Entre Carl Schmitt y Thomas Hobbes . Un es tudio del liberalismo moderno a partir del pensamiento de Leo Strauss

Directory of Open Access Journals (Sweden)

José Daniel Parra Quintero

2010-01-01

Full Text Available El presente ensayo es una lectura sobre el liberalismo moderno desde el pensamiento de Leo Strauss. A partir de su análisis del Concepto de lo político de Carl Schmitt y su crítica de la "despolitización y neutralización" liberal, Strauss responde con una afirmación del problema del derecho natural, para lo cual es fundamental como primer paso estudiar la filosofía política de Thomas Hobbes. Desde allí Strauss se plantea un punto de contraste hacia una consideración clásica del derecho natural que pueda hacer frente al nihilismo político o cosmopolitanismo apolítico en la modernidad tardía, resultado ambos tanto del histori-cismo radical como del positivismo metodológico. Strauss antepone a la afirmación de la voluntad del poder soberano la búsqueda del derecho natural como representación de la idea de la justicia.

EL DISEÑO SOCIOINSTITUCIONAL DE LAS CIUDADES EN LA SOCIEDAD DEL APRENDIZAJE

OpenAIRE

José Gerardo Moreno Ayala

2011-01-01

El objetivo del presente trabajo es formular los criterios y principios de sentido comúnque la sociedad del aprendizaje impone al diseño socioinstitucional de las ciudades. De esta manera, en la primera parte del trabajo, se expone que desde las tres últimas décadas del siglo XX el mundo se encuentra frente a una transformación radical caracterizada por un cambio de paradigmas tecnoeconómicos: del fordista-keynesiano a otro definido como informático global. Con la finalidad de comprender camb...

Evaluación nematicida del aceite esencial de Tagetes zypaquirensis en el manejo del nematodo Meloidogyne spp.

Directory of Open Access Journals (Sweden)

David Eduardo Álvarez

2016-06-01

Full Text Available El lulo (Solanum quitoense Lam. es un frutal andino de gran importancia económica en Colombia, sin embargo, las áreas sembradas y rendimientos han sufrido una evidente reducción debido al ataque de patógenos como el nematodo Meloidogyne spp., que ha ocasionado pérdidas de hasta 50%. En la naturaleza existen diferentes recursos vegetales con propiedades nematicidas, destacándose al género Tagetes. El objetivo de esta investigación fue evaluar la actividad nematicida del aceite esencial de Tagetes zypaquirensis sobre Meloidogyne spp. Bajo condiciones de invernadero se evaluaron cuatro concentraciones del aceite esencial (100, 200, 400, 800mg/kg de suelo las cuales fueron aplicadas a un suelo con juveniles de segundo estadio del nematodo +400 J2/100g. Además, se establecieron tres comparadores: un tratamiento sin aplicación de aceite esencial, un suelo sin nematodo y un suelo tratado con i.a carbofuran (33,2% bajo una dosis de 2cc/L. Para cada tratamiento, las variables a evaluar fueron: severidad, altura de planta, peso fresco y seco al aire, peso fresco radical, número de huevos del nematodo/100g raíz y número de J2/100g de suelo. Los componentes mayoritarios del aceite esencial de T. zypaquirensis fueron dihidrotagetona y E-tagetona con una proporción relativa de 42,2 y 22,9%, respectivamente. Los resultados indicaron, que la concentración 800mg/kg de aceite esencial presentó la misma acción nematicida que el suelo tratado con carbofuran al reducir las poblaciones de Meloidogyne spp. y presentar valores similares en las variables fitométricas. Se concluye que el aceite esencial T. zypaquirensis puede ser una alternativa para el manejo de la enfermedad del nudo radical.

La reemergencia del discurso nacional-popular en la nueva izquierda latinoamericana

DEFF Research Database (Denmark)

Cancino, Hugo

2012-01-01

En este artículo analizamos la reemergencia del discurso nacional-popular. Los movimientos nacional-populares son un fenómeno recurrente en la historia de América Latina. Las revoluciones y los movimientos sociales más significativos del siglo XX fueron los movimientos nacional-populares. Para...... nuevo Estado, a través de la democracia radical, los cuales sustituyen la oligarquía del Estado y de la Nación Criolla que excluyeron indígenas y mestizos del poder y de la riqueza. Palabras claves: Discurso; Nacional-popular; Izquierda...

Jorge Isaacs: El espíritu radical de un poeta y sus frustraciones políticas

Directory of Open Access Journals (Sweden)

Raúl Vallejo Corral

2015-02-01

Full Text Available Jorge Isaacs es conocido por María (1867, novela cumbre del romanticismo americano. Pero Isaacs, además, fue un político liberal radical que llevó adelante una revolución, en enero de 1880, movido por sus principios ideológicos en medio de lo que él consideraba la traición de los liberales. La revolución, embebida de romanticismo, fue una empresa romántica destinada al fracaso desde un principio. Este artículo, a partir del estudio de los documentos de la época, analiza de qué manera Isaacs desarrolló sus actividades militantes, como superintendente de Educación, primero, como congresista, después, y como revolucionario, en el marco del proceso de recuperación del poder por parte de los conservadores. Asimismo, este artículo se enfoca en el espíritu romántico que animó a Isaacs y cómo se expresó a través de la palabra encendida de los manifiestos, proclamas, cartas e informes recopilados por el propio Isaacs en su libro La revolución radical en Antioquia (1880.   Jorge Isaacs is well-known for Maria (1867, which is considered the most important novel of Latin American romanticism. But Isaacs was also a radical liberal politician who carried forward a revolution, in January 1880, moved by his ideological principles in the midst of what he considered to be the treason of the liberals. From the very beginning, this revolution, which was immersed in romanticism, was an enterprise destined to fail. This article, based on the study of documents from that time, analyzes the way in which Isaacs developed his militant activities firstly as an Education inspector, then as a congressman, and finally as a revolutionary in the framework of the recovery process by the conservative party. Likewise, this article focuses on the romantic spirit that inspired Isaacs and how he expressed himself through his passionate words present in manifestos, proclamations, letters, and reports compiled by Isaacs himself in The Radical Revolution in

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

International Nuclear Information System (INIS)

Mieden, O.J.

1989-01-01

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

A radical approach to radical innovation

NARCIS (Netherlands)

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

2014-01-01

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

Relationship between Root Growth of 'Thompson Seedless' Grapevines and Soil Temperature Relación entre el Crecimiento Radical de Vid 'Thompson Seedless' y la Temperatura del Suelo

Directory of Open Access Journals (Sweden)

Rodrigo Callejas R

2009-12-01

Full Text Available With the purpose of characterizing the growth of the root system of table grapes (Vitis vinifera L. cv. Thompson Seedless and its relationship with soil temperature, research was carried out during the 2004-2005 growing season in vineyards in the Copiapó and Huasco Valleys. Four plants were chosen and rhizotrons were used to measure the growth of the root system. Measurements were performed once a week from September 2004 to September 2005, estimating the intensity of root growth and its annual distribution in the ranges of 0 to 40, 40 to 80 and 80 to 120 cm of soil depth. Temperature sensors were installed in four plants at 25, 50, 75 and 100 cm of soil depth, and the temperature was registered every 1 h. The thermal diffusivity of the soil was calculated based on the annual mean temperature and annual thermal amplitude values. Root growth occurred throughout the year, presenting lower intensity in July (winter. Root systems presented different patterns in the distribution of growth intensity in the three soil depths, with variations in the order of five times in maximum annual growth intensity among sites. High thermal diffusivity in soils favored root growth.Con el objetivo de caracterizar el crecimiento del sistema radical de la vid (Vitis vinifera L. cv. Thompson Seedless y su relación con la temperatura del suelo, durante la temporada 2004-2005 se llevó a cabo un estudio en parronales ubicados en los valles de Copiapó y Huasco. Se instalaron cuatro cámaras de observación de raíces o rizotrones en plantas homogéneas, en plena producción, pie franco, sanas, y ubicadas en diferentes localidades de la región. Las mediciones del crecimiento de las raíces se efectuaron semanalmente, desde septiembre de 2004 hasta completar 1 año, estimándose la intensidad de crecimiento radical anual y su distribución en los rangos de 0 a 40, 40 a 80 y 80 a 120 cm de profundidad. Adicionalmente, se instalaron sensores de temperatura a 25, 50, 75 y

La ética del discurso ante el desafío del (neopopulismo en Latinoamérica y la radicalización de la democracia

Directory of Open Access Journals (Sweden)

Carlos Andrés Duque Acosta

2014-06-01

Full Text Available En este trabajo se indaga por la posible (incompatibilidad de dos formas de comprender los fenómenos ético-políticos contemporáneos: la ética del discurso de Jürguen Habermas y la política como construcción hegemónica en un contexto (neopopulista de Ernesto Laclau, en relación con las condiciones de posibilidad de la Democracia Radical en el contexto latinoamericano actual. Se espera ilustrar la posibilidad de tal (incompatibilidad con el caso del gobierno del presidente ecuatoriano, Rafael Correa.

Radicalization In Pakistan And The Spread Of Radical Islam In Pakistan

Directory of Open Access Journals (Sweden)

Bahir ahmad

2015-08-01

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

Manipulating radicals: Using cobalt to steer radical reactions

OpenAIRE

Chirilă, A.

2017-01-01

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

Free radical inactivation of trypsin

International Nuclear Information System (INIS)

Cudina, Ivana; Jovanovic, S.V.

1988-01-01

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

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

International Nuclear Information System (INIS)

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

1978-01-01

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

Guest Editorial: Processes of Radicalization and De-Radicalization

Directory of Open Access Journals (Sweden)

Donatella Della Porta

2012-05-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2009-08-01

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

Radical, reformist and aborted liberalism: origins of national regimes in Central America Liberalismo radical, reformista y frustrado: orígenes de los regímenes nacionales en América central

Directory of Open Access Journals (Sweden)

James MAHONEY

2011-06-01

Full Text Available During the twentieth century, the countries of Central America were characterized by remarkably different political regimes: military-authoritarianism in Guatemala and El Salvador, progressive democracy in Costa Rica and traditional-authoritarianism in Honduras and Nicaragua. This article explains these contrasting regime outcomes by exploring the agrarian and state-building reforms pursued by political leaders during the nineteenth– and early twentieth century liberal reform period. Based on differences in the transformation of state and class structures, three types of liberalism are identified: radical liberalism in Guatemala and El Salvador, reformist liberalism in Costa Rica and aborted liberalism in Honduras and Nicaragua. It is argued that these types of liberalism set the Central American countries on contrasting paths of political development, culminating in diverse regime outcomes.Durante el siglo XX, los países de América Central se caracterizaron por tener regímenes políticos muy diferentes: el autoritarismo militar en Guatemala y El Salvador; la democracia progresista en Costa Rica y el autoritarismo tradicional en Honduras y Nicaragua. Este artículo explica los resultados de estos distintos regímenes mediante la exploración de las reformas agrarias y de la construcción del Estado llevadas a cabo por los líderes políticos durante el siglo XIX y principios del periodo de reformas liberales del siglo XX. Basándose en las diferencias de la transformación del Estado y de las estructuras de clases, se pueden identificar tres tipos de liberalismo: liberalismo radical en Guatemala y El Salvador; liberalismo reformista en Costa Rica y liberalismo frustrado en Honduras y Nicaragua. Se argumenta que estos tipos de liberalismo condujeron a los países de América Central a caminos contrarios al desarrollo político, culminando así en regímenes con resultados diversos.

Radical Change by Entrepreneurial Design

National Research Council Canada - National Science Library

Roberts, Nancy C

1998-01-01

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

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

OpenAIRE

Walton, J.C.; Williams, F.

2015-01-01

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

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

International Nuclear Information System (INIS)

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

1987-01-01

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

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

International Nuclear Information System (INIS)

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

2000-01-01

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

Comparación de costes de tres tratamientos del cáncer de próstata localizado en España: prostatectomía radical, braquiterapia prostática y radioterapia conformacional externa 3D Cost comparison of three treatments for localized prostate cancer in Spain: radical prostatectomy, prostate brachytherapy and external 3D conformal radiotherapy

Directory of Open Access Journals (Sweden)

Virginia Becerra Bachino

2011-02-01

Full Text Available Objetivo: Comparar los costes de los tratamientos más establecidos para el cáncer de próstata localizado según grupos de riesgo, edad y comorbilidad, desde la perspectiva del proveedor asistencial. Métodos: Comparación de costes en pacientes reclutados consecutivamente entre 2003 y 2005 en una unidad funcional de tratamiento del cáncer de próstata. La utilización de servicios hasta 6 meses después del inicio del tratamiento se obtuvo de las bases de datos hospitalarias, y los costes directos se estimaron mediante cálculo microcoste. La información sobre las características clínicas de los pacientes y los tratamientos recogió prospectivamente. Los costes se compararon mediante tests no paramétricos de comparación de medianas (Kruskall-Wallis y un modelo semilogarítmico de regresión múltiple. Resultados: La diferencia de costes fue estadísticamente significativa: medianas de 3229.10 €, 5369.00 € y 6265.60 € para los pacientes tratados con radioterapia conformacional externa 3D, braquiterapia, y prostatectomía radical retropública, respectivamente (pObjective: To compare the initial costs of the three most established treatments for clinically localized prostate cancer according to risk, age and comorbidity groups, from the healthcare provider's perspective. Methods: We carried out a cost comparison study in a sample of patients consecutively recruited between 2003 and 2005 from a functional unit for prostate cancer treatment in Catalonia (Spain. The use of services up to 6 months after the treatment start date was obtained from hospital databases and direct costs were estimated by micro-cost calculation. Information on the clinical characteristics of patients and treatments was collected prospectively. Costs were compared by using nonparametric tests comparing medians (Kruskall-Wallis and a semi-logarithmic multiple regression model. Results: Among the 398 patients included, the cost difference among treatments was

Free radical transfer in polymers

International Nuclear Information System (INIS)

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

1998-01-01

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

Las derechas españolas ante la crisis del 98

Directory of Open Access Journals (Sweden)

Pedro Carlos GONZÁLEZ CUEVAS

2010-02-01

Full Text Available RESUMEN: El "Desastre" español del 98 no puede considerarse como un hecho castizo de la historia nacional. Es un fenómeno europeo, que afectó a naciones como Francia, Italia y Portugal. Estos desastres de carácter militar coinciden, además, con un período de crisis intelectual —"revuelta contra el positivismo"— y con los inicios de procesos de transformación social y política. Todo lo cual generó, en la mayoría de los países europeos, una profunda crisis de legitimación de los sistemas políticos liberales y la decadencia de las ideologías políticas tradicionales, dando lugar al desarrollo, en el campo de la derecha, de un conservadurismo radical, cuyos máximos teorizantes fueron Charles Maurras y Maurice Barrés. En España, el avance hacia formas de conservadurismo radical o "nacionalismo integral" fue mucho más lento, debido a la emergencia de los nacionalismos periféricos catalán y vasco, a la debilidad del sentimiento nacional español, a la ausencia de reivindicaciones territoriales y de enemigos externos. No obstante, el conjunto de la derecha española de la época reaccionó ante el "Desastre" y ante los nuevos retos ideológicos y políticos con una sensación de interrogación, que les llevó a un replanteamiento de sus posiciones; a lo que hay que sumar las reflexiones de los regeneracionistas y de los representantes intelectuales del "espíritu del 98", cuyas reflexiones críticas sobre el "problema de España" introdujeron nuevas perspectivas en el desarrollo del nacionalismo español. Todo lo cual incidió decisivamente en la génesis posterior de la derecha radical española. Palabras Clave: Crisis finisecular, nacionalismo español, derechas políticas, regeneracionismos, intelectuales. ABSTRACT: The Spanish disaster of 1898 cannot be considered as a uniquely Spanish event in the history of the nation. It was a European phenomenon, which affected nations such as France, Italy and Portugal. These disasters

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

Directory of Open Access Journals (Sweden)

Béla Fiser

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

Realidad y actualidad. Una primera aproximación al tema del cuerpo

Directory of Open Access Journals (Sweden)

Espinoza Lolas, Ricardo

2013-04-01

Full Text Available This article explores the later thought of Zubiri, i.e. so-called noology, from viewpoint of the trilogy of intelligence: sentient intelligence (1980-1983 and writing on the concept of matter, the links between reality and actuality as the conceptua underpinning for an understanding of a philosophy of the human body that integrates both the philosophy of Zubiri over the course of his work and also enables us to understand man in his radical constituent bodily unity in the cosmos and the world.El presente artículo indaga en el pensamiento del último Zubiri, esto es, llamado noología, y desde la trilogía de la inteligencia: Inteligencia sentiente (1980-1983 y del escrito El concepto de materia, la articulación entre realidad y actualidad como soporte conceptual para comprender una filosofía del cuerpo humano que integre, por una parte, la filosofía zubiriana a lo largo de su obra y, por otra parte, que nos posibilite entender al hombre en su radical unidad corporal constitutiva tanto en el cosmos como en el mundo.

Erector spinae plane block for radical mastectomy: A new indication?

Science.gov (United States)

Veiga, M; Costa, D; Brazão, I

2018-02-01

The erector spinae plane block is a technique recently described by Forero et al. in September 2016. It has applications in the control of chronic pain with neuropathic component of the chest wall, and for pain control in thoracoscopic surgery. In this article, we describe the use of this technique as part of a multimodal analgesic approach in a 40-year-old woman, who underwent radical mastectomy due to breast cancer. By performing this block before anesthetic induction, we have achieved an opioid sparing effect, avoiding a possible immunomodulatory effect, although not yet proven in humans. During hospitalization, the patient reported no pain (0/10 in numeric scale), without resorting to rescue analgesia. The easy, fast and safe execution of erector spinae plane block makes it a promising technique in the context of surgical pain during radical mastectomy. Copyright © 2017 Sociedad Española de Anestesiología, Reanimación y Terapéutica del Dolor. Publicado por Elsevier España, S.L.U. All rights reserved.

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

Science.gov (United States)

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

2013-10-23

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

Physiology of free radicals

Directory of Open Access Journals (Sweden)

Stevanović Jelka

2011-01-01

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

MARIO VARGAS LLOSA: LA FICCIONALIZACIÓN DE LA HISTORIA EN LA GUERRA DEL FIN DEL MUNDO

Directory of Open Access Journals (Sweden)

Horst Nitschack

2011-11-01

Full Text Available En la novela La Guerra del fin del mundo Mario Vargas Llosa presenta una reescritura y ficcionalización del texto fundacional Os Sertdes de Euclides da Cunha. El presente artículo sitúa esta novela en el momento de un cambio radical de las convicciones ideológicas y políticas de Mario Vargas Llosa en la década de los 70 y se propone analizar de qué manera las nuevas posiciones neoliberales asumidas por el autor se reflejan en la poética de la novela. Como argumento central se sostiene que en el proceso de ficcionalización del texto referencial de Euclides da Cunha se dejan descubrir dos estrategias: la primera es la individualización de la Historia, es decir, la narración privilegia las experiencias subjetivas de los protagonistas para explicar sus disposiciones a la violencia; en la segunda, la ficcionalización asume una paradoja: finge representar lo irrepresentable advirtiendo al mismo tiempo al lector que se trata solamente de ficción, es decir, ella responsabiliza al propio lector en qué medida él está dispuesto a identificar la narración con la 'verdad' histórica. En los dos casos nos encontramos frente a una poética que valoriza la responsabilidad individual y lo subjetivo en vez de la dependencia individual de lo colectivo y del compromiso de la narración con la historia objetiva.In the novel The War of the End of the World (La guerra del fin del mundo Mario Vargas Llosa presents a rewriting and fictionalization of Euclides da Cunha's foundational text Os Sertdes. The article relates this novel to the radical change in Mario Vargas Llosa's ideological and political convictions in the 1970s and intends to analyze how the author's neo-liberal positions are reflected in the poetics of this novel. The central argument is that in this process of fictionalization of Euclides da Cunha's text, two strategies can be discovered: the first being the individualization of History, that is, the narrative privileges the subjective

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

Science.gov (United States)

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

2015-04-01

Peroxidases have great potential as industrial biocatalysts. In particular, the oxidative polymerization of phenolic compounds catalyzed by peroxidases has been extensively examined because of the advantage of this method over other conventional chemical methods. However, the industrial application of peroxidases is often limited because of their rapid inactivation by phenoxyl radicals during oxidative polymerization. In this work, we report a novel protein engineering approach to improve the radical stability of horseradish peroxidase isozyme C (HRPC). Phenylalanine residues that are vulnerable to modification by the phenoxyl radicals were identified using mass spectrometry analysis. UV-Vis and CD spectra showed that radical coupling did not change the secondary structure or the active site of HRPC. Four phenylalanine (Phe) residues (F68, F142, F143, and F179) were each mutated to alanine residues to generate single mutants to examine the role of these sites in radical coupling. Despite marginal improvement of radical stability, each single mutant still exhibited rapid radical inactivation. To further reduce inactivation by radical coupling, the four substitution mutations were combined in F68A/F142A/F143A/F179A. This mutant demonstrated dramatic enhancement of radical stability by retaining 41% of its initial activity compared to the wild-type, which was completely inactivated. Structure and sequence alignment revealed that radical-vulnerable Phe residues of HPRC are conserved in homologous peroxidases, which showed the same rapid inactivation tendency as HRPC. Based on our site-directed mutagenesis and biochemical characterization, we have shown that engineering radical-vulnerable residues to eliminate multiple radical coupling can be a good strategy to improve the stability of peroxidases against radical attack. © 2014 Wiley Periodicals, Inc.

Sobre el mal radical. Ensayo de la heterodoxia kantiana

Directory of Open Access Journals (Sweden)

Gómez Caffarena, José

2004-06-01

Full Text Available The kantian theory of a «radical evil inhabiting human nature» contrasts with a general anthropological optimistic tenor perceptible in kantian philosophy. It meant a significant turning point in the often too superficial optimistic trends of the Enlightenment. Hut its literal sense (appealing to an act of pre-individual freedom has an obvious difficulty. The present paper proposes an heterodox interpretation, which would avoid the difficulty, although so losing part of the tempting enigmatic reach of the kantian proposal.

La teoría del «mal radical en la naturaleza humana», expuesta por Kant en La religión dentro de los límites de la mera razón, hace contraste con el optimismo antropológico que empapa el Criticismo. Constituyó, sin duda, una importante denuncia frente a la banalidad de muchos optimismos ilustrados. Pero su letra (acto de libertad pre-individual tiene una obvia dificultad. El artículo propone una reinterpretación que la evitaría, aunque desdramatizando un tanto el tentador alcance enigmático de la propuesta kantiana.

Efectos radicales de un encuentro, lo contingente, lo inevitable/Radical effects of an encounter, the contingent, the inevitable

Directory of Open Access Journals (Sweden)

Alba Fernández

2010-03-01

Full Text Available A partir de la pregunta por la posibilidad del diálogo entre psicoanálisis y filosofía, los autores se proponen un recorrido por algunas de las cuestiones que dicha relación auspicia. Asumiendo la imposibilidad de homogeneidad de una filosofía y de un psicoanálisis, se problematiza entorno a lo aleatorio del encuentro posible, a la vez que se presume lo ineluctable del mismo. Tomando los discursos que de un campo y otro hacen referencia a la utopía, pero también a la posibilidad de esta conjunción con el extranjero, los autores subrayan la importancia del amor. El amor será el operador que propicie la radical singularidad de un encuentro, del cual se saldrá no beneficiado ni oprimido, tal vez más inseguro, más delicado, más quebradizo, pero lleno de esperanzas que aún no tienen nombre. From the question based on the possibility of the dialogue between psychoanalysis and philosophy, the authors have set out a route in which some of the questions of such relation foster. Assuming that the impossible homogeneity between a philosophy and a psychoanalysis will give problematic environment to the possible random encounter, in turn suppose the ineluctable of itself. Taking the speeches from one field and from another, both make reference to the utopia, but also to the possibility of this conjunction with the foreigner; could emphasize the importance of love according to authors. Love will be the conductor which will encourage the radical singularity of an encounter, from which not only there will not be no favored, but also no oppressed. However, it could be more unsecured, more delicate, more fragile, but full of hope that have no name yet.

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

Science.gov (United States)

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

2005-01-21

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

La reforma de la Ley Orgánica del Tribunal Constitucional

Directory of Open Access Journals (Sweden)

Manuel Aragón

2008-01-01

Full Text Available i. Objetivo y estructura del presente trabajo. ii. La pertinencia de la reforma. iii. El estatus del Tribunal Constitucional. iv. El recurso de amparo. v. Los asuntos de Pleno. vi. El funcionamiento interno del Tribunal. Reglas comunes de procedimiento y régimen del personal. vii. Consideraciones generales: el significado de la reforma. A. El alcance de la reforma. 1. Una reforma intensa de la lotc. 2. Lo que la reforma no incluye. B. La importancia de la reforma. 1. Transformación radical del recurso de amparo. 2. Cambios en el sistema de justicia constitucional. 3. Una precisión necesaria: el nuevo amparo-control no significa que el Tribunal Constitucional pierda por completo su dimensión de tribunal de tutela de los derechos fundamentales, sino que se transforma el significado de dicha función. 4. Eficacia de la reforma

La reforma de la Ley Orgánica del Tribunal Constitucional

Directory of Open Access Journals (Sweden)

Manuel Aragón

2008-12-01

Full Text Available i. Objetivo y estructura del presente trabajo. ii. La pertinencia de la reforma. iii. El estatus del Tribunal Constitucional. iv. El recurso de amparo. v. Los asuntos de Pleno. vi. El funcionamiento interno del Tribunal. Reglas comunes de procedimiento y régimen del personal. vii. Consideraciones generales: el significado de la reforma. A. El alcance de la reforma. 1. Una reforma intensa de la lotc. 2. Lo que la reforma no incluye. B. La importancia de la reforma. 1. Transformación radical del recurso de amparo. 2. Cambios en el sistema de justicia constitucional. 3. Una precisión necesaria: el nuevo amparo-control no significa que el Tribunal Constitucional pierda por completo su dimensión de tribunal de tutela de los derechos fundamentales, sino que se transforma el significado de dicha función. 4. Eficacia de la reforma

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

Science.gov (United States)

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

2009-01-01

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

Enfoque integral del paciente con pie diabético

Directory of Open Access Journals (Sweden)

Galia Fonseca Portilla

1996-04-01

Full Text Available Debe tenerse en cuenta que el diagnóstico de Diabetes Mellitus supone un cambio radical en las costumbres del paciente y que alcanzarlo puede requerir largo tiempo, por esto es necesario que los pacientes asistan a control cada dos o tres meses ye n cada visita insistirle en la importancia de curaciones. Si se continúa apoyando sobre la úlcera, se siguen exprimiendo, como esponja, las bacterias. Para el manejo del pie diabético se distinguen: prevención primaria (detección precoz del pie en riesgo, prevención secundaria (cuidado adecuado de las úlceras grado 1, 2 por el equipo interdisciplinario y prevención terciaria (a nivel hospitalario, para evitar la amputación de los pies con úlceras grado 3-5.

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

International Nuclear Information System (INIS)

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

1998-01-01

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

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

OpenAIRE

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

2014-01-01

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

Homegrown religious radicalization

DEFF Research Database (Denmark)

Khawaja, Iram

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

Laparoscopic radical trachelectomy.

Science.gov (United States)

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

2012-01-01

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

Radical Evil

Directory of Open Access Journals (Sweden)

Carlos Manrique

2007-12-01

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

Conductismo Radical o Acerca del Vino Nuevo y el Odre Viejo Radical Behaviorism or About the New Wine and the Old Wine Skin

Directory of Open Access Journals (Sweden)

Alejandro Pool

2005-05-01

Full Text Available El Conductismo Radical, cuyo más destacado exponente fue B. F. Skinner, es a menudo mal entendido y criticado tanto en ámbitos académicos como profanos. A esta actitud contribuyen diversos factores: culturales, ideológicos y políticos. Este trabajo ofrece una mirada panorámica sobre aquellos puntos más controversiales de dicha teoría y algunas de las críticas que se le han formulado, con lo que se pretende problematizar algunas de las ideas o supuestos que la psicología ha asumido como certezas sin previo cuestionamiento, y cuyo debate podría contribuir al desarrollo de esta ciencia.Radical Behaviorism, whose most important exponent was B. F. Skinner, is often misunderstood and criticized in academic and non academic circles. Different cultural, ideological and politic factors help to contribute to this attitude. The present paper offers a panoramic view of the most controversial issues about this theory and some of its critics. The aim is to discuss some of the ideas or hypothesis that psychology has assumed as certainties without any questioning, considering that a debate on this ideas could contribute to the development of this science.

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

OpenAIRE

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

2014-01-01

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

Radical constructivism: Between realism and solipsism

Science.gov (United States)

Martínez-Delgado, Alberto

2002-11-01

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

Comunicació d'èxit : Estudi del cas Rec.0 Experimental Stores

OpenAIRE

Farreras Pérez, Laura

2015-01-01

El present projecte estudia la comunicació de barri a partir de la iniciativa Rec.0 Experimental Stores. És la posada en escena del concepte 'pop up stores' al vell barri industrial del Rec d'Igualada. Descomptes radicals en una experiència de compra diferent, on el valor afegit ve donat per les activitats complementàries. La proposta d'un pla de comunicació culmina l'estudi. El presente proyecto estudia la comunicación de barrio a partir de la iniciativa Rec.0 Experimental Stores. Es la p...

Salvage robotic radical prostatectomy

Directory of Open Access Journals (Sweden)

Samuel D Kaffenberger

2014-01-01

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

Muoniated acyl and thioacyl radicals

International Nuclear Information System (INIS)

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

2006-01-01

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

Muoniated acyl and thioacyl radicals

Energy Technology Data Exchange (ETDEWEB)

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

2006-03-31

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

Muonium and muonic radicals

International Nuclear Information System (INIS)

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

1985-01-01

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

Una aproximación a la derecha radical sueca en perspectiva comparada con Finlandia

Directory of Open Access Journals (Sweden)

Miriam Ureta García

2017-11-01

Full Text Available La investigación propone realizar una aproximación analítica a los partidos de derecha radical Demócratas de Suecia y Verdaderos Finlandeses en perspectiva comparada. Para ello se presentará una caracterización teórica de la tipología de nuevos partidos europeos de derecha radical y sus componentes ideológicos; el marco a través del cual analizar sus líderes, el perfil general de su electorado y las razones que impulsan a votar a esta nueva familia de formaciones. Una vez sintetizado brevemente el marco general a partir de la literatura existente, se procederá a su aplicación a los casos de Demócratas de Suecia y Verdaderos Finlandeses, desgranando comparativamente las claves analíticas que dotan a ambas organizaciones de significación.

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

DEFF Research Database (Denmark)

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

1996-01-01

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

La emergencia del feminismo en la Argentina: un análisis de las tramas discursivas a comienzos del siglo XX

Directory of Open Access Journals (Sweden)

Natalia Martínez Prado

2015-03-01

Full Text Available En el presente artículo nos propusimos reconstruir algunos de los sentidos dominantes que adquirieron las primeras prácticas reconocidas como “feministas” a partir de una aproximación a sus (des articulaciones con otras prácticas femeninas. Sosteniendo una concepción anti-esencialista, relacional y radical de la identidad, nuestro análisis se detiene en la lectura de dos corpus textuales de las activistas a comienzos del siglo XX. Analizamos el discurso de las anarquistas desde el periódico: “La Voz de la Mujer” y nos detenemos en la tesis doctoral de Elvira López, defendida en 1901 y titulada: “El movimiento feminista. Primeros trazos del feminismo en Argentina”.

Studies of radiation-produced radicals and radical ions. Progress report, June 1, 1981-August 31, 1982

International Nuclear Information System (INIS)

Williams, T.F.

