduction to the concepts and techniques mentioned above, the experimental apparatus used in these experiments is described in detail. The basis and methods used in the treatment of data, especially in the dissociation dynamics experiments, are then put forward.

  13. Enacting a social ecology: radically embodied intersubjectivity

    PubMed Central

    McGann, Marek

    2014-01-01

    Embodied approaches to cognitive science frequently describe the mind as “world-involving,” indicating complementary and interdependent relationships between an agent and its environment. The precise nature of the environment is frequently left ill-described, however, and provides a challenge for such approaches, particularly, it is noted here, for the enactive approach which emphasizes this complementarity in quite radical terms. This paper argues that enactivists should work to find common cause with a dynamic form of ecological psychology, a theoretical perspective that provides the most explicit theory of the psychological environment currently extant. In doing so, the intersubjective, cultural nature of the ecology of human psychology is explored, with the challenges this poses for both enactivist and ecological approaches outlined. The theory of behavior settings (Barker, 1968; Schoggen, 1989) is used to present a framework for resolving some of these challenges. Drawing these various strands together an outline of a radical embodied account of intersubjectivity and social activity is presented. PMID:25477844

  14. Anion photoelectron spectroscopy of radicals and clusters

    SciTech Connect

    Travis, Taylor R.

    1999-12-01

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C2H and C4H. Other radicals studied include NCN and I3. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I3 revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  15. Plasma Diagnostics of Free Radical Species.

    NASA Astrophysics Data System (ADS)

    Harkin, Carmel Geraldine

    Available from UMI in association with The British Library. The work described in this thesis involved the use of a variety of spectroscopic techniques in the analysis of the free radical species NH_2 and SiCl_2. Time delayed emission spectroscopy was used to examine the phosphor, BaClF:Sm ^{2+}, and ruby. High resolution polarised fluorescence has been used to study the dynamics of the NH_2 -H and NH_2-He collision systems. Interesting propensity rules have been observed on the angular momentum number, N, and the projection quantum numbers in the molecule frame, K_{a} and K _{c}, which are in disagreement with previous published work. Polarised collision features and the evidence of reactive collisions have also been observed. A study of the effects of plasma conditions on the emission of species produced by the decomposition of the SiCl_4 plasma, in a microwave argon discharge, has been carried out. Bands at 330 nm and 390 nm, previously assigned to the SiCl_2 radical, have been shown to respond differently to varying SiCl_4 flow rates. The structure at 390 nm may be due to Si_2. Time resolved emission spectroscopy has been used to examine the feasibility of using a phosphor BaClF:Sm ^{2+} and/or ruby, doped with various Cr^{3+} ion concentrations, as a suitable material for remote sensor applications, ultimately for the production of a fibre optic temperature sensor.

  16. Nitrate radicals and biogenic volatile organic compounds ...

    EPA Pesticide Factsheets

    Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in

  17. The Rovibronic Spectra of the Cyclopentadienyl Radical

    NASA Astrophysics Data System (ADS)

    Sharma, Ketan; Miller, Terry A.; Stanton, John F.; Nesbitt, David

    2017-06-01

    Cyclopentadienyl (Cp) radical has been subject to numerous studies for the greater part of half a century. Experimental work has involved photo-electron spectroscopy, laser induced fluorescence excitation and emission, infrared absorption spectroscopy, and recently rotationally resolved spectra in the CH stretch region taken at JILA. Even more theoretical works appear in the literature, but substantial advances in computation have occurred since their completion. Cp's highly symmetric (D_{5h}) structure and doubly degenerate electronic ground (˜{X}^2E_1^{''}), which is subject to linear Jahn-Teller distortion, have been a great motivation for work on it. We have commenced new computational work to obtain a broad understanding of the electronic, vibrational, and rotational, i.e. rovibronic, structure of the Cp radical as revealed by its spectra, with particular emphasis on the new infrared spectra. The goal is to guide experiments and their analyses and reconcile results from spectroscopy and quantum chemistry calculations. T. Ichino, et al. J. Chem. Phys. 129, 084310 (2008) L. Yu, S. C. Foster, J. M. Williamson, M. C. Heaven and T. A. Miller J. Phys. Chem. 92, 4263 (1988) B. E. Applegate, A. J. Bezant and T. A. Miller J. Chem. Phys 114, 4869 (2001) D. Leicht, M. Kaufmann, G. Schwaab, and M. Havenith J. Chem. Phys. 145, 7 (2016), 074304.

  18. Peroxy radical detection by chemical amplification (PERCA)

    NASA Technical Reports Server (NTRS)

    Stedman, D. H.

    1986-01-01

    Important reactions of atmospheric free radicals are the chain oxidation of NO and CO. Thus: H2O + NO yields OH + NO2; OH + CO yields H + CO2; H + O2 + M yields HO2 + M. In most models, the need to know the free radical concentration could also be described as the need to know the rate of the above oxidation chain in the atmosphere. It is the total rate of this chain (also carried by RO2 and RO) which was measured using the PERCA. The PERCA is thus essentially a RO sub X meter. The PERCA works by adding excess CO (10%) and NO (5ppm) to a stream of air and measuring the NO2 produced after 3s of reaction time. Since other processes produce NO2, the chain reaction is modulated by switching the CO for N2. The chain length is limited by the reaction OH + NO yields HONO and is modeled to be somewhat over 1000. Measured chain lengths agree with the modeled numbers.

  19. [A trial of laparoscopic assisted radical nephrectomy].

    PubMed

    Hayakawa, K; Nishiyama, T; Ohashi, M; Ishikawa, H; Hata, M

    1997-09-01

    We tried a new procedure of gas-less laparoscopy assisted radical nephrectomy. Prior to insertion of laparoscope, pararectal incision approximately 7 cm in length was made to enter into the intraabdominal cavity. A 12 mm trocar was placed just below the umbilicus and a flexible electroscope was inserted through it. A 10 cm size disposable fan for lifting up the abdominal wall was indwelled through the under space of trocar port. After appropriately lifting up the abdominal wall, a 10 mm trocar for working channel was placed at mid-axillar line. Under laparoscopic and trans-laparotomic views, radical nephrectomy was performed using the combined technique of laparoscopic and open surgery. Seven patients have been successfully treated with this procedure. The mean operating time of this procedure was significantly shorter than that of totally laparoscopic nephrectomy. The recovery time from the operation was as short as usual laparoscopic nephrectomy. We thought that this procedure could open a new scope of laparoscopic surgery.

  20. Free radical facilitated damage of ungual keratin.

    PubMed

    Khengar, Rajeshree H; Brown, Marc B; Turner, Rob B; Traynor, Matthew J; Holt, Katherine B; Jones, Stuart A

    2010-09-01

    Thioglycolic acid (TA) and urea hydrogen peroxide (urea H(2)O(2)) are thought to disrupt alpha-keratin disulfide links in the nail. However, optimal clinical use of these agents to improve the treatment of nail disorders is currently hindered by a lack of fundamental data to support their mechanism of action. The aim of this study was to investigate how the redox environment of ungual keratin, when manipulated by TA and urea H(2)O(2), influenced the properties of the nail barrier. Potentiometric and voltammetric measurements demonstrated that urea H(2)O(2) obeyed the Nernst equation for a proton coupled one-electron transfer redox process while TA underwent a series of redox reactions that was complicated by electrode adsorption and dimer formation. The functional studies demonstrated that nail permeability, measured through TBF penetration (38.51+/-10.94 microg/cm(2)/h) and nail swelling (244.10+/-14.99% weight increase), was greatest when relatively low concentrations of the thiolate ion were present in the applied solution. Limiting the thiolate ion to low levels in the solution retards thiolate dimerisation and generates thiyl free radicals. It appeared that this free radical generation was fundamental in facilitating the redox-mediated keratin disruption of the ungual membrane. Copyright 2010 Elsevier Inc. All rights reserved.

  1. Diffusive confinement of free radical intermediates in the OH radical oxidation of semisolid aerosols

    DOE PAGES

    Wiegel, Aaron A.; Liu, Matthew J.; Hinsberg, William D.; ...