1982-01-01

The discovery and characterization of novel radical ions produced by the γ irradiation of solids continues to be a fertile field for investigation. This Progress Report describes the generation and ESR identification of several new paramagnetic species, some of which have long been sought as important intermediates in radiation chemistry. We have also contributed to a general theoretical problem in ESR spectroscopy. Solid-state studies of electron attachment reactions, both non-dissociative and dissociative, reveal interesting structural and chemical information about the molecular nature of these processes for simple compounds. In particular, ESR measurements of the spin distribution in the products allow a fairly sharp distinction to be drawn between radical anions and radical-anion pairs or adducts. Dimer radical anion formation can also take place but the crystal structure plays a role in this process, as expected. Some radical anions undergo photolysis to give radical-anion pairs which may then revert back to the original radical anion by a thermal reaction. The chemistry of these reversible processes is made more intricate by a competing reaction in which the radical abstracts a hydrogen atom from a neighboring molecule. However, the unraveling of this complication has also served to extend our knowledge of the role of quantum tunneling in chemical reactions. The results of this investigation testify to the potential of solid-state techniques for the study of novel and frangible radical ions. Progress in this field shows no sign of abating, as witness the recent discovery of perfluorocycloalkane radical anions and alkane radical cations

Muonium-containing vinyl radicals

International Nuclear Information System (INIS)

Rhodes, C.J.; Symons, M.C.R.; Roduner, E.; Heming, M.

1987-01-01

Exposure of trimethylsilylacetylene and bis(trimethylsilyl)acetylene to positive muons gave radicals whose muon-electron hyperfine coupling constants establish that the corresponding vinyl radicals were formed. (author)

Radicals in arithmetic

NARCIS (Netherlands)

W.J. Palenstijn (Willem Jan)

2014-01-01

htmlabstractLet K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement

Características clínico patológicas del cáncer de cérvix uterino recurrente después de cirugía radical primaria.

Directory of Open Access Journals (Sweden)

Pedro Aguilar

2012-03-01

Full Text Available Objetivo: Describir las características clínico patológicas del cáncer de cérvix uterino recurrente, sitio y tiempo de recurrencia, y sobrevida después de la recurrencia de acuerdo a las variables de pronóstico en pacientes con cirugía radical primaria. Material y métodos: Estudio descriptivo, observacional y retrospectivo, tipo serie de casos, realizado en el Instituto Nacional de Enfermedades Neoplásicas de Lima Perú entre 1990 y 2005. Se incluyeron todas las pacientes con cáncer de cérvix uterino estadios IB1 y IIA a quienes se les realizó cirugía radical primaria y que tuvieron recurrencia. Las curvas de sobrevida fueron construidas con el método de Kaplan-Meier. Resultados: Se realizaron 609 histerectomías radicales tipo III, 53(8,7% tuvieron recurrencia. La edad promedio al diagnóstico de la recurrencia fue 44,5 años, el tiempo medio desde la cirugía hasta la recurrencia 18,9 meses y el sitio de recurrencia más frecuente fue a distancia (41,5% seguido por recurrencia central y pélvica. El sitio de recurrencia y los márgenes quirúrgicos tuvieron significancia estadística con respecto al tiempo de recurrencia. La terapia de salvataje más frecuente fue la radioterapia (45%. La sobrevida promedio después de la recurrencia fue 26,9 meses y la tasa de sobrevida a 5 años 9,4%. Conclusiones: El cáncer cervical recurrente es poco frecuente, afecta a mujeres jóvenes y el sitio de recurrencia más frecuente es metástasis a distancia. El tiempo de recurrencia es más corto cuando la recurrencia es central y los márgenes quirúrgicos están afectados. La sobrevida después de la recurrencia en cáncer cervical tratado con cirugía radical es baja.

Multiple free-radical scavenging capacity in serum

Science.gov (United States)

Oowada, Shigeru; Endo, Nobuyuki; Kameya, Hiromi; Shimmei, Masashi; Kotake, Yashige

2012-01-01

We have developed a method to determine serum scavenging-capacity profile against multiple free radical species, namely hydroxyl radical, superoxide radical, alkoxyl radical, alkylperoxyl radical, alkyl radical, and singlet oxygen. This method was applied to a cohort of chronic kidney disease patients. Each free radical species was produced with a common experimental procedure; i.e., uv/visible-light photolysis of free-radical precursor/sensitizer. The decrease in free-radical concentration by the presence of serum was quantified with electron spin resonance spin trapping method, from which the scavenging capacity was calculated. There was a significant capacity change in the disease group (n = 45) as compared with the healthy control group (n = 30). The percent values of disease’s scavenging capacity with respect to control group indicated statistically significant differences in all free-radical species except alkylperoxyl radical, i.e., hydroxyl radical, 73 ± 12% (p = 0.001); superoxide radical, 158 ± 50% (p = 0.001); alkoxyl radical, 121 ± 30% (p = 0.005); alkylperoxyl radical, 123 ± 32% (p>0.1); alkyl radical, 26 ± 14% (p = 0.001); and singlet oxygen, 57 ± 18% (p = 0.001). The scavenging capacity profile was illustrated using a radar chart, clearly demonstrating the characteristic change in the disease group. Although the cause of the scavenging capacity change by the disease state is not completely understood, the profile of multiple radical scavenging capacities may become a useful diagnostic tool. PMID:22962529

Preoperative radiochemotherapy and radical surgery in comparison with radical surgery alone

International Nuclear Information System (INIS)

Mohr, C.; Schettler, D.; Bohndorf, W.

1994-01-01

A multicentric, randomized study of squamous cell carcinoma (SCC) of the oral cavity and the oropharynx has been undertaken by DOeSAK. The results after radical surgery alone have been compared with the results of combined preoperative radiochemotherapy followed by radical surgery. Patients with primary (biopsy proven) SCC of the oral cavity or the oropharynx with tumor nodes metastasis (TNM) stages T2-4, N0-3, M0 were included in the study. A total of 141 patients were treated by radical surgery alone, whereas 127 patients were treated by radical surgery preceded by preoperative radiochemotherapy. The pre-operative treatment consisted of conventionally fractioned irradiation on the primary and the regional lymph nodes with a total dose of 36 Gy (5 x 2 Gy per week) and low-dose cisplatin chemotherapy with 5 x 12.5 mg cisplatin per m 2 of body surface during the first week of treatment. Radical surgery according to be DOeSAK definitions (DOeSAK, 1982) was performed after a delay of 10-14 days. During the follow-up period, 28.2% of all patients suffered from locoregional recurrence, and 27.2% of the patients died. The percentages were higher after radical surgery alone for locoregional recurrence (31% and 15.6%) and for death (28% and 18.6%). The life-table analysis showed improved survival rates of 4.5% after 1 year and 8.3% after 2 years in the group of patients treated with combined therapy. The demonstrated improvement appeared to be significant with the Gehan-Wilcoxon test as well as with the log rank test below a P value of 5%. (au) (29 refs.)

Radicals in arithmetic

NARCIS (Netherlands)

Palenstijn, Willem Jan

2014-01-01

Let K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement group. We give

Radicalization as a Vector: Exploring Non-Violent and Benevolent Processes of Radicalization.

Directory of Open Access Journals (Sweden)

Ken Reidy

2018-03-01

Full Text Available Successful radicalization posits three outcomes: extremism, terrorism or both. As these are undesirable, radicalization is understood as wholly malevolent and governments work to prevent and/or stop it. Nonetheless, a handful of scholars have recognized that the same radicalization process which results in either outcome may, theoretically at least, also have beneficial outcomes such as environmental awareness or human rights. This article explores one such outcome. Based on interviews with British Muslim aid workers (n=6 operating in Jihadist conflict zones post Arab spring and using constructivist grounded theory, it illustrates how the research participants radicalized to humanitarianism which resulted in them assisting the most plighted of Muslims by deploying to the most wanton of areas: ones commonly referred to as Jihadist conflict zones. Evidently, these destinations are shared with Jihadists and given the array of other observable similarities (socio-demographics and [pre-]mobilization behaviours, these morally opposed groups become conflated by the security services. This is further compounded by the fact that Jihadists manipulate and/or impersonate aid workers so as to funnel people and funds. To distinguish both, this article documents the benevolent pathway of the research participants and juxtaposes it to scholarly knowledge on Jihadist pathways. Socialization was revealed to be the key distinguishing feature rather than descriptive risk factors (such as ideology or moral outrage because the process of radicalization was not found to be the start of the radicalized pathway. It concludes that benevolently radicalized Islamic groups constitute an effective means of pathway divergence for particular typologies by offering an attractive and prosocial alternative to Jihadism. This strengths-based preventative approach (“what’s right” takes the form of a community-centric market competitor to Jihadism rather than a problem

Radical cations of quadricyclane and norbornadiene in polar ZSM-5 matrices: Radical cation photochemical transformations without photons

International Nuclear Information System (INIS)

Barnabas, M.V.; Trifunac, A.D.

1994-01-01

Radical cations of quadricyclane (Q) and norbornadiene (NBD) are produced by γ-radiolysis in zeolites. In polar ZSM-5, only one radical cation is initially observed below 100K. Increasing the temperature above 200K gives rise to the cyclopentadiene radical cation. Higher temperatures (>360K) give rise to the cyclopenten-4-yl radical. The observation of cyclopentadiene radical cation implies the occurrence of the reverse Diels-Alder reaction. This is a thermally forbidden, photochemically allowed, process, which is made possible by the interaction of the polar zeolite matrix sites with parent NBD and Q radical cations

Influence of planting methods on root development, crop productivity and water use efficiency in maize hybrids Influencia de métodos de siembra sobre el desarrollo radical, productividad y eficiencia del uso del agua en híbridos de maíz

Directory of Open Access Journals (Sweden)

Muhammad B. Khan

2012-12-01

ó un sistema radical bien desarrollado, raíz primaria más larga, mayor número de raíces laterales, y mayor tasa de crecimiento radical, en 'Pioneer-30Y87' plantado en surcos, lo que condujo a mayores WUE, rendimiento de grano y sus rasgos relacionados. El mismo híbrido sembrado en surcos presentó mayores índice de área foliar y tasa de crecimiento del cultivo, máximo rendimiento neto y relación beneficio:costo. En general, la siembra en surco mejoró el desarrollo radical resultando en mejores alometría, productividad (5,45 t ha-1, y WUE (1,35 kg m-3, en todos los híbridos de maíz. Aunque los híbridos de maíz mostraron respuesta diferente a los diferentes métodos de siembra, máximos rendimientos de grano (5,63 t ha-1, WUE (1,41 kg m-3, y retornos económicos netos se observaron en el híbrido Pioneer 30Y87.

Youth De-Radicalization: A Canadian Framework

Directory of Open Access Journals (Sweden)

Hafal (Haval Ahmad

2017-09-01

Full Text Available Youth radicalization leading to violence has become a growing fear among Canadians, as terrorist attacks are carried out in Western states. Although Canada has suffered relatively fewer acts of violence, this fear has intensified and a de-radicalization strategy is needed in the Canadian context. In a qualitative case study methodology, interviews were conducted with school counsellors, religious leaders, and academics to explore solutions to youth radicalization. Youth de-radicalization approaches from the United Kingdom were analyzed and found that community-based initiatives were missing from programming. Social identity theory is used to explain that youth join radicalized groups to feel a sense of belonging and have to be provided an alternative and moderate group identity to de-radicalize. This study found youth de-radicalization in Canada is best served through a community collaboration approach.

El concepto de justicia penal restaurativa en la construcción del marco teórico

Directory of Open Access Journals (Sweden)

Jorge Pesqueira Leal

2014-07-01

Full Text Available El concepto de justicia restaurativa genera un cambio radical en la común definición de justicia, puesto que enriquece el papel del Estado en el interés y preocupación por todos los actores del conflicto penal, la víctima, victimario y sociedad, además de que se modifica la respuesta punitiva del Estado al infractor, pasando al empleo de los mecanismos readaptadores, sin dejar de lado la concepción del delito como un agravio a toda la sociedad.Así, la justicia restaurativa se ocupa de la satisfacción de las necesidades de las víctimas procurando llevar las cosas a su estado anterior, de la readaptación del victimario y del reconocimiento de sus responsabilidades para con las víctimas al igual que con la sociedad.

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

Science.gov (United States)

El-Agamey, Ali; McGarvey, David J

2016-01-01

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

Glutathione as a radical scavenger and the biological consequences of thiyl radical production

International Nuclear Information System (INIS)

Winterbourn, C.C.

1996-01-01

A large number of compounds that have toxic effects can be metabolised to free radicals and secondary reactive oxygen species. These may be directly damaging or affect cell function by altering regulatory mechanisms through changing redox status. Protection is provided by an integrated system of antioxidant defenses. This includes reduced glutathione (GSH), one of the functions of which is as a free radical scavenger. For GSH to be an effective radical scavenging antioxidant, therefore, it must act in concert with superoxide dismutase to remove the superoxide so generated. Superoxide is produced in a variety of metabolic processes. It is also a secondary product of radicals reacting with oxygen either directly or through GSH. The biological reactivity of superoxide has been the subject of much debate ever since the discovery of superoxide dismutase in 1968. It has more recently become apparent that its rapid reaction with nitric oxide to give peroxynitrite, and its ability to reversibly oxidise and inactivate iron sulphur enzymes, contribute to the toxicity of superoxide. Another mechanism that could be important involves addition reactions of superoxide with other radicals to give organic peroxides. This reaction, to form a tyrosine peroxide, has come to authors attention through the study of the scavenging of tyrosyl radicals by GSH. It is also shown that a tyrosine peroxide is a major product of the oxidation of tyrosine by neutrophils

Taking a radical position: Evidence for position specific radical representations in Chinese character recognition using masked priming ERP

Directory of Open Access Journals (Sweden)

I-Fan eSu

2012-09-01

Full Text Available In the investigation of orthographic representation of Chinese characters, one question that has stimulated much research is whether radicals (character components are specified for spatial position in a character (e.g. Ding, Peng, & Taft, 2004; Tsang & Chen, 2009. Differing from previous work, component or radical position information in this study is conceived in terms of relative frequency across different positions of characters containing it. A lexical decision task in a masked priming paradigm focusing on radicals with preferred position of occurrence was conducted. A radical position that encompasses more characters than other positions was identified to be the preferred position of a particular radical. The prime that was exposed for 96ms might share a radical with the target in the same or different positions. Moreover, the shared radical appeared either in its preferred or non-preferred position in the target. While response latencies only revealed the effect of graphical similarity, both effects of graphical similarity and radical position preference were found in the ERP results. The former effect was reflected in greater positivity in occipital P1 and greater negativity in N400 for radicals in different positions in prime and target characters. The latter effect manifested as greater negativity in occipital N170 and greater positivity in frontal P200 in the same time window elicited by radicals in their non-preferred position. Equally interesting was the reversal of the effect of radical position preference in N400 with greater negativity associated with radicals in preferred position. These findings identify the early ERP components associated with activation of position-specific radical representations in the orthographic lexicon, and reveal the change in the nature of competition from processing at the radical level to the lexical level.

Radical production in biological systems

International Nuclear Information System (INIS)

Johnson, J.R.; Akabani, G.

1994-10-01

This paper describes our effort to develop a metric for radiation exposure that is more fundamental than adsorbed dose and upon which a metric for exposure to chemicals could be based. This metric is based on the production of radicals by the two agents. Radicals produced by radiation in biological systems commonly assumed to be the same as those produced in water despite the presence of a variety of complex molecules. This may explain why the extensive efforts to describe the relationship between energy deposition (track structure) and molecular damage to DNA, based on the spectrum of radicals produced, have not been successful in explaining simple biological effects such as cell killing. Current models assume that DNA and its basic elements are immersed in water-like media and only model the production and diffusion of water-based radicals and their interaction with DNA structures; these models lack the cross sections associated with each macro-component of DNA and only treat water-based radicals. It has been found that such models are not realistic because DNA is not immersed in pure water. A computer code capable of simulating electron tracks, low-energy electrons, energy deposition in small molecules, and radical production and diffusion in water like media has been developed. This code is still in at a primitive stage and development is continuing. It is being used to study radical production by radiation, and radical diffusion and interactions in simple molecular systems following their production. We are extending the code to radical production by chemicals to complement our PBPK modeling efforts. It therefore has been developed primarily for use with radionuclides that are in biological materials, and not for radiation fields

"Los avisadores del fuego": Rosenzweig, Benjamin, Kafka

Directory of Open Access Journals (Sweden)

Mate, Reyes

2000-12-01

Full Text Available There were thinkers who foretold in their time the signs of the coming catastrophe. They were not prophets but fine analysts. We are referring to Rosenzweig, Benjamin and Kafka. In the "idealism" of the philosophy that comes from Jonia and reaches Jena, Rosenzweig animadverted on the tendency to a totalitarianism that potentially converted it into an "ontology of war". Benjamin brought to light the radical ambiguity within the concept of progress, so fundamental to the illustrated thought. Barbarism, in general, and fascism, in particular, are not the opposite to progress but one of its possibilities. That fatal possibility is, for the victim, the rule. Kafka traced with foresight the fascist reduction of man to bare life in the recurrent animalisation of his characters, as well as the denial of the other in those presented as victims of incommunications.

Hubo pensadores que supieron leer en su tiempo signos de la catástrofe venidera. No eran profetas sino finos analistas. Nos referimos a Rosenzweig, Benjamin y Kafka. Rosenzweig denunció en el "idealismo" de la filosofía que viene desde Jonia y llega hasta Jena la tendencia a un totalitarismo que la convertía en potencialmente en una "ontología de la guerra". Benjamin dejó constancia de la ambigüedad radical del concepto de progreso, tan fundamental para el pensamiento ilustrado. La barbarie, en general, y el fascismo, en particular, no son lo opuesto al progreso sino una de sus posibilidades. Esa fatal posibilidad es, para la víctima, la norma. Kafka capta anticipadamente la reducción fascista del hombre a nuda vida en la recurrente animalización de sus personajes, así como la negación del otro en sus personajes víctimas de la incomunicación.

The Public Action of Unconstitutionality in Colombia in the 19th Century Seen Through the Law Regarding the Colegio Mayor del Rosario

OpenAIRE

Malagón Pinzón, Miguel

2007-01-01

En este artículo se muestra como funcionó la Acción Pública de Inconstitucionalidad en el período del liberalismo radical en Colombia, durante el siglo XIX. Se estudia una ley del año de 1879 proferida por el Estado Soberano de Cundinamarca, por medio de la cual se restringe la autonomía del Colegio Mayor del Rosario. Dicha norma fue demanda por dos ex_rectores, estudiada por la Corte Suprema y finalmente anulada por el Senado de los Estados Unidos de Colombia. The following article demons...

Chemical repair of trypsin-histidinyl radical

International Nuclear Information System (INIS)

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

1991-01-01

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

Métodos indirectos para estimar masa radical en caña de azúcar, variedad CC 8592

Directory of Open Access Journals (Sweden)

Mejia M. S.

2004-12-01

Full Text Available En casas de malla (31°C, 58% HR se evaluaron tres metodologías no destructivas (capacitancia eléctrica, amperaje, resistencia eléctrica para estimar la masa radical en caña de azúcar variedad CC 8592. El material vegetal se sometió a diferentes niveles de humedad en el sustrato. Se utilizó un diseño completamente al azar, con 13 repeticiones; las plantas se sembraron en materos plásticos (3 kg con cachaza - carbonilla (3:1; 24 horas antes de las mediciones se saturó el sustrato con agua. Mediante regresión lineal se obtuvieron las siguientes ecuaciones que relacionaron capacitancia (X con masa radical fresca (Y: Y = 6.841X - 49.623 (R2 = 0.829, P < 0.001, y con la masa radical seca: Y = 0.9546X - 7.4649 (R2 = 0.545, P < 0.001. La relación del amperaje con la masa radical fresca fue: Y = 0.4138X - 48.194 (R2 = 0.850, P <0.001 y con la masa radical seca: Y = 0.0577X - 7.2575 (R2 = 0.559, P <0.001; este método presentó mayor confiabilidad que el del capacitómetro. El método de la resistencia eléctrica no presentó resultados confiables. ABSTRACT Indirect methods to estimate the root biomass in sugar cane, cultivar CC 8592. In greenhouses (31°C, 58% RH three nondestructive methods were evaluated (electrical capacitance, amperage electrical resistance to estimate the root biomass. There was used a completely randomized design, with 4 treatments and 13 replications, the plants were seeded in plastic pots (3 kg using a mix of cachaza and fine coal (3:1; 24 hours before the measurements the substrate was saturated with water. By means of linear regression were obtained the following equations that relate fresh root (Y and capacitance (X: Y = 6.841X - 49.623 (R2 = 0.829, P < 0.001; and dry root biomass to capacitance: Y = 0.9546X - 7.4649 (R2 = 0.545, P < 0.001. The relation of fresh root biomass and amperage was Y = 0.4138X - 48.194 (R2 = 0.850, P < 0.001 and dry root biomass with amperage, Y = 0.0577X - 7.2575 (R2 = 0.559, P

Gnosticism and Radical Feminism

DEFF Research Database (Denmark)

Cahana, Jonathan

2016-01-01

and radical feminism would easily fall under this definition. There is, however, one major difference: since radical feminism is a relatively recent phenomenon which also benefited from modern modes of text production and preservation, almost all of the sources are still with us. This, in turn, may allow us...... to use radical feminism to make certain aspects of ancient Gnosticism re-emerge from their long submersion, provided that enough similarities can be independently drawn between the two phenomena to merit such a comparison. This paper therefore presents a comparison between concepts and positions...

Radical's view of sciences

International Nuclear Information System (INIS)

Mittal, J.P.

2004-01-01

Full text: General concept in radiation biology is that free radicals are highly reactive and they can damage vital cellular molecules leading to injurious effects. However, in this talk, evidence will be presented through the techniques of electron paramagnetic resonance ( EPR ) and pulse radiolysis that free radicals can be highly selective in their reaction with the target molecules. In addition, attempts will be made to present a brief account of emerging scenario of free radical generation, identification and their involvement in radiation damage mechanisms in chemical and biological systems

EPR spin trapping of protein radicals

DEFF Research Database (Denmark)

Davies, Michael Jonathan; Hawkins, Clare Louise

2004-01-01

Electron paramagnetic resonance (EPR) spin trapping was originally developed to aid the detection of low-molecular-mass radicals formed in chemical systems. It has subsequently found widespread use in biology and medicine for the direct detection of radical species formed during oxidative stress...... tumbling radicals are often broad and relatively poor in distinctive features, a number of techniques have been developed that allow a wealth of information to be obtained about the nature, site, and reactions of such radicals. This article summarizes recent developments in this area and reviews selected...... examples of radical formation on proteins....

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

Science.gov (United States)

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

1991-03-01

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

Metal-Diazo Radicals of α-Carbonyl Diazomethanes

Science.gov (United States)

Li, Feifei; Xiao, Longqiang; Liu, Lijian

2016-03-01

Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

Reaction between protein radicals and other biomolecules

DEFF Research Database (Denmark)

Østdal, H.; Davies, M.J.; Andersen, Henrik Jørgen

2002-01-01

The present study investigates the reactivity of bovine serum albumin (BSA) radicals towards different biomolecules (urate, linoleic acid, and a polypeptide, poly(Glu-Ala-Tyr)). The BSA radical was formed at room temperature through a direct protein-to-protein radical transfer from H(2)O(2....... Subsequent analysis showed a decrease in the concentration of urate upon reaction with the BSA radical, while the BSA radical in the presence of poly(Glu-Ala-Tyr) resulted in increased formation of the characteristic protein oxidation product, dityrosine. Reaction between the BSA radical and a linoleic acid...

Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons

International Nuclear Information System (INIS)

Bors, W.; Saran, M.; Michel, C.

1982-01-01

The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (radicalsOH) and hydrated electrons (e - sub(aq)), while superoxide anions (O 2 - ) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation. (author)

Formation of long-lived radicals on proteins by radical transfer from heme enzymes--a common process?

DEFF Research Database (Denmark)

Ostdal, H; Andersen, H J; Davies, Michael Jonathan

1999-01-01

concentrations were observed after limited digestion, although this effect was less marked with the HRP/H2O2/BSA system than with Fe(III)Mb/H2O2/BSA, consistent with different modes of radical transfer. More extensive digestion of BSA decreased the radical concentration to levels below those detected with native...... investigated using horseradish peroxidase (HRP)/H2O2, in the presence and absence of added tyrosine. Incubation of HRP with H2O2 and bovine or human serum albumins, in the presence and absence of tyrosine, gave long-lived albumin-derived radicals as detected by EPR spectroscopy. Evidence has been obtained...... for these albumin radicals being located on buried tyrosine residues on the basis of blocking experiments. The effect of protein conformation on radical transfer has been investigated using partial proteolytic digestion prior to protein oxidation. With HRP/H2O2/BSA and Fe(III)Mb/H2O2/BSA increased radical...

Negatividad e intersubjetividad. La dimensión originaria del conflicto en Kojève y en Sartre

Directory of Open Access Journals (Sweden)

Maximiliano Basilio Cladakis

2017-01-01

Full Text Available El artículo aborda la lógica a partir de la cual el correlato de la libertad como negatividad radical es el conflicto como dimensión originaria de la intersübjetividad en Alexandre Kojève y Jean Paul Sartre. Se examina la interpretación realizada por el pensador ruso del capítulo iv de la Fenomenología del espíritu y la importancia de la "dialéctica del amo y del esclavo" como clave del pensamiento hegeliano; así como la forma en que las premisas ontológicas expuestas en El ser y la nada se presentan como elementos constitutivos de la comprensión de la intersubjetividad como dialéctica subjetivación-objetivación.

Radical surgery compared with intracavitary cesium followed by radical surgery in cervical carcinoma stage IB

Energy Technology Data Exchange (ETDEWEB)

Tinga, D.J.; Bouma, J.; Aalders, J.G. (Dept. of Obstetrics and Gynaecology, State Univ. Hospital, Groningen (Netherlands)); Hollema, H. (Dept. of Pathology, State Univ. Hospital, Groningen (Netherlands))

1990-01-01

Forty-nine patients aged {le} 45 years, with cervical carcinoma stage IB ({le} 3 cm) were treated with either primary radical surgery (n = 26), or intracavitary irradiation followed by radical surgery (n = 23). With primary surgery, ovarian function had been preserved in 15 of the 25 patients, who were alive and well. Seven of the primary surgery patients were irradiated postoperatively and 2 others with a central recurrence were cured by irradiation. One other patient, who was not irradiated postoperatively, had an intestinal metastasis and died of the disease. If any of the adverse prognostic factors (as reported in the literature) had been considered as an indication for postoperative irradiation, 17 patients instead of 7 would have been irradiated after primary radical surgery. In the comparable group of 23 patients treated by intracavitary irradiation and radical surgery (and in 4 cases postoperative irradiation as well) there was no recurrence. There was no significant statistical difference between the treatment results in the cesium + surgery group and those who underwent primary radical surgery. Young patients with early cervical carcinoma without prognostic indicators for postoperative irradiation can benefit from primary radical surgery, because their ovarian function can be preserved. (authors).

Radical surgery compared with intracavitary cesium followed by radical surgery in cervical carcinoma stage IB

International Nuclear Information System (INIS)

Tinga, D.J.; Bouma, J.; Aalders, J.G.; Hollema, H.

1990-01-01

Forty-nine patients aged ≤ 45 years, with cervical carcinoma stage IB (≤ 3 cm) were treated with either primary radical surgery (n = 26), or intracavitary irradiation followed by radical surgery (n = 23). With primary surgery, ovarian function had been preserved in 15 of the 25 patients, who were alive and well. Seven of the primary surgery patients were irradiated postoperatively and 2 others with a central recurrence were cured by irradiation. One other patient, who was not irradiated postoperatively, had an intestinal metastasis and died of the disease. If any of the adverse prognostic factors (as reported in the literature) had been considered as an indication for postoperative irradiation, 17 patients instead of 7 would have been irradiated after primary radical surgery. In the comparable group of 23 patients treated by intracavitary irradiation and radical surgery (and in 4 cases postoperative irradiation as well) there was no recurrence. There was no significant statistical difference between the treatment results in the cesium + surgery group and those who underwent primary radical surgery. Young patients with early cervical carcinoma without prognostic indicators for postoperative irradiation can benefit from primary radical surgery, because their ovarian function can be preserved. (authors)

Free radicals in an Adamantane matrix. XI. Electron paramagnetic resonance study of conformations in the β-halo-tert-butyl radicals

International Nuclear Information System (INIS)

Lloyd, R.V.; Wood, D.E.

1975-01-01

The β-halo-tert-butyl radicals were prepared by x-irradiation of the corresponding isobutyl halides in an adamantane matrix at 77 0 K and their conformations were determined by analysis of their EPR spectra. The radicals are nonplanar at the radical site, the fluoro and chloro radicals trans eclipsed and the bromo and iodo radicals gauche staggered with respect to the relative orientation of the carbon halogen bond and the direction of the singly occupied orbital. Vibration-rotation motions about the favored conformation are much larger for the fluoro radical than for the others. The rate of interconversion of the inequivalent methylene protons is approximately 1.5 x 10 9 sec -1 for the bromo radical at 202 0 K while it is too slow to measure for the iodo radical at the same temperature. The barrier to interconversion has a lower limit of 3 kcal/mol for the bromo radical and higher than that for the iodo radical. The halogen and proton hfsc in gauss and the g values for the XCH 2 C(CH 3 ) 2 radicals are: 19 F = 103.7, CH 2 = 10.4, CH 3 = 23.3, g = 2.0030 at 214 K; 35 Cl = 19.5, CH 2 = 6.3, CH 3 = 21.1, g = 2.0042 at 215 K; 81 Br = 6.7, CH 2 = 21.4, 42.7, CH 3 = 21.4, g = 2.0010 at 202 K; 127 I = 7.0, CH 2 = 21.9, 43.8, CH 3 = 21.9, g = 2.0009 at 208 K. The fluoro radical decays to nonradical products above 318 0 K, the chloro radical converts to 2-methyl allyl radical above 306 0 K, the bromo radical converts to tert-butyl radical by exchange with a matrix proton (or deuteron) at 209 0 K as does the iodo radical above 225 0 K. Photolysis with a Xe lamp converts the bromo and iodo radicals to nonradical products in less than the experimental time constant of 0.3 sec. The hypothesis is put forward that the nonplanarity and high barrier to rotation observed explain the retention of stereochemical configuration in reactions involving β-chloro, β-bromo, and β-iodo alkyl radicals. (auth)

Estudio del desarrollo radical en almácigo de híbridos f1 de café obtenidos por cultivo de tejidos

Directory of Open Access Journals (Sweden)

Fabián Echeverría

2014-01-01

Full Text Available Plántulas de Híbridos F1 de café, obte - nidas por embriogénesis somática indirecta, fueron aclimatizadas bajo condiciones de inver - nadero, en 2 tipos de contenedores: bandeja con sustrato convencional y malla biodegradable con turba comprimida (Jiffy®. A los 2 meses, las plántulas fueron transferidas a bolsa con sus - trato convencional y desarrolladas en el vivero. Se evaluó el desarrollo y calidad de la planta 8 meses después de su crecimiento en almácigo. Se encontró 33% de raíces rectas y 65% con morfologías anormales como estrangulamien - tos, serpenteadas y bifurcaciones, las cuales tuvieron respectivamente menores valores en los parámetros de largo, grosor y peso, tanto en el sistema radical como aéreo. En cuanto al tipo de contenedor, se obtuvo mayor crecimiento en las plántulas desarrolladas en Jiffy® con res - pecto a las de bandejas, sin embargo, aquellas que preservaron la envoltura durante la etapa de vivero, tuvieron menor crecimiento y desarrollo, con respecto de aquellas que les fue retirado. Se recomienda retirar la cobertura del Jiffy® previo a la siembra en bolsa, así como mejorar la técnica de inmersión temporal para evitar anormalidades morfológicas en los embriones producidos.

17.9.3 Radical cations of diazo compounds

Science.gov (United States)

Davies, A. G.

This document is part of Subvolume E2 `Phosphorus-Centered Radicals, Radicals Centered on Other Heteroatoms, Organic Radical Ions' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

Inhibition of radiation-induced DNA strand breaks by hoechst 33258: OH-radical scavenging and DNA radical quenching

International Nuclear Information System (INIS)

Adhikary, A.; Bothe, E.; Von Sonntag, C.; Adhikary, A.

1997-01-01

The minor-groove-binding dye Hoechst 33258 has been found to protect pBR322 DNA in aqueous solution against radiation-induced single-strand breaks (ssb). This protective effect has been assumed to be largely due to the scavenging of the strand-break-generating OH radicals by Hoechst. From D 37 values for ssb at different Hoechst concentrations the value of the OH radical scavenging constant of DNA-bound Hoechst has been estimated at k Ho/DNA = 2.7 * 10 11 dm 3 mol -1 . This unexpectedly high value has led us to study the reactions of OH radicals with Hoechst in the absence and in the presence of double-stranded calf thymus DNA (ds DNA) by pulse radiolysis, and the formation of radiation-induced ssb by low angle laser light scattering. The D 37 /D 37 0 values at different Hoechst concentrations agree with the values obtained by Martin and al. and demonstrate the protection. However, this protection cannot be explained on the basis of OH radical scavenging alone using the above rate constants. There must, in addition, be some quenching of DNA radicals. Hoechst radicals are formed in the later ms time range, i.e a long time after the disappearance of the OH radicals. This delayed Hoechst radical formation has been assigned to a a reaction of DNA radicals with Hoechst, thereby inhibiting strand breakage. In confirmation, pulse radiolysis of aqueous solution of nucleotides in the presence of Hoechst yields a similar delayed Hoechst radical formation. The data indicate that in DNA the cross-section of this quenching has a diameter of 3 to 4 base pairs per Hoechst molecule. (N.C.)

Radical-Local Teaching and Learning

DEFF Research Database (Denmark)

Hedegaard, Mariane; Chaiklin, Seth

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

Electronic structure of Co islands grown on the {radical}3 x {radical}3-Ag/Ge(111) surface

Energy Technology Data Exchange (ETDEWEB)

Huang, Xiao-Lan; Chou, Chi-Hao; Lin, Chun-Liang; Tomaszewska, Agnieszka; Fu, Tsu-Yi, E-mail: phtifu@phy.ntnu.edu.tw

2011-09-30

By means of room temperature scanning tunneling spectroscopy (RT STS), we have studied the electronic structure of two different Ag/Ge(111) phases as well as Co islands grown on the {radical}3 x {radical}3-Ag/Ge (111) forming either {radical}13 x {radical}13 or 2 x 2 patterns. The spectrum obtained from 4 x 4-Ag/Ge(111) structure shows the existence of a shoulder at 0.7 V which is also present in the electronic structure of the Ge(111)-c2 x 8 and indicates donation of Ge electrons to electronic states of the Ag-driven phase. However, this fact is not supported by the electronic spectrum taken from the {radical}3 x {radical}3-Ag/Ge (111). The complexity of the Co-{radical}13 x {radical}13 islands bonding with the substrate is mirrored by a large number of peaks in their electronic spectra. The spectra obtained from the Co-2 x 2 islands which had grown on the step differ from those taken from Co-2 x 2 islands located along the edge of the terrace by a number of peaks at negative sample bias. This discrepancy is elucidated in terms of dissimilarities of Co-substrate interaction accompanying Co islands growth on different areas of the stepped surface.

Understanding political radicalization: The two-pyramids model.

Science.gov (United States)

McCauley, Clark; Moskalenko, Sophia

2017-04-01

This article reviews some of the milestones of thinking about political radicalization, as scholars and security officials struggled after 9/11 to discern the precursors of terrorist violence. Recent criticism of the concept of radicalization has been recognized, leading to a 2-pyramids model that responds to the criticism by separating radicalization of opinion from radicalization of action. Security and research implications of the 2-pyramids model are briefly described, ending with a call for more attention to emotional experience in understanding both radicalization of opinion and radicalization of action. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

Orgasm after radical prostatectomy

NARCIS (Netherlands)

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

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

O Behaviorismo Radical como filosofia da mente Radical Behaviorism as philosophy of mind

Directory of Open Access Journals (Sweden)

Carlos Eduardo Lopes

2003-01-01

Full Text Available O Behaviorismo Radical de B. F. Skinner é constantemente acusado de eliminar a mente de sua explicação do comportamento humano. Uma análise do livro The Concept of Mind, de Gilbert Ryle, sugere a possibilidade de defender a existência de uma mente relacional, diferente da categoria de existência da mente defendida em interpretações cartesianas (mente substancial. A análise de alguns textos de Skinner sugere que o conceito de uma mente relacional também pode ser defendido no Behaviorismo Radical. Esse fato, culminaria na possibilidade de que, além de filosofia da Ciência do Comportamento, o Behaviorismo Radical, também pode ser uma filosofia da mente, o que traria conseqüências ao estudo e à aplicação da Análise do Comportamento.B. F. Skinner's Radical Behaviorism has been repeatedly accused of eliminating the mind from its explanation of human behavior. An analysis of Gilbert Ryle's book, The Concept of Mind, suggests the possibility of defending the existence of a relational mind, different from the category of existence of mind defended in Cartesian interpretations (substantial mind. The analysis of some texts of Skinner suggests that the concept of a relational mind can also be defended in Radical Behaviorism. This fact would lead to the possibility that, beyond a philosophy of Behavior Science, Radical Behaviorism may also be a philosophy of mind, which would bring consequences to the study and application of Analysis of Behavior.

Muonium radicals in benzene-styrene mixtures

International Nuclear Information System (INIS)

Ng, B.W.; Stadlbauer, J.W.; Walker, D.C.

1984-01-01

Muonium radicals were observed through their μ + SR precession frequencies in high transverse magnetic fields in pure benzene, pure styrene and their mixtures, all as liquids at room temperature. In benzene-styrene mixtures, the radicals obtained in each pure liquid are both present, so no slow (10 -9 -10 -5 s) intermolecular exchange occurs; but strong selectivity was found with the formation of the radical from styrene being about eight-times more probable than the radical from benzene. (Auth.)

Laparoscopic radical cystectomy: key points

Directory of Open Access Journals (Sweden)

D. V. Perlin

2018-01-01

Full Text Available Background. Radical cystectomy remains the golden standard for treatment of muscle invasive bladder cancer. Objective: to duplicate with highest accuracy the open radical cystectomy procedure, which we successfully utilized earlier in our clinic, in the of laparoscopic conditions in order to preserve the advantages of minimally invasive procedures and retain the reliability of the tried and tested open surgery.Materials and methods. In the report were included 35 patients (27 men and 8 women with bladder cancer, who underwent laparoscopic radical cystectomy in Volgograd Regional Center of Urology and Nephrology between April 2013 and March 2016. Only the patients who had been submitted to full intracorporal ileal conduits were included.Results. The mean operative time was 378 minutes, the mean blood loss was 285 millilitres, the mean length of hospital stay was 12.4 days, only 20 % of patients required the narcotic anesthetics. The postoperative complication rate was 11.4 %. However, the majority of the patients were successfully treated with minimally invasive procedures. Generally, our results were similar to other reported studies.Conclusion. Laparoscopic radical cystectomy is a safe and efficient modality of treatment of bladder cancer. However, it needs more procedures and longer observation period to establish laparoscopic radical cystectomy as an alternative to open radical cystectomy.

Gelman: El salario del impío

Directory of Open Access Journals (Sweden)

Jorge José Monteleone

2000-11-01

Full Text Available En su "Discurso sobre lírica y sociedad", Theodor W Adorno señala que el poema lírico debe presentar un alto "grado de interiorización y una radical individuación". Es decir, que el contenido del poema será tanto más objetivo y motivado socialmente cuanto menos se "tematice" en el la relación entre el yo y la sociedad y que el sujeto estará menos ausente de la forma poética que lo presenta, cuanto mas se sumerja y olvide en la objetividad social del lenguaje. A k luz de esas nociones pueden leerse dos libros de Juan Gelman, que se refieren explícitamente al exilio: Bajo la lluvia ajena (notas al pie de una derrota (1984 y Salarios del impío (1993. Entre uno y otro se percibe una progresiva individuación que permite alcanzar formalmente en el lenguaje poético una eficaz representación imaginaria del hecho histórico opresivo, que elude la reducción temática. Asimismo, la noción de posterioridad, con k cual se reinscribe y reorganiza la significación de un hecho traumático del pasado en un trabajo de la memoria, permitiría revisar aquella célebre advertencia de Adorno según la cual seria imposible escribir poesía después de un genocidio.

Gelman: El salario del impío

Directory of Open Access Journals (Sweden)

Jorge José Monteleone

2001-11-01

Full Text Available En su "Discurso sobre lírica y sociedad", Theodor W Adorno señala que el poema lírico debe presentar un alto "grado de interiorización y una radical individuación". Es decir, que el contenido del poema será tanto más objetivo y motivado socialmente cuanto menos se "tematice" en el la relación entre el yo y la sociedad y que el sujeto estará menos ausente de la forma poética que lo presenta, cuanto mas se sumerja y olvide en la objetividad social del lenguaje. A k luz de esas nociones pueden leerse dos libros de Juan Gelman, que se refieren explícitamente al exilio: Bajo la lluvia ajena (notas al pie de una derrota (1984 y Salarios del impío (1993. Entre uno y otro se percibe una progresiva individuación que permite alcanzar formalmente en el lenguaje poético una eficaz representación imaginaria del hecho histórico opresivo, que elude la reducción temática. Asimismo, la noción de posterioridad, con k cual se reinscribe y reorganiza la significación de un hecho traumático del pasado en un trabajo de la memoria, permitiría revisar aquella célebre advertencia de Adorno según la cual seria imposible escribir poesía después de un genocidio.

Effects of Molecular Iodine and 4-tert-Butylcatechol Radical Inhibitor on the Radical Polymerization of Styrene

Directory of Open Access Journals (Sweden)

Mojtaba Bozorg

2017-05-01

Full Text Available The presence of molecular iodine was studied in relation the molecular weight and molecular weight distribution of polystyrene, produced by radical poly merization. Radical polymerization of styrene initiated by 2,2׳-azobisisobutyronitrile (AIBN was performed at 70°C in the presence of molecular iodine. The synthesized polymers were characterized by gel permeation chromatography (GPC and proton- nuclear magnetic resonance (1H NMR techniques. The results of these reactions including conversion data, number-average molecular weight and molecular weight distribution were compared with those obtained for styrene radical polymerization initiated by AIBN at the same temperature in the absence of molecular iodine. It was found that the presence of iodine had a profound effect on the molecular weight and its distribution in the produced polystyrene. This was attributed to the ability of iodine to control the polymerization of styrene initiated by AIBN via reverse iodine transfer polymerization (RITP mechanism. The polymer produced by this method had a molecular weight of 10600 g/mol with a molecular weight polydispersity index of 1.3. Due to the importance of induction period in reverse iodine transfer radical polymerization, increasing the temperature to 120°C during the induction period resulted in shorter induction periods and the produced species led to better control of the molecular weight. Also, due to the role of iodine molecules as a radical inhibitor, the presence of a secondary radical inhibitor, i.e. 4-tert-butylcatechol, along with the iodine was investigated in radical polymerization of polystyrene initiated by AIBN. It was observed that the secondary radical inhibitor prevented the consumption of the iodine molecules by the radicals produced from decomposition of the AIBN initiator; therefore, alkyl halides were not produced during the induction period.

Radical chemistry of artemisinin

Energy Technology Data Exchange (ETDEWEB)

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

2011-12-29

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

Radical chemistry of artemisinin

Science.gov (United States)

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

2010-12-01

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

Radical chemistry of artemisinin

International Nuclear Information System (INIS)

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

2010-01-01

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

Radical chemistry of artemisinin

Energy Technology Data Exchange (ETDEWEB)

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

2010-12-29

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

Oxygen free radicals in rheumatoid arthritis

NARCIS (Netherlands)

P. Biemond (Pieter)

1986-01-01

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

Free radicals in health and disease

International Nuclear Information System (INIS)

Gonet, B.

1993-01-01

Free radicals appear in the cells as the result of exogenic factors (ionizing radiation, UV) or reactions naturally occurring in the cell. Free radical reactions may cause destruction of macromolecules (DNA, lipids, proteins). Free radical pathology is important in many diseases and aging processes in organisms

Free radicals in wood induced by γ-radiation

International Nuclear Information System (INIS)

Xu Honglin; Zhang Wenhui

1994-01-01

The free radicals in wood induced by γ-radiation were studied by electron spin resonance. The fine structure of the ESR signal from sawdust samples irradiated could be resolved into various radicals. These free radicals have a very long lifetime. The major spectrum for the free radicals will exponentially increased along with the radiation dose according to Y 1-Exp(-α a D). The intensity of radiation radicals is dependent on tree species. The stronger the intensity of mechanic free radicals is, the stronger the intensity of radiation free radicals

Tratamiento quirúrgico de las colecciones agudas y crónicas del pericardio

Directory of Open Access Journals (Sweden)

Orestes Noel Mederos Curbelo

Full Text Available Introducción: las colecciones agudas o crónicas del pericardio con frecuencia producen una compresión del corazón que en los casos crónicos conlleva invalidez y, en los agudos, peligro de muerte por taponamiento cardíaco. Objetivo: caracterizar a los pacientes intervenidos quirúrgicamente en el Hospital Universitario "Comandante Manuel Fajardo" entre 1995 y 2012 a causa de colecciones pericárdicas. Métodos: se realizó un estudio descriptivo transversal con los pacientes atendidos quirúrgicamente en dicha institución por colecciones del pericardio. Constituyeron el universo 24 pacientes: 22 con colecciones agudas y 2 con colecciones crónicas. Resultados: la causa más frecuente de los derrames agudos fue la pericarditis aguda idiopática (25 %. Las colecciones crónicas fueron por pericarditis fibrosa de causa idiopática en el 100 % de los enfermos. La intervención realizada fue la resección del pericardio y el drenaje de las colecciones agudas mediante toracotomía izquierda o por vía preperitoneal subxifoidea. En las colecciones de origen maligno se realizó la resección pericárdica con fines paliativos y, en los derrames por lesión traumática del corazón, la sutura de este órgano fue el tratamiento quirúrgico empleado en todos los casos. En las pericarditis constrictivas, la pericardiectomía radical fue el tratamiento empleado en el 100 % de los casos. Conclusiones: el tratamiento quirúrgico en las colecciones agudas y crónicas del pericardio permite drenar el contenido por una ventana pericárdica obtenida por toracoscopia o por vía preperitoneal subxifoidea, mientras que la toracotomía izquierda es útil en las emergencias. En los derrames crónicos con fibrosis y síntomas de insuficiencia cardíaca, la pericardiectomía radical mediante esternotomía media ofrece los mejores resultados.

Radical-Local Teaching and Learning

DEFF Research Database (Denmark)

Hedegaard, Mariane; Chaiklin, Seth

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

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

Science.gov (United States)

Baum, William M

2011-01-01

B. F. Skinner founded both radical behaviorism and behavior analysis. His founding innovations included: a versatile preparation for studying behavior; explicating the generic nature of stimulus and response; a pragmatic criterion for defining behavioral units; response rate as a datum; the concept of stimulus control; the concept of verbal behavior; and explicating the explanatory power of contingencies. Besides these achievements, however, Skinner also made some mistakes. Subsequent developments in radical behaviorist thought have attempted to remedy these mistakes. Moore's book presents a “party line” version of radical behaviorism. It focuses narrowly on a few of Skinner's concepts (mostly mentalism and verbal behavior) and contains no criticism of his mistakes. In fact, Moore adds a few mistakes of his own manufacture; for example, he insists that the mental realm does not exist—an unprovable and distracting assertion. The book's portrayal of behavior analysis would have been current around 1960; it mentions almost none of the developments since then. It also includes almost no developments in radical behaviorism since Skinner. Moore's book would give an unwary reader a highly distorted picture of contemporary behavior analysis and radical behaviorism.

Hydroxyl and Hydroperoxy Radical Chemistry during the MCMA-2006 Field Campaign: Measurement and Model Comparison

Science.gov (United States)

Dusanter, S.; Vimal, D.; Stevens, P. S.; Volkamer, R.; Molina, L. T.

2007-12-01

The Mexico City Metropolitan Area (MCMA) field campaign, held in March 2006, was a unique opportunity to collect data in one of the most polluted megacities in the world. Such environments exhibit a complex oxidation chemistry involving a strong coupling between odd hydrogen radicals (HOX=OH+HO2) and nitrogen oxides species (NOX=NO+NO2). High levels of volatile organic compounds (VOCs) and NOX control the HOX budget and lead to elevated tropospheric ozone formation. The HOX-NOX coupling can be investigated by comparing measured and model-predicted HOx concentrations. Atmospheric HOX concentrations were measured by the Indiana University laser-induced fluorescence instrument and data were collected at the Instituto Mexicano del Petroleo between 14 and 31 March. Measured hydroxyl radical (OH) concentrations are comparable to that measured in less polluted urban environments and suggest that the OH concentrations are highly buffered under high NOX conditions. In contrast, hydroperoxy radical (HO2) concentrations are more sensitive to the NOX levels and are highly variable between different urban sites. Enhanced levels of OH and HO2 radicals were observed on several days between 9h30-11h00 AM and suggest an additional HOX source for the morning hours and/or a fast HOX cycling under the high NOX conditions of the MCMA. A preliminary investigation of the HOX chemistry occurring in the MCMA urban atmosphere was performed using a photochemical box model based on the Regional Atmospheric Chemistry Mechanism (RACM). Model comparisons will be presented and the agreement between measured and predicted HOX concentrations will be discussed.

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

Science.gov (United States)

Yeung, Pui-sze; Ho, Connie Suk-han; Chan, David Wai-ock; Chung, Kevin Kien-hoa

2016-01-01

A 3-year longitudinal study among 239 Chinese students in Grades 2-4 was conducted to investigate the relationships between orthographic skills (including positional and functional knowledge of semantic radicals and phonetic radicals, and orthographic memory of radicals) and Chinese literacy skills (word reading, word spelling, reading…

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

Directory of Open Access Journals (Sweden)

John C. Walton

2015-02-01

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

Radical-pair based avian magnetoreception

Science.gov (United States)

Procopio, Maria; Ritz, Thorsten

2014-03-01

Behavioural experiments suggest that migratory birds possess a magnetic compass sensor able to detect the direction of the geomagnetic. One hypothesis for the basis of this remarkable sensory ability is that the coherent quantum spin dynamics of photoinduced radical pair reactions transduces directional magnetic information from the geomagnetic field into changes of reaction yields, possibly involving the photoreceptor cryptochrome in the birds retina. The suggested radical-pair based avian magnetoreception has attracted attention in the field of quantum biology as an example of a biological sensor which might exploit quantum coherences for its biological function. Investigations on such a spin-based sensor have focussed on uncovering the design features for the design of a biomimetic magnetic field sensor. We study the effects of slow fluctuations in the nuclear spin environment on the directional signal. We quantitatively evaluate the robustness of signals under fluctuations on a timescale longer than the lifetime of a radical pair, utilizing two models of radical pairs. Our results suggest design principles for building a radical-pair based compass sensor that is both robust and highly directional sensitive.

Radically enhanced molecular recognition

KAUST Repository

Trabolsi, Ali

2009-12-17

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

Radically enhanced molecular recognition

KAUST Repository

Trabolsi, Ali; Khashab, Niveen M.; Fahrenbach, Albert C.; Friedman, Douglas C.; Colvin, Michael T.; Coti, Karla K.; Bení tez, Diego S.; Tkatchouk, Ekaterina; Olsen, John Carl; Belowich, Matthew E.; Carmieli, Raanan; Khatib, Hussam A.; Goddard, William Andrew III; Wasielewski, Michael R.; Stoddart, Fraser Fraser Raser

2009-01-01

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

Formation and spectroscopy of {alpha}-muoniated radicals

Energy Technology Data Exchange (ETDEWEB)

McKenzie, I.; Brodovitch, J.C.; Ghandi, K.; Kecman, S.; Percival, P.W

2003-02-01

Several novel {alpha}-muoniated radicals have been produced by the reaction of muonium with compounds containing diazo, isocyanate or carbene functional groups. In {alpha}-muoniated radicals the muon is attached directly to the radical centre; they can be formed either directly or indirectly via a {beta}-muoniated radical intermediate. The hyperfine coupling constants of the resulting radicals have been measured by transverse field muon spin rotation and muon avoided level-crossing resonance. The effect of muonium substitution was investigated for cases where ESR data are available for comparison.

Formation and spectroscopy of α-muoniated radicals

International Nuclear Information System (INIS)

McKenzie, I.; Brodovitch, J.C.; Ghandi, K.; Kecman, S.; Percival, P.W.

2003-01-01

Several novel α-muoniated radicals have been produced by the reaction of muonium with compounds containing diazo, isocyanate or carbene functional groups. In α-muoniated radicals the muon is attached directly to the radical centre; they can be formed either directly or indirectly via a β-muoniated radical intermediate. The hyperfine coupling constants of the resulting radicals have been measured by transverse field muon spin rotation and muon avoided level-crossing resonance. The effect of muonium substitution was investigated for cases where ESR data are available for comparison

Semantic Radicals Contribute More Than Phonetic Radicals to the Recognition of Chinese Phonograms: Behavioral and ERP Evidence in a Factorial Study

Directory of Open Access Journals (Sweden)

Xieshun Wang

2017-12-01

Full Text Available The Chinese phonograms consist of a semantic radical and a phonetic radical. The two types of radicals have different functional contributions to their host phonogram. The semantic radical typically signifies the meaning of the phonogram, while the phonetic radical usually contains a phonological clue to the phonogram’s pronunciation. However, it is still unclear how they interplay with each other when we attempt to recognize a phonogram because previous studies rarely manipulated the functionality of the two types of radicals in a single design. Using a full factorial design, the present study aimed to probe this issue by directly manipulating the functional validity of the two types of radicals in a lexical decision task with both behavioral and event-related potential (ERP measurements. The results showed that recognition of phonograms which were related to their semantic radicals in meaning took a shorter reaction time, showed a lower error rate, and elicited a smaller P200 and a larger N400 than did recognition of those which had no semantic relation with their semantic radicals. However, the validity of phonetic radicals did not show any main effect or interaction with that of semantic radicals on either behavioral or ERP measurements. These results indicated that semantic radicals played a dominant role in the recognition of phonograms. Transparent semantic radicals, which provide valid semantic cues to phonograms, can facilitate the recognition of phonograms.

Pyrimidine nucleobase radical reactivity in DNA and RNA

Science.gov (United States)

Greenberg, Marc M.

2016-11-01

Nucleobase radicals are major products of the reactions between nucleic acids and hydroxyl radical, which is produced via the indirect effect of ionizing radiation. The nucleobase radicals also result from hydration of cation radicals that are produced via the direct effect of ionizing radiation. The role that nucleobase radicals play in strand scission has been investigated indirectly using ionizing radiation to generate them. More recently, the reactivity of nucleobase radicals resulting from formal hydrogen atom or hydroxyl radical addition to pyrimidines has been studied by independently generating the reactive intermediates via UV-photolysis of synthetic precursors. This approach has provided control over where the reactive intermediates are produced within biopolymers and facilitated studying their reactivity. The contributions to our understanding of pyrimidine nucleobase radical reactivity by this approach are summarized.

Quantification of hydroxyl radical produced during phacoemulsification.

Science.gov (United States)

Gardner, Jonathan M; Aust, Steven D

2009-12-01

To quantitate hydroxyl radicals produced during phacoemulsification with various irrigating solutions and conditions used in cataract surgery. Chemistry and Biochemistry Department, Utah State University, Logan, Utah, USA. All experiments were performed using an Infiniti Vision System phacoemulsifier with irrigation and aspiration. Hydroxyl radicals were quantitated using electron spin resonance spectroscopy and a spectrophotometric assay for malondialdehyde, which is formed by the oxidation of deoxyribose by the hydroxyl radical. Hydroxyl radical production increased during longitudinal-stroking phacoemulsification as power levels were increased in a nonlinear, nonexponential fashion. The detection of hydroxyl radical was reduced in irrigating solutions containing organic molecules (eg, citrate, acetate, glutathione, dextrose) and further reduced in Navstel, an irrigating solution containing a viscosity-modifying agent, hydroxypropyl methylcellulose. Hydroxyl radicals produced in settings representative of those used in phacoemulsification cataract surgery were quantitated using the deoxyribose method. Hydroxyl radical production was dependent on the level of ultrasound power applied and the irrigating solution used. Oxidative stress on the eye during phacoemulsification may be minimized by using irrigating solutions that contain organic molecules, including the viscosity-modifying agent hydroxypropyl methylcellulose, that can compete for reaction with hydroxyl radicals.

Free radicals in biology. Volume II

International Nuclear Information System (INIS)

Pryor, W.A.

1976-01-01

This volume continues the treatment of topics in free radical biology and free radical pathology from Volume I. In the first chapter, pyridinyl radicals, radicals which are models for those derived from NAD, are discussed. Pyridinyl radicals can be synthesized and isolated and directly studied in a number of chemical systems. The next chapter treats the role of glutathione in the cell. It is becoming even more apparent that this vital thiol controls a large number of important cellular functions. The GSH/GSSG balance has recently been implicated as a control for cellular development; this balance also may be important in relaying the effects of oxidants from one site to another in the body. The next chapter outlines the reactions of singlet oxygen; some of these involve free radicals and some do not. This reactive intermediate appears to be important both in photochemical smog and in cellular chemistry where singlet oxygen is produced by nonphotochemical processes. The production of free radicals from dry tissues, a controversial area with conflicting claims is reviewed. The next chapter outlines the current status of the studies of photochemical smog. The next two chapters treat specific reactive materials which are present in smog. The first discusses the chemistry of nitrogen oxides and ozone. The second chapter treats the chemistry of the peroxyacyl nitrites. These compounds, although present in only small concentration, are among the most toxic components of smog. The last two chapters treat radiation damage to proteins and radiation protection and radical reactions produced by radiation in nucleic acids

O conceito de mal radical The concept of radical evil

Directory of Open Access Journals (Sweden)

Adriano Correia

2005-01-01

Full Text Available A noção de mal radical aparece em Kant no contexto da discussão da religião nos limites da simples razão e busca dar conta da complexa relação entre o respeito pela lei moral e o amor-próprio na definição do móbil para a ação. Na busca por identificar o fundamento da propensão para o mal no homem, Kant se vê diante da dificuldade de ter de articular natureza e liberdade, e ainda que a noção de mal radical possa conservar algumas ambigüidades, permite conceber uma noção de responsabilidade compatível com uma inata propensão para o mal. Neste texto busco explicitar alguns passos fundamentais na construção do conceito por Kant.The concept of radical evil appears in Kant's theory when he discusses the religion in the limits of the mere reason and aims explain the complex relationship between respect for the moral law and the self-love, for establish the motive of the action. By aiming identify the basis of human inclination to evil, Kant is faced with the trouble of have to put nature and freedom in connection. Despite of the concept of radical evil retain some ambiguity, it allows conceive a notion of responsibility suitable to an inherent inclination to evil. In this paper is my purpose to explain some basic moments of Kantian formulation of that notion.

HPLC-ESR techniques for detection of complex trapped radicals

International Nuclear Information System (INIS)

Tu Tiecheng; Dong Jirong; Lin Nianyun; Xie Leidong; Liu Rengzhong

1992-01-01

High performance liquid chromatography (HPLC) and ESR combined examination of radical species is an advanced techniques for separation and identification of complex radical species. At SRCL, Waters 990 HPLC has been used to separate the complex trapped radicals and Varian E-112 ESR spectrometer to record the spectra of single trapped radicals after HPLC separation. The advantages of the combined techniques are described as bellow: HPLC is used to separate the long-lived complex trapped radicals derived from reaction of short-lived radicals with spin trap. ESR spectra from single trapped radicals, obtained following HPLC separation of complex trapped radicals, are recorded one by one and well resolved. The structures of short-lived radicals can be inferred from the ESR spectra of the long-lived trapped radicals

Scavenging of free-radical metabolites of aniline xenobiotics and drugs by amino acid derivatives: toxicological implications of radical-transfer reactions.

Science.gov (United States)

Michail, Karim; Baghdasarian, Argishti; Narwaley, Malyaj; Aljuhani, Naif; Siraki, Arno G

2013-12-16

We investigated a novel scavenging mechanism of arylamine free radicals by poly- and monoaminocarboxylates. Free radicals of arylamine xenobiotics and drugs did not react with oxygen in peroxidase-catalyzed reactions; however, they showed marked oxygen uptake in the presence of an aminocarboxylate. These free-radical intermediates were identified using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and electron paramagnetic resonance (EPR) spectrometry. Diethylenetriaminepentaacetic acid (DTPA), a polyaminocarboxylate, caused a concentration-dependent attenuation of N-centered radicals produced by the peroxidative metabolism of arylamines with the subsequent formation of secondary aliphatic carbon-centered radicals stemming from the cosubstrate molecule. Analogously, N,N-dimethylglycine (DMG) and N-methyliminodiacetate (MIDA), but not iminodiacetic acid (IDA), demonstrated a similar scavenging effect of arylamine-derived free radicals in a horseradish peroxidase/H2O2 system. Using human promyelocytic leukemia (HL-60) cell lysate as a model of human neutrophils, DTPA, MIDA, and DMG readily reduced anilinium cation radicals derived from the arylamines and gave rise to the corresponding carbon radicals. The rate of peroxidase-triggered polymerization of aniline was studied as a measure of nitrogen-radical scavenging. Although, IDA had no effect on the rate of aniline polymerization, this was almost nullified in the presence of DTPA and MIDA at half of the molar concentration of the aniline substrate, whereas a 20 molar excess of DMPO caused only a partial inhibition. Furthermore, the yield of formaldehyde, a specific reaction endproduct of the oxidation of aminocarboxylates by aniline free-radical metabolites, was quantitatively determined. Azobenzene, a specific reaction product of peroxidase-catalyzed free-radical dimerization of aniline, was fully abrogated in the presence of DTPA, as confirmed by GC/MS. Under aerobic conditions, a radical-transfer reaction

Reactions of carbonate radical with cobalt(II) aminopolycarboxylates

International Nuclear Information System (INIS)

Mandal, P.C.; Bardhan, D.K.; Bhattacharyya, S.N.