    2017-02-07

    Multiphase chemical reactions (gas + solid/liquid) involve a complex interplay between bulk and interface chemistry, diffusion, evaporation, and condensation. Reactions of atmospheric aerosols are an important example of this type of chemistry: the rich array of particle phase states and multiphase transformation pathways produce diverse but poorly understood interactions between chemistry and transport. Their chemistry is of intrinsic interest because of their role in controlling climate. Their characteristics also make them useful models for the study of principles of reactivity of condensed materials under confined conditions. Previously, we have reported a computational study of the oxidation chemistry of a liquidmore » aliphatic aerosol. In this study, we extend the calculations to investigate nearly the same reactions at a semisolid gas-aerosol interface. A reaction-diffusion model for heterogeneous oxidation of triacontane by hydroxyl radicals (OH) is described, and its predictions are compared to measurements of aerosol size and composition, which evolve continuously during oxidation. Our results are also explicitly compared to those obtained for the corresponding liquid system, squalane, to pinpoint salient elements controlling reactivity. The diffusive confinement of the free radical intermediates at the interface results in enhanced importance of a few specific chemical processes such as the involvement of aldehydes in fragmentation and evaporation, and a significant role of radical-radical reactions in product formation. The simulations show that under typical laboratory conditions semisolid aerosols have highly oxidized nanometer-scale interfaces that encapsulate an unreacted core and may confer distinct optical properties and enhanced hygroscopicity. This highly oxidized layer dynamically evolves with reaction, which we propose to result in plasticization. The validated model is used to predict chemistry under atmospheric conditions, where the OH

  2. Diffusive confinement of free radical intermediates in the OH radical oxidation of semisolid aerosols.

    PubMed

    Wiegel, Aaron A; Liu, Matthew J; Hinsberg, William D; Wilson, Kevin R; Houle, Frances A

    2017-03-01

    Multiphase chemical reactions (gas + solid/liquid) involve a complex interplay between bulk and interface chemistry, diffusion, evaporation, and condensation. Reactions of atmospheric aerosols are an important example of this type of chemistry: the rich array of particle phase states and multiphase transformation pathways produce diverse but poorly understood interactions between chemistry and transport. Their chemistry is of intrinsic interest because of their role in controlling climate. Their characteristics also make them useful models for the study of principles of reactivity of condensed materials under confined conditions. In previous work, we have reported a computational study of the oxidation chemistry of a liquid aliphatic aerosol. In this study, we extend the calculations to investigate nearly the same reactions at a semisolid gas-aerosol interface. A reaction-diffusion model for heterogeneous oxidation of triacontane by hydroxyl radicals (OH) is described, and its predictions are compared to measurements of aerosol size and composition, which evolve continuously during oxidation. These results are also explicitly compared to those obtained for the corresponding liquid system, squalane, to pinpoint salient elements controlling reactivity. The diffusive confinement of the free radical intermediates at the interface results in enhanced importance of a few specific chemical processes such as the involvement of aldehydes in fragmentation and evaporation, and a significant role of radical-radical reactions in product formation. The simulations show that under typical laboratory conditions semisolid aerosols have highly oxidized nanometer-scale interfaces that encapsulate an unreacted core and may confer distinct optical properties and enhanced hygroscopicity. This highly oxidized layer dynamically evolves with reaction, which we propose to result in plasticization. The validated model is used to predict chemistry under atmospheric conditions, where the OH

  3. Formation of stable radicals in the radiolysis of perfluoroalkanes

    SciTech Connect

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

    1984-01-01

    The radiolysis of fluorinated aliphatic hydrocarbons by gamma radiation from /sup 60/Co is discussed. Particularly, the formation of stable alkyl radicals is investigated. The kinetics of the formation and accumulation of the alkyl radicals is virtually independent of the molecular weight and viscosity of the original hydrocarbon fraction. The high stability of the radicals is assumed to be caused by the intramolecular steric isolation of the free valence.

  4. Generation of Free Radicals during Cold Injury and Rewarming

    DTIC Science & Technology

    1988-01-01

    an episode of ischemia /reperfusion, with simultaneous generation of free radicals which, at least in part, may be responsible for cellular injury...of oxygen- free radicals in ischemic tissue injury in island skin flaps . Ann Surg 198:87-90, 1983. 12 9. Jolly SR, Kane WJ, Bailie MB, et al. Canine...Young Investigator Awacd Lectuce 0Will be published in J. Angiology 0 o Lililt L:JL c PI I GENERATION OF FREE RADICALS DURING COLD INJURY AND

  5. A methylflavan with free radical scavenging properties from Pancratium littorale.

    PubMed

    Ioset, J R; Marston, A; Gupta, M P; Hostettmann, K

    2001-01-01

    The isolation of 7,4'-dihydroxy-8-methylflavan (1) from the dichloromethane extract of Pancratium littorale stem was guided by an assay for free radical scavenging activity towards the 2,2-diphenyl-1-picryl-hydrazyl radical (DPPH). The structure of 1 was established by spectrometric methods including UV, EI mass spectrometry, 1H and 13C-NMR. The free radical scavenging properties of 1 were quantified in solution using spectrophotometry.

  6. 2 D-Hyperfine sublevel correlation spectroscopy of tyrosyl radicals

    NASA Astrophysics Data System (ADS)

    Deligiannakis, Y.; Ivancich, A.; Rutherord, A. W.

    2002-04-01

    Hyperfine sublevel correlation (HYSCORE) spectroscopy has been used to study the tyrosyl radicals in Photosystem II and bovine liver catalase. The HYSCORE data allow a complete resolution of all the 1H hyperfine tensors of these radicals. The present work shows that the proper analysis of the HYSCORE data allows the complete assignment of the 1H-hyperfine tensors in tyrosine radicals and this offers an alternative experimental tool relative to ENDOR.

  7. [Radicalism and feminism: The case of Poulain de la Barre].

    PubMed

    Pellegrin, Marie-Frédérique

    2015-12-01

    Early modern radicalism and its criteria are described and defined by Jonathan Israel in various works. Poulain de la Barre, one of the first modern feminist thinkers, first is used by Israel as an example of the so-called radical Enlightenment and finally is rejected as such. This case study exhibed the necessity of questionning the coherence of the required criteria for defining a « radical » thinker, especially when examinating carefully the last paragraph of Spinoza's Political Treatise.

  8. New reagents for detecting free radicals and oxidative stress.

    PubMed

    Barzegar Amiri Olia, Mina; Schiesser, Carl H; Taylor, Michelle K

    2014-09-21

    Free radicals and oxidative stress play important roles in the deterioration of materials, and free radicals are important intermediates in many biological processes. The ability to detect these reactive species is a key step on the road to their understanding and ultimate control. This short review highlights recent progress in the development of reagents for the detection of free radicals and reactive oxygen species with broad application to materials science as well as biology.

  9. Radical addition-initiated domino reactions of conjugated oxime ethers.

    PubMed

    Ueda, Masafumi

    2014-01-01

    The application of conjugated oxime ethers to the synthesis of complex chemical scaffolds using domino radical reactions has been described in detail. The triethylborane-mediated hydroxysulfenylation reaction allows for the regioselective construction of a carbon-sulfur bond and a carbon-oxygen bond in a single operation for the formation of β-hydroxy sulfides. This reaction proceeds via a radical pathway involving regioselective thiyl addition and the subsequent trapping of the resulting α-imino radical with O₂, where the imino group enhances the stability of the intermediate radical. Hydroxyalkylation reactions that occur via a carbon radical addition reaction followed by the hydroxylation of the resulting N-borylenamine with O₂ have also been developed. We investigated sequential radical addition aldol-type reactions in detail to explore the novel domino reactions that occur via the generation of N-borylenamine. The radical reaction of a conjugated oxime ether with triethylborane in the presence of an aldehyde affords γ-butyrolactone via sequential processes including ethyl radical addition, the generation of N-borylenamine, an aldol-type reaction with an aldehyde, and a lactonization reaction. A novel domino reaction has also been developed involving the [3,3]-sigmatropic rearrangement of N-boryl-N-phenoxyenamine. The triethylborane-mediated domino reactions of O-phenyl-conjugated oxime ethers afforded the corresponding benzofuro[2,3-b]pyrrol-2-ones via a radical addition/[3,3]-sigmatropic rearrangement/cyclization/lactamization cascade.