1992-01-01

Reactions of carbonate (CO 3 - radical) and bicarbonate (HCO 3 radical) radicals generated by photolysis of a carbonate or bicarbonate solution at pH 11.2 and 8.5, respectively, with Co(II) complexes of iminodiacetic acid (IDA) and ethylenediaminetetraacetic acid (EDTA) have been studied. The rate constants for the reactions were in the order of 10 6 -10 7 dm 3 mol -1 s -1 . From the time-resolved spectroscopy of the products formed after reaction of CO 3 - radical or HCO 3 radical, it is observed that CO 3 - radical or HCO 3 radical oxidize the metal center to its higher oxidation state. (author) 26 refs.; 2 figs.; 1 tab

Self-Terminating, Oxidative Radical Cyclizations

Directory of Open Access Journals (Sweden)

Uta Wille

2004-05-01

Full Text Available The recently discovered novel concept of self-terminating, oxidative radical cyclizations, through which alkynes can be converted into carbonyl compounds under very mild reaction conditions using O-centered inorganic and organic radicals as oxidants, is described

La reconversión del Instituto Cajal

Directory of Open Access Journals (Sweden)

García Segura, Luis Miguel

2007-10-01

Full Text Available The Spanish government created in 1902 a research laboratory for Cajal, 1906 Nobel Prize and founder of modern neuroscience. The laboratory was translated, enlarged and renamed as Instituto Cajal in 1993 and incorporated to the CSIC in 1939. The excessive morphological specialization of the institute and the explosion of neuroscience as a multidisciplinary discipline were the conditions for a radical renovation initiated in 1985 under the auspices of the presidency of the CSIC and following the recommendations of several international advisory boards. The transformation of the Cajal Institute in a competitive multidisciplinary research centre culminated in 1989, with the inauguration of new facilities in its present location. As a result of the extreme success of this transformation the Cajal Institute has now grown to unpredicted dimensions of infrastructure and personnel that demand a new physical location to allow for its continuous growth as a leading European center in neuroscience research.El Gobierno español creó en 1902 un laboratorio para Cajal, premio Nobel en 1906 y fundador de la neurociencia moderna. En 1933 el laboratorio fue trasladado, ampliado y denominado Instituto Cajal y en 1939 se incorporó al CSIC. La excesiva especialización morfológica del instituto y la explosión de la neurociencia como un campo multidisciplinar fueron condiciones que impulsaron una renovación radical, que fue iniciada en 1985 bajo los auspicios de la presidencia del CSIC y siguiendo las recomendaciones de varios comités internacionales de evaluación. La transformación del Instituto Cajal en un centro de investigación internacionalmente competitivo se culminó en 1989, con la inauguración de su sede actual. El extraordinario éxito de la reconversión ha llevado al Instituto Cajal a crecer a unas dimensiones de infraestructura y personal que han superado todas las previsiones y que demandan una nueva ubicación para mantenerse como uno de los

La literatura cubana del 98: paisaje después de la batalla

OpenAIRE

Fornet, Jorge; Pontificia Universidad Javeriana, Bogotá

2014-01-01

En 1882, con la aparición del poemario que cambió de forma radical la poesía en nuestra lengua, daba los primeros pasos aquel movimiento que, nacido en América, llegaba al clímax con la obra de Rubén Darío. Años después, el venezolano Manuel Díaz Rodríguez se refería a la labor fecundante de España como"retorno de las carabelas". "Por él", agregaba Rodó en 1916, "la ruta de los conquistadores se tornaría del ocaso al naciente". Lo cierto es que, con "Ismaelillo", José Martí inicia el modernis...

Oxidation of aromatic amines and diamines by OH radicals. Formation and ionization constants of amine cation radicals in water

International Nuclear Information System (INIS)

Hayon, E.; Rao, P.S.

1975-01-01

The one-electron oxidation by hydroxyl radicals of aromatic amines and diamines in water was studied using the fast-reaction technique of pulse radiolysis and kinetic absorption spectrophotometry. The following compounds were examined: N,N,N 1 ,N 1 - tetramethyl-p-phenylenediamine (TMPD), p-phenylenediamine (PD), N,N-dimethyl-p-phenylenediamene (DMPD), N,N,N 1 ,N 1 -tetramethylbenzidine (TMB), and diphenylamine (DPA). The main initial reaction of the OH radicals is suggested to be an addition to these compounds to give absorption spectra which absorb strongly in the visible and uv regions. These OH radical adducts decay by first-order kinetics and have lifetimes of approximately 5-50 μsec, dependent on the pH, buffer concentration, and the nature of the aromatic amines and diamines. They decay to give species with somewhat similar absorption spectra and extinction coefficients, which are very long lived in the absence of oxygen. The latter species are assigned to the cation radicals TMPD. + , PD. + , DMPD. + , TMB. + , and DPA. + . The OH radical adducts and the cation radicals have acid-base properties. The pK/sub a/ values of the cation radicals TMPDH. 2+ , PDH. 2+ , DMPDH. 2+ , TMBH. 2+ , and DPAH. 2+ were found to be 5.3, 5.9, 6.1, 5.1, and 4.2, respectively. The results indicate that these aromatic amines and diamines can be oxidized by free radicals to yield the corresponding cation radicals. (U.S.)

Near-Infrared Free-Radical and Free-Radical-Promoted Cationic Photopolymerizations by In-Source Lighting Using Upconverting Glass.

Science.gov (United States)

Kocaarslan, Azra; Tabanli, Sevcan; Eryurek, Gonul; Yagci, Yusuf

2017-11-13

A method is presented for the initiation of free-radical and free-radical-promoted cationic photopolymerizations by in-source lighting in the near-infrared (NIR) region using upconverting glass (UCG). This approach utilizes laser irradiation of UCG at 975 nm in the presence of fluorescein (FL) and pentamethyldiethylene triamine (PMDETA). FL excited by light emitted from the UCG undergoes electron-transfer reactions with PMDETA to form free radicals capable of initiating polymerization of methyl methacrylate. To execute the corresponding free-radical-promoted cationic polymerization of cyclohexene oxide, isobutyl vinyl ether, and N-vinyl carbazole, it was necessary to use FL, dimethyl aniline (DMA), and diphenyliodonium hexafluorophosphate as sensitizer, coinitiator, and oxidant, respectively. Iodonium ions promptly oxidize DMA radicals formed to the corresponding cations. Thus, cationic polymerization with efficiency comparable to the conventional irradiation source was achieved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

La Representación de la Mujer y los Ideales del Pensamiento Colombiano de Finales del Siglo XIX y Comienzos del Siglo XX: la Metáfora de la Falsa Inclusión

Directory of Open Access Journals (Sweden)

Adriana Yamile Suárez Reina

2014-01-01

Full Text Available A finales del siglo XIX y comienzos del siglo XX el proceso de construcción de la nación colombiana transitó por dos cami- nos adversos: el Periodo Radical -de corte liberal- y el Periodo de la Regeneración -de tinte conservador-. A partir de este contexto histórico-social se analiza la representación que se hace de la mujer durante este cambio de siglo, con el ánimo de evidenciar que el imaginario de género que se construyó allí está marcado por la metáfora de la falsa inclusión, es decir, que cada periodo a través de la noción que configura del poder, incluye a la mujer para, paradójicamente, excluirla. A partir de dicha metáfora este texto termina con un breve acercamiento a la propuesta de Tomás Carrasquilla y su personaje de Bárbara Caballero en La Marquesa de Yolombó y cómo este muestra la diatriba a la que se enfrentaba la mujer: tradición vs. independencia.

OH radical induced depolymerization of poly(methacrylic acid)

Science.gov (United States)

Ulanski, Piotr; Bothe, Eberhard; von Sonntag, Clemens

1999-05-01

Hydroxyl radicals (generated pulse radiolytically in dilute N 2O-saturated aqueous solutions) react with poly(methacrylic acid) producing two kinds of radicals. The primary radical is converted into a secondary one by H-abstraction ( k=3.5 × 10 2 s -1) as monitored by changes in the UV spectrum. Subsequently, the secondary radicals undergo chain scission ( k=1.8 s -1 at pH 7-9). This process has been followed both by spectrophotometry as well as by conductometry. In competition with the bimolecular decay of the radicals the ensuing end-chain radicals undergo efficient depolymerization resulting in the release of monomer. Since the lifetime of the radicals is much longer at high pH, where the polymer attains a rod-like conformation, depolymerization is most efficient in basic solution.

Electron spin resonance study of radicals in irradiated polyethylene

International Nuclear Information System (INIS)

Fujimura, Takashi

1979-02-01

In order to elucidate radiation effect in polyethylene, the nature and behavior of radicals produced in polyethylene and the model compound of polyethylene irradiated at 77 0 K were studied by using electron spin resonance. The structure of radical pairs, which are composed of two radicals produced very closely each other, was investigated in drawn polyethylene and the single crystal of n-eicosane. The radical pairs of intrachain type and interchain type were found in polyethylene and n-eicosane respectively. It was suggested that these two types of radical pairs are the precursors of double bonds and crosslinks respectively. The thermal decay reactions of radicals themselves produced in irradiated polyethylene were investigated. It was made clear that the short range distances between two radicals play an important role in the decay reaction of alkyl radicals at low temperatures. The trapping regions of radicals were studied and it was clarified that allyl radicals, which are produced by the reaction of alkyl radicals with double bonds, are trapped both in the crystalline and non-crystalline regions. (author)

Redox properties of free radicals

International Nuclear Information System (INIS)

Neta, P.

1981-01-01

Results of electron transfer reactions observed and monitored by pulse radiolysis are reported. This technique allows determination of the first one-electron reduction or oxidation of a compound rather than the overall two-electron transfer usually reported. Pulse radiolysis allows the determination of absolute rate constants for reactions of free radicals and helps elucidate the mechanisms involved. Studies using this technique to study radicals derived from quinones, nitro compounds, pyridines, phenols, and anilines are reported. Radicals of biochemical interest arising from riboflavin, ascorbic acid, vitamin K 3 , vitamin E, MAD + , porphyrins, etc. have also been studied

Hot wire radicals and reactions

International Nuclear Information System (INIS)

Zheng Wengang; Gallagher, Alan

2006-01-01

Threshold ionization mass spectroscopy is used to measure radical (and stable gas) densities at the substrate of a tungsten hot wire (HW) reactor. We report measurements of the silane reaction probability on the HW and the probability of Si and H release from the HW. We describe a model for the atomic H release, based on the H 2 dissociation model. We note major variations in silicon-release, with dependence on prior silane exposure. Measured radical densities versus silane pressure yield silicon-silane and H-silane reaction rate coefficients, and the dominant radical fluxes to the substrate

Synthesis and Characterization of Ethylenedithio-MPTTF-PTM Radical Dyad as a Potential Neutral Radical Conductor

DEFF Research Database (Denmark)

Souto, Manuel; Bendixen, Dan; Jensen, Morten

2016-01-01

During the last years there has been a high interest in the development of new purely-organic single-component conductors. Very recently, we have reported a new neutral radical conductor based on the perchlorotriphenylmethyl (PTM) radical moiety linked to a monopyrrolo-tetrathiafulvalene (MPTTF...

Efecto secuestrador del D-002 sobre radicales hidroxilo en mucosa gástrica

Directory of Open Access Journals (Sweden)

Yohani Pérez Guerra

2012-03-01

Full Text Available Introducción: el agente causal de la ulceración gástrica está asociado al desequilibrio entre factores agresivos y defensivos que actúan sobre la mucosa gástrica. El D-002, mezcla de seis alcoholes alifáticos primarios superiores purificada de la cera de abejas, produce efectos gastroprotectores mediados por múltiples mecanismos y reducción de la peroxidación lipídica en la mucosa gástrica. Objetivo: determinar si el D-002 es capaz de capturar el radical hidroxilo añadido in vitro o generado in vivo en ratas con úlcera gástrica inducida por indometacina. Métodos: En la experiencia in vitro el D-002 se añadió a concentraciones entre 0,9 y 1 000 mg/mL. En la experiencia in vivo las ratas se distribuyeron en seis grupos: un control negativo y cinco que recibieron indometacina: un control positivo tratado con el vehículo, tres con D-002 (5, 25, y 100 mg/kg, respectivamente, p.o. y otro con omeprazol (20 mg/kg i.p.. Los tratamientos se administraron una hora (vehículo y D-002 o 30 min (omeprazol, respectivamente, antes de inducir las úlceras. En ambas experiencias se tomaron alícuotas de mucosa gástrica, y se determinó el daño a la 2-desoxirribosa por el radical hidroxilo. Resultados: la administración oral del D-002, no in vitro, protegió a la 2-desoxirribosa del daño oxidativo de modo marcado, significativo y dependiente de la dosis con respecto al control positivo. Conclusiones: los resultados indican que la capacidad del D-002 (25 y 100 mg/kg administrado por vía oral para secuestrar el radical hidroxilo, generado en la mucosa gástrica por la indometacina, pudiera contribuir a sus efectos antioxidantes y gastroprotectores sobre el daño que los antiinflamatorios no esteroideos producen sobre la mucosa gástrica.

Free radicals trapped in polyethylene matrix

International Nuclear Information System (INIS)

Shimada, S.; Maeda, M.; Hori, Y.; Kashiwabara, H.

1977-01-01

Two types of alkyl radicals were found to be trapped in irradiated crystals grown from polyethylene solution. One of them corresponds to the broad sextet pattern of the e.s.r. spectrum and the other corresponds to the sharp sextet pattern. The free radicals attributed to the broad sextet began to disappear at a lower temperature than the temperature at which the free radicals attributed to the sharp sextet disappeared. When butadiene molecules were brought into contact with the specimen, the decay of the free radicals corresponding to the broad sextet was accelerated. When the specimen was subjected to fuming nitric acid treatment, no broad sextet was observed. The mat of the crystals was aligned so that the c-axes of its crystallites were perpendicular to its surface. The broad sextet showed no anisotropy when the angle between the direction of applied magnetic field and that of the c-axis of the crystallite was varied. On the other hand, the sharp component of the spectrum showed apparent anisotropy. It can be concluded that the broad component comes from the free radicals trapped in the lamellar surface and the sharp component is attributed to the free radicals trapped in the inner part of the crystallite. (author)

The role of melanin as protector against free radicals in skin and its role as free radical indicator in hair

Science.gov (United States)

Herrling, Thomas; Jung, Katinka; Fuchs, Jürgen

2008-05-01

Throughout the body, melanin is a homogenous biological polymer containing a population of intrinsic, semiquinone-like radicals. Additional extrinsic free radicals are reversibly photo-generated by UV and visible light. Melanin photochemistry, particularly the formation and decay of extrinsic radicals, has been the subject of numerous electron spin resonance (ESR) spectroscopy studies. Several melanin monomers exist, and the predominant monomer in a melanin polymer depends on its location within an organism. In skin and hair, melanin differs in content of eumelanin or pheomelanin. Its bioradical character and its susceptibility to UV irradiation makes melanin an excellent indicator for UV-related processes in both skin and hair. The existence of melanin in skin is strongly correlated with the prevention against free radicals/ROS generated by UV radiation. Especially in the skin melanin (mainly eumelanin) ensures the only natural UV protection by eliminating the generated free radicals/ROS. Melanin in hair can be used as a free radical detector for evaluating the efficacy of hair care products. The aim of this study was to investigate the suitability of melanin as protector of skin against UV generated free radicals and as free radical indicator in hair.

Harry Potter contra el legalismo, o la magia republicana del pluralismo jurídico

Directory of Open Access Journals (Sweden)

Luis Gómez Romero

2014-07-01

Full Text Available Este ensayo acomete una crítica radical de las ideologías legalistas mediante una revisión de las fuentes del derecho en clave pluralista. Los textos literarios –concretamente, las novelas de Harry Potter– son catalogados como fuentes del derecho. A estos efectos, se considera que el derecho inscrito en los mundos narrativos ficticios concierne al derecho en el mundo y las vidas de los públicos que los leen. El derecho es literatura, y la literatura es derecho. Sobre esta base, el artículo analiza la fabulación sobre el imperio de la ley en las novelas potterianas desde una perspectiva republicana.

Free radicals generated by radiolysis of aqueous solutions

International Nuclear Information System (INIS)

Schwarz, H.A.

1981-01-01

The free radicals produced in the radiolysis of aqueous solutions span the range of redox potentials from -2.9 to +2.65 volts. The identity and nature of these radicals were discussed. Most of the discussion was results obtained with low LET radiation sources ( 60 Co gamma radiation or electron accelerators). Water radiolysis provides the synthesis of many radicals and radical ions in aqueous solution. The primary radicals, e/sub aq/ - H, OH, are well characterized. The radical population can be made to be 90% pure OH (or O - ) if N 2 O solutions are irradiated, the remaining 10% being H atoms. 55% of the radicals can be converted to H atoms in acid solution or in neutral phosphate solutions(e/sub aq/ - reacts with H 2 PO 4- to produce H). The remaining 45% (OH radicals) are difficult to convert to H by reaction with H 2 , due to the slow rate of the reaction. About 100 atmospheres of H 2 are required to do the conversion in less than 10 - 6 sec. 3 figures, 3 tables. (DP)

Radical carbonylations using a continuous microflow system

Directory of Open Access Journals (Sweden)

Takahide Fukuyama

2009-07-01

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

Radical-Mediated Enzymatic Polymerizations

Science.gov (United States)

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

Efecto de cuatro manejos del suelo sobre la densidad de raíces absorbentes en durazno [prunus pérsica (l batsch] a 10 cm de profundidad

Directory of Open Access Journals (Sweden)

Andrés Gómez

2011-10-01

Full Text Available El árbol de Durazno (P. pérsica está constituido por dos partes estructurales: una epigea, conformada por el tronco que soporta el sistema caulinar, y otra hipogea que constituye el sistema radicular. Este último, de acuerdo con la base morfoanatómica y las funciones específicas, presenta varios tipos de raíces: absorbentes, de transición y de conducción. Las absorbentes (de color blanquecino translúcido son fisiológicamente muy activas y representanentre el 80 y el 85% de la totalidad del sistema radical. Aunque las raícesde los árboles frutales se desarrollan siguiendo un patrón genético, algunas condiciones medio ambientales producen variaciones morfológicas en su desarrollo. En este trabajo se estudió la densidad del aparato radical absorbente en el cultivo de Durazno (variedad Dorado, a 10 cm de profundidad. Se empleó la técnica volumen del cilindro, en función del manejo del suelo, utilizando 2 tipos de coberturas (cobertura viva, cobertura muerta, control dearvenses con herbicida y un referente tradicional con labranza. Los resultados mostraron que la cobertura con material vegetal muerto, sobre el suelo (10 cm de profundidad bajo el diámetro de la copa del árbol (160 cm, generóun mayor desarrollo del sistema radicular, evidente en una mayor densidad.

Allylthioketone Mediated Free Radical Polymerization of Methacrylates

Directory of Open Access Journals (Sweden)

Feng Zhong

2017-11-01

Full Text Available By combination of high trapping free radical efficiency of the thioketone and resonance of the allylic radical, a new type of mediating agent, 1,3,3-triphenylprop-2-ene-1-thione (TPPT has been successfully synthesized, and then is used to study controlled free radical polymerization of methacrylates. Very stable TPPT radicals at the end of poly(methyl methacrylate (PMMA are detected in the polymerization of MMA using TPPT and AIBN as the control agent and initiator. The MALDI-TOF MS spectra are used to identify terminal groups of the resultant poly(glycidyl methacrylate (PGMA, and major component of the obtained polymer has the structure, (CH32(CNC-PGMA-C7H9O3. Chain extension reaction tests ascertain formation of the dead polymers during the polymer storage and purification process of the polymers. Owing to very slow fragmentation reaction of the TPPT-terminated polymethacrylate radical and addition reaction of this radical with a primary radical, the growing chain radicals are difficult to be regenerated, leading to an unobvious change of the molecular weight with monomer conversion. The molecular weights of polymers can be controlled by the ratios of monomer/initiator and TPPT/initiator. However, the first order kinetics of the polymerization and the polymers with narrow polydispersity are obtained, and these phenomena are discussed. This study provides useful information on how to design a better controlling agent.

Fluorescence lifetime measurement of radical ions

International Nuclear Information System (INIS)

Ichinose, Nobuyuki; Kinugasa, Jun-ichiro; Hagiri, Masahide; Nakayama, Toshihiro; Murakami, Hiroshi; Kishimoto, Maki; Daido, Hiroyuki

2004-01-01

One-photonic excitation of a charge transfer complex of hexamethoxybenzene (HMB) and nitrosonium tetrafluoroborate (NO + BF 4 - ) in acetonitrile afforded fluorescences emission from excited radical cation of HMB (HMB + *). Lifetime of the excited radical ion species was measured to be 7 ps by the pump-probe transient absorption technique. The lifetime was much shorter than that of free radical ion (63 ps), indicating the presence of an interaction between HMB + * and NO in the excited complex. (author)

Generation and propagation of radical reactions on proteins

DEFF Research Database (Denmark)

Hawkins, C L; Davies, Michael Jonathan

2001-01-01

The oxidation of proteins by free radicals is thought to play a major role in many oxidative processes within cells and is implicated in a number of human diseases as well as ageing. This review summarises information on the formation of radicals on peptides and proteins and how radical damage may...... be propagated and transferred within protein structures. The emphasis of this article is primarily on the deleterious actions of radicals generated on proteins, and their mechanisms of action, rather than on enzymatic systems where radicals are deliberately formed as transient intermediates. The final section...

Radical scavenging activity of crude polysaccharides from Camellia sinensis

Directory of Open Access Journals (Sweden)

Yang Fan

2011-01-01

Full Text Available A preparation of crude polysaccharides (TPS was isolated from Camellia sinensis by precipitation and ultrafiltration. TPS1, TPS2, and TPS3 had molecular weights of 240, 21.4, and 2.46 kDa, respectively. The radical scavenging activities of TPS were evaluated by DPPH free radical, hydroxyl radical and superoxide radical scavenging. These results revealed that TPS exhibited strong radical scavenging activity in a concentration-dependent manner. TPS3 with lowest molecular weight showed a higher radical scavenging activity.

Vibronic Spectroscopy of the Phenylcyanomethyl Radical

Science.gov (United States)

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

2011-06-01

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

Introducing Stable Radicals into Molecular Machines.

Science.gov (United States)

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.

Some reactions of oxidizing radicals with enzymes in aqueous solution

International Nuclear Information System (INIS)

Cundall, R.B.; Bisby, R.H.; Hoe, S.T.; Sims, H.E.; Anderson, R.F.

1979-01-01

A range of oxidizing radicals including some inorganic radical anions and the superoxide radical, can be generated by radiolysis of aqueous solutions. These radicals are more selective in their reactions with amino acids than the hydroxyl radical. Factors controlling the apparent reactivity of radical anions with proteins, such as free radical equilibria and ion-binding, are described. The superoxide radical inactivates papain by reaction with the cysteine residue. This reaction has been studied in solutions subjected to radiations of varying linear energy transfer. (Auth.)

Long-lived gas-phase radicals from combustion

Energy Technology Data Exchange (ETDEWEB)

Kaneko, Takashi; Furusawa, Koji; Amano, Toshiji; Okubo, Yoichi; Tsuchiya, Jun' ichi; Yoshizawa, Fujiroku; Akutsu, Yoshiaki; Tamura, Masamitsu; Yoshida, Tadao (Univ. of Tokyo (Japan))

1989-04-20

On indoor air pollution or fire, it is feared that the gas-phase radicals from the combustion of inflammables or fuel seriously exert an influence on the organisms as harmful matter. The gas-phase radicals were studied using the electron spin resonance (ESR) spin-trapping technique. For the spin trap solution, 0.1 mol solution of {alpha}-phenyl-N-t-butylnitron in benzene was used. As a result, apparently long-lived and highly reactive oxygen-centered radicals were detected in the smoke from polyethylene, polypropylene, polystyrene, polymethylmethacrylate, cellulose, kerosene, benzene, acetone, methanol and butylalcohol. It is suggested that the production mechanism for the radicals should be different from olefin-NOx-air system reaction, which is considered for the radicals from cigarette smoke. 11 refs., 6 figs., 2 tabs.

[Research progress on free radicals in human body].

Science.gov (United States)

Wang, Q B; Xu, F P; Wei, C X; Peng, J; Dong, X D

2016-08-10

Free radicals are the intermediates of metabolism, widely exist in the human bodies. Under normal circumstances, the free radicals play an important role in the metabolic process on human body, cell signal pathway, gene regulation, induction of cell proliferation and apoptosis, so as to maintain the normal growth and development of human body and to inhibit the growth of bacteria, virus and cancer. However, when organic lesion occurs affected by external factors or when equilibrium of the free radicals is tipped in the human body, the free radicals will respond integratedly with lipids, protein or nucleic acid which may jeopardize the health of human bodies. This paper summarizes the research progress of the free radicals conducted in recent years, in relations to the perspective of the types, origins, test methods of the free radicals and their relationship with human's health. In addition, the possible mechanisms of environmental pollutants (such as polycyclic aromatic hydrocarbons) mediating oxidative stress and free radicals scavenging in the body were also summarized.

Deciphering free-radical code of radiation effects

International Nuclear Information System (INIS)

Volovyk, S.; Bazyka, D.; Loganovsky, K.; Bebeshko, V.

2007-01-01

Complete text of publication follows. Objective: Ionizing radiation is fundamental environmental factor for life origin and evolution. Free radicals, primordial 'sea' for life conceiving and existence, induced by cosmic and terrestrial background radiation, are evolutionally archetypal, ubiquitous, and omnipotent in physiological- pathophysiological dichotomy. Classical free-radical paradigm in radiation biology and medicine, focused in essence on oxidative damage, needs new conceptualization and generalization. Methods: Suggested novel insights into free radicals dual immanent nature and functions in organism systems are based on original concepts of radicals dynamic charge transfer (CT) - redox ambivalence (interactional nucleo-, electro-, and ambiphilicity spectrum); pertinent chemical reactivity and selectivity delocalization model; physiological functional ambivalence and complementarity, and dynamic free-radical homeostasis. Results: Subtle perturbations in radicals CT spatiotemporal homeodynamics, in responsive signaling / controlling networks, concomitant alterations in genes expression, transcription, and apoptosis, redox control of mitochondrial ET chain, telomere/telomerase balance, DNA CT, circadian clock, hemispheric biochemical dominance/accentuation, including alteration of nitric oxide-superoxide complementarity, membranes permeability, neurotransmission pattern, synaptic circuitry, etc under radiation exposure have more fundamental impact on organism systems (especially CNS and CVS) deterioration than simple radicals inflicted oxidative (nitrosative) damage of cellular constituents. Conclusions: This novel conceptualization of free-radical paradigm constitutes new dimension in deciphering molecular mechanisms of radiation effects on subtle borderline norm-pathology and continuity-discontinuity dichotomy in organisms systems disorders - CT(redox)omics, which involves investigation of CT, redox, and spin states of free radicals, DNA bases

Overexpression of snapdragon Delila (Del) gene in tobacco enhances anthocyanin accumulation and abiotic stress tolerance.

Science.gov (United States)

Naing, Aung Htay; Park, Kyeung Il; Ai, Trinh Ngoc; Chung, Mi Young; Han, Jeung Sul; Kang, Young-Wha; Lim, Ki Byung; Kim, Chang Kil

2017-03-23

Rosea1 (Ros1) and Delila (Del) co-expression controls anthocyanin accumulation in snapdragon flowers, while their overexpression in tomato strongly induces anthocyanin accumulation. However, little data exist on how Del expression alone influences anthocyanin accumulation. In tobacco (Nicotiana tabacum 'Xanthi'), Del expression enhanced leaf and flower anthocyanin production through regulating NtCHS, NtCHI, NtF3H, NtDFR, and NtANS transcript levels. Transgenic lines displayed different anthocyanin colors (e.g., pale red: T 0 -P, red: T 0 -R, and strong red: T 0 -S), resulting from varying levels of biosynthetic gene transcripts. Under salt stress, the T 2 generation had higher total polyphenol content, radical (DPPH, ABTS) scavenging activities, antioxidant-related gene expression, as well as overall greater salt and drought tolerance than wild type (WT). We propose that Del overexpression elevates transcript levels of anthocyanin biosynthetic and antioxidant-related genes, leading to enhanced anthocyanin production and antioxidant activity. The resultant increase of anthocyanin and antioxidant activity improves abiotic stress tolerance.

Zwitterion radicals and anion radicals from electron transfer and solvent condensation with the fingerprint developing agent ninhydrin.

Science.gov (United States)

Schertz, T D; Reiter, R C; Stevenson, C D

2001-11-16

Ninhydrin (the fingerprint developing agent) spontaneously dehydrates in liquid ammonia and in hexamethylphosphoramide (HMPA) to form indantrione, which has a sufficiently large solution electron affinity to extract an electron from the solvent (HMPA) to produce the indantrione anion radical. In liquid NH(3), the presence of trace amounts of amide ion causes the spontaneous formation of an anion radical condensation product, wherein the no. 2 carbon (originally a carbonyl carbon) becomes substituted with -NH(2) and -OH groups. In HMPA, the indantrione anion radical spontaneously forms condensation products with the HMPA to produce a variety of zwitterionic radicals, wherein the no. 2 carbon becomes directly attached to a nitrogen of the HMPA. The mechanisms for the formation of the zwitterionic paramagnetic condensation products are analogous to that observed in the reaction of ninhydrin with amino acids to yield Ruhemann's Purple, the contrast product in fingerprint development. The formation of anion and zwitterionic radical condensation products from ninhydrin and nitrogen-containing solvents may represent an example of a host of analogous polyketone-solvent reactions.

Free radical scavenging injectable hydrogels for regenerative therapy

Energy Technology Data Exchange (ETDEWEB)

Komeri, Remya [Sree Chitra Tirunal Institute for Medical Sciences and Technology, Polymer Science Division, BMT Wing, Thiruvananthapuram 695 012, Kerala State (India); Thankam, Finosh Gnanaprakasam [Dept. of Biomedical Sciences, Creighton University, 2500 California Plaza, Omaha NE68178 (United States); Muthu, Jayabalan, E-mail: mjayabalan52@gmail.com [Sree Chitra Tirunal Institute for Medical Sciences and Technology, Polymer Science Division, BMT Wing, Thiruvananthapuram 695 012, Kerala State (India)

2017-02-01

Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07 kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. - Graphical abstract: Injectable hydrogel with inherent free radical scavenging property for regenerative tissue engineering application. - Highlights: • Novel injectable hydrogel (PEAX-P) is prepared using D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer

Free radical scavenging injectable hydrogels for regenerative therapy

International Nuclear Information System (INIS)

Komeri, Remya; Thankam, Finosh Gnanaprakasam; Muthu, Jayabalan

2017-01-01

Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07 kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. - Graphical abstract: Injectable hydrogel with inherent free radical scavenging property for regenerative tissue engineering application. - Highlights: • Novel injectable hydrogel (PEAX-P) is prepared using D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer

Radical Transversal Lightlike Submanifolds of Indefinite Para-Sasakian Manifolds

OpenAIRE

Shukla S.S.; Yadav Akhilesh

2014-01-01

In this paper, we study radical transversal lightlike submanifolds and screen slant radical transversal lightlike submanifolds of indefinite para-Sasakian manifolds giving some non-trivial examples of these submanifolds. Integrability conditions of distributions D and RadTM on radical transversal lightlike submanifolds and screen slant radical transversal lightlike submanifolds of indefinite para-Sasakian manifolds, have been obtained. We also study totally contact umbilical radical transvers...

Structure and reactivity of the N-acetyl-cysteine radical cation and anion: does radical migration occur?

NARCIS (Netherlands)

Osburn, S.; Berden, G.; Oomens, J.; O'Hair, R.A.J.; Ryzhov, V.

2011-01-01

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

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

NARCIS (Netherlands)

Osburn, S.; G. Berden,; Oomens, J.; O' Hair, R. A. J.; Ryzhov, V.

2011-01-01

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

Cation radicals of xanthophylls.

Science.gov (United States)

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

2007-10-01

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

Condiloma gigante del pene (Tumor de Buschke-Lowenstein: Presentación de un caso Peneal Buschke-Lowenstein tumor: Case report

Directory of Open Access Journals (Sweden)

A.A. Núñez Serrano

2009-03-01

Full Text Available El condiloma gigante del pene o tumor de Buschke- Lowenstein, es un tumor epitelial benigno de origen viral y sexualmente transmisible, que en raros casos puede malignizar. Presentamos un paciente en el que el condiloma de localización peneana, creció rápidamente y destruyó estructuras. Su histología se caracteriza por papilomatosis y acantosis endo y exofítica. Existen diferentes tratamientos del tumor, pero el más efectivo es la extirpación quirúrgica radical para evitar recidivas y malignización.Buschke-Lowenstein tumour is an epithelial benign tumour sexually transmitted with a viral origin. We present a case of peneal localization with exofitic growth, compression and displacement of the deeper tissues, ulceration and urethral fistulae. Histology is characterized by papillomatosis and endo or exophytic acantosis. Local malignancy is still discussed. There are many possible treatments, but radical excision is the best to avoid malignant transformation and recurrences.

Hitos de la perspectiva molar del condicionamiento clásico

Directory of Open Access Journals (Sweden)

Andrés M. Pérez Acosta

2003-01-01

Full Text Available En este artículo se revisan los acontecimientos históricos fundamentales en la teoría del condicionamiento clásico como fenómeno psicológico –comportamental o cognoscitivo–, es decir, desde una perspectiva molar, en oposición a una perspectiva molecular, que es propia de las neurociencias. Se analizan los siguientes acontecimientos o hitos: la teoría reflexológica de Vladimir Bechterev, la perspectiva conductista radical de B. F. Skinner, el modelo de Rescorla y Wagner (1972, los modelos atencionales de Mackintosh (1975 y de Pearce y Hall (1980, las teorías que se basan en los procesos oponentes, de Allan Wagner (1981; Wagner & Brandon, 1989, y las teorías que se basan en el control temporal del comportamiento (Gallistel & Gibbon, 2002.

Aplicación del índice pronóstico AGES para el tratamiento del carcinoma bien diferenciado de la tiroides Application of AGES prognostic rate for treatment of a well differentiated thyroid carcinoma

Directory of Open Access Journals (Sweden)

Gimel Sosa Martín

2009-09-01

Full Text Available INTRODUCCIÓN. En la actualidad la selección del tratamiento quirúrgico adecuado en pacientes con carcinoma diferenciado de la tiroides en etapas tempranas es controversial. La presente investigación tuvo el objetivo de describir y evaluar los resultados del diagnóstico y tratamiento de esta enfermedad en un período de 5 años. MÉTODOS. Se realizó un estudio observacional, descriptivo con elementos analíticos incorporados, y prospectivo para la recolección de información de los pacientes atendidos por presentar nódulo de la tiroides, en el ISMM «Dr. Luis Díaz Soto», entre enero del 2002 y diciembre del 2006. A estos pacientes con cánceres bien diferenciados en etapas I y II según la clasificación internacional de tumores, ganglios y metástasis, se les aplicó de forma retrospectiva el índice de pronóstico AGES. RESULTADOS. La muestra estudiada estuvo constituida por 73 pacientes, de los cuales 69 eran mujeres (94,5 %. Del total de pacientes estudiados, 42 presentaron tumores benignos (57,5 % y 31, malignos (42,5 %. De los 31 casos diagnosticados como carcinomas mediante parafina, 21 obtuvieron puntuación menor de 4 según el índice AGES (menor riesgo, y solo 11 de estos (67,7 % recibieron una cirugía conservadora de la tiroides. CONCLUSIONES. Existió una buena concordancia entre la biopsia por aspiración con aguja fina y la parafina, por lo que la primera se considera de valor en la exploración de un nódulo de la tiroides. El índice AGES no siempre fue tomado en cuenta para la selección del tipo de cirugía, con tendencia a la cirugía más radical. Las complicaciones mayores se asociaron con mayor frecuencia a la cirugía radical.INTRODUCTION: At the present times, the selection a suitable surgical treatment for patients presenting with an early differentiated thyroid carcinoma is a controversial question. The aim of present research was to describe and to assessment the diagnosis results and the treatment of this

Violent Radicalization in Europe

DEFF Research Database (Denmark)

Dalgaard-Nielsen, Anja

2010-01-01

When, why, and how do people living in a democracy become radicalized to the point of being willing to use or directly support the use of terrorist violence against fellow citizens? This question has been at the center of academic and public debate over the past years as terrorist attacks...... within this field and to answer the question: From an empirical point of view, what is known and what is not known about radicalization connected to militant Islamism in Europe?...

Application of ABTS radical cation for selective on-line detection of radical scavengers in HPLC eluates

NARCIS (Netherlands)

Koleva, [No Value; Niederlander, HAG; van Beek, TA

2001-01-01

The radical cation 2,2 ' -azinobis-(3 -ethylbenzothiazoline-6-sulfonate), (ABTS(.+)) was utilized in an on-line HPLC method for the detection of radical scavengers in complex matrixes. The HPLC-separated analytes react postcolumn with the preformed ABTS(.+), and the induced bleaching is detected as

Karol Wojtyla: el surgimiento de una vocación a indagar por la verdad del hombre

Directory of Open Access Journals (Sweden)

Andrés Felipe López López

2013-06-01

Full Text Available El incesante retorno de Karol Wojtyla al estudio del hombre y la defensa de la dignidad de la persona no son hechos producto del azar o del mero interés del pensador, sino que son resultado de la experiencia del fenómeno del totalitarismo durante el transcurso de la Segunda Guerra Mundial; además, sufrió todo el desprecio de la barbarie nazi y la posterior llegada del comunismo a su nación; estas “ideologías del mal” como él las llamó, dan cuenta de la naturaleza verdadera y radical del mal, del olvido del otro y de la desestimación sistemática por la vida humana. Este artículo es una descripción del ejercicio de poder y dominación ejecutados concretamente por Adolf Hitler a Polonia durante el paso de la guerra por ese país, tierra natal del Papa. El objeto de estudio es la comprensión, en términos de causalidad, del pensamiento de Wojtyla: personalismo y humanismo cristiano; los términos “totalitarismo”, “geopolíica”, “personalismo” y la figura de Hitler son esenciales. Los pensadores no se hacen solos, su temperamento es fruto del contexto en el que vivieron. En este análisis, para hacer más fina esa comprensión pretendida, son citados otros autores que han ampliado el horizonte de comprensión sobre el fenómeno citado, por ejemplo Hannah Arendt y Joan Carles Mélich.

Critical appraisal of outcomes following open radical prostatectomy.

Science.gov (United States)

Galvin, David J; Eastham, James A

2009-05-01

Radical prostatectomy has evolved enormously over the last 25 years. Improvements include the use of smaller incisions, reduced blood loss, shorter hospital stays, and surgical refinement to improve the recovery of continence and potency. In addition, new technologies and minimally invasive techniques with the potential to further improve patient outcomes have been introduced. This article focuses on outcomes with open radical prostatectomy and is not meant to compare open radical prostatectomy and minimally invasive approaches. Despite a lack of randomized controlled trials, strong observational cohort studies demonstrate lower rates of positive surgical margins, high 10-year and 15-year biochemical recurrence-free rates, excellent prostate cancer-specific mortality rates, and improved recovery of urinary incontinence and erectile function after open radical prostatectomy. We review publications from the past 24 months regarding oncologic outcome, continence, and erectile function, as well as some earlier manuscripts that emphasize key aspects of open radical prostatectomy. Today open radical prostatectomy is a less-invasive procedure with low morbidity providing excellent control of clinically localized prostate cancer. Although open radical prostatectomy now accounts for a minority of radical prostatectomies in the United States, the concepts that have improved oncologic and quality-of-life outcomes are equally applicable to minimally invasive procedures.

NOx removal characteristics of corona radical shower with ammonia and methylamine radical injections

Energy Technology Data Exchange (ETDEWEB)

Urashima, K.; Ara, M.; Chang, J.S. [McMaster Univ., Hamilton, ON (Canada). Dept. of Engineering Physics; Uchida, Y. [Aichi Inst. of Technology, (Japan). Dept. of Engineering

2010-07-01

Air pollutants such as nitrogen oxides (NOx) and sulfur oxides (SOx) are the major cause of acid rain. There are different types of NOx and SOx conversion techniques such as wet scrubber, selective catalytic reactor, sorbent injection, and low NOx burner. Non-thermal plasma techniques have also been utilized in commercial plants, but the energy efficiency of the non-thermal plasma reactors have not yet been optimized. The direct plasma treatments of flue gases including, the electron beam, barrier discharge and pulsed corona reactors, may lose input energy to activate unwanted components of flue gases such as carbon dioxide (CO{sub 2}) and nitrogen (N{sub 2}). The corona discharge ammonia radical shower system has demonstrated significant NOx removal with higher energy efficiency for large bench scale and pilot plant tests for combustion exhausts. An experiment has also demonstrated that methane can replace ammonia as an injection gas with less NOx removal efficiency. This paper presented an experimental investigation that compared methylamine radical injection with traditional ammonia and methane radical injections. The paper discussed the bench scale test facilities and corona radical shower plasma reactor. It was concluded that the processes to form ammonium nitrate could be observed from trace white solid particles deposited on the reactor wall as observed by scanning electron microscopy pictures. 10 refs., 5 figs., 2 appendices.

Radical Sustainable Innovation of office buildings

DEFF Research Database (Denmark)

Koch, Christian; Berker, Thomas; Koch-Ørvad, Nina

2017-01-01

by high degrees of newness in the entire life cycle. RSI should offer significant enhancements of known benefits, entirely new benefits, or substantial cost reductions, leading to the transformation of existing markets, the creation of sustainable growth, and global sustainability. Thus, if buildings were....../could be radically new. How to evaluate radicality is a major challenge. It is tentatively proposed, to use standards for sustainable office buildings. Standards are developed to accelerate the sustainable development but has to some extent come to constrain possibilities of radical innovation. As the criteria...... of newness is incorporated in standards, going beyond them, could be viewed as radical. Empirically a selection of international cases of office buildings with very high scores of BREEAM, LEED and DGNB are examined. Six selected cases were analysed more in detail, one of them, Geelens...

User involvement competence for radical innovation

DEFF Research Database (Denmark)

Lettl, Christopher

2007-01-01

-assisted navigation systems. The case study analysis reveals that firms who closely interact with specific users benefit significantly for their radical innovation work. These users have a high motivation toward new solutions, are open to new technologies, possess diverse competencies, and are embedded into a very......One important market related capability for firms which seek to develop radical innovations is the competence to involve the 'right' users at the 'right' time in the 'right' form. While former studies have identified a rather passive role of users in the radical innovation process, this paper...

User involvement competence for radical innovation

DEFF Research Database (Denmark)

Lettl, Christopher

2007-01-01

One important market related capability for firms which seek to develop radical innovations is the competence to involve the 'right' users at the 'right' time in the 'right' form. While former studies have identified a rather passive role of users in the radical innovation process, this paper......-assisted navigation systems. The case study analysis reveals that firms who closely interact with specific users benefit significantly for their radical innovation work. These users have a high motivation toward new solutions, are open to new technologies, possess diverse competencies, and are embedded into a very...

Protonated o-semiquinone radical as a mimetic of the humic acids native radicals: A DFT approach to the molecular structure and EPR properties

Science.gov (United States)

Witwicki, Maciej; Jezierska, Julia

2012-06-01

Organic radicals are known to be an indispensable component of the humic acids (HA) structure. In HA two forms of radicals, stable (native) and short-lived (transient), are identified. Importantly, these radical forms can be easily differentiated by electron paramagnetic resonance (EPR) spectroscopy. This article provides a DFT-based insight into the electronic and molecular structure of the native radicals. The molecular models including an increase of the radical aromaticity and the hydrogen bonding between the radical and other functional groups of HA are taken under investigation. In consequence the interesting pieces of information on the structure of the native radical centers in HA are revealed and discussed, especially in terms of differences between the electronic structure of the native and transient forms.

La implantacion del enfoque constructivista en el aula de ciencia: Estudio de caso multiple

Science.gov (United States)

Arroyo Betancourt, Luz I.

Esta investigacion estudia la implantacion del enfoque constructivista en tres aulas de ciencia del contexto puertorriqueno. Se auscultaron las practicas educativas que utilizan maestras consideradas constructivistas y la correspondencia de sus practicas educativas con los elementos esenciales de la didactica que proponen los teoricos de los planteamientos constructivistas. Se ausculto, ademas, a que vision del enfoque constructivista responden las expresiones de las maestras acerca de su practica educativa y como compara con su quehacer, a la luz de los elementos esenciales de las visiones constructivistas piagetiana, social y radical. Se utilizo el diseno de estudio descriptivo de caso multiple. El estudio se baso en entrevistas a profundidad, revision de documentos y observacion no participativa a la sala de clases. El contexto fueron tres escuelas publicas de la Region Educativa de San Juan, una elemental, una intermedia y una superior. Los resultados confirmaron que la transicion hacia el enfoque constructivista es un proceso que toma tiempo, dedicacion y la participacion en adiestramientos y readiestramientos acerca del nuevo enfoque. Las maestras coinciden en la mayoria de las practicas educativas que utilizan para implantar el enfoque constructivista de ensenanza y difieren en algunas debido, probablemente, a que han tenido que adaptarlas a los correspondientes niveles de ensenanza: elemental, intermedio y superior. Dos de las maestras planifican por conceptos generadores, mientras que una de ellas planifica siguiendo la guia que recibe del Departamento de Educacion. Difieren ademas, en el enfasis que confieren al inquirir cientifico. Con relacion a la correspondencia entre la vision manifestada por las maestras a la luz de las visiones piagetiana, social y radical, aparentemente, las preguntas del protocolo de entrevistas no lograron evocar la informacion con suficiente profundidad, por lo que la investigadora tuvo que inferir las visiones de las

Intramolecular hydrogen bonding in malonaldehyde and its radical analogues.

Science.gov (United States)

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

2017-09-28

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

Hydroxyl radical reactivity with diethylhydroxylamine

International Nuclear Information System (INIS)

Gorse, R.A. Jr.; Lii, R.R.; Saunders, B.B.

1977-01-01

Diethylhydroxylamine (DEHA) reacts with gas-phase hydroxyl radicals on every third collision, whereas the corresponding reaction in aqueous solution is considerably slower. The high gas-phase reactivity explains the predicted inhibitory effect of DEHA in atmospheric smog processes. Results from the studies in the aqueous phase are helpful in predicting the mechanism of the reaction of DEHA with hydroxyl radicals

Radical dematerialization and degrowth

Science.gov (United States)

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'.

Thermal evolution of the morphology of Ni/Ag/Si(111)-{radical}3 Multiplication-Sign {radical}3 surface

Energy Technology Data Exchange (ETDEWEB)

Tomaszewska, Agnieszka; Huang, Xiao-Lan; Chang, Kuo-Wei; Fu, Tsu-Yi, E-mail: phtifu@phy.ntnu.edu.tw

2012-08-31

The temperature-driven changes in morphology of the interface formed by room temperature (RT) deposition of Ni atoms onto an Ag/Si(111)-{radical}3 Multiplication-Sign {radical}3 surface were investigated by scanning tunneling microscopy. Roughly 70% of Ni deposition diffused into bulk substrate within the temperature range between RT and 573 K. The images as obtained after annealing up to 670 K correspond to the formation of nano-sized islands of nickel silicides. Two types of islands, large triangular islands typical of the whole range of applied coverage, and smaller islands of different shapes, coexist at Ni coverage higher than 1 monolayer. Annealing above 870 K led to the formation of a 7 Multiplication-Sign 7 phase in coexistence with small 5 Multiplication-Sign 5 domains at the expense of a complete disappearance of the {radical}3 Multiplication-Sign {radical}3 phase. Also, formation of Ni,Si alloy was observed at the temperature, along with segregation of bulk-dissolved Ni species onto the surface. - Highlights: Black-Right-Pointing-Pointer We examine changes in morphology of Ni/Ag/Si(111)-{radical}3 Multiplication-Sign {radical}3 surface upon annealing. Black-Right-Pointing-Pointer 70% of deposited Ni atoms diffuse into the bulk after annealing at 570 K. Black-Right-Pointing-Pointer A variety of nano-sized Ni, Si islands develops after annealing at 670 K. Black-Right-Pointing-Pointer 5 Multiplication-Sign 5 reconstruction as an evidence for mass transport during the island growth.

Ring-Expansion/Contraction Radical Crossover Reactions of Cyclic Alkoxyamines: A Mechanism for Ring Expansion-Controlled Radical Polymerization

Directory of Open Access Journals (Sweden)

Atsushi Narumi

2018-06-01

Full Text Available Macrocyclic polymers present an important class of macromolecules, displaying the reduced radius of gyration or impossibility to entangle. A rare approach for their synthesis is the ring expansion-controlled radical “vinyl” polymerization, starting from a cyclic alkoxyamine. We here describe ring-expansion radical crossover reactions of cyclic alkoxyamines which run in parallel to chain-propagation reactions in the polymerization system. The radical crossover reactions extensively occurred at 105–125 °C, eventually producing high molecular weight polymers with multiple inherent dynamic covalent bonds (NOC bonds. A subsequent ring-contraction radical crossover reaction and the second ring-expansion radical crossover reaction are also described. The major products for the respective three stages were shown to possess cyclic morphologies by the molecular weight profiles and the residual ratios for the NOC bonds (φ in %. In particular, the high φ values ranging from ca. 80% to 98% were achieved for this cyclic alkoxyamine system. This result verifies the high availability of this system as a tool demonstrating the ring-expansion “vinyl” polymerization that allows them to produce macrocyclic polymers via a one-step vinyl polymerization.

Biochemistry and pathology of radical-mediated protein oxidation

DEFF Research Database (Denmark)

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

1997-01-01

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

How to counter radical narratives: Dutch deradicalization policy in the case of Moluccan and Islamic radicals

NARCIS (Netherlands)

Demant, F.; de Graaf, B.

2010-01-01

This article deals with the role of government in encouraging the decline of radical movements. The question posed is: "Which story can the government tell to encourage the decline of radical groups and the disengagement of their members?" The article makes use of the survey of factors promoting

Structure and Reactivity of the Glutathione Radical Cation: Radical Rearrangement from the Cysteine Sulfur to the Glutamic Acid alpha-Carbon Atom

NARCIS (Netherlands)

Osburn, S.; Berden, G.; Oomens, J.; Gulyuz, K.; Polfer, N.C.; O'Hair, R.A.J.; Ryzhov, V.

2013-01-01

A gas-phase radical rearrangement through intramolecular hydrogen-atom transfer (HAT) was studied in the glutathione radical cation, [-ECG](+.), which was generated by a homolytic cleavage of the protonated S-nitrosoglutathione. Ion-molecule reactions suggested that the radical migrates from the

Photodynamically generated bovine serum albumin radicals

DEFF Research Database (Denmark)

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

1998-01-01

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

The Rise of Radicals in Bioinorganic Chemistry

OpenAIRE

Gray, Harry B.; Winkler, Jay R.

2016-01-01

Prior to 1950, the consensus was that biological transformations occurred in two-electron steps, thereby avoiding the generation of free radicals. Dramatic advances in spectroscopy, biochemistry, and molecular biology have led to the realization that protein-based radicals participate in a vast array of vital biological mechanisms. Redox processes involving high-potential intermediates formed in reactions with O_2 are particularly susceptible to radical formation. Clusters of tyrosine (Tyr) a...

Radical prostatectomy. Results and indications

International Nuclear Information System (INIS)

Jacqmin, D.

1997-01-01

Radical prostatectomy is the surgical curative treatment of localized prostate cancer. The survival is good in young patients (<70) with T2 N0M0 tumors and more than 10 year's life expectancy. Side-effects are urinary incontinence, impotence and anastomosis stricture. Quality of life should be considered as an important factor for the choice of the patient between radical prostatectomy, radiotherapy and follow-up. (author)

Responsibility for radical change in addressing climate change

NARCIS (Netherlands)

Bouvrie, des N.; Karlsson-Vinkhuyzen, S.I.S.E.; Jollands, N.

2015-01-01

To radically address the problem of climate change, it is not enough to modify specific attitudes and behaviors while upholding the present paradigms. This article aims to show why modifications will never bring about radical carbon emission reductions. We discuss what it implies to desire radical

Una crónica freudiana del cuerpo

Directory of Open Access Journals (Sweden)

Mario Orozco Guzmán

2012-01-01

Full Text Available EI objetivo fundamental fue emprender una lectura desconstructiva de la noción de cuerpo en Freud. Los objetivos especfficos: a interrogar el empleo de la noción de cuerpo, en Freud, en diversos contextos de análisis. Como los relativos a la estructura histerica, la sexualidad, el narcisismo y la cultura, entre otros; b marcar algunas encrucijadas epistemológicas y rutas de inflexion critica, en el pensamiento de Freud, en relación con este termino estelar y c producir significaciones ineditas al tensar el discurso freudiano, descomponiendo y desgranando sus puntualizaciones. EI proceso metodol6gico suscribe la propuesta de Jacques Derrida para efectuar una desconstrucción del discurso que permita su reformulación al desconectarlo de sus nexos establecidos y anudarlo a otros componentes. Los resultados, en terminos de descubrimiento desconstructivo, mostraron que el discurso histerico descubrió la subversión del sujeto con el cuerpo. La pulsión determinó una conexión inusitada entre cuerpo sexuado y psiquismo inconsciente. EI cuerpo torturado develó la presencia de torbellino del goce. EI cuerpo-Narciso reveló no sólo las investiduras de amor al cuerpo, sino tambien las del odio. Las psicosis demostraron que la ensambladura yo-cuerpo se puede desbaratar. La voluntad de dominio propio de una cultura de imperativos se exhibe muy radical en su aplicación al cuerpo. En conclusión, la exploraci6n crftica del discurso freudiano sobre el cuerpo culmina en la distancia a la que se puede encontrar el yo de un ideal de adecuación y obediencia. Es tan rebelde y tan revelador como el inconsciente. Por eso el empeño atroz en someterlo.

Measurements of hydroxyl and hydroperoxy radicals during CalNex-LA: Model comparisons and radical budgets

Science.gov (United States)

Griffith, S. M.; Hansen, R. F.; Dusanter, S.; Michoud, V.; Gilman, J. B.; Kuster, W. C.; Veres, P. R.; Graus, M.; de Gouw, J. A.; Roberts, J.; Young, C.; Washenfelder, R.; Brown, S. S.; Thalman, R.; Waxman, E.; Volkamer, R.; Tsai, C.; Stutz, J.; Flynn, J. H.; Grossberg, N.; Lefer, B.; Alvarez, S. L.; Rappenglueck, B.; Mielke, L. H.; Osthoff, H. D.; Stevens, P. S.

2016-04-01

Measurements of hydroxyl (OH) and hydroperoxy (HO2*) radical concentrations were made at the Pasadena ground site during the CalNex-LA 2010 campaign using the laser-induced fluorescence-fluorescence assay by gas expansion technique. The measured concentrations of OH and HO2* exhibited a distinct weekend effect, with higher radical concentrations observed on the weekends corresponding to lower levels of nitrogen oxides (NOx). The radical measurements were compared to results from a zero-dimensional model using the Regional Atmospheric Chemical Mechanism-2 constrained by NOx and other measured trace gases. The chemical model overpredicted measured OH concentrations during the weekends by a factor of approximately 1.4 ± 0.3 (1σ), but the agreement was better during the weekdays (ratio of 1.0 ± 0.2). Model predicted HO2* concentrations underpredicted by a factor of 1.3 ± 0.2 on the weekends, while measured weekday concentrations were underpredicted by a factor of 3.0 ± 0.5. However, increasing the modeled OH reactivity to match the measured total OH reactivity improved the overall agreement for both OH and HO2* on all days. A radical budget analysis suggests that photolysis of carbonyls and formaldehyde together accounted for approximately 40% of radical initiation with photolysis of nitrous acid accounting for 30% at the measurement height and ozone photolysis contributing less than 20%. An analysis of the ozone production sensitivity reveals that during the week, ozone production was limited by volatile organic compounds throughout the day during the campaign but NOx limited during the afternoon on the weekends.

An Appreciation of Free Radical Chemistry

Indian Academy of Sciences (India)

... Lecture Workshops · Refresher Courses · Symposia · Live Streaming. Home; Journals; Resonance – Journal of Science Education; Volume 10; Issue 9. An Appreciation of Free Radical Chemistry - 6. Experiments Involving Free Radicals. G Nagendrappa. Classroom Volume 10 Issue 9 September 2005 pp 79-84 ...

Reorientation dynamics of cyclohexadienyl radicals in zeolites

International Nuclear Information System (INIS)

Stolmar, M.; Roduner, E.; Dilger, H.; Himmer, U.; Shelley, M.; Reid, I.D.

1997-01-01

The dynamics of the muonium substituted cyclohexadienyl radical adsorbed on silicalite and NaZSM-5 is investigated by means of avoided level crossing muon spin resonance. The influence of benzene loading on the mobility of the radical is studied. At low loadings the radicals were found to be located on a single adsorption site where they undergo a wobbling type of motion. With increasing loading an additional species adsorbed on a different site is observed

Entre el liberalismo radical y la necesidad: los debates en torno al monopolio estatal del tabaco en México, 1821-1824

Directory of Open Access Journals (Sweden)

Jesús Hernández Jaimes

2011-12-01

Full Text Available La empresa estatal del tabaco fue una de las fuentes de recursos más importantes para el gobierno virreinal novohispano desde el último cuarto del siglo XVIII. Una vez conseguida la independencia, la clase política y algunos sectores económicos se enfrascaron en una disputa en torno al destino de dicho monopolio. Para algunos, su existencia contrariaba los principios modernos del liberalismo, además de que encarnaba el supuesto despotismo del régimen colonial que se buscaba sepultar. Para otros, la precariedad de la Hacienda nacional justificaba su continuidad. Creían que la construcción del Estado requería necesariamente de una constitución hacendaria en la que el estanco del tabaco debía tener un lugar relevante. Este ensayo da cuenta de este intenso debate ocurrido en el momento fundacional del nuevo país y se analizan las ideas políticas y económicas, así como los intereses en torno al estanco del tabaco.The tobacco monopoly was one of the most important financial resources of the New Spain's viceregal government during the last twenty-five years of the eighteenth-century. Once Mexico achieved independence, politicians and representatives of various economic interests became absorbed in a dispute over its future. Some thought that its existence went against modern liberal principals, as well as exemplifying the Colonial regime's alleged despotism from which the new nation was trying to escape. Others believed that the fragility of the Public Treasury justified its survival. They thought that the tobacco monopoly was necessary for the construction of the State and the constitution of a viable tax system. Without the State no liberty could be guaranteed. This essay describes the intense debate on this subject which occurred during the foundational moments of the new country. It also analyses the political and economic ideas that were discussed and the interests that were involved in them.

Interactions between simple radicals and water

International Nuclear Information System (INIS)

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

2008-01-01

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

Muon level crossing resonance spectroscopy applied to free-radical formation

International Nuclear Information System (INIS)

Venkateswaran, K.; Barnabas, M.V.; Walker, D.C.

1989-01-01

Muon Level Crossing Resonance Spectroscopy has been used to explore two aspects of muonium chemistry: unique free radicals and muonated radical yields. (1) A variety of new free-radicals have been seen by LCR. For instance, in thioacetamide the only radical produced from muonium is the S sm-bullet radical formed when Mu adds to the C of the C=S bond. In allylbenzene a whole range of radicals form with substantial yields (two side-chain and three ring additions); whereas in styrene, 85% of the radicals have Mu bonded to the end C of the side-chain and there is no meta-adduct at all. (2) Absolute yields of the radicals formed by interaction of muonium atoms in water with acrylamide as a solute (and with benzene in n-hexane) have shown that all muons not directly incorporated into diamagnetic molecules (such as MuH) appear as muonated free radicals. i.e. the missing fraction is found

Geminate free radical processes and magnetic field effects

International Nuclear Information System (INIS)

Eveson, Robert W.

2000-01-01

This thesis is concerned with the study of the dynamics of radical pair recombination reactions in solution by flash photolysis Electron Spin Resonance (ESR) and the influence of low static external magnetic fields upon them (MFE). An outline of the concepts of ESR is presented, followed by the theories of Chemically Induced Dynamic Electron Polarisation (CIDEP) of transient radical pairs. This is then followed by a brief review of the flash photolysis ESR apparatus and application of the Bloch equations to solve the equations of time-resolved ESR. Completing the theory section is an overview of the mechanisms by which magnetic fields alter the course of a geminate radical pair reaction in solution. Experimental CIDEP observations of the radical pair produced on photolysis of 1,3-dihydroxypropanone are simulated using polarisation theory and applied to a random-walk diffusion model to find, for the first time, the geminate reaction probability in solutions of varying viscosity. CIDEP spectra of the radical pair formed on photolysis of hydroxypropanone in contrast are not accounted for by current polarisation theory. The discrepancy is due to moderately fast relaxation of the acyl radical, CH 3 CO·, which alters the relative intensities in the ST 0 RPM pattern of the counter radical. Calculations taking into account this now provide an adequate basis for simulation of the spectrum. This method also, in principle, represents a new method for the measurement of phase relaxation times. Concluding the ESR work is a CIDEP study of 2,4,6-trimethylbenzoyl diphenylphosphine oxide. Unusual spin polarisation phenomena are found. The time-resolved optical absorption spectroscopy technique used for detecting low magnetic field effects on neutral radical pair reactions is described. Various improvements to the experiment are discussed which result in the observation of the low field effect for a neutral radical pair produced by Norrish type II chemistry. This is followed by an

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

Science.gov (United States)

Van Hoomissen, Daniel J; Vyas, Shubham

2017-11-16

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

Comparative study of radical oxidation of DNA and its nucleosides by hydroxyl radicals and ferryl ions generated by the Fenton reaction

International Nuclear Information System (INIS)

Mouret, J.F.; Berger, M.; Anselmino, C.; Polverelli, M.; Cadet, J.

1991-01-01

A comparative study of the reaction of hydroxyl radicals and Fenton type oxidative species with DNA and 2'-deoxyribonucleosides was investigated. This study was based on the characterization of the diamagnetic products resulting from the chemical transformation of the transient radicals. Emphasis was placed on the radical oxidative reactions of the purine nucleosides. It is interesting to note that oxidative purine radicals can be reduced by reagents such as ascorbic acid or N,N,N',N'-tetramethyl-1, 4-p-phenylenediamine. The observed differences in the nature of the decomposition products resulting from the Fenton reaction are not consistent with the nature of the oxidative species (hydroxyl radicals or ferryl ions) involved, but due to the presence of ferrous sulfate [fr

Photoactivation of isoflavonoid phytoalexins: involvement of free radicals

International Nuclear Information System (INIS)

Bakker, J.; Gommers, F.J.; Smits, L.; Fuchs, A.; Vries, F.W. de

1983-01-01

Ultraviolet irradiation of isoflavonoid phytoalexins phaseollin, 3.6a. 9-trihydroxypterocarpan, glyceollin, tuberosin and pisatin, but not medicarpin, brought about inactivation of glucose-6-phosphate dehydrogenase in an in vitro assay system. Photoinactivation of the enzyme by photoactivated pisatin in air-saturated solutions was hardly affected by singlet oxygen quenchers such as NaN 3 , bovine serum albumin, histidine or methionine. Neither addition of the hydroxyl radical scavengers mannitol, Na-benzoate and ethanol nor the presence of catalase or superoxide dismutase protected the enzyme against photoinactivation, suggesting that OHradical, H 2 O 2 and O 2 radical are not the reactive oxygen species involved. However, the free radical scavenger S-(2-amino-ethyl)isothiouronium bromide hydrobromide (AET) protected the enzyme against inactivation by photoactivated pisatin. Direct evidence for the generation of free radicals was obtained by ESR measurements of solutions of phaseollin, pisatin and medicarpin in hexane irradiated with ultraviolet light in the presence or absence of O 2 . Phaseollin produced the most stable free radicals, whereas medicarpin hardly gave rise to free radical formation; pisatin took a somewhat intermediate position by producing a strong ESR signal which, however, decayed rather quickly. These results indicate free radical formation as the cause for photoinactivation of enzymes by photoactivated isoflavonoid phytoalexins. (author)

Enhancing production through optimisation of DPPH and radical ...