  10. Role of hydroxyl radical during electrolytic degradation of contaminants.

    PubMed

    Li, Liang; Goel, Ramesh K

    2010-09-15

    The role of hydroxyl radical is investigated in electrochemical oxidation of organic contaminants with naphthalene as a model compound. The strategy employed was competitive kinetic for hydroxyl radical between naphthalene and other hydroxyl scavengers if the hydroxyl radical is produced in situ at the anode by the electrolysis of water. Methanol, d3-methanol, acetone and d6-acetone were used as competitors for hydroxyl radical and their molar concentrations were calculated based on their reaction constants with hydroxyl radical. The hydroxyl radical was not responsible for naphthalene loss in these experiments. The first order reaction rate constants in the batch experiments containing only naphthalene, 2 mM of each of acetone and d6-acetone were 0.093, 0.094 and 0.118 h(-1), respectively. Higher concentrations (4 mM) acetone and d6-acetone did not affect naphthalene degradation. Rate constants using methanol and d6-methanol as competitors for hydroxyl radical in batch degradations test were 0.128 and 0.099 h(-1), respectively. Based on the naphthalene degradation trends and reaction rate constants, it was concluded that, under the given set of conditions, hydroxyl radical was not responsible for naphthalene degradation during electrolytic degradation tests. This research suggests that the role of hydroxyl radical should be considered very carefully in modeling such indirect electrolytic oxidation processes. Published by Elsevier B.V.

  11. Product detection of the CH radical reaction with acetaldehyde.

    PubMed

    Goulay, Fabien; Trevitt, Adam J; Savee, John D; Bouwman, Jordy; Osborn, David L; Taatjes, Craig A; Wilson, Kevin R; Leone, Stephen R

    2012-06-21

    The reaction of the methylidyne radical (CH) with acetaldehyde (CH(3)CHO) is studied at room temperature and at a pressure of 4 Torr (533.3 Pa) using a multiplexed photoionization mass spectrometer coupled to the tunable vacuum ultraviolet synchrotron radiation of the Advanced Light Source at Lawrence Berkeley National Laboratory. The CH radicals are generated by 248 nm multiphoton photolysis of CHBr(3) and react with acetaldehyde in an excess of helium and nitrogen gas flow. Five reaction exit channels are observed corresponding to elimination of methylene (CH(2)), elimination of a formyl radical (HCO), elimination of carbon monoxide (CO), elimination of a methyl radical (CH(3)), and elimination of a hydrogen atom. Analysis of the photoionization yields versus photon energy for the reaction of CH and CD radicals with acetaldehyde and CH radical with partially deuterated acetaldehyde (CD(3)CHO) provides fine details about the reaction mechanism. The CH(2) elimination channel is found to preferentially form the acetyl radical by removal of the aldehydic hydrogen. The insertion of the CH radical into a C-H bond of the methyl group of acetaldehyde is likely to lead to a C(3)H(5)O reaction intermediate that can isomerize by β-hydrogen transfer of the aldehydic hydrogen atom and dissociate to form acrolein + H or ketene + CH(3), which are observed directly. Cycloaddition of the radical onto the carbonyl group is likely to lead to the formation of the observed products, methylketene, methyleneoxirane, and acrolein.

  12. Complex Biotransformations Catalyzed by Radical S-Adenosylmethionine Enzymes*

    PubMed Central

    Zhang, Qi; Liu, Wen

    2011-01-01

    The radical S-adenosylmethionine (AdoMet) superfamily currently comprises thousands of proteins that participate in numerous biochemical processes across all kingdoms of life. These proteins share a common mechanism to generate a powerful 5′-deoxyadenosyl radical, which initiates a highly diverse array of biotransformations. Recent studies are beginning to reveal the role of radical AdoMet proteins in the catalysis of highly complex and chemically unusual transformations, e.g. the ThiC-catalyzed complex rearrangement reaction. The unique features and intriguing chemistries of these proteins thus demonstrate the remarkable versatility and sophistication of radical enzymology. PMID:21771780

  13. Biochemistry of free radicals: from electrons to tissues.

    PubMed

    Boveris, A

    1998-01-01

    Free radicals are chemical species with an unpaired electron in the outer valence orbitals. The unpaired electron makes them paramagnetic (physics) and relatively reactive (chemistry). The free radicals that are normal metabolites in aerobic biological systems have varied reactivities, ranging from the high reactivity of hydroxyl radical (t1/2 = 10(-9) s) to the low reactivity of melanins (t1/2 = days). The univalent reduction of oxygen that takes place in mammalian organs produces superoxide radicals at a rate of about 2% of the total oxygen uptake. The primary production of superoxide radicals sustains a free radical chain reaction involving a series of reactive oxygen species (hydrogen peroxide, hydroxyl and peroxyl radical and singlet oxygen). Nitric oxide is almost unreactive as free radical except for its termination reaction with superoxide radical to yield the strong oxidant peroxynitrite. Nitric oxide also reacts with ubiquinol in a redox reaction, with cytochrome oxidase competitively with oxygen, and oxymyoglobin and oxyhemoglobin displacing oxygen. Septic shock and endotoxemia produce muscle dysfunction and oxidative stress due to increased steady state concentrations of reactive oxygen and nitrogen species.

  14. The nighttime production of OH radicals in the continental troposphere

    NASA Astrophysics Data System (ADS)

    Bey, Isabelle; Aumont, Bernard; Toupance, Gérard

    1997-05-01

    Chemical pathways involved in the nocturnal production of hydroxyl radical (OH) and associated peroxy radicals (HO2 and RO2) are quantified for various environmental situations of the continental troposphere by means of numerical simulations. In the nocturnal stable layer, most of the OH radicals are directly produced by VOC+O3 reactions in rural and semipolluted environments while in urban environments, they result mainly from the radical chain propagation from RO2 and HO2. The radical propagation is mainly driven by NO: the nitrate radical (NO3) plays no role in such processes but is significantly involved in the direct formation of RO2 radicals. Above the nocturnal stable layer, whatever the environmental situation, OH radicals are mainly due to radical chain propagation in which NO3 plays a significant role. The nighttime simulated OH concentrations are 3 × 104 to 5 × 105 and 1 × 104 to 5 × 104 molec cm-3 for the nocturnal stable and residual layers respectively.

  15. Promotion of cell proliferation using atmospheric-pressure radical source

    NASA Astrophysics Data System (ADS)

    Ito, Masafumi; Okachi, Masashi; Koizumi, Takayoshi; Oh, Jun-Seok; Hashizume, Hiroshi; Murata, Tomiyasu; Hori, Masaru

    2016-09-01

    In this study, we have focused on the effects of neutral radicals on cell proliferation and treated budding yeasts and mouse fibroblast cells in solutions using neutral radical source, which can selectively supply neutral radicals without charged species and optical emissions. The activation and inactivation effects of neutral oxygen or nitrogen-oxide radicals on cells were investigated using a cell count and a colony count method, respectively. The radical densities supplied from the radical source were measured using VUVAS and UVAS. Based on the measurements of free residual chloride and hydrogen peroxide concentrations in the solutions treated with radicals, we have investigated their effects on the activation and the inactivation. From these results, we have concluded that the main factor for the inactivation in PBS solutions is due to the hypochlorous acid generated in the PBS irradiated with oxygen radicals. On the other hand, we have found that the main factor for the promotion is not the hypochlorous acid but other radicals. This work was partly supported by MEXT-Supported Program for the Strategic Research Foundation at Private Universities (S1511021), JSPS KAKENHI Grant Numbers 26286072 and project for promoting Research Center in Meijo University.

  16. Migration of hydrogen radicals through clathrate hydrate cages

    NASA Astrophysics Data System (ADS)

    Alavi, Saman; Ripmeester, John A.

    2009-09-01

    Electronic structure calculations are used to determine energy barriers to hydrogen radical migration in structure II clathrate small and large cages. Migration of H-radicals through pentagonal and hexagonal faces of small and large cages are considered and energies barriers calculated at the MP2 level with the 6-311++G( d, p) basis set are 61 and 17 kJ mol -1, respectively. Energy barriers (with tunneling corrections) are used to estimate escape rates from the cages and to explain results of recent experiments on the transformation of n-propyl radical in the propane hydrate and the behavior of hydrogen radicals in tetrahydrofuran/H 2 hydrates.

  17. Formation and reactivity of vinylperoxyl radicals in aqueous solutions

    SciTech Connect

    Khaikin, G.I.; Neta, P.