African Journals Online (AJOL)

... of dry matter for DPPH radical scavenging activity. Methanol had the lowest value (78 mg g-1 dry matter) for polyphenol extracts and 80 mg g-1 for the DPPH radical scavenging activity. The main extract compounds were gallic acid, catechin and epicatechin. Key Words: High density lipids, polyphenol, radical scavenging ...

Hydroxyl-radical induced dechlorination of pentachlorophenol in water

International Nuclear Information System (INIS)

He Yongke; Wu Jilan; Fang Xingwang; Sonntag, C. von

1998-01-01

The hydroxyl-radical induced dechlorination of pentachlorophenol (PCP) in water has been investigated pulse radiolytically. Hydroxyl radicals react with PCP by both electron transfer and addition. The former process results in pentachlorophenoxyl radicals (PCP-O), the latter process followed by rapid HCl elimination gives birth to deprotonated hydroxytetrachlorophenoxyl radicals ( - O-TCP-O). These phenoxyl radicals exhibit maximum absorption around 452 nm, which hinders the proper estimation of the ratio of the two processes. However, these two processes cause different changes in conductivity. In basic solution, the electron transfer causes a conductivity increase due to the formation of OH - whereas an addition followed by HCl elimination results in a conductivity decrease. The concurrence of these two processes reduces the relative variation in conductivity, from which about 53% electron transfer is deduced

Exploring the Theories of Radicalization

Directory of Open Access Journals (Sweden)

Maskaliūnaitė Asta

2015-12-01

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

Superoxide radical (O2-) reactivity with respect to glutathione

International Nuclear Information System (INIS)

Sekaki, A.; Gardes-Albert, M.; Ferradini, C.

1984-01-01

Influence of superoxide radicals formed during gamma irradiation of glutathione in aerated aqueous solutions is examined. Solutions are buffered at pH7 and contain sodium formate for capture of H and OH radicals which are transformed in COO - radicals and then O 2 - radicals. G value of glutathione disparition vs glutathione concentration are given with and without enzyme or catalase. Reaction mechanism are interpreted [fr

Reactions of melatonin with radicals in deoxygenated aqueous solution

International Nuclear Information System (INIS)

Stasica, P.; Ulanski, P.; Rosiak, J.M.

1998-01-01

Reactions of melatonin (N-acetyl-5-methoxytryptamine) with radiolytically generated radicals were studied. Reaction of melatonin with OH radicals is diffusion-controlled (k=1.2 x 10 10 dm 3 mol -1 x s -1 ), the main (but not the only one) intermediate being the indolyl-type radical, while the rate constant for the reaction with hydrated electrons is k=4.3 x 10 8 dm 3 x mol -1 x s -1 . Melatonin is capable of scavenging tert-butanol radicals, while its reactivity towards polymer radicals of poly(acrylic acid) and poly(vinyl pyrrolidone) is very low. (author)

Local excision of early rectal cancer: is transanal endoscopic microsurgery an alternative to radical surgery? Escisión local del cáncer de recto en estadio precoz: ¿representa la microcirugía transanal endoscópica una alternativa a la cirugía radical?

Directory of Open Access Journals (Sweden)

P. Palma

2009-03-01

Full Text Available Objective: transanal endoscopic microsurgery (TEM allows locally complete excision of rectal neoplasms and provides an alternative to conventional surgery for benign tumours. However, its role in the curative treatment of invasive carcinoma is controversial. This paper examines the results of TEM compared with radical surgery (RS for T1 rectal cancer. Methods: 51 patients with T1 rectal tumours treated by RS, or local excision by means of TEM were included. The following parameters were evaluated: operating time, blood loss, hospital stay and complications, as well as local recurrence rate and survival. Results: 17 patients were treated by RS and 34 by TEM. Operative time, blood loss, and duration of hospitalization were significantly lower in the TEM group compared with the RS group. In the RS group there were 4 patients with complications which required an operative revision (23.5%, compared to 1 reintervention (2.9% in the TEM group. Local recurrence was 5.88% (n = 2 in the TEM group compared with none after RS (p = 0.547. The overall survival and disease-free survival showed not significant statistical differences between both groups (p = 0.59; p = 1.000, resp.. Conclusions: although local recurrence was only observed after local excision, patients treated with TEM showed no significant differences in terms of overall survival and disease-free survival compared with patients who underwent RS. Inasmuch as local excision represents a minimally invasive technique in terms of morbidity, mortality and functional outcome, TEM should be offered as a valid option for well selected patients with early rectal cancer.Objetivo: la cirugía transanal endoscópica (TEM permite la resección completa de neoplasias de recto siendo una alternativa a la cirugía convencional para tumores benignos. Existe controversia sobre su papel en el tratamiento curativo del cáncer de recto. Esta publicación compara los resultados entre la resección radical (RS y la ex

Perfil y evolución del sistema de partidos en Chile

Directory of Open Access Journals (Sweden)

Paulo HIDALGO

2009-11-01

Full Text Available RESUMEN: Este artículo analiza los aspectos principales del sistema de partidos chileno. En primer lugar, se estudian los aspectos principales de los partidos políticos y su configuración histórica. En segundo lugar, se ofrece una breve descripción del derrumbe de la democracia y el papel de los partidos en ese cuadro. En tercer lugar, se presenta un bosquejo de la transición a la democracia y luego se examina el desempeño de cada conglomerado partidario en las primeras elecciones fundacionales. Finalmente se esbozan algunos de los desafíos que se le presenta al sistema partidario desde un punto de vista que enfatiza la noción de una democracia radical.ABSTRACT: This article discusses the main aspects of the chilean party system. Firstly there is a brief analysis of the main features of the political parties and their historical configuration. Secondly there is a short description of the breakdown of democracy and the role of the parties in it. Thirdly there is an outline of the transition to democracy with the election of Patricio Alwyn and then we examine the performance of each party in the founding elections after the autocratic period. Finally we conclude with some of the challenges facing the new borra chilean democracy, in particular with reference to a notion of a radical democracy.

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

Science.gov (United States)

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

2015-04-01

Sulfate radical (SO4(-)) based oxidation is discussed as a potential water treatment option and is already used in ground water remediation. However, the complex SO4(-) chemistry in various matrices is poorly understood. In that regard, the fast reaction of SO4(-) with Cl(-) is of high importance since Cl(-) belongs to the main constituents in aqueous environments. This reaction yields chlorine atoms (Cl) as primary products. Cl initiate a cascade of subsequent reactions with a pH dependent product pattern. At low pH ( 5 Cl mainly react with water yielding hydroxyl radicals. Thus, at moderate Cl(-) concentrations (mM range) the SO4(-)-based process may be converted into a conventional (hydroxyl radical -based) advanced oxidation process. The conversion of SO4(-) into OH, however, is interrupted in presence of bicarbonate by scavenging of Cl. Copyright © 2014. Published by Elsevier Ltd.

Free radical scavenging injectable hydrogels for regenerative therapy.

Science.gov (United States)

Komeri, Remya; Thankam, Finosh Gnanaprakasam; Muthu, Jayabalan

2017-02-01

Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. Copyright © 2016 Elsevier B.V. All rights reserved.

IRON AND FREE RADICAL OXIDATIONS IN CELL MEMBRANES

Science.gov (United States)

Schafer, Freya Q.; Yue Qian, Steven; Buettner, Garry R.

2013-01-01

Brain tissue being rich in polyunsaturated fatty acids, is very susceptible to lipid peroxidation. Iron is well known to be an important initiator of free radical oxidations. We propose that the principal route to iron-mediated lipid peroxidations is via iron-oxygen complexes rather than the reaction of iron with hydrogen peroxide, the Fenton reaction. To test this hypothesis, we enriched leukemia cells (K-562 and L1210 cells) with docosahexaenoic acid (DHA) as a model for brain tissue, increasing the amount of DHA from approximately 3 mole % to 32 mole %. These cells were then subjected to ferrous iron and dioxygen to initiate lipid peroxidation in the presence or absence of hydrogen peroxide. Lipid-derived radicals were detected using EPR spin trapping with α-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN). As expected, lipid-derived radical formation increases with increasing cellular lipid unsaturation. Experiments with Desferal demonstrate that iron is required for the formation of lipid radicals from these cells. Addition of iron to DHA-enriched L1210 cells resulted in significant amounts of radical formation; radical formation increased with increasing amount of iron. However, the exposure of cells to hydrogen peroxide before the addition of ferrous iron did not increase cellular radical formation, but actually decreased spin adduct formation. These data suggest that iron-oxygen complexes are the primary route to the initiation of biological free radical oxidations. This model proposes a mechanism to explain how catalytic iron in brain tissue can be so destructive. PMID:10872752

ESR study of the anion radicals of 5-nitropyrimidines: conversion to iminoxy radicals

International Nuclear Information System (INIS)

Sevilla, M.D.; Clark, C.; Failor, R.

1976-01-01

The anion radicals of a number of 5-nitropyrimidines have been investigated by ESR spectroscopy. The anions are formed by electrolysis in dimethylformamide and by electron attachment in aqueous glasses, 12 M LiCl--D 2 O and 8 M NaOD. The electrolysis of 5-nitrouracil and 5-nitro-6-methyluracil results in relatively stable anion radicals. The results for 5-nitrouracil give evidence for two or perhaps three anions which differ only by the degree of ring nitrogen protonation. The results for 5-nitro-6-methyluracil suggest that the nitro group of the anion is twisted so that it is coupled only weakly to the ring π-electron system. The anions of 5-nitrouracil, 5-nitroorotic acid, 5-nitrobarbituric acid, and 5-nitro-6-methyluracil have been produced in the alkaline and neutral aqueous glasses. The anisotropic spectra found have been analyzed with the aid of computer simulations which assume axial symmetry. For example, the analysis of the spectrum of 5-nitrouracil anion in 12 M LiCl yields A/sub parallel//sup N/ = 33; A/sub perpendicular to//sup N/ = 5, a 6 /sup H/ = 5.5 G, g/sub parallel/ = 2.0016, and g/sub perpendicular to/ = 2.0059. A concentration dependence in the splittings is noted and discussed. Ultraviolet photolysis of the anions of 5-nitro-6-methyluracil and 5-nitrobarbituric acid results in the formation of iminoxy radicals. Mechanisms of formation of the iminoxy radicals are discussed and results found in this work are compared to results found in single crystals and aqueous solution

Comparison of Nerve-Sparing Radical Hysterectomy and Radical Hysterectomy: a Systematic Review and Meta-Analysis

Directory of Open Access Journals (Sweden)

Zhuowei Xue

2016-05-01

Full Text Available Background/Aims: Radical hysterectomy (RH for the treatment of cervical cancer frequently caused pelvic organ dysfunctions. This study aimed to compare the results of pelvic organ function and recurrence rate after Nerve sparing radical hysterectomy (NSRH and RH treatment through systematic review and meta-analysis. Methods: PubMed, Web of Science and China Knowledge Resource Integrated Database were searched from inception to 25 February 2015. Studies of cervical cancer which reported radical hysterectomy or nerve sparing radical hysterectomy were included. The quality of included studies was evaluated using the guidelines of Cochrane Handbook for Systematic Reviews of Interventions. Statistical analysis was performed using Review Manager 5.3 software (Cochrane Collaboration. Results: A total of 20 studies were finally included. Meta-analysis demonstrated that NSRH was associated with less bladder and anorectal dysfunction than RH. The time to bladder and anorectal function recovery after NSRH was shorter than RH. Patients undergoing NSRH also scored higher than patients undergoing RH at Female Sexual Function Index (FSFI. On the other hand, the local recurrence and overall recurrence rate were similar between NSRH and RH. Conclusion: NSRH may be an effective technique for lowering pelvic organ dysfunction and improving the function recovery without increasing the recurrence rate of cervical cancer.

Flavonoids as scavengers of nitric oxide radical.

NARCIS (Netherlands)

van Acker, S.A.B.E.; Tromp, M.N.J.L.; Haenen, G.R.M.M.; van der Vijgh, W.J.F.; Bast, A.

1995-01-01

Flavonoids are a group of naturally occurring compounds used, e.g., in the treatment of vascular endothelial damage. They are known to be excellent scavengers of oxygen free radicals. Since the nitric oxide radical (

Progress on resonance ionization detection of combustion radicals

International Nuclear Information System (INIS)

Cool, T.A.

1994-01-01

Selective laser ionization techniques are used in our 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. The progress made on the following three separate experiments during the past year is briefly described in this report. Flame Radical Concentration Measurements with VUV Spectroscopy; observation of hyperfine quantum beats in cyanogen; and the spectroscopy of the ClCO radical

Radical production in the radiolysis of benzene

International Nuclear Information System (INIS)

LaVerne, J.A.; Araos, M.S.

1998-01-01

Complete text of publication follows. Benzene is the prototypical aromatic compound and yet the radiation chemistry of the radicals formed in its radiolysis is not well understood. Temporal information on the yield of phenyl radical, the major radical produced in the radiolysis, is important for understanding the radiation chemistry of many other types of aromatic compounds including some polymers. The effects of track structure on the production of phenyl radicals have been examined using iodine-scavenging techniques. The variation of the yields of iodobenzene and the other major molecular products such as biphenyl as a function of iodine concentration gives a good indication of the competition kinetics occurring in particle tracks. Experimental results of the scavenger experiments will be shown and their implications in the radiolysis of condensed hydrocarbons will be discussed

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

Science.gov (United States)

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

2015-01-01

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

Alkyl Radicals as Hydrogen Bond Acceptors: Computational Evidence

DEFF Research Database (Denmark)

Hammerum, Steen

2009-01-01

Spectroscopic, energetic and structural information obtained by DFT and G3-type computational studies demonstrates that charged proton donors can form moderately strong hydrogen bonds to simple alkyl radicals. The presence of these bonds stabilizes the adducts and modifies their structure......, and gives rise to pronounced shifts of IR stretching frequencies and to increased absorption intensities. The hydrogen bond acceptor properties of alkyl radicals equal those of many conventional acceptors, e.g., the bond length changes and IR red-shifts suggest that tert-butyl radicals are slightly better...... acceptors than formaldehyde molecules, while propyl radicals are as good as H2O. The hydrogen bond strength appears to depend on the proton affinity of the proton donor and on the ionization energy of the acceptor alkyl radical, not on the donor-acceptor proton affinity difference, reflecting...

Incontinence and Erectile Dysfunction Following Radical Prostatectomy: A Review

Directory of Open Access Journals (Sweden)

Gerasimos Alivizatos

2005-01-01

Full Text Available Radical prostatectomy remains the treatment of choice for localized prostate cancer in age-appropriate and health-appropriate men. Although cancer control is the most important aspect of a radical prostatectomy, minimization of postoperative morbidity, especially urinary incontinence and erectile dysfunction, is becoming a greater concern. We reviewed recent data available on Medline regarding the incidence, pathophysiology, evaluation, and treatment of incontinence and sexual dysfunction after radical prostatectomy. Health-related quality of life issues have been specifically addressed. Although low incidences of incontinence and erectile dysfunction after radical prostatectomy have been reported in the hands of experienced surgeons, the literature review revealed a great variety, with incontinence rates ranging from 0.3–65.6% and potency rates ranging from 11–87%. Several factors contribute to this wide difference, the most important being the application of a meticulous surgical technique. General and cancer-specific health-related quality of life is not being affected after radical prostatectomy. The incidence of incontinence and erectile dysfunction is higher after radical prostatectomy when compared to the incidence observed when other therapies for localized prostate cancer are applied. However, the majority of the patients undergoing radical prostatectomy would vote for the operation again. Today, avoidance of major complications after radical prostatectomy depends mostly on a high-quality surgical technique. When incontinence or erectile dysfunction persists after radical prostatectomy, the majority of the treated patients can be managed effectively by various methods.

'Los avisadores del fuego': Franz Rosenzweig, Walter Benjamin y Franz Kafka

OpenAIRE

Mate, M. Reyes; Mayorga, Juan

2000-01-01

Hubo pensadores que supieron leer en su tiempo signos de la catástrofe venidera. No eran profetas sino finos analistas. Nos referimos a Rosenzweig, Benjamin y Kafka. Rosenzweig denunció en el "idealismo" de la filosofía que viene desde Jonia y llega hasta Jena la tendencia a un totalitarismo que la convertía en potencialmente en una "ontología de la guerra". Benjamin dejó constancia de la ambigüedad radical del concepto de progreso, tan fundamental para el pensamiento ilustrado. La barbarie, ...

Formation of radical cations of diaryloxadiazoles

International Nuclear Information System (INIS)

Helmstreit, W.

1988-01-01

The nature of the formation of the radical cation of the 2,5-bis-(p-diethylaminophenyl)-1,3,4-oxadiazole (PC) in liquid n-butyl chloride and acetonitrile has been investigated by observing excited state fluorescence and transient absorption using nanosecond pulse radiolysis and laser flash photolysis. The formation of solute oxonium ions has also been observed. At concentrations -4 mol dm -3 the growth time at which the transient absorption of the radical cation reaches the maximum follows the rise time of the electron pulse ( 2 laser yields the solute radical cation in an acetonitrile solution of 2 x 10 -4 mol dm -3 PC via an electronically excited state. Here, the generation time was smaller than 5 ns. The yield of the cation is increased by addition of CCl 4 . A reaction mechanism is proposed that explains the fast cation formation in terms of an exciplex formed by interaction between an electronically excited state of diaryloxadiazole and the ground state of the solvent. This exciplex yields the solute radical cation. (author)

Radical feminists & trans activists truce

OpenAIRE

Mackay, F.

2014-01-01

#GenderWeek: Truce! When radical feminists and trans feminists empathise\\ud Feminist Times\\ud By Finn Mackay \\ud read all #GenderWeek articles.\\ud We wanted to explore the ground between the polarised, entrenched positions in the so-called “TERF-war”. Radical feminists on one pole, trans-inclusionary feminists and trans activists on the other. The disputed territory being women-only space, language and the ever changing legal framework surrounding gender.\\ud Entrenchment leads to stalemate. S...

Leadership Styles for the Five Stages of Radical Change

Science.gov (United States)

1998-04-01

radical change. This article continues prior work on radical change with theory and research on leadership style. The result is a model of radical...every stage of that process. Leadership style and organiza- tional change theory and re- search have ex- isted for de- cades, but have rarely con...phase, inspire and en- ergize them to adopt the change after it Figure 3. Senior Manager Leadership Styles for the Five Phases of Radical Change Phase

Radical scavenging propensity of Cu2 +, Fe3 + complexes of flavonoids and in-vivo radical scavenging by Fe3 +-primuletin

Science.gov (United States)

Jabeen, Erum; Janjua, Naveed Kausar; Ahmed, Safeer; Murtaza, Iram; Ali, Tahir; Hameed, Shahid

2017-01-01

Cu2 + and Fe3 + complexes of three flavonoids (morin or mo, quercetin or quer and primuletin or prim) were synthesized with the objective of improving antioxidant capacities of flavonoids. The radical scavenging activities of pure flavonoids and their metal complexes were assayed to monitor their tendencies towards sequestering of radicals at physiological conditions. The scavenger potencies of metal-flavonoid complexes were significantly higher than those of the parent flavonoids. Further, influence of the solvent polarity on the radical capturing by flavonoids and their metal complexes was in favor for the polar solvent. Fe3 +-prim displayed its radical scavenging ability via up gradation of CAT and SOD activities in in-vivo antioxidant assays.

Muon substituted free radicals

International Nuclear Information System (INIS)

Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Gygax, F.N.; Brinkman, G.A.; Louwrier, P.W.F.; McKenna, D.; Ramos, M.; Webster, B.C.

1984-01-01

Spin polarized energetic positive muons are injected as magnetic probes into unsaturated organic liquids. They are implemented via fast chemical processes ( -10 s) in various molecules. Of particular interest among these are muonium substituted free radicals. The technique allows determination of accurate rate coefficients for fast chemical reactions of radicals. Furthermore, radiochemical processes occuring in picoseconds after injection of the muon are studied. Of fundamental interest are also the structural and dynamical implications of substituting a proton by a muon, or in other terms, a hydrogen atom by a muonium atom. Selected examples for each of these three types of experiments are given. (Auth.)

Hispanoamericanos en Londres a comienzos del siglo XIX

Directory of Open Access Journals (Sweden)

Manuel Ortuño Martínez

1999-01-01

Full Text Available Durante las primeras décadas en del siglo XIX en Londres coincidieron los exiliados liberales procedentes de España y los patriotas insurgentes de las provincias de América. Desde Miranda a Rocafuerte, pasando por Bello, Alvear, Moreno, Sarratea, Teresa de Mier, Palacio Fajardo, Irisarri, Belgrano, los Fagoaga y Alamán, buscaban el apoyo de la Gran Bretaña y el reconocimiento de la independencia, que se retrasó hasta 1824. Con ellos convivió en Londres Xavier Mina el joven liberal radical español que luchó en México contra el absolutismo de Fernando VIIDuring the three first decade of the xix Century in London the Spanish Liberal exiles were living among the insurgents patriots coming from Spanish America, From Miranda to Rocafuerte through Bello, Alvear, Moreno, Sarratea, Teresa de Mier, Palacio Fajardo, Irisarri, Belgrano, the Fagoaga's and Alamán, all of them were seeking for the United Kingdom support and recognition to their Independence, finally arrived at 1824. The yound radical liberal Xavier Mina was there before he goes to México to fight against the Ferdinand VII absolutism.

Fast beam studies of free radical photodissociation

Energy Technology Data Exchange (ETDEWEB)

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

1993-12-01

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

Total free radical species and oxidation equivalent in polluted air.

Science.gov (United States)

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.

Reactions of inorganic free radicals with liver protecting drugs

International Nuclear Information System (INIS)

Gyoergy, I.; Foeldiak, G.; Blazovics, A.; Feher, J.

1990-01-01

Liver protecting drugs, silibinin, a flavonolignane, and the dihydroquinoline derivatives, CH 402 and MTDQ-DA, were shown to inhibit processes in which enzymatically or non-enzymatically generated free radicals were involved. Inorganic free radicals (N 3 , (SCN) 2 - , OH, Trp, CO 2 - , O 2 - ) produced by pulse radiolysis readily react with the compounds, which transform into exceptionally long-lived, unreactive transients. Time evolution of the UV and visible spectra indicate that oxidising radicals form a phenoxyl type radical from silibinin, while OH forms an adduct by attacking, simultaneously, at various sites of the molecule. Superoxide radicals reduce silibinin and oxidise CH 402 and MTDQ-DA. It is concluded that the drugs might exhibit antioxidant behavior in living systems. (author)

Radical Islamism and Failed Developmentalism

OpenAIRE

Rahnema, Saeed

2008-01-01

The rise of radical Islamism in recent years does not limit the applicability of the concept of cultural nationalism. Rather the two are intertwined in ways which this article will attempt to highlight. Islam took specific national forms as modern nation-states arose and the contemporary resurgence of radical Islamism also follows that modern pattern. I examine the emergence of the three most important movements in the Islamic world, namely, the Muslim Brotherhood in Egypt, Jama'at-e Islami i...

Juventud, identidad y cultura: El rock radical vasco en la década de los 80

Directory of Open Access Journals (Sweden)

Paulí DÁVILA BALSERA

2010-03-01

Full Text Available RESUMEN: La transición democrática en el País Vasco supuso el auge de ciertas manifestaciones culturales que trataban de reconstruir las señas de identidad colectiva, a partir de la recuperación del euskara. En un contexto de crisis de valores y de expectativas futuras, una parte de la juventud vasca encontró una forma de expresión musical en el denominado rock radical vasco, de amplia resonancia social, donde se ponía de manifiesto una serie de características propias de este fenómeno musical, además de otras que lo vinculan con la situación política y cultural del país. En este artículo pretendemos mostrar este fenómeno desde una perspectiva más amplia, como es la cultura popular y ciertas manifestaciones de alfabetización y socialización de una parte de la juventud vasca. ABSTRACT: The transition to democracy in the Basque Country involved the rise of certain cultural manifestations attempting to rebuild signs of collective identity, taking the recovery of the Basque language as a starting point. Within a context of crisis of values and future expectations, one part of the Basque youth discovered a form of musical expression in the so called Basque radical rock, having wide social resonance, in which a series of characteristics typical of this musical phenomenon were prominent, in addition to others linking it to the political and cultural situation of the country. In this article we intend to illustrate this phenomenon from a wider perspective, such as popular culture and certain manifestations of literacy and socialisation of one section of the young people.

Hybrid radical energy storage device and method of making

Science.gov (United States)

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.

Repair Activity of trans-Resveratrol toward 2'-Deoxyguanosine Radicals.

Science.gov (United States)

Cheng, Xing; An, Ping; Li, Shujin; Zhou, Liping

2018-04-26

In the present study, the repair activity of trans-resveratrol toward 2'-deoxyguanosine (dGuo) radicals in polar and nonpolar solvents was studied using density functional theory. The hydrogen transfer/proton coupled electron transfer and single electron transfer (SET) mechanisms between trans-resveratrol and dGuo-radicals were considered. Taking into consideration the molar fraction of neutral trans-resveratrol (ROH) and anionic trans-resveratrol (RO - ), the overall rate constants for repairing dGuo-radicals by trans-resveratrol are 9.94 × 10 8 and 2.01 × 10 9 dm 3 mol -1 s -1 in polar and nonpolar solvents, respectively, and the overall rate constant of repairing cation radical (dGuo •+ ) by trans-resveratrol via an SET mechanism is 7.17 × 10 9 dm 3 mol -1 s -1 . The repair activity of RO - toward dGuo-radicals is better than that of ROH, but the repair activity of ROH toward dGuo •+ is better than that of RO - . Unfortunately, neither ROH nor RO - can repair the 2'-deoxyribose radicals of dGuo. It can therefore be concluded that trans-resveratrol is an effective antioxidant for repairing base radicals of dGuo and dGuo •+ . The study can help us understand the repair activity of trans-resveratrol toward dGuo radicals.

Reaction kinetics of resveratrol with thiyl and alkoxyl radicals

International Nuclear Information System (INIS)

Dzeba, I.; Mihaljevic, B.

2011-01-01

Complete text of publication follows. Plant derived resveratrol (trans-3,5,4'-trihydroxystilbene) possesses a broad spectrum of biological activities, one of them are very well known its antioxidative properties. Our work aims to provide kinetic data with regard to the reactivity of resveratrol with uninvestigated short-lived bioradicals, identified as mediators in oxidative lipid degradation processes. Radicals of our interest are alkoxyl radicals, well known propagators of the chain free radical reactions in lipids, and thiyl radicals which protect lipids from their degradation pathway, but at the same time cause the isomerization of the double bonds. In order to investigate these reactions of resveratrol laser flash photolysis was used. On the basis of competitive kinetics the rate constants were determined under pseudo-first order conditions in acetonitrile solutions at room temperature. Thiyl radicals were generated indirectly in solution containing 1-octadecanthiol and photosensitive benzophenone in acetonitrile using the light pulses at 347 nm from ruby laser. Tert-butoxyl radicals were generated directly by peroxide bond cleavage from di-tert-butyl peroxide in acetonitrile by light pulses of Nd:YAG at 355 nm, and ruby at 347 nm. Obtained rate constants for the reactions of resveratrol and radicals generated by laser flash photolysis will be summarized and compared with rare literature data for the rate constants of investigated reactions of resveratrol and other radicals generated by pulse radiolysis.

Historia de una coma. Gadamer y el sentido del ser

OpenAIRE

Vattimo, Gianni

2005-01-01

A partir de la doble posibilidad de traducir en las lenguas románicas la expresión gadameriana «Sein, das verstanden werden kann, ist Sprache» como «El ser, que puede ser comprendido, es lenguaje» o como «El ser que puede ser comprendido es lenguaje», se consideran las importantes repercusiones ontológicas que tendría una interpretación más moderada (y más habitual) de ese enunciado (la primera exhibida), o una lectura más radical y nihilista (la que aquí se defiende) del mismo (la ...

Free radicals created by radiation and aging symptoms

International Nuclear Information System (INIS)

Ashry, O.M.

2012-01-01

The universality of aging implies that its cause is basically the same in all species. A free radical hypothesis of aging has been proposed that the free radicals produced during normal metabolism of the cell over time damage DNA and other macromolecules leading to degenerative diseases, malignancies, and eventual death of vital cells which in turn causes aging and death of the organism. This hypothesis is supported by several observations. Radiation produces its biologic effect through free radical formation and causes premature aging. Second, the age pigment lipo fuscin is associated with lipid peroxidation. The hypothesis that oxygen radicals play a role in aging is also supported by the observation that, in general, long-lived species produce less endogenous free oxygen radicals because of their lower metabolic rate. Long-lived animals also have more superoxide dismutase than do their short-lived counterparts, and animal species with the longest lifespan have the highest levels of superoxide dismutase. Oxidative DNA damage is rapidly and effectively repaired. It has been estimated that there are several thousand oxidative DNA damage sites in a human cell every day, and the majority of these are repaired. However, a small fraction of unrepaired lesions could cause permanent changes in DNA and might be a major contributor to aging and cancer. A consequence of the free radical hypothesis of aging is the idea that free radical scavenging agents might be used to prevent aging. (author)

Characterization of fatty acids, bioactive lipids, and radical scavenging activity of Canterbury bells seed oil

Directory of Open Access Journals (Sweden)

Hassanien, M. F.R.

2014-06-01

Full Text Available The aim of this study was to characterize the chemical composition and radical scavenging activity of Canterbury bells (Campanula medium seed oil. C. medium seeds contained 9.2% extractable oil. The lipid classes, fatty acids, phytosterol and tocopherol composition of C. medium seed oil were determined. The amount of neutral lipids in the oil was the highest, followed by glycolipids and phospholipids. Linoleic and oleic were the main fatty acids. C. medium oil is characterized by high levels of phytosterols and β-sitosterol was the main compound. β-Tocopherol constituted 42.5% of the total tocopherol content followed by γ-tocopherol. The radical scavenging activity (RSA toward 1,1-diphenyl-2-picrylhydrazyl (DPPH radicals and galvinoxyl radicals of C. medium oil were higher than those of extra virgin olive oil. The diverse potential uses of C. medium oil may make this plant industrially important.El objetivo de este estudio fue caracterizar la composición química y la actividad de captación de radicales de aceites de semillas de campanillas de Canterbury (Campanula medium. Las semillas de C. medium contenían 9,2 % de aceite extraíble. Se determinó la composición de las diferentes clases de lípidos, ácidos grasos, fitoesteroles y tocoferoles. La cantidad de lípidos neutros en el aceite fue mayoritario, seguido de glicolípidos y fosfolípidos. Linoleico y oleico fueron los ácidos grasos principales. El aceite de C. medium se caracteriza por altos niveles de fitoesteroles y β-sitosterol fue el compuesto principal. β-tocoferol constituía 42,5 % del contenido total de tocoferol seguido de γ-tocoferol. La actividad de captación de radicales (RSA a 1,1-difenil-2- picrilhidrazil (DPPH y radicales galvinoxil de C. medium fueron superiores a las de aceite de oliva virgen extra. Los diversos usos potenciales de los aceites de C. medium pueden hacer que esta planta pueda ser importante industrialmente.

Multiple free-radical scavenging (MULTIS) capacity in cattle serum.

Science.gov (United States)

Sueishi, Yoshimi; Kamogawa, Erisa; Kimura, Anna; Kitahara, Go; Satoh, Hiroyuki; Asanuma, Taketoshi; Oowada, Shigeru

2017-01-01

Multiple free-radical scavenging (MULTIS) activity in cattle and human sera was evaluated with electron spin resonance spectroscopy. Scavenging rates against six active species, namely hydroxyl radical, superoxide anion, alkoxyl radical, alkylperoxyl radical, methyl radical, and singlet oxygen were quantified. The difference in the electron spin resonance signal intensity in the presence and absence of the serum was converted into the scavenging rates. Comparative MULTIS measurements were made in sera from eight beef cattle, three fetal calves and fifteen healthy human volunteers. Further, we determined the MULTIS value of albumin, the most abundant component in serum. MULTIS values in cattle sera indicated higher scavenging activity against most free radical species tested than human sera. In particular, cattle serum scavenging activities against superoxide and methyl radical were higher than human serum by 2.6 and 3.7 fold, respectively. In cattle serum, albumin appears to play a dominant role in MULTIS activity, but in human serum that is not the case. Previous data indicated that the abundance of uric acid in bovine blood is nearly 80% less than humans; however, this difference does not explain the deviation in MULTIS profile.

Aerosol Fragmentation Driven by Coupling of Acid-Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals.

Science.gov (United States)

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

2017-08-10

A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps with physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular

Photoionization of the OH radical

International Nuclear Information System (INIS)

Dehmer, P.M.

1985-01-01

The hydroxyl radical (OH) is one of the most thoroughly studied free radicals because of its importance in atmospheric chemistry, combustion processes, and the interstellar medium. Detailed experimental and theoretical studies have been performed on the ground electronic state (X 2 PI/sub i/) and on the four lowest bound excited electronic states (A 2 Σ + , B 2 Σ + , D 2 Σ - , and C 2 Σ + ). However, because it is difficult to distinguish the spectrum of OH from the spectra of the various radical precursors, the absorption spectrum in the wavelength region below 1200 A has not been well characterized. In the present work, the spectrum of OH has been determined in the wavelength region from 750 to 950 A using the technique of photoionization mass spectrometry. This technique allows complete separation of the spectrum of OH from that of the other components of the discharge and permits the unambiguous determination of the spectrum of OH

La Ley 1122 del 2007.

Directory of Open Access Journals (Sweden)

Zoilo Cuéllar-Montoya

2007-03-01

Fueron numerosas las reuniones que sostuvieron las directivas de la Academia con diferentes Senadores – Dilian Francisca Toro, Rafael Pardo Rueda, Alejandro Guerra, Eduardo Benítez, Flor Gnecco, Alfonso Angarita Baracaldo, Germán Vargas Lleras y muchos más – y con el Ministro de la Protección Social y su Viceministro de Salud, con el fin de impulsar nuestro proyecto. Sin embargo, primó el denominado 052, de iniciativa gubernamental, impulsado por el propio Ministro de la Protección y por un grupo de Senadores liderados por Eduardo Benítez el cual, al final, supuestamente acumulado a los 12 restantes, terminó hundiéndose al finalizar la legislatura que terminó en junio de 2006, al impulso de fuerzas negativas soterradas. Al iniciarse la actual legislatura, bajo la Presidencia del Senado y del Congreso de la Senadora Dilian Francisca Toro, ésta radicó un nuevo Proyecto, y lo propio hizo el Ministerio de la Protección Social y diferentes sectores políticos; lideró la acumulación de un número importante de proyectos e impulsó, en Cámara y Senado, la consideración del proyecto acumulado, hasta obtener su aprobación total, la cual se convirtió en la Ley 1122 de 2007, en relación a la cual el Doctor Herman Redondo, Vicepresidente de la Asociación Médica Colombiana, verdadero experto en el tema y asesor externo de nuestra Comisión de Salud, realizó una concienzuda crítica, sobre la que me apoyo para la redacción de esta nota...

Mechanisms of free radical-induced damage to DNA.

Science.gov (United States)

Dizdaroglu, Miral; Jaruga, Pawel

2012-04-01

Endogenous and exogenous sources cause free radical-induced DNA damage in living organisms by a variety of mechanisms. The highly reactive hydroxyl radical reacts with the heterocyclic DNA bases and the sugar moiety near or at diffusion-controlled rates. Hydrated electron and H atom also add to the heterocyclic bases. These reactions lead to adduct radicals, further reactions of which yield numerous products. These include DNA base and sugar products, single- and double-strand breaks, 8,5'-cyclopurine-2'-deoxynucleosides, tandem lesions, clustered sites and DNA-protein cross-links. Reaction conditions and the presence or absence of oxygen profoundly affect the types and yields of the products. There is mounting evidence for an important role of free radical-induced DNA damage in the etiology of numerous diseases including cancer. Further understanding of mechanisms of free radical-induced DNA damage, and cellular repair and biological consequences of DNA damage products will be of outmost importance for disease prevention and treatment.

Efecto del Hierro en el Desarrollo de las Raíces de las Plantas

Directory of Open Access Journals (Sweden)

Correa Velásquez Jairo

1964-08-01

Full Text Available Se investigó el efecto del hierro en el desarrollo de las raíces del cacao, el café y el fríjol. También se observó la velocidad de recuperación de la clorofila en plantas cloróticas de cacao y café, al agregarles cantidades crecientes de hierro, y el efecto de dicha recuperación sobre el desarrollo radical. Además, se estudió el grado de absorción y movilización de Fe50 en plantas de cacao, y el efecto de distintas dosis de hierro en el crecimiento de raíces aisladas cacao, café y fríjol. Las plantas fueron cultivadas en el invernadero en solución HoagIand N° 2 sin Fe y las raíces para cultivo se obtuvieron de semillas germinadas en el laboratorio. Se usaron plantas de cacao del clon uf 668 de 3 meses y de café (variedad caturra con la misma edad. El hierro radiactivo utilizado fue en forma de cloruro (Fe59 cl 3 y el agregado a la solución o al follaje, en forma de quelato (Fe E. D. T. A.. Las adiciones de este elemento se hicieron cuando las plantas mostraban síntomas característicos de su deficiencia. Hubo una recuperación casi total de la clorosis y tanto el volumen como la longitud radical aumentaron con las aplicaciones crecientes de hierro, aunque la longitud relativa de los tallos mostró una tendencia decreciente. En las hojas de cacao se presentó una acumulación del Fe y su movilización hacia los demás órganos de la planta fue lenta y en proporción reducida en relación con el total absorbido. Igual cosa sucedió con el Fe50 suministrado a las raíces. No se pudieron observar los efectos del Fe en el crecimiento de raíces aisladas de cacao, café y fríjol, pues el desarrollo fue muy reducido, debido a que la rápida oxidación de los tejidos (al separar aquéllas del resto de la planta redujo la viabilidad a unos pocos días.

Acyclic diastereoselection in prochiral radical addition to prochiral olefins.

Science.gov (United States)

Sibi, Mukund P; Rheault, Tara R; Chandramouli, Sithamalli V; Jasperse, Craig P

2002-03-27

The stereochemical preference (syn or anti) when prochiral radicals add to prochiral acceptors is of fundamental interest. The primary focus of this research was to determine which factors influence the relative stereochemistry between the beta and gamma chiral centers when these are formed concurrently. While moderate diastereoselectivity was found for addition of alkyl (6a-d) and alpha-alkoxy radicals (16a-c) (15:1 anti). Steric influence in alkyl radical additions was difficult to evaluate due to decreased reactivity when using bulky reaction partners; however, more reactive alpha-alkoxy radicals, it was found that increasing steric bulk leads to moderate increases in selectivity. In addition, higher selectivity was observed when employing lanthanide Lewis acids whose environment (reactivity) was modified using achiral additives, suggesting a potentially simple means for selectivity enhancements in radical reactions. Overall these results indicate that significant stereoelectronic effects are necessary to achieve high levels of selectivity in prochiral radical additions to prochiral acceptors.

El decadentismo en la derecha radical contemporánea

Directory of Open Access Journals (Sweden)

Miguel Ángel Simón Gómez

2007-07-01

Full Text Available The main concern this articles deals with is, first, the elusive conceptual definition of the «radical right». In the last years a, so called, new consensus, has been developed in the literature of this field. The core of this new consensus about the radical right is the palingentic form of nationalism, form this pant of view the decadentism and the claim for a social renewal is a central point in the political thought of the radical right. In this article we deal with the decadent subjects of the radical right, pointing mainly to the apocalyptic tone of some major contributors of the radical right in the interwar France and Germany. In the second part we analyze the role of decadentism in the cotemporary work of some relevant authors of the European radical right, Alain de Benoist and Julius Evola. Finally we translate their idea of decadence of Europe to the political arena as shown the discourses of some right extremist European parties.

Peces del Noroeste del Ecuador

OpenAIRE

Barriga, Ramiro

1994-01-01

La ictiofauna del occidente del Ecuador es poco conocida. Los peces del noroccidente son diferentes a los del suroccidente del Ecuador. 34 familias y 82 especies fueron colectadas que equivale al 11 % de las especies de peces continentales registradas en el Ecuador. Icteogeográficamente se sabe que la costa ecuatoriana posee dos provincias: la del Pacifico Norte y la del Guayas, se determinó que el límite de las dos provincias es el río Santiago ya que las especies del mencionado río so...

Tin-free enantioselective radical reactions using silanes.

Science.gov (United States)

Sibi, Mukund P; Yang, Yong-Hua; Lee, Sunggi

2008-12-04

Readily available hexyl silane is an excellent choice as a H-atom donor and a chain carrier in Lewis acid mediated enantioselective radical reactions. Conjugate radical additions to alpha,beta-unsaturated imides at room temperature proceed in good yields and excellent enantioselectivities.

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

Directory of Open Access Journals (Sweden)

Jose R. Colombo Jr.

2007-01-01

Full Text Available PURPOSE: To report the 5-year oncological outcomes of patients undergoing laparoscopic radical nephrectomy for renal cancer compared to a cohort of patients undergoing open radical nephrectomy. METHODS: We retrospectively analyzed the data of 88 patients undergoing radical nephrectomy for renal cell carcinoma prior to January 2000. Of these, 45 patients underwent laparoscopic radical nephrectomy, and 43 patients underwent open radical nephrectomy. Inclusion criteria comprised clinically organ-confined tumors of 15 cm or less in size without concomitant lymphadenopathy or vena cava thrombus. Oncological follow-up data were obtained from charts, radiological reports, and phone calls to patients or their families, and were calculated from the date of surgery to the date of last appointment with physician or date of death. RESULTS: All laparoscopic procedures were completed without open conversion. On comparing the laparoscopic radical nephrectomy and open radical nephrectomy groups, mean tumor size was 5. 8 vs 6.2 cm (P = . 44, mean blood loss was 183 vs 461 mL (P = . 004, and mean operative time was 2.8 vs 3.7 hrs (P OBJETIVO: Relatar os resultados oncológicos após 5 anos de seguimento em pacientes submetidos a nefrectomia radical laparoscópica para tratamento do câncer renal, comparando esses com os resultados obtidos com um grupo de pacientes submetidos a nefrectomia radical aberta. MÉTODOS: Foram analisadas retrospectivamente as informações obtidas de 88 pacientes submetidos a nefrectomia radical para o tratamento do carcinoma renal realizadas previamente a Janeiro de 2000. Destes pacientes, 45 foram tratados com nefrectomia radical laparoscópica e 43 com nefrectomia radical aberta. Foram incluídos pacientes com tumores localizados com tamanho máximo de 15 cm, sem adenopatia ou sinal de envolvimento de veia renal na avaliação radiologica pré-operatória. As informações sobre o seguimento dos pacientes foram obtidas a partir de

Synthesis of fused azole-piperidionoses: A free radical cyclization approach

Energy Technology Data Exchange (ETDEWEB)

Marco-Contelles, Jose; Alhambra Jimenez, Carolina [Instituto de Quimica Organica General (CSIC), Madrid (Spain)

1999-08-01

A new strategy has been reported for the synthesis of fused azole-piperidinoses featuring and unprecedented and very efficient 6-exo-trig free radical cyclization onto heterocyclic sugar templates. These compounds are key intermediates for the synthesis of known or analogues of azole-glycosidase inhibitors. In this communication we describe our recent and successful results on the synthesis of fused triazole-piperidinoses. Radical precursors have been prepared by standard methodologies from 1, 2:5, 6-bis-O-isopropylidene-{alpha}-D-glucofuranose (4) via triazoles linked at C3 with {beta}-orientation, readily obtained by 1, 3-dipolar cycloaddition of azide 5 with diethyl acetylenedicarboxylate or methyl propiolate, and by S{sub N}2 displacement of the tosylate at C3 with 1, 2, 4-triazole in compound 20. The key 6-exp-trig free radical cyclizations proceeded in the usual conditions [tributyltin hydride or tris(trimethylsily)silane, AIBN, toluene] yielding the azaannulated sugars 9, 11, 19 and 23 in good or excellent yields. A mechanism for these cyclizations has been proposed. [Spanish] Se ha informado una nueva estrategia para la sintesis azol-piperidinosas fusionadas mediante una ciclizacion 6-exo-trig muy eficiente y sin precedentes, sobre plantillas de azucares heterociclicos. Estos compuestos son intermediarios claves para la sintesis de inhibidores de azol-glicosidasa conocidos analogos de ellos. En esta comunicacion describimos nuestros resultados recientes y exitosos sobre la sintesis de triazol-piperidinosas. Los precursores de radicales fueron preparados por la metodologia usual a partir de 1, 2:5, 6-bis-O-isopropiliden-{alpha}-D-glucofuranosa (4) via triazoles unidos en C3, con orientacion {beta}, los cuales se obtienen facilmente por cicloadicion 1, 3-dipolar de la azida 5 con acetilendicarboxilato de dietilo o propiolato de metilo y por desplazamiento S{sub N}2 del tosilato en C3 con 1, 2, 4-triazol en el compuesto 20. Las ciclizaciones 6-exo

Psychopathology according to behaviorism: a radical restatement.

Science.gov (United States)

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.

Hearing Status after Radical Mastoidectomy without Tympanoplasty.

Science.gov (United States)

Khan, Shamaila Nawaz; Udaipurwala, Iqbal Hussain; Mehmood, Talat; Rahat, Zahid Mehmood

2017-12-01

To find out the impairment of hearing associated with radical mastoidectomy by measuring the quantitative difference in the functional hearing level before and after radical mastoidectomy operation without tympanoplasty. Cross-sectional comparative study. Department of Otorhinolaryngology and Head Neck Surgery, Bahawal Victoria Hospital, Bahawalpur and PNS Shifa Hospital, Karachi, from November 2009 to January 2013. Eighty-five patients, diagnosed clinically as chronic suppurative otitis media with extensive cholesteatoma having history of ear discharge and hearing impairment for more than 6 weeks duration and requiring radical mastoidectomy for treatment, were included in this study. Pure tone audiogram was done before and after radical mastoidectomy. Hearing impairment was compared in each patient before and after the operation. Among the 85 patients, 54 (63.5%) were males and 31 (36.5%) were females, with the age ranged between 18 to 63 years, mean age being 42.31 4.8 years. The mean increase in hearing loss after radical mastoidectomy in air conduction was 7.19 dB, bone conduction was 4.16 dB, and air-bone gap was 3.75 dB (0.001). The ear became dry and safe in 82 patients (96.5%) out of a total of 85, and only 3 patients required revision surgery at a second stage. Radical mastoidectomy has a least negligible effect on hearing status and one should not limit this technique due to the concern of aggravated hearing in patients with extensive cholesteatoma at the cost of dry and safe ears, which should be of prime importance.

Functionalized graphene quantum dots loaded with free radicals combined with liquid chromatography and tandem mass spectrometry to screen radical scavenging natural antioxidants from Licorice and Scutellariae.

Science.gov (United States)

Wang, Guoying; Niu, XiuLi; Shi, Gaofeng; Chen, Xuefu; Yao, Ruixing; Chen, Fuwen

2014-12-01

A novel screening method was developed for the detection and identification of radical scavenging natural antioxidants based on a free radical reaction combined with liquid chromatography with tandem mass spectrometry. Functionalized graphene quantum dots were prepared for loading free radicals in the complex screening system. The detection was performed with and without a preliminary exposure of the samples to specific free radicals on the functionalized graphene quantum dots, which can facilitate charge transfer between free radicals and antioxidants. The difference in chromatographic peak areas was used to identify potential antioxidants. This is a novel approach to simultaneously evaluate the antioxidant power of a component versus a free radical, and to identify it in a vegetal matrix. The structures of the antioxidants in the samples were identified using tandem mass spectrometry and comparison with standards. Fourteen compounds were found to possess potential antioxidant activity, and their free radical scavenging capacities were investigated. The order of scavenging capacity of 14 compounds was compared according to their free radical scavenging rate. 4',5,6,7-Tetrahydroxyflavone (radical scavenging rate: 0.05253 mL mg(-1) s(-1) ) showed the strongest capability for scavenging free radicals. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unimolecular reaction dynamics of free radicals

International Nuclear Information System (INIS)

Terry A. Miller

2006-01-01

Free radical reactions are of crucial importance in combustion and in atmospheric chemistry. Reliable theoretical models for predicting the rates and products of these reactions are required for modeling combustion and atmospheric chemistry systems. Unimolecular reactions frequently play a crucial role in determining final products. The dissociations of vinyl, CH2= CH, and methoxy, CH3O, have low barriers, about 13,000 cm-1 and 8,000 cm-1, respectively. Since barriers of this magnitude are typical of free radicals these molecules should serve as benchmarks for this important class of reactions. To achieve this goal, a detailed understanding of the vinyl and methoxy radicals is required. Results for dissociation dynamics of vinyl and selectively deuterated vinyl radical are reported. Significantly, H-atom scrambling is shown not to occur in this reaction. A large number of spectroscopic experiments for CH3O and CHD2O have been performed. Spectra recorded include laser induced fluorescence (LIF), laser excited dispersed fluorescence (LEDF), fluorescence dip infrared (FDIR) and stimulated emission pumping (SEP). Such results are critical for implementing dynamics experiments involving the dissociation of methoxy

Neuroprotection by Radical Avoidance: Search for Suitable Agents

Directory of Open Access Journals (Sweden)

Rüdiger Hardeland

2009-12-01

Full Text Available Neurodegeneration is frequently associated with damage by free radicals. However, increases in reactive oxygen and nitrogen species, which may ultimately lead to neuronal cell death, do not necessarily reflect its primary cause, but can be a consequence of otherwise induced cellular dysfunction. Detrimental processes which promote free radical formation are initiated, e.g., by disturbances in calcium homeostasis, mitochondrial malfunction, and an age-related decline in the circadian oscillator system. Free radicals generated at high rates under pathophysiological conditions are insufficiently detoxified by scavengers. Interventions at the primary causes of dysfunction, which avoid secondary rises in radical formation, may be more efficient. The aim of such approaches should be to prevent calcium overload, to reduce mitochondrial electron dissipation, to support electron transport capacity, and to avoid circadian perturbations. l-Theanine and several amphiphilic nitrones are capable of counteracting excitotoxicity and/or mitochondrial radical formation. Resveratrol seems to promote mitochondrial biogenesis. Mitochondrial effects of leptin include attenuation of electron leakage. Melatonin combines all the requirements mentioned, additionally regulates anti- and pro-oxidant enzymes and is, with few exceptions, very well tolerated. In this review, the perspectives, problems and limits of drugs are compared which may be suitable for reducing the formation of free radicals.

Analysis of radicals induced in irradiated foods

International Nuclear Information System (INIS)

Kishida, Keigo; Kaimori, Yoshihiko; Kawamura, Shoei; Sakamoto, Yuhki; Nakamura, Hideo; Ukai, Mitsuko; Kikuchi, Masahiro; Shimoyama, Yuhei; Kobayashi, Yasuhiko

2012-01-01

By electron spin resonance (ESR) spectroscopy, we revealed free radicals in γ-ray irradiated foods; black pepper, green coffee bean and ginseng. We also analyzed the decay behavior of radiation induced free radicals during storage of irradiated foods. The ESR spectrum of experimental irradiated foods consists of a sextet signal centered at g=2.0 and a singlet signal at the same g-value position and a singlet signal at g=4.0. The singlet signal at g=2.0 is originated from organic free radicals and its peak intensity showed the dependence of γ-ray irradiation dose levels. The signal intensity was decreased during storage. Only after 3 hours of radiation treatment the peak intensity was decreased fast and after that the intensity was decreased slowly. The relaxation times, T 1 and T 2 , of radiation induced free radicals showed the variations before and after irradiation. During long time storage period it was shown that T 1 was increased and T 2 was decreased. By analysis of decay process using the simulation methods based on the theory of reaction speed, it is considered that at least two kinds of radicals were induced in irradiated foods during long time storage. (author)

Electron spin resonance spectroscopy of organic radicals spectroscopy of organic radicals

CERN Document Server

Gerson, Fabian

2006-01-01

""This book should serve as a comprehensive one-volume source for finding what is known about the splitting constants and g factors of virtually all types of organic radicals."" Journal of the American Chemistry Society, 2004, Vol. 126 No. 20

Laparoscopically assisted vaginal radical trachelectomy

International Nuclear Information System (INIS)

Bielik, T.; Karovic, M.; Trska, R.

2013-01-01

Purpose: Radical trachelectomy is a fertility-sparing procedure with the aim to provide adequate oncological safety to patients with cervical cancer while preserving their fertility. The purpose of this study was to retrospectively evaluate, in a series of 3 patients, the feasibility, morbidity, and safety of laparoscopically assisted vaginal radical trachelectomy for early cervical cancer. Patients and Methods: Three non consecutive patients with FIGO stage IA1 and IB1 cervical cancer was evaluated in a period of years 2008 - 2011. The patients underwent a laparoscopic pelvic lymphadenectomy and radical parametrectomy class II procedure according to the Piver classification. The section of vaginal cuff, trachelectomy, permanent cerclage and isthmo-vaginal anastomosis ware realised by vaginal approach. Results: The median operative time, the median blood loss and the mean number of resected pelvic nodes was comparable with published data. Major intraoperative complications did not occur and no patient required a blood transfusion. The median follow-up time was 33 (38-59) months. One vaginal recurrence occurred in 7 months after primary surgery. The patient was underwent a radicalisation procedure and adjuvant oncologic therapy and now is free of disease. Conclusions: Laparoscopically assisted vaginal radical trachelectomy (LAVRT)may be an alternative in fertility-preserving surgery for early cervical cancer. The procedure offers patients potential benefits of minimally invasive surgery with adequate oncological safety, but it should be reserved for oncologic surgeons trained in advanced laparoscopic procedures. (author)

Gamma-sterilization-induced radicals in biodegradable drug delivery systems

International Nuclear Information System (INIS)

Maeder, K.; Swartz, H.M.; Domb, A.

1996-01-01

Electron paramagnetic resonance (EPR) spectroscopy (1.2 and 9.25 GHz, 25 o C) was used to characterize free radicals in gamma-ray sterilized biodegradable polymers of the type which are in clinical use. Free radicals were detected in all irradiated polymer samples. The temperature of irradiation (25 o vs dry ice temperature) had only a minor influence on the yield of radicals and the shape of the EPR spectra. In contrast, the composition of the polymers and the drugs incorporated in them did strongly influence the amount of radiation-induced free radicals and their reactivity. In general, polymers with high melting points and crystallinity had the highest yields of radicals observable at room temperature. We were able to use the free radicals induced by the usual sterilization procedures to follow the penetration of water and the degradation of the polymers in vitro and in vivo. The ability of in vivo EPR to follow drug delivery noninvasively and continuously in vivo, using the free radicals induced in the usual sterilization process indicates that this approach could be applied immediately for the characterization of these drug delivery systems in experimental animals and in the near future should be able to be used in human subjects. (author)

Moment matrices, border bases and radical computation

NARCIS (Netherlands)

B. Mourrain; J.B. Lasserre; M. Laurent (Monique); P. Rostalski; P. Trebuchet (Philippe)

2013-01-01

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

Moment matrices, border bases and radical computation

NARCIS (Netherlands)

B. Mourrain; J.B. Lasserre; M. Laurent (Monique); P. Rostalski; P. Trebuchet (Philippe)

2011-01-01

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

Free Radical Scavenging and Cellular Antioxidant Properties of Astaxanthin.

Science.gov (United States)

Dose, Janina; Matsugo, Seiichi; Yokokawa, Haruka; Koshida, Yutaro; Okazaki, Shigetoshi; Seidel, Ulrike; Eggersdorfer, Manfred; Rimbach, Gerald; Esatbeyoglu, Tuba

2016-01-14

Astaxanthin is a coloring agent which is used as a feed additive in aquaculture nutrition. Recently, potential health benefits of astaxanthin have been discussed which may be partly related to its free radical scavenging and antioxidant properties. Our electron spin resonance (ESR) and spin trapping data suggest that synthetic astaxanthin is a potent free radical scavenger in terms of diphenylpicryl-hydrazyl (DPPH) and galvinoxyl free radicals. Furthermore, astaxanthin dose-dependently quenched singlet oxygen as determined by photon counting. In addition to free radical scavenging and singlet oxygen quenching properties, astaxanthin induced the antioxidant enzyme paroxoanase-1, enhanced glutathione concentrations and prevented lipid peroxidation in cultured hepatocytes. Present results suggest that, beyond its coloring properties, synthetic astaxanthin exhibits free radical scavenging, singlet oxygen quenching, and antioxidant activities which could probably positively affect animal and human health.

Reaction kinetics of resveratrol with tert-butoxyl radicals

International Nuclear Information System (INIS)

Džeba, Iva; Pedzinski, Tomasz; Mihaljević, Branka

2012-01-01

The rate constant for the reaction of t-butoxyl radicals with resveratrol was studied under pseudo-first order conditions. The rate constant was determined by measuring the phenoxyl radical formation rate at 390 nm as function of resveratrol concentration in acetonitrile. The rate constant was determined to be 6.5×10 8 M −1 s −1 . This high value indicates the high reactivity consistent with the strong antioxidant activity of resveratrol. - Highlights: ► tert-butoxyl radicals were generated directly using laser flash photolysis. ► Rate constant was determined by the phenoxyl radical formation rate in acetonitrile. ► Rate constant was determined to be 6.5×10 8 M −1 s −1 .

Photoisomerization and photodissociation dynamics of reactive free radicals

Energy Technology Data Exchange (ETDEWEB)

Bise, Ryan T. [Univ. of California, Berkeley, CA (United States)

2000-08-01

The photofragmentation pathways of chemically reactive free radicals have been examined using the technique of fast beam photofragment translational spectroscopy. Measurements of the photodissociation cross-sections, product branching ratios, product state energy distributions, and angular distributions provide insight into the excited state potential energy surfaces and nonadiabatic processes involved in the dissociation mechanisms. Photodissociation spectroscopy and dynamics of the predissociative $\\tilde{A}$²A₁ and $\\tilde{B}$²A₂ states of CH₃S have been investigated. At all photon energies, CH₃ + S(³P_j), was the main reaction channel. The translational energy distributions reveal resolved structure corresponding to vibrational excitation of the CH₃ umbrella mode and the S(³P_j) fine-structure distribution from which the nature of the coupled repulsive surfaces is inferred. Dissociation rates are deduced from the photofragment angular distributions, which depend intimately on the degree of vibrational excitation in the C-S stretch. Nitrogen combustion radicals, NCN, CNN and HNCN have also been studied. For all three radicals, the elimination of molecular nitrogen is the primary reaction channel. Excitation to linear excited triplet and singlet electronic states of the NCN radical generates resolved vibrational structure of the N₂ photofragment. The relatively low fragment rotational excitation suggests dissociation via a symmetric C_2V transition state. Resolved vibrational structure of the N₂ photofragment is also observed in the photodissociation of the HNCN radical. The fragment vibrational and rotational distributions broaden with increased excitation energy. Simple dissociation models suggest that the HNCN radical isomerizes to a cyclic intermediate (c-HCNN) which then dissociates via a tight cyclic

Uma análise behaviorista radical dos sonhos A radical behaviorist analysis of the dreams

Directory of Open Access Journals (Sweden)

Francynete Melo e Silva

2000-01-01

Full Text Available Embora não haja um consenso acerca de questões sobre o que são os sonhos, porque sonhamos, etc., a maioria dos estudos sobre a natureza dos sonhos concorda que ela está relacionada a condições internas do organismo. Contrariamente, o behaviorismo radical analisa os sonhos como comportamentos privados, sendo produtos das histórias filogenética, ontogenética e cultural. Neste sentido, este trabalho tem como objetivo analisar os sonhos a partir da perspectiva behaviorista radical, considerando-os como comportamentos perceptuais encobertos, argumentando-se que são aprendidos. Afirma-se que a interpretação dos sonhos é impossível se não se conhecem as contingências de reforço com as quais a pessoa está interagindo.In spite of the fact that there is no consensus concerning questions about the nature and origin of dreams, the majority of the studies on the nature of the dreams agrees that they are related to internal conditions of the organism. As opposed to that notion, the radical behaviorism analyses the dreams as private behaviors and, thus, as products of philogenetical, ontogenetical, and cultural histories. In this sense, this paper aims to analyze the dreams from a radical behaviorism perspective, considering them as private events, perceptual behaviors, and arguing that they are learned processes. It is asserted that the dreams interpretation is impossible if the contingencies that control such activity are unknown.

Microbial fuel cell as a free-radical scavenging tool

International Nuclear Information System (INIS)

Koleva, Ralitza; Yemendzhiev, Hyusein; Nenov, Valentin

2017-01-01

Microbial fuel cells (MFCs) are known for their capability to directly convert organic substrates into electricity by the biochemical activity of specific microorganisms. Availability of a proper terminal electron acceptor is crucial for this process. Free radicals, with their one or more unpaired electrons, are extremely reducible and could be considered as electron acceptors in terms of cathodic processes in MFC. During this reduction, free radicals could be transformed in the same manner as they are transformed by antioxidants. The present study investigated this opportunity by utilization of 2,2-diphenyl-1-picrylhydrazyl (150 mmol/dm"3 methanol solution) as a free-radical molecule. During the studied process, over 90% radical neutralization was observed in less than 16 hours. The results obtained demonstrate for the first time the potential of MFC type bioelectrochemical systems to serve as a free-radical scavenging tool and to provide antioxidant and anti-radical activity. In this way, this study opens a completely new field of research and application of bio-electrochemical systems

Moment matrices, border bases and radical computation

NARCIS (Netherlands)

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

2013-01-01

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

Inhomogeneous ensembles of radical pairs in chemical compasses

Science.gov (United States)

Procopio, Maria; Ritz, Thorsten

2016-11-01

The biophysical basis for the ability of animals to detect the geomagnetic field and to use it for finding directions remains a mystery of sensory biology. One much debated hypothesis suggests that an ensemble of specialized light-induced radical pair reactions can provide the primary signal for a magnetic compass sensor. The question arises what features of such a radical pair ensemble could be optimized by evolution so as to improve the detection of the direction of weak magnetic fields. Here, we focus on the overlooked aspect of the noise arising from inhomogeneity of copies of biomolecules in a realistic biological environment. Such inhomogeneity leads to variations of the radical pair parameters, thereby deteriorating the signal arising from an ensemble and providing a source of noise. We investigate the effect of variations in hyperfine interactions between different copies of simple radical pairs on the directional response of a compass system. We find that the choice of radical pair parameters greatly influences how strongly the directional response of an ensemble is affected by inhomogeneity.

Loading of free radicals on the functional graphene combined with liquid chromatography-tandem mass spectrometry screening method for the detection of radical-scavenging natural antioxidants.