    1995-03-30

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

  18. Participation of free radicals in the photodecomposition of active dyes

    SciTech Connect

    Anisimov, V.M.; Anisimova, O.M.; Dzhanashvilli, M.E.; Krichevskii, G.E.

    1985-06-10

    This paper investigates the effect of the free radicals in the medium on the photodecomposition of these active azo and anthraquinone dyes. The semilogarithmic anamorphoses of the kinetic curves showed that the rate of consumption of nitroxyl radical decreased in time in the presence of the dyes. The efficiency of the photodecomposition of the active dyes in an ETC film in the presence and absence of benzyl was studied to evaluate the role of free radicals in the photobleaching of the dies. The kinetic dependences obtained for active yellow 2KT are shown. The relative efficiency of the photoinitiation of free radicals by some active dyes was determined.

  19. Methylglyoxal as a scavenger for superoxide anion-radical.

    PubMed

    Shumaev, K B; Lankin, V Z; Konovalova, G G; Grechnikova, M A; Tikhaze, A K

    2016-07-01

    Methylglyoxal at a concentration of 5 mM caused a significant inhibition of superoxide anion radical (O2 (·-)) comparable to the effect of Tirone. In the process of O2 (·-) generation in the system of egg phosphatidylcholine liposome peroxidation induced by the azo-initiator AIBN, a marked inhibition of chemiluminescence in the presence of 100 mM methylglyoxal was found. At the same time, methylglyoxal did not inhibit free radical peroxidation of low-density lipoprotein particles, which indicates the absence of interaction with methylglyoxal alkoxyl and peroxyl polyenoic lipid radicals. These findings deepen information about the role of methylglyoxal in the regulation of free radical processes.

  20. Methylation of 2'-deoxyguanosine by a free radical mechanism.

    PubMed

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

    2009-09-24

    The mechanistic aspects of the methylation of guanine in DNA initiated by methyl radicals that are derived from the metabolic oxidation of some chemical carcinogens remain poorly understood. In this work, we investigated the kinetics and the formation of methylated guanine products by two methods: (i) the combination of *CH3 radicals and guanine neutral radicals, G(-H)*, and (ii) the direct addition of *CH3 radicals to guanine bases. The simultaneous generation of *CH3 and dG(-H)* radicals was triggered by the competitive one-electron oxidation of dimethyl sulfoxide (DMSO) and 2'-deoxyguanosine (dG) by photochemically generated sulfate radicals in deoxygenated aqueous buffer solutions (pH 7.5). The photolysis of methylcob(III)alamin to form *CH3 radicals was used to investigate the direct addition of these radicals to guanine bases. The major end products of the radical combination reactions are the 8-methyl-dG and N2-methyl-dG products formed in a ratio of 1:0.7. In contrast, the methylation of dG by *CH3 radicals generates mostly the 8-methyl-dG adduct and only minor quantities of N2-methyl-dG (1:0.13 ratio). The methylation of the self-complementary 5'-d(AACGCGAATTCGCGTT) duplexes was achieved by the selective oxidation of the guanines with carbonate radical anions in the presence of DMSO as the precursor of *CH3 radicals. The methyl-G lesions formed were excised by the enzymatic digestion and identified by LC-MS/MS methods using uniformly 15N-labeled 8-methyl-dG and N2-methyl-dG adducts as internal standards. The ratios of 8-methyl-G/N2-methyl-G lesions derived from the combination of methyl radicals with G(-H)* radicals positioned in double-stranded DNA or that with the free nucleoside dG(-H)* radicals were found to be similar. Utilizing the photochemical method and dipropyl or dibutyl sulfoxides as sources of alkyl radicals, the corresponding 8-alkyl-dG and N2-alkyl-dG adducts were also generated in ratios similar to those obtained with DMSO.

  1. ’Living’ Radical Polymerization. 1. Possibilities and Limitations

    DTIC Science & Technology

    1994-06-30

    AD-A281 042 OFFICE OF NAVAL RESEARCH / CONTRACT N00014-94-1-0l01 R&T Code 31321075 Technical Report No. 16 " LIVING " RADICAL POLYMERIZATION. I...Report # 16 4. TITLE AND SUBTITLE S. FUNDING NUMBERS " Living " Radical Polymerization. I. Possibilities and Limitations N00014-94-1-0101 6. AUTHOR(S) D...preparation of polymers with controlled macromolecular structure in a " living " radical process requires low stationary concentration of growing radicals

  2. Stable All-Organic Radicals with Ambipolar Charge Transport.

    PubMed

    Reig, Marta; Gozálvez, Cristian; Jankauskas, Vygintas; Gaidelis, Valentas; Grazulevicius, Juozas V; Fajarí, Lluís; Juliá, Luis; Velasco, Dolores

    2016-12-19

    A series of neutral long-lived purely organic radicals based on the stable [4-(N-carbazolyl)-2,6-dichlorophenyl]bis(2,4,6-trichlorophenyl)methyl radical adduct (Cbz-TTM) is reported herein. All compounds exhibit ambipolar charge-transport properties under ambient conditions owing to their radical character. High electron and hole mobilities up to 10(-2) and 10(-3)  cm(2)  V(-1)  s(-1) , respectively, were achieved. Xerographic single-layered photoreceptors were fabricated from the radicals studied herein, exhibiting good xerographic photosensitivity across the visible spectrum.

  3. Hydroxyl radical buffered by isoprene oxidation over tropical forests

    NASA Astrophysics Data System (ADS)

    Taraborrelli, D.; Lawrence, M. G.; Crowley, J. N.; Dillon, T. J.; Gromov, S.; Groß, C. B. M.; Vereecken, L.; Lelieveld, J.

    2012-03-01

    The hydroxyl radical is a key oxidant in the Earth's atmosphere. This short-lived highly reactive molecule plays an important role in the degradation of volatile organic compounds, leading to the production of ozone and the formation and growth of aerosol particles. In this way, hydroxyl radicals influence air quality and regional climate. Measurements over tropical forests suggest that hydroxyl radicals are recycled following reaction with the volatile organic compound isoprene, but the chemistry underpinning this observation is uncertain. Here, we propose a detailed chemical mechanism for the oxidation of isoprene by hydroxyl radicals. The photo-oxidation of unsaturated hydroperoxy-aldehydes--a product of isoprene oxidation--is a central part of the mechanism; their photolysis initiates a hydroxyl radical production cascade that is limited by the reaction of hydroperoxy-aldehydes with the hydroxyl radical itself. We incorporate this mechanism into a global atmospheric chemistry model and find that measurements of hydroxyl radical concentrations over a pristine region of the Amazon, and in moderately polluted conditions, are captured well. On the basis of this agreement, we suggest that isoprene oxidation can buffer hydroxyl radical concentrations, by serving as both a sink and source for these radicals.

  4. Superoxide Free Radicals Are Produced in Glyoxysomes 1

    PubMed Central

    Sandalio, Luisa M.; Fernández, Victor M.; Rupérez, Francisco L.; Del Río, Luis A.

    1988-01-01

    The production of superoxide free radicals in pellet and supernatant fractions of glyoxysomes, specialized plant peroxisomes from watermelon (Citrullus vulgaris Schrad.) cotyledons, was investigated. Upon inhibition of the endogenous superoxide dismutase, xanthine, and hypoxanthine induced in glyoxysomal supernatants the generation of O2− radicals and this was inhibited by allopurinol. In glyoxysomal pellets, NADH stimulated the generation of superoxide radicals. Superoxide production by purines was due to xanthine oxidase, which was found predominantly in the matrix of glyoxysomes. The generation of O2− radicals in glyoxysomes by endogenous metabolites suggests new active oxygen-related roles for glyoxysomes, and for peroxisomes in general, in cellular metabolism. PMID:16666081

  5. Gas-phase radical chemistry in the troposphere.

    PubMed

    Monks, Paul S

    2005-05-01

    Atmospheric free radicals are low concentration, relatively fast reacting species whose influence is felt throughout the atmosphere. Reactive radicals have a key role in maintaining a balanced atmospheric composition through their central function in controlling the oxidative capacity of the atmosphere. In this tutorial review, the chemistry of three main groups of atmospheric radicals HO(x), NO(x) and XO(x)(X = Cl, Br, I) are examined in terms of their sources, interconversions and sinks. Key examples of the chemistry are given for each group of radicals in their atmospheric context.

  6. The scavenging reactions of nitrogen dioxide radical and carbonate radical by tea polyphenol derivatives: a pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Miao, Jin-Ling; Wang, Wen-Feng; Pan, Jing-Xi; Lu, Chang-Yuan; Li, Rong-Qun; Yao, Si-De

    2001-02-01

    The reactions of tea polyphenol derivatives, including epicatechin (EC) and epigallocatechin gallate (EGCG), with nitrogen dioxide radical (NO 2rad ) and carbonate radical (CO 3rad - ) have been studied in detail using time-resolved pulse radiolysis technique. In all the cases, the corresponding phenoxyl radical was formed through electron transfer reaction. From the build-up kinetics of the phenoxyl radicals and the decay kinetics of CO 3rad - radical, the reaction rate constants of EC, EGCG with NO 2rad and CO 3rad - were determined to be 9.0×10 7, 1.2×10 8 and 5.6×10 8, 6.6×10 8 dm 3 mol -1 s -1, respectively. Therefore, tea polyphenol derivatives proved to be efficient scavengers of NO 2rad and CO 3rad - radicals.

  7. Red-Light-Induced Decomposition of an Organic Peroxy Radical: A New Source of the HO2 Radical.

    PubMed

    Kumar, Manoj; Francisco, Joseph S

    2015-12-21

    The gas-phase decomposition of the α-hydroxy methylperoxy radical has been theoretically examined, and the results provide insight into a new source of the hydroperoxy radical (HO2 ) in the troposphere. Bimolecular peroxy decomposition is promoted by the red-light or near-IR radiation excitation. The calculations suggest for the first time, an important chemical role for the H2 O⋅HO2 radical complex that exist in significant abundance in the troposphere. In particular, the reaction of organic peroxy radicals with the HO2 radical and the H2 O⋅HO2 radical complex represent an autocatalytic source of atmospheric HO2 . This reaction is a new example of red-light-initiated atmospheric chemistry that may help in understanding the discrepancy between the observed and measured levels of the HOx at sunrise. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Development of atomic radical monitoring probe and its application to spatial distribution measurements of H and O atomic radical densities in radical-based plasma processing

    SciTech Connect

    Takahashi, Shunji; Takashima, Seigo; Yamakawa, Koji; Den, Shoji; Kano, Hiroyuki; Takeda, Keigo; Hori, Masaru

    2009-09-01

    Atomic radicals such as hydrogen (H) and oxygen (O) play important roles in process plasmas. In a previous study, we developed a system for measuring the absolute density of H, O, nitrogen, and carbon atoms in plasmas using vacuum ultraviolet absorption spectroscopy (VUVAS) with a compact light source using an atmospheric pressure microplasma [microdischarge hollow cathode lamp (MHCL)]. In this study, we developed a monitoring probe for atomic radicals employing the VUVAS with the MHCL. The probe size was 2.7 mm in diameter. Using this probe, only a single port needs to be accessed for radical density measurements. We successfully measured the spatial distribution of the absolute densities of H and O atomic radicals in a radical-based plasma processing system by moving the probe along the radial direction of the chamber. This probe allows convenient analysis of atomic radical densities to be carried out for any type of process plasma at any time. We refer to this probe as a ubiquitous monitoring probe for atomic radicals.

  9. The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

    NASA Astrophysics Data System (ADS)

    Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; Troy, Tyler P.; Ahmed, Musahid; Robichaud, David J.; Nimlos, Mark R.; Daily, John W.; Ellison, G. Barney

    2016-07-01

    Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H513CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H513CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).

  10. Inclusive jet production at {radical}s =630 GeV and a test of scaling at CDF

    SciTech Connect

    Bhatti, A.A.; CDF Collaboration

    1996-10-01

    A preliminary measurement of the inclusive jet cross section at {radical}{ital s} = 630 GeV is presented. The data are compared with NLO QCD predictions. The ratio of scaled inclusive jet cross section a {radical}{ital s} = 1800 GeV and {radical}{ital s} = 630 GeV is presented and compared with previous CDF results and QCD predictions.

  11. The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical.

    PubMed

    Buckingham, Grant T; Porterfield, Jessica P; Kostko, Oleg; Troy, Tyler P; Ahmed, Musahid; Robichaud, David J; Nimlos, Mark R; Daily, John W; Ellison, G Barney

    2016-07-07

    Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H5 (13)CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H5 (13)CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).

  12. The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

    SciTech Connect

    Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; Troy, Tyler P.; Ahmed, Musahid; Robichaud, David J.; Nimlos, Mark R.; Daily, John W.; Ellison, G. Barney

    2016-07-05

    Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 us. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H5 13CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H5 13CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).

  13. A ring theoretic approach to radicals of extensions

    NASA Astrophysics Data System (ADS)

    Williams, Jessica Lynn

    The Jacobson radical of a ring was first formally studied in 1945 by Nathan Jacobson and is an important object in modern abstract algebra. The analogous notion of the Jacobson radical for a module is referred to as the radical of a module. The radical of a module is the intersection of all its maximal submodules. In general, the radical of a module is simpler than the module itself and contains important information about the module. The study of the radical of a module often appears as an incidental to other investigations. This thesis represents work towards understanding the radical of a module extension. Given a ring R and R-modules A,B,X such that X is an extension of B by A as in the short exact sequence 0 → A → X → B → 0; we seek to determine properties of the radical of X, denoted radX. These properties are dependent on the ring R and properties of the modules A and B. In this thesis we examine several different types of extensions and discuss a phenomenon in which a non-zero radical implies a split sequence. We work in the context of rings and their ideals. Extensions of abelian groups provide motivation for the results we prove about injectivity of radicals of extensions involving divisible modules and torsion modules. We are able to prove such properties of the radical for extensions of modules over principal ideal domains and Dedekind domains. Expanding upon these cases, we explore a more general construction of an extension and use it to explain our motivating abelian group results. We use the theorems proven about this construction to remark on possible generalizations to other types of rings and modules. We conclude with plans to generalize our statements by translating into terms of infinite matrices and h-local rings.

  14. Petroleum films exposed to sunlight produce hydroxyl radical.

    PubMed

    Ray, Phoebe Z; Tarr, Matthew A

    2014-05-01

    Sunlight exposed oil films on seawater or pure water produced substantial amounts of hydroxyl radical as a result of irradiation. Oil was collected from the surface of the Gulf of Mexico following the Deepwater Horizon spill and exposed to simulated sunlight in thin films over water. Photochemical production of hydroxyl radical was measured with benzoic acid as a selective chemical probe in the aqueous layer. Total hydroxyl radical formation was studied using high benzoic acid concentrations and varying exposure time. The total amount of hydroxyl radical produced in 24 h irradiations of thin oil films over Gulf of Mexico water and pure water were 3.7×10(-7) and 4.2×10(-7) moles respectively. Steady state concentrations of hydroxyl radical were measured using a competition kinetics approach. Hydroxyl radical concentrations of 1.2×10(-16) to 2.4×10(-16) M were observed for seawater and pure water under oil films. Titanium dioxide (TiO2) nanomaterials were added to the system in an effort to determine if the photocatalyst would enhance oil photodegradation. The addition of TiO2 nanoparticles dramatically changed the observed formation rate of hydroxyl radical in the systems with NP water at pH 3, showing increased formation rate in many cases. With photocatalyst, the steady state concentration of radical decreased, predominantly due to an increase in the hydroxyl radical scavenging rate with oxide present. This study illustrates that oil is a strong and important source of hydroxyl radical when exposed to sunlight. The fate of oil and other dissolved species following oil spills will be heavily dependent on the formation and fate of hydroxyl radical. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Free radicals and antioxidants at a glance using EPR spectroscopy.