Science.gov (United States)

Wang, Guoying; Shi, Gaofeng; Chen, Xuefu; Chen, Fuwen; Yao, Ruixing; Wang, Zhenju

2013-11-13

A novel free radical reaction combined with liquid chromatography electrospray ionization tandem mass spectrometry (FRR-LC-PDA-ESI/APCI-MS/MS) screening method was developed for the detection and identification of radical-scavenging natural antioxidants. Functionalized graphene was prepared by chemical method for loading free radicals (superoxide radical, peroxyl radical and PAHs free radical). Separation was performed with and without a preliminary exposure of the sample to specific free radicals on the functionalized graphene, which can facilitate reaction kinetics (charge transfers) between free radicals and potential antioxidants. The difference in chromatographic peak areas is used to identify potential antioxidants. The structure of the antioxidants in one sample (Swertia chirayita) is identified using MS/MS and comparison with standards. Thirteen compounds were found to possess potential antioxidant activity, and their free radical-scavenging capacities were investigated. The thirteen compounds were identified as 1,3,5-trihydroxyxanthone-8-O-β-D-glucopyranoside (PD1), norswertianin (PD2), 1,3,5,8-tetrahydroxyxanthone (PD3), 3, 3', 4', 5, 8-penta hydroxyflavone-6-β-D-glucopyranosiduronic acid-6'-pentopyranose-7-O-glucopyranoside (PD4), 1,5,8-trihydroxy-3-methoxyxanthone (PD5), swertiamarin (PS1), 2-C-β-D-glucopyranosyl-1,3,7-trihydroxylxanthone (PS2), 1,3,7-trihydroxylxanthone-8-O-β-D-glucopyranoside (PL1), 1,3,8-trihydroxyl xanthone-5-O-β-D-glucopyranoside (PL2), 1,3,7-trihydroxy-8-methoxyxanthone (PL3), 1,2,3-trihydroxy-7,8-dimethoxyxanthone (PL4), 1,8-dihydroxy-2,6-dimethoxy xanthone (PL5) and 1,3,5,8-tetramethoxydecussatin (PL6). The reactivity and SC50 values of those compounds were investigated, respectively. PD4 showed the strongest capability for scavenging PAHs free radical; PL4 showed prominent scavenging capacities in the lipid peroxidation processes; it was found that all components in S. chirayita exhibited weak reactivity in the superoxide

Ileana Diéguez. 'Cuerpos sin duelo. Iconografía y teatralidad del dolor'. Córdoba (Arg.): Ediciones DocumentA/Escénicas, 2013.

OpenAIRE

Tatiana Bubnova

2016-01-01

Cuerpos sin duelo. Iconografía y teatralidad del dolor es un libro estupendamente escrito y académicamente riguroso. Al mismo tiempo es un libro abominable. Lo es porque trata de una manera anatómica, al mismo tiempo que inquietante y reflexiva, aquello que todos sabemos que existe, pero no queremos enterarnos. La cuestión de la estética y del arte actual también es una línea magistral de este libro, problema que se replantea de una manera radical.

Radical polarization in double switching of external magnetic field

International Nuclear Information System (INIS)

Lukzen, N.N.; Morozov, V.A.; Sagdeev, R.Z.

1999-01-01

Theoretical treatment of radical spin evolution under the action of double switching of external magnetic field is proposed. Account is taken of evolution of the radical spin state during laser pulse which generates paramagnetic particles. It is shown that the most effective beats in the nuclear magnetization of diamagnetic products of recombination occur upon the jump into zero magnetic field after laser pulse. The phase of observed beats bears information about the type of the initial radical polarization. The frequency of the beats is determined by radical hyperfine structure. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

Crotylations of alpha-carbonyl radicals with crotylstannane.

Science.gov (United States)

Sibi, Mukund P; Miyabe, Hideto

2002-10-03

Electrophilic radicals undergo crotylation with crotylstannane with moderate to good efficiency. The reaction provides the syn isomer as the major product. The present methodology is complementary to Claisen protocols for the synthesis of gamma,delta-unsaturated carboxylic acid derivatives. Details of the new radical methodology are presented. [reaction: see text

Radical Behaviorism and Buddhism: Complementarities and Conflicts

Science.gov (United States)

Diller, James W.; Lattal, Kennon A.

2008-01-01

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

DPPH and oxygen free radicals as pro-oxidant of biomolecules.

Science.gov (United States)

Letelier, María Eugenia; Molina-Berríos, Alfredo; Cortés-Troncoso, Juan; Jara-Sandoval, José; Holst, Marianne; Palma, Karina; Montoya, Margarita; Miranda, Dante; González-Lira, Víctor

2008-03-01

Numerous investigations exist about the alterations that oxygen free radicals can provoke on biomolecules; these modifications can be prevented and/or reversed by different antioxidants agents. On the other hand, 2,2-diphenyl-1-picrylhydrazyl radical (DPPH), a stable nitrogen synthetic radical, is used to evaluate the antioxidant capacity of medicinal herbal products; however, the structural changes that this radical provoke on the herbal active principles are not clear yet. In this work, we compared the redox reactivity of oxygen free radicals and DPPH radical on phospholipids and protein thiol groups present in rat liver microsomes. Cu2+/ascorbate was used as generator system of oxygen free radical and as antioxidant, an extract of Buddleja globosa's leaves. Cu2+/ascorbate provoked microsomal lipid peroxidation, microsomal thiols oxidation and oxygen consumption; all of these phenomena were inhibited by B. globosa extract. On the other hand, DPPH was bleached in different extension by the herbal extract and phosphatidyl choline; beside, DPPH decreased microsomal thiols content, but this phenomenon were not prevented by the herbal extract. Furthermore, DPPH did not induce oxygen consumption and neither modified the oxygen consumption induced by Cu2+/ascorbate. Distinct redox mechanisms may explain the differences between the reactivity of DPPH and oxygen free radicals on biomolecules, which is discussed.

Lipid-derived free radical production in superantigen-induced interstitial pneumonia

Science.gov (United States)

Miyakawa, Hisako; Mason, Ronald P.; Jiang, JinJie; Kadiiska, Maria B.

2009-01-01

We studied the free radical generation involved in the development of interstitial pneumonia (IP) in an animal model of autoimmune disease. We observed an electron spin resonance (ESR) spectrum of α-(4-pyridyl-1-oxide)-N-tert-butylnitrone (POBN) radical adducts detected in the lipid extract of lungs in autoimmune-prone mice after intratracheal instillation of staphylococcal enterotoxin B. The POBN adducts detected by ESR were paralleled by infiltration of macrophages and neutrophils in the bronchoalveolar lavage fluid. To further investigate the mechanism of free radical generation, mice were pretreated with the macrophage toxicant gadolinium chloride, which significantly suppressed the radical generation. Free radical generation was also decreased by pretreatment with the xanthine oxidase (XO) inhibitor allopurinol, the iron chelator Desferal, and the inducible nitric oxide synthase (iNOS) inhibitor 1400W. Histopathologically, these drugs significantly reduced both the cell infiltration to alveolar septal walls and the synthesis of pulmonary collagen fibers. Experiments with NADPH oxidase knockout mice showed that NADPH oxidase did not contribute to lipid radical generation. These results suggest that lipid-derived carbon-centered free radical production is important in the manifestation of IP and that a macrophage toxicant, an XO inhibitor, an iron chelator, and an iNOS inhibitor protect against both radical generation and the manifestation of IP. PMID:19376221

Influence of Free Radicals on the Intrinsic MRI Relaxation Properties.

Science.gov (United States)

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. T 1 and T 2 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 T 1 , which was proportional to the H 2 O 2 concentration, and a relatively small reduction in T 2 (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.

Radicals of DNA and DNA nucleotides generated by ionising radiation

International Nuclear Information System (INIS)

Przybytniak, G.

2004-01-01

A first stage of cell processes leading to DNA damage of initiated by radical reactions. In a model system such transformations were generated by ionising radiation which involves production of electron loss and electron gain centers of the substrate and radical formation. Using cryogenic ESR spectroscopy it was found that the DNA nucleotides, which convert to radical anions upon electron capture undergo the separation of unpaired spin and charge due to protonation. Circular and linear dichroism studies enabled to conclude that iron ions(III) induce strong changes in the DNA helical structure indicating their coordination with nitrogen bases. The repair of DNA radicals produced via radiolytic oxidation, i.e. the guanine radical cation and the allyl type radical of thymine, is possible at elevated temperatures due to the involvement of sulphydryl groups. The influence of the thiol charge is then limited

Free radical-scavenging delta-lactones from Boletus calopus.

Science.gov (United States)

Kim, Jin-Woo; Yoo, Ick-Dong; Kim, Won-Gon

2006-12-01

The methanol extracts from the fruiting body of the mushroom Boletus calopus showed free radical-scavenging activity. Bioactivity-guided fractionation of the methanol extracts led to a new hydroxylated calopin named calopin B, along with the known delta-lactones calopin and cyclocalopin A. The structure of the new calopin analogue was elucidated by spectroscopic methods. All compounds showed potent free radical-scavenging activity against superoxide, DPPH, and ABTS radicals with IC (50) values of 1.2 - 5.4 microg/mL.

MISCONCEPTIONS AND NON-SCIENTIFIC CONCEPTS ON FREE RADICALS

Directory of Open Access Journals (Sweden)

Rosiris Sindeaux de Alencar Pires de Oliveira

2016-11-01

Full Text Available INTRODUCTION: Misconceptions or alternative conceptions are defined as conceptions that are somewhat different from the scientifically accepted ones and are known to be highly resistant to changes. Free radicals are a widely publicized subject in the media due to their putative importance in human aging and health. Free radicals are a subject susceptible to misconceptions widely spread by the media supporting prejudicial advertising inducing antioxidant consumption. OBJECTIVES: Identify and categorized different free radicals misconceptions published in printed media. MATERIALS AND METHODS: Revista Veja (Digital Archive, the weekly magazine with the largest circulation in Brazil, was selected for this investigation. Period analyzed: from 01/01/2000 to 31/07/2014 with search terms Free radicals and antioxidants. Passages selected were classified as: Right Concept (RC, Wrong Concept (WC, Misconception (MC, Inadequate generalization (IG, Inductive [to misconceptions] Concept (IC, Inductive [to misconceptions] Information (II, and Not fit the inclusion criteria (NFIC. Each one of these categories were further subdivided. DISCUSSION AND RESULTS: 79 magazine articles, advertisements and information materials were found which led to 293 text passages. 56.3% were MC, 21.4% II, 8.8% IC, 5.4% IG, 3.4% RC, 2.7% WR, 2.0% NFIC. The most frequently subcategory in each category was: MC: x [something] combats free radicals (22.6%; II: x [substance] is antioxidant (54.0%; IC: x [something] increases free radicals production (34.6%; IG: antioxidant x [substance] combats cancer (56.3%; RC: too much vitamins and minerals is harmful to health (30.0%; WR: free radicals are formed during oxygen conversion to energy process (25.0%. CONCLUSION: Magazine analysis reveal non-scientific concepts (MC, II, IC and IG to be highly frequent, notably misconceptions. Moreover, non-scientific concepts together reach 91.8% of all concepts while right concepts respond for only 2

Formation and thermal transformations of radicals in γ-irradiated cellulose

International Nuclear Information System (INIS)

Ershov, B.G.; Isakova, O.V.

1984-01-01

The work is aimed at more detailed theoretical analysis of the structure of radicals in cellulose gamma-irradiated at 77 K, specification of the mechanism of their formation, as well as studying reactions of transformation of radicals in the case of temperature increase. It is established that in the case of cellulose gamma-irradiation radicals appear with the localization of an unpaired electron in 1 and 4 positions of the pyranose cycle the formation of which is accompanied by the disruption of the glycoside bound. Thermal transformations of these radicals are conditioned by their dehydration and occur with the formation of radicals of the allelow type

Carbonate radical anion-induced electron transfer in bovine serum albumin

Energy Technology Data Exchange (ETDEWEB)

Joshi, Ravi [Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085 (India)]. E-mail: rjudrin@yahoo.com; Mukherjee, T. [Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

2006-07-15

Reaction of native and thermally denatured bovine serum albumin (BSA) with carbonate radical anion (CO{sub 3}{sup -} radical) has been studied using pulse radiolysis technique. Scavenging of CO{sub 3}{sup -} radical by native BSA and consequent electron transfer from tyrosine to tryptophan radical has been observed to occur with almost same rate constant (k{approx}1.7x10{sup 8} dm{sup 3} mol{sup -1} s{sup -1}) at pH 8.8. Effect of structural changes, due to thermal denaturation, on scavenging of CO{sub 3}{sup -} radical and the electron transfer process have been studied and discussed in this paper.

Competing with the radical right: Distances between the European radical right and other parties on typical radical right issues

NARCIS (Netherlands)

Immerzeel, T.; Lubbers, M.; Coffé, H.

2016-01-01

The popularity of European Radical Right Populist parties (RRPs) has led to investigations into the distances between RRPs' and other parties' stances regarding immigration. This article adds to this literature by investigating the distance between RRPs and the other parties on a wider variety of

Competing with the radical right. Distances between the European radical right and other parties on typical radical right issues

NARCIS (Netherlands)

Immerzeel, T.; Lubbers, M.; Coffe, H.R.

2015-01-01

The popularity of European Radical Right Populist parties (RRPs) has led to investigations into the distances between RRPs’ and other parties’ stances regarding immigration. This article adds to this literature by investigating the distance between RRPs and the other parties on a wider variety of

Von Glaserfeld`s Radical Constructivism: A Critical Review

Science.gov (United States)

Hardy, Michael D.

We explore Ernst von Glaserfelds radical constructivism, its criticisms, and our own thoughts on what it promises for the reform of science and mathematics teaching. Our investigation reveals that many criticisms of radical constructivism are unwarranted; nevertheless, in its current cognitivist form radical constructivism may be insufficient to empower teachers to overcome objectivist cultural traditions. Teachers need to be empowered with rich understandings of philosophies of science and mathematics that endorse relativist epistemologies; for without such they are unlikely to be prepared to reconstruct their pedagogical practices. More importantly, however, is a need for a powerful social epistemology to serve as a referent for regenerating the culture of science education. We recommend blending radical constructivism with Habermas theory of communicative action to provide science teachers with a moral imperative for adopting a constructivist epistemology.

Moderate and Radical Islam

National Research Council Canada - National Science Library

Rabasa, Angel

2005-01-01

This report presents the statement of Angel Rabasa, PhD, Senior Policy Analyst, The RAND Corporation, to the Committee on Armed Services, Defense Review Terrorism and Radical Islam Gap Panel, United...

Anatomical landmarks of radical prostatecomy.

Science.gov (United States)

Stolzenburg, Jens-Uwe; Schwalenberg, Thilo; Horn, Lars-Christian; Neuhaus, Jochen; Constantinides, Costantinos; Liatsikos, Evangelos N

2007-03-01

In the present study, we review current literature and based on our experience, we present the anatomical landmarks of open and laparoscopic/endoscopic radical prostatectomy. A thorough literature search was performed with the Medline database on the anatomy and the nomenclature of the structures surrounding the prostate gland. The correct handling of puboprostatic ligaments, external urethral sphincter, prostatic fascias and neurovascular bundle is necessary for avoiding malfunction of the urogenital system after radical prostatectomy. When evaluating new prostatectomy techniques, we should always take into account both clinical and final oncological outcomes. The present review adds further knowledge to the existing "postprostatectomy anatomical hazard" debate. It emphasizes upon the role of the puboprostatic ligaments and the course of the external urethral sphincter for urinary continence. When performing an intrafascial nerve sparing prostatectomy most urologists tend to approach as close to the prostatic capsula as possible, even though there is no concurrence regarding the nomenclature of the surrounding fascias and the course of the actual neurovascular bundles. After completion of an intrafascial technique the specimen does not contain any periprostatic tissue and thus the detection of pT3a disease is not feasible. This especially becomes problematic if the tumour reaches the resection margin. Nerve sparing open and laparoscopic radical prostatectomy should aim in maintaining sexual function, recuperating early continence after surgery, without hindering the final oncological outcome to the procedure. Despite the different approaches for radical prostatectomy the key for better results is the understanding of the anatomy of the bladder neck and the urethra.

Habitat of in vivo transformation influences the levels of free radical scavengers in Clinostomum complanatum: implications for free radical scavenger based vaccines against trematode infections.

Science.gov (United States)

Zafar, Atif; Rizvi, Asim; Ahmad, Irshad; Ahmad, Masood

2014-01-01

Since free radical scavengers of parasite origin like glutathione-S-transferase and superoxide dismutase are being explored as prospective vaccine targets, availability of these molecules within the parasite infecting different hosts as well as different sites of infection is of considerable importance. Using Clinostomum complanatum, as a model helminth parasite, we analysed the effects of habitat of in vivo transformation on free radical scavengers of this trematode parasite. Using three different animal models for in vivo transformation and markedly different sites of infection, progenetic metacercaria of C. complanatum were transformed to adult ovigerous worms. Whole worm homogenates were used to estimate the levels of lipid peroxidation, a marker of oxidative stress and free radical scavengers. Site of in vivo transformation was found to drastically affect the levels of free radical scavengers in this model trematode parasite. It was observed that oxygen availability at the site of infection probably influences levels of free radical scavengers in trematode parasites. This is the first report showing that habitat of in vivo transformation affects levels of free radical scavengers in trematode parasites. Since free radical scavengers are prospective vaccine targets and parasite infection at ectopic sites is common, we propose that infections at different sites, may respond differently to free radical scavenger based vaccines.

Detection of free radicals by radical trapping and 15N NMR spectroscopy in copolymerization of methyl acrylate and styrene

NARCIS (Netherlands)

Kelemen, P.; Klumperman, B.

2003-01-01

The macroradicals taking part in the copolymn. of Me acrylate and styrene were trapped by reaction with a 15N labeled stable nitroxyl radical at 70 DegC. The nitroxyl radical is formed in situ from a thermally instable alkoxyamine precursor. 15N NMR spectroscopy is applied to detect the trapping

El reconocimiento de derechos a las parejas del mismo sexo: el camino hacia un concepto de familia pluralista

Directory of Open Access Journals (Sweden)

Paula Andrea Ceballos Ruiz

2012-12-01

Full Text Available El presente artículo contiene los resultados finales del proyecto de investigación realizado durantelos años 2010 y 2011 por el grupo de investigación en Derecho “Filius”, adscrito al programade Derecho de la Corporación Universitaria Empresarial Alexander von Humboldt de la ciudadde Armenia (Quindío. Dicho proyecto tiene como objetivo general “establecer el concepto defamilia que se maneja en el ordenamiento jurídico colombiano a partir de las sentenciasde la Corte Constitucional que reconocen derechos a las parejas del mismo sexo”, para lo cual se realizó una línea jurisprudencial de las sentencias de esta corporación en las que sediscuten derechos de parejas del mismo sexo, lo cual permitió concluir que, a pesar del granavance que se produce en Colombia a partir de la Sentencia C-075 de 2007 en materia dereconocimiento de derechos a estas parejas, en todas estas sentencias, la Corte siempre senegó a reconocerles el estatus de familia, y solo hasta el año 2011, mediante Sentencia C-577,la Corte admite que las parejas del mismo sexo constituyen una familia, modificando deforma radical la doctrina constitucional que mantuvo el criterio de heterosexualidad comodefinitorio del concepto de familia.

Donor free radical explosive composition

Science.gov (United States)

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.

Free radicals in chemical carcinogenesis.

Science.gov (United States)

Clemens, M R

1991-12-15

During the past decade, remarkable progress has been made in our understanding of cancer-causing agents, mechanisms of cancer formation and the behavior of cancer cells. Cancer is characterized primarily by an increase in the number of abnormal cells derived from a given normal tissue, invasion of adjacent tissues by these abnormal cells, and lymphatic or blood-borne spread of malignant cells to regional lymph nodes and to distant sites (metastasis). It has been estimated that about 75-80% of all human cancers are environmentally induced, 30-40% of them by diet. Only a small minority, possibly no more than 2% of all cases, result purely from inherent genetic changes. Several lines of evidence confirm that the fundamental molecular event or events that cause a cell to become malignant occur at the level of the DNA and a variety of studies indicate that the critical molecular event in chemical carcinogenesis is the interaction of the chemical agent with DNA. The demonstration that DNA isolated from tumor cells can transfect normal cells and render them neoplastic provides direct proof that an alteration of the DNA is responsible for cancer. The transforming genes, or oncogenes, have been identified by restriction endonuclease mapping. One of the characteristics of tumor cells generated by transformation with viruses, chemicals, or radiation is their reduced requirement for serum growth factors. A critical significance of electrophilic metabolites of carcinogenes in chemical carcinogenesis has been demonstrated. A number of "proximate" and "ultimate" metabolites, especially those of aromatic amines, were described. The "ultimate" forms of carcinogens actually interact with cellular constituents to cause neoplastic transformation and are the final metabolic products in most pathways. Recent evidence indicates that free radical derivatives of chemical carcinogens may be produced both metabolically and nonenzymatically during their metabolism. Free radicals carry no

First examples of intramolecular addition of primary amidyl radicals to olefins

Energy Technology Data Exchange (ETDEWEB)

Gaudreault, P.; Drouin, C.; Lessard, J. [Sherbrooke Univ., PQ (Canada). Dept. de Chimie

2005-07-01

This paper presents the first examples of radical cyclization involving a primary amidyl radical and a pendant olefin. Amidyl radicals have attracted interest in terms of their structure, reactivity, and ways to generate them. The intramolecular addition of an amidyl radical on a pendant olefin appears to be a powerful synthetic tool for creating nitrogen-containing heterocycles. Although several examples of cyclization involving secondary amidyl radicals are cited in the the literature, there are no examples of a successful cyclization involving a primary amidyl radical. This is because all attempts to prepare the usual radical precursors have failed when applied to olefinic primary amides. This study reveals that N-(phenylthio) derivatives of olefinic primary amides can be easily prepared and that nitrogen heterocycles resulting from their radical cyclization can be obtained in good to very good yields. Four olefinic primary amides were chosen as models for radical cyclization of primary amidyl radicals. They were prepared from the corresponding carboxylic acids via the acid chlorides. Conversion of primary amides into suitable amidyl radical precursors was also examined. The study showed that N-(phenylthio) amides could be easily prepared by following a slightly modified protocol developed by Esker and Newcomb, by reacting the anion of the amide with phenylsulfenyl chloride. In particular, olefinic N-(phenylthio) amides were prepared and used as primary amidyl radical precursors in a reaction with a solution of 2,2'-azobis(isobutyronitrile) in catalytic quantities and tributyltin hydride in benzene. The resulting yields of cyclic products ranged from 63 to 85 per cent. The intent of the study was to demonstrate that it is no longer necessary to prepare an N-protected precursor and then remove the protecting group after cyclization. Further studies are currently underway. 10 refs., 1 tab.

Radical Documentaries, Neoliberal Crisis and Post-Democracy

Directory of Open Access Journals (Sweden)

Eugenia Siapera

2017-12-01

Full Text Available This article examines radical documentaries in Greece as a response to neoliberal crisis and post democracy. In a context where mainstream media have made themselves irrelevant, facing historical lows in trust and credibility, we found that radical documentaries have emerged outside the commodification of information and form part of the growing social or solidarity economy in Greece. Our analysis shows that these documentaries operate through a different political economy, that involves collaborative practices and that they are firmly oriented towards society rather than the political sphere. Overall, we found that radical documentaries are seeking to recuperate the media through engaging professional media workers, journalists, film directors, academics and actors; they operate through reclaiming media know-how; through radicalizing the financing, production and distribution by refusing to participate in commodification processes; and through recreating commonalities by thematizing the common, the public, and responsibility towards others.Their specific political role is found to be one of helping to restore the social body and to contribute to processes of commoning, whereby solidarity and social trust is recovered.

Evidence of radicals created by plasma in bacteria in water

International Nuclear Information System (INIS)

Lee, Chae Bok; Na, Young Ho; Hong, Tae-Eun; Choi, Eun Ha; Uhm, Han S.; Baik, Ku Youn; Kwon, Gichung

2014-01-01

Heavy water (D 2 O) was introduced into a non-thermal plasma-jet (NTPJ) device to generate deuterium monoxide (OD) radicals at room temperature. Owing to the similar reactivity and low prevalence of deuterium in nature, OD radicals can be utilized to visualize the OH radical interactions with water and living cells. Escherichia coli in water were treated with OD radicals, and D atom incorporation into cells was visualized using time-of-flight SIMS and Nano-SIMS. The results show that D atoms from NTPJ reach the cytoplasm of E. coli in H 2 O, indicating the usefulness of this OD-tracking method for the study of radical interactions with living cells.

Free radicals of an aromatic nature in air samples from iron foundries

Energy Technology Data Exchange (ETDEWEB)

Westerberg, L M

1982-01-01

Free radicals of relatively long life were identified as spin adducts of phenyl-N-tert-butylnitrone. Pyrolysis studies showed the radicals were oxy-radicals. The hyperfine splitting constants of spin adducts of radicals from the pyrolysis in air of benzo(a)pyrene, coal tar pitch, and moulding sand containing hard coal dust were the same as those of the radicals found in foundry air. Since these radicals can bind to DNA, they must be considered when estimating the hazardous effects of polluted air.

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

International Nuclear Information System (INIS)

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

1980-01-01

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

Introduction: Radical Teaching About Human Rights Part II

Directory of Open Access Journals (Sweden)

Michael Bennett

2016-02-01

Full Text Available In our introduction to the first of these two issues of Radical Teacher devoted to “Radical Teaching About Human Rights,” we cautioned that all forms of Human Rights Education (HRE are not radical.  The problem, we pointed out, with rights discourse is that it can mask the politics of how rights are defined, whose rights are recognized, and how they are enforced.  This problem becomes evident when HRE is bound up with a neoliberal, or worse than neoliberal, perspective that points fingers at others and rallies troops for supposedly humanitarian interventions while eliding the role of the United States as an imperializing settler colonial state.  Fortunately, we have once again received several essays that seem to us to be aware of this danger and provide admirable examples of radical teaching about human rights.

Electron spin resonance of spin-trapped radicals of amines and polyamines. Hydroxyl radical reactions in aqueous solutions and. gamma. radiolysis in the solid state

Energy Technology Data Exchange (ETDEWEB)

Mossoba, M.M.; Rosenthal, I.; Riesz, P. (National Cancer Inst., Bethesda, MD (USA))

1982-06-15

The reactions of hydroxyl radicals with methylamine, dimethylamine, trimethylamine, diethylamine, sec-butylamine, ethylene-diamine, 1,3-diaminopropane, putrescine, cadaverine, 1,7-diaminoheptane, ornithine, spermidine, spermine, agmatine, and arcaine in aqueous solutions have been investigated by spin-trapping and esr. Hydroxyl radicals were generated by the uv photolysis of H/sub 2/O/sub 2/ and 2-methyl-2-nitrosopropane (MNP) was used as the spin-trap. The effects of ionizing radiation on the same polyamines in the polycrystalline state were also investigated. The free radicals produced by ..gamma..-radiolysis of these solids at room temperature in the absence of air were identified by dissolution in aqueous solutions of MNP. The predominant reaction of OH radicals with amines and polyamines below pH 7 was the abstraction of hydrogen atoms from a carbon that is not adjacent to the protonated amino group. For agmatine and arcaine which contain guanidinium groups abstraction occurred from the ..cap alpha..-CH. Dimethylamine was oxidized to the dimethylnitroxyl radical by H/sub 2/O/sub 2/ in the dark. ..gamma..-Radiolysis of polyamines in the polycrystalline state generated radicals due to H-abstraction from either the ..cap alpha..-Ch or from a carbon atom in the middle of the alkyl chain. The deamination radical was obtained from ornithine.

Oxidative degradation of lignin by photochemical and chemical radical generating systems

International Nuclear Information System (INIS)

Gold, M.H.; Kutsuki, H.; Morgan, M.A.

1983-01-01

Oxidation of specifically radiolabeled 14 C-lignins by UV/H 2 O 2 , Fenton's reagent, photosensitizing riboflavin, UV- and γ-irradiation was examined. In the presence of UV/H 2 O 2 , a hydroxyl radical (radicalOH) generating system, 14 C-methoxy, 2-[ 14 C-sidechain] and 14 C-ring labeled lignin were rapidly and extensively degraded as measured by gel filtration of the reaction products on Sephadex LH-20. This suggested that exposure to radicalOH leads to rapid, nonspecific lignin degradation. Rapid degradation of 14 C-methoxy, 2-[ 14 C-sidechain] and 14 C-ring labeled lignin also occurred in the presence of the radicalOH generating system, Fenton's reagent, confirming the primary role of radicalOH in these reactions. Photosensitizing riboflavin, also capable of effecting transformation of organic compounds via Type I hydrogen radical abstractions, caused extensive oxidative degradation of 14 C-methoxy labeled lignin and significant degradation of 2-[ 14 C-sidechain] and 14 C-ring labeled lignin. In addition, UV- and γ-irradiation caused slower but extensive degradation of the polymers, probably via radical type mechanisms. All of these results indicate that radicalOH as well as organic radical generating systems are effective agents for the purpose of degrading this heterogeneous, optically inactive and random biopolymer. (author)

Measuring Atmospheric Free Radicals Using Chemical Amplification

Science.gov (United States)

1988-05-01

CH 3Br, H2S, and SO2 [Logan et al., 1981]. Recently, the OH radical has been determined as the dominant loss mechanism for isoprene and monoterpenes ...W. Heaps, D. Philen, and T. McGee, Bondary Layer Measurements of the OH Radical in the Vicinity of an Isolated Power Plant Plume: SO2 and NO2

Radicals derived from acetaldehyde and vinyl alcohol.

Science.gov (United States)

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

2017-10-18

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 ν 3 (3076 cm -1 ) and ν 4 (2999 cm -1 ) C-H stretches for syn-vinyl alcohol and all but one of the vibrational modes for anti-vinyl alcohol (ν 1 -ν 14 ) are yet to be observed experimentally. For the acetyl radical, ν 6 (1035 cm -1 ), ν 11 (944 cm -1 ), ν 12 (97 cm -1 ), and accounting for our changes to the assignment of the 1419.9 cm -1 experimental mode, ν 10 (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 ν 4 rather than to ν 10 . Our work also strongly supports reassignment of the ν 10 and ν 11 fundamentals of the vinoxy radical. We suggest that the bands assigned to the overtones of these fundamentals were in fact combination bands. Our

Analysis of radicals of irradiated garlic

International Nuclear Information System (INIS)

Kameya, Hiromi; Kaimori, Yoshihiko; Ukai, Mitsuko

2010-01-01

The detection method of gamma ray irradiated garlic using Electron Spin Resonance(ESR)spectroscopy was studied. The ESR spectrum was consisted of one singlet signal at g=2.00. This signal is due to an organic free radical. Upon irradiation, the intensity of the signal was increased. Also two signals due to cellulose radical were detected nearby the singlet. The intensity of the singlet signal was increased as depend on the increase of the irradiation dose level. (author)

Aminoxyl (nitroxyl) radicals in the early decomposition of the nitramine RDX.

Science.gov (United States)

Irikura, Karl K

2013-03-14

The explosive nitramine RDX (1,3,5-trinitrohexahydro-s-triazine) is thought to decompose largely by homolytic N-N bond cleavage, among other possible initiation reactions. Density-functional theory (DFT) calculations indicate that the resulting secondary aminyl (R2N·) radical can abstract an oxygen atom from NO2 or from a neighboring nitramine molecule, producing an aminoxyl (R2NO·) radical. Persistent aminoxyl radicals have been detected in electron-spin resonance (ESR) experiments and are consistent with autocatalytic "red oils" reported in the experimental literature. When the O-atom donor