    PubMed

    Spasojević, Ivan

    2011-01-01

    The delicate balance between the advantageous and detrimental effects of free radicals is one of the important aspects of human (patho)physiology. The controlled production of reactive oxygen and nitrogen species has an essential role in the regulation of various signaling switches. On the other hand, imbalanced generation of radicals is highly correlated with the pathogenesis of many diseases which require the application of selected antioxidants to regain the homeostasis. In the era of growing interest for redox processes, electron paramagnetic resonance (EPR) spectroscopy is arguably the best-suited technique for such research due to its ability to provide a unique insight into the world of free radicals and antioxidants. Herein, I present the principles of EPR spectroscopy and the applications of this method in assessing: (i) the oxidative status of biological systems, using endogenous long-lived free radicals (ascorbyl radical (Asc(•)), tocopheroxyl radical (TO(•)), melanin) as markers; (ii) the production of short-lived radicals (hydroxyl radical (OH(•)), superoxide radical anion (O(2)(•-)), sulfur- and carbon-centered radicals), which are implicated in both, oxidative stress and redox signaling; (iii) the metabolism of nitric oxide (NO(•)); (iv) the antioxidative properties of various drugs, compounds, and natural products; (v) other redox-relevant parameter. Besides giving a comprehensive survey of up-to-date literature, I also provide illustrative examples in sufficient detail to provide a means to exploit the potential of EPR in biochemical/physiological/medical research. The emphasis is on the features and characteristics (both positive and negative) relevant for EPR application in clinical sciences. My aim is to encourage fellow colleagues interested in free radicals and antioxidants to expand their base knowledge or methods used in their laboratories with data acquired by EPR or some of the EPR techniques outlined in this review, in order to

  16. Spectroscopy, Kinetics, and Dynamics of Combustion Radicals

    SciTech Connect

    Nesbitt, David J.

    2013-08-06

    Spectroscopy, kinetics and dynamics of jet cooled hydrocarbon transients relevant to the DOE combustion mission have been explored, exploiting i) high resolution IR lasers, ii) slit discharge sources for formation of jet cooled radicals, and iii) high sensitivity detection with direct laser absorption methods and near the quantum shot noise limit. What makes this combination powerful is that such transients can be made under high concentrations and pressures characteristic of actual combustion conditions, and yet with the resulting species rapidly cooled (T ≈10-15K) in the slit supersonic expansion. Combined with the power of IR laser absorption methods, this provides novel access to spectral detection and study of many critical combustion species.

  17. Interpersonal psychoanalysis' radical façade.

    PubMed

    Hirsch, Irwin

    2002-01-01

    The participant-observation model initiated the relational turn, as well as the shift from modernism to postmodernism in psychoanalysis. This two-person, coparticipant conceptualization of the psychoanalytic situation moved psychoanalysis from the realm of alleged objective science toward intersubjectivity and hermeneutics. From this perspective, the analyst as subjective other is constantly engaged affectively with the patient in ways that are very often out of awareness. Analyst and patient both, for better or for worse, are believed to unwittingly influence one another. This description of the analytic dyad has led many to mistakingly conclude that interpersonal psychoanalysts advocate wittinly affective expressiveness, often in the form of deliberate self-disclosure of feelings, as part of a standard analytic stance. Upon closer examination, radical interventions are no more emblematic of interpersonal analysts than they are of analysts from most other traditions, though the interpersonalists have indeed expanded what had theretofore been a rather narrow repertoire of interventions.

  18. Hydroxyl radical Thymine adduct induced DNA damages

    NASA Astrophysics Data System (ADS)

    Schyman, Patric; Eriksson, Leif A.; Zhang, Ru bo; Laaksonen, Aatto

    2008-06-01

    DNA damages caused by a 5-hydroxy-5,6-dihydrothymine-6-yl radical (5-OHT-6yl) abstracting a C2‧ hydrogen from a neighboring sugar (inter-H abstraction) have been theoretically investigated using hybrid DFT in gas phase and in water solution. The inter-H abstraction was here shown to be comparable in energy (24 kcal mol-1) with the intra-H abstraction in which the 5-OHT-6yl abstracts a C2‧ hydrogen from its own sugar. The effect of a neutrally or a negatively charged phosphate group was also studied and the results show no significant impact on the activation energy of the hydrogen abstraction whereas base release and strand break reactions are affected.

  19. Oxygen radical functionalization of boron nitride nanosheets.

    PubMed

    Sainsbury, Toby; Satti, Amro; May, Peter; Wang, Zhiming; McGovern, Ignatius; Gun'ko, Yurii K; Coleman, Jonathan

    2012-11-14

    The covalent chemical functionalization of exfoliated hexagonal boron-nitride nanosheets (BNNSs) is achieved by the solution-phase oxygen radical functionalization of boron atoms in the h-BN lattice. This involves a two-step procedure to initially covalently graft alkoxy groups to boron atoms and the subsequent hydrolytic defunctionalization of the groups to yield hydroxyl-functionalized BNNSs (OH-BNNSs). Characterization of the functionalized-BNNSs using HR-TEM, Raman, UV-vis, FTIR, NMR, and TGA was performed to investigate both the structure of the BNNSs and the covalent functionalization methodology. OH-BNNSs were used to prepare polymer nanocomposites and their mechanical properties analyzed. The influence of the functional groups grafted to the surface of the BNNSs is investigated by demonstrating the impact on mechanical properties of both noncovalent and covalent bonding at the interface between the nanofiller and polymer matrixes.

  20. Electron affinities of atoms, molecules and radicals

    NASA Astrophysics Data System (ADS)

    Christodoulides, A. A.; McCorkle, D. L.; Christophorou, L. G.

    The theoretical, semiempirical and experimental methods employed to determine electron affinities (EAs) of atoms, molecules and radicals, and summarize the EA data obtained by these methods were reviewed. The detailed processes underlying the principles of the experimental methods are discussed very briefly. It is, nonetheless, instructive to recapitulate the definition of EA and those of the related quantities, namely, the vertical detachment energy, VDE, and the vertical attachment energy, VAE. The EA of an atom is defined as the difference in total energy between the ground state of the neutral atom (plus the electron at rest at infinity) and its negative ion. The EA of a molecule is defined as the difference in energy between the neutral molecule plus an electron at rest at infinity and the molecular negative ion when both, the neutral molecules and the negative ion, are in their ground electronic, vibrational and rotational states.

  1. Semiconductor Photocatalysis for Chemoselective Radical Coupling Reactions.

    PubMed

    Kisch, Horst

    2017-04-18

    problem of quantitative comparisons of photocatalytic activities or apparent quantum yields and propose a basic three-step mechanistic model. Finally, we address the question whether or not the unique photoredox properties of simple inorganic semiconductor powders may lead to previously unknown visible light induced organic syntheses. For that, we summarize novel radical C-C- and C-N- couplings photocatalyzed by self-prepared cadmium sulfide powders. Electron acceptor and donor substrates like imines or 1,2-diazenes, and cyclic olefins or unsaturated ethers, respectively, undergo a linear addition reaction. The hitherto unknown products have all been isolated in good to moderate yields and may be of pharmaceutical interest. In the first reaction step photogenerated electron-hole pairs produce through proton-coupled electron transfer the corresponding radicals. Their subsequent chemoselective heterocoupling affords the products, correlating with an insertion of the imine or 1,2-diazene into an allylic C(sp(3))-H bond of the donor substrate. In the absence of an imine or 1,2-diazene, cyclic allyl/enol ethers are dehydrodimerized under concomitant hydrogen evolution. Even a visible light photosulfoxidation of alkanes is catalyzed by titania. In these heterogeneous photoredox reactions the role of the semiconductor photocatalyst is multifunctional. It induces favorable substrate preorientations in the surface-solvent layer, it catalyzes proton-coupled interfacial electron transfer to and from substrates generating intermediate radicals, and it enables their subsequent chemoselective coupling in the surface-solvent interface. Different from molecular photosensitizers, which enable only one one-electron transfer with one single substrate, photoexcited semiconductors induce two concerted one-electron transfer reactions with two substrates. This is because the light generated electron-hole pairs are trapped at distinct surface sites and undergo proton-coupled interfacial electron

  2. Mechanism for diamond growth from methyl radicals

    NASA Astrophysics Data System (ADS)

    Harris, Stephen J.

    1990-06-01

    We use a 9-carbon model compound to describe a proposed mechanism for homoepitaxial growth of diamond from methyl radicals on a hydrogenated, electrically neutral (100) surface. We estimate enthalpy and entropy changes for each step in the mechanism using group additivity methods, taking into account the types of bonding and steric repulsions found on the (100) surface. Rate constants are estimated based on analogous reactions for hydrocarbon molecules, while gas phase species concentrations are taken from our previous measurements. The rate equations are then integrated. The method, which contains no adjustable parameters or phenomenological constants, predicts a growth rate of between 0.06 and 0.6 μm/h, depending on the local details of the surface. Uncertainties related to the use of a model compound rather than diamond are discussed. The analysis demonstrates that the proposed mechanism is feasible.

  3. ESR study of free radicals in mango

    NASA Astrophysics Data System (ADS)

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

    2010-01-01

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

  4. Radical SBr: A challenge to spectroscopists?

    NASA Astrophysics Data System (ADS)

    Ornellas, Fernando R.

    2006-09-01

    A theoretical description of the electronic states of the SBr radical at a high level of correlation effects treatment is presented for the first time. Most of its potential energy curves have a repulsive nature, but a set of bound Π2 states should provide a means for the experimental characterization of this species. The ground state can support over 40 vibrational states, but transitions from the 2Π2 state, with a very shallow well (four levels), should have intensities spread over a maximum around v″=10; lower vibrational levels can only be accessed for transitions from two high-lying Rydberg states. A whole set of spectroscopic constants, including vibrationally averaged spin-orbit coupling constants, and radiative transition probabilities and lifetimes quantify the theoretical description, thus supplying reliable results to guide the experimental investigation of this species.

  5. Rovibronic Variational Calculations of the Nitrate Radical

    NASA Astrophysics Data System (ADS)

    Changala, Bryan; Baraban, Joshua H.; Stanton, John F.

    2015-06-01

    In recent years, sophisticated diabatic Hamiltonians have been developed in order to understand the low-energy vibronic level structure of the nitrate radical (NO_3), which exhibits strong coupling between the ~X and doubly degenerate ~B states. Previous studies have reproduced the observed vibronic level positions up to 2000 wn~above the zero-point level, yet the rotational structure has remained uninvestigated with ab initio methods. In this talk, we present calculations of the N≥0 rovibronic structure of low-lying vibronic states of NO_3, in which complicated rovibrational and Coriolis interactions have been observed. Our results include calculations using both adiabatic and diabatic Hamiltonians, enabling a direct comparison between the two. We discuss extensions of our treatment to include spin-orbit and spin-rotation effects.

  6. [Radical treatment of invasive bladder cancer].

    PubMed

    Lopatkin, N A; Darenkov, S P; Chernyshev, N V; Sokolov, A E; Gorilovskiĭ, M L; Akmatov, N A; Samsonov, Iu V

    2003-01-01

    We have conducted a retrospective analysis of radical cystectomy in 53 patients (45 males and 8 females, 85 and 15%, respectively) with invasive bladder cancer (BC) treated in the Research Institute of Urology in 1997-2002. Stages T2N0M0, pT3aN0M0, T3bN0M0, pT4aN0M0, pT4aN1-2M0 were in 4 (7.5%), 13 (25%), 21 (40%), 7 (12.5%), 8 (15%) cases, respectively. Well differentiated transitional cell BC (G1) was detected in 1 (2%) patient, moderately differentiated (G2) in 16 (30%) cases, poorly differentiated (G3) in 36 (68%) patients. The following methods of urine derivation were used: orthotopic plastic surgery (n = 3, 6%), ureterocutaneostomy (n = 4, 8%), Mainz pouch II operation (n = 16, 30%), Hassan operation (n = 5, 9%), Bricker procedure (n = 22, 44%), transureteroanastomosis (n = 3, 6%). In the postoperative period there was one lethal outcome, early complications in 5 (9%) patients, late complications in 9 (17%) patients. Distant metastases to the lungs, bones and iliac lymph nodes after treatment were detected in 3, 2 and 3 patients, respectively. One patient had a local pelvic recurrence. For 53 patients 2-year corrected survival was 68 +/- 12.0%. We have come to the conclusion that the only radical surgical treatment of invasive BC is cystectomy, limitations to which are connected only with complexity of subsequent urine derivation.

  7. Superoxide Radical Lifetime on the Martian Surface

    NASA Astrophysics Data System (ADS)

    Zent, A. P.; Ichimura, A.; Quinn, R. C.

    2005-08-01

    We have examined the formation and stability of the superoxide radical O2-, which has been hypothesized as a potential Mars oxidant. Rutile (TiO2) was heated to ˜ 400 degrees C under vacuum. The samples were tipped off in ampules under 8-9 torr O2, photolyzed with a Hg lamp for 30 minutes; EPR spectra were immediately obtained at 77K. The signature of O2- was clearly observed in the rutile. The sealed ampules were stored at room temperature for up to 2 weeks without any decrease in the number of spins. The same process, applied to rutile that was not baked out yielded superoxide signals that could not be detected once the photolyzing flux was cut off. To examine the effects of partial dehydration, we carried out the same series of experiments on rutile that was baked out at 200 degrees C. This material showed decay of superoxide spins to zero in less than 10 minutes. This qualitative pattern is also observed in experiments on anatase (Attwood, et al., , 2003). We hypothesize that O2- can be stabilized against reaction with H2O and OH by crystalline surface defects. On hydrated surfaces, O2- must compete for stabilizing sites, and the population is quickly extinguished; in dehydrated samples, it can migrate to stabilizing defects. Once sorbed, the O2- radical is stable in the presence of H2O. OMEGA Mars Express data (Poullet et al, 2005) suggest one to several percent adsorbed H2O across the Martian surface, which will significantly decrease O2- lifetime. One possibility for subsurface stabilization of O2- can be postulated based on EPR spectra of anatase, exposed to H2O2 in our lab in 1996, and which in 2005 shows the signature of O2-. Evidently, H2O2 can convert to stable O2- on some surfaces. This hypothesis might allow subsurface diffusion of H2O2, followed by conversion to O2-.

  8. Vibronic emission spectroscopy of benzyl-type radicals: Jet-cooled 2-fluoro-5-chlorobenzyl radical

    NASA Astrophysics Data System (ADS)

    Yoon, Young Wook; Chae, Sang Youl; Lee, Sang Kuk

    2014-07-01

    We produced the vibronically excited but jet-cooled 2-fluoro-5-chlorobenzyl radical by corona discharge of precursor 2-fluoro-5-chlorotoluene with a large amount of carrier gas He using a pinhole-type glass nozzle in a technique of corona excited supersonic jet expansion. The vibronic emission spectrum was recorded using a long-path double monochromator in the visible region. From an analysis of the spectrum, we determined the electronic energy of the D1 → D0 transition and vibrational mode frequencies in the ground electronic state of the 2-fluoro-5-chlorobenzyl radical for the first time. In addition, substituent effect on electronic transition energy was discussed for substituents on the benzene ring.

  9. Spectroscopy of Benzyl-Type Radicals Generated by Electric Discharge : Jet-Cooled Dichlorobenzyl Radicals

    NASA Astrophysics Data System (ADS)

    Yoon, Young Wook; Lee, Sang Kuk

    2013-06-01

    The technique of corona excited supersonic expansion coupled with a pinhole-type glass nozzle has been proved a useful laser-free spectroscopic tool for observation of vibronic emission spectra of large aromatic molecules, especially for molecular radicals which are long believed to play an important role as a reaction intermediate in aromatic chemical reactions. The vibronic emission spectra recorded with a long-path monochromator exhibit the electronic transition energy in the D_1 → D_0 transition and vibrational mode frequencies at the D_0 state. In this laboratory, all six isomeric dichlorobenzyl radicals have been produced from the corona discharge of corresponding dichlorotoluenes seeded in a large amount of inert carrier gas He. The vibronic emission spectra show very weak intensity due to the existence of Cl atoms in the precursor molecules and possible breakdown of benzene ring by free Cl atoms. Nevertheless, we clearly identified the origin band and a few well-known vibrational modes for each isomer. From an analysis of the spectra observed, we determined the energy of electronic transition and several vibrational modes in the ground electronic state. Also, the red-shift of the origin band from the parental benzyl radical clearly shows the substituent effect of Cl atoms on electronic energy, for which we satisfactorily explain in terms of the shape of the molecular planes and position of the nodal points at a given electronic state, recently developed in this laboratory for identification of isomeric multi-substituted benzyl-type radicals. Y. W. Yoon, C. S. Huh, and S. K. Lee, Chem. Phys. Lett. {550}, 58 (2012). S. K. Lee and S. J. Kim, Chem. Phys. Lett. {412}, 88 (2005).

  10. Free Radical Timer of Aging: from Chemistry of Free Radicals to Systems Theory of Reliability.

    PubMed

    Koltover, Vitaly K

    2017-01-01

    There are two generally known concepts in biology of aging. Accordingly to the first one, there is a program of aging. The alternative concept advocates that aging proceeds stochastically. In this area of research, free radical-theory of aging, which was put forward by Denham Harman in fifties of XXth century, has determined the most heuristic line. The goal of this review is to demonstrate how the aging program and the aging stochastics are united on the basis of the systems theory of reliability. On this basis, universal features of aging, such as the exponential growth of mortality rate with time and correlation of longevity with the species-specific resting metabolism, are naturally explained. The stochastic malfunctions of the mitochondrial electron transport nanoreactors, which produce the oxygen anion-radicals (O2•-) as by-products of respiration, seem to be of first importance. As a reducing agent, O2•- affects the ratio of NAD(P)H/NAD(P)+ and, by changing the activity of sirtuins, slows down renewal of biomolecular constructs. As a consequence, the oxidative-stress products and other metabolic slag accumulate with the resulting impetus to autophagic or apoptotic cell death accompanied with age-associated clinical disorders. Based on this reliability-theory approach, one can estimate that the longevity of human brain could reach 250 years should the antioxidant defense against the free-radical failures be perfect. Thus, the free-radical redox timer serves as effective stochastic mechanism of realization of the programmed deficiency in reliability of biomolecular constructs.

  11. Praxis: The Making of Australia's Radical Education Dossier

    ERIC Educational Resources Information Center

    Harris, Kevin

    2014-01-01

    "Radical Education Dossier" is arguably the most successful independent continuous radical educational publication ever produced; made without financial support or institutional backing of any kind, surviving on the will and efforts of changing Editorial Collectives for more than 60 Issues over three decades, directly influencing at…

  12. The Hope of Radical Education: A Conversation with Henry Giroux.

    ERIC Educational Resources Information Center

    Journal of Education, 1988

    1988-01-01

    Radical education is questioning institutions and assumptions about education. An interview presents ideas of the spokesperson, Henry Giroux. They include the following: (1) traditional thinkers have the wrong perception of education; (2) education should engender empowerment; (3) radical education goes beyond a Marxist perspective; and (4)…

  13. Radicalizing Learning: Adult Education for a Just World

    ERIC Educational Resources Information Center

    Brookfield, Stephen D.; Holst, John D.

    2010-01-01

    This book offers new readings of the theory, politics, policy, and practice of radical adult education and learning where people's lives are understood as complex and interrelated matters. Brookfield and Holst's poetics and deeply human prose sound rebellious; the authors confront some of the main radical trends in the field of adult education…

  14. A Student Experiment for Measuring Rate Constants of Radical Recombination.

    ERIC Educational Resources Information Center

    Bartle, K. D.; And Others

    1978-01-01

    This experiment is designed specifically for students with little knowledge of radical reactions and provides an introduction to the gas-phase chemistry of radicals. Experimental planning based on the student's own observation is an important component of the experiment. (Author/MA)

  15. Mechanistic Enzymology of the Radical SAM Enzyme DesII.

    PubMed

    Ruszczycky, Mark W; Liu, Hung-Wen

    2015-04-01

    DesII is a member of the radical SAM family of enzymes that catalyzes radical-mediated transformations of TDP-4-amino-4,6-didexoy-D-glucose as well as other sugar nucleotide diphosphates. Like nearly all radical SAM enzymes, the reactions begin with the reductive homolysis of SAM to produce a 5'-deoxyadenosyl radical which is followed by regiospecific hydrogen atom abstraction from the substrate. What happens next, however, depends on the nature of the substrate radical so produced. In the case of the biosynthetically relevant substrate, a radical-mediated deamination ensues; however, when this amino group is replaced with a hydroxyl, one instead observes dehydrogenation. The factors that govern the fate of the initially generated substrate radical as well as the mechanistic details underlying these transformations have been a key focus of research into the chemistry of DesII. This review will discuss recent discoveries pertaining to the enzymology of DesII, how it may relate to understanding other radical-mediated lyases and dehydrogenases and the working hypotheses currently being investigated regarding the mechanism of DesII catalysis.

  16. The Hope of Radical Education: A Conversation with Henry Giroux.

    ERIC Educational Resources Information Center

    Journal of Education, 1988

    1988-01-01

    Radical education is questioning institutions and assumptions about education. An interview presents ideas of the spokesperson, Henry Giroux. They include the following: (1) traditional thinkers have the wrong perception of education; (2) education should engender empowerment; (3) radical education goes beyond a Marxist perspective; and (4)…

  17. Radical [1,3]-Rearrangements of Breslow Intermediates

    PubMed Central

    Alwarsh, Sefat; Xu, Yi; Qian, Steven

    2015-01-01

    Breslow intermediates that bear radical stabilizing N-substituents including benzyl, cinnamyl, and diarylmethyl undergo facile homolytic C-N bond scission under mild conditions to give products of formal [1,3]-rearrangement rather than benzoin condensation. EPR experiments and computational analysis support a radical mechanism. Implications for thiamine based enzymes are discussed. PMID:26553753

  18. Radical versus Social Constructivism: Dilemma, Dialogue, and Defense

    ERIC Educational Resources Information Center

    Belbase, Shashidhar

    2011-01-01

    This paper aims to discuss epistemological and philosophical foundation of meaningful learning and teaching mathematics and science from the perspective of radical and social constructivism. I have reflected on my experiences of radical and social constructivism through dilemma, dialogue, and defense of my personal epistemology of learning. I went…

  19. Confirmed Assignments of Isomeric Dimethylbenzyl Radicals Generated by Corona Discharge

    NASA Astrophysics Data System (ADS)

    Yoon, Young Wook; Lee, Sang Kuk

    2012-06-01

    Polymethylbenzyl radicals, multi-methyl-substituted benzyl radicals, have been believed to be an ideal model for understanding the torsional effect of methyl group and substitution effect on electronic transition. These radicals are mainly generated from polymethylbenzenes by electric discharge for spectroscopic observation. However, the existence of several methyl groups on the benzene ring may produce several isomeric polymethylbenzyl radicals by removing one of the C-H bonds of each methyl group at different substitution position, which makes the assignment of spectrum ambiguous. In this work, the controversial vibronic assignments of isomeric dimethylbenzyl radicals were clearly resolved by using different precursors. By using corresponding dimethylbenzyl chlorides as precursors, we identified the origins of the vibronic bands of the dimethylbenzyl radicals generated by corona discharge of precursors 1,2,3- and 1,2,4-trimethylbenzenes. From the analysis of the spectra observed from the dimethylbenzyl chlorides in a corona excited supersonic expansion using a pinhole-type glass nozzle, we revised previous assignments of the 2,6- and 2,3-dimethylbenzyl radicals as well as the 3,4-, 2,4-, and 2,5-dimethylbenzyl radicals. In addition, spectroscopic data of electronic transition and vibrational mode frequencies in the ground electronic state of each isomer were accurately determined by comparing them with those obtained by an ab initio calculation and with the known vibrational data of precursors.

  20. Influence of Free Radicals on the Intrinsic MRI Relaxation Properties.

    PubMed

    Tain, Rong-Wen; Scotti, Alessandro M; Li, Weiguo; Zhou, Xiaohong Joe; Cai, Kejia

    2017-01-01

    Free radicals are critical contributors in various conditions including normal aging, Alzheimer's disease, cancer, and diabetes. Currently there is no non-invasive approach to image tissue free radicals based on endogenous contrast due to their extremely short lifetimes and low in vivo concentrations. In this study we aim at characterizing the influence of free radicals on the MRI relaxation properties. Phantoms containing free radicals were created by treating egg white with various H 2 O 2 concentrations and scanned on a 9.4 T MRI scanner at room temperature. T1 and T2 relaxation maps were generated from data acquired with an inversion recovery sequence with varied inversion times and a multi-echo spin echo sequence with varied echo times (TEs), respectively. Results demonstrated that free radicals express a strong shortening effect on T1, which was proportional to the H 2 O 2 concentration, and a relatively small reduction in T2 (<10%). Furthermore, the sensitivity of this approach in the detection of free radicals was estimated to be in the pM range that is within the physiological range of in vivo free radical expression. In conclusion, the free radicals show a strong paramagnetic effect that may be utilized as an endogenous MRI contrast for its non-invasive in vivo imaging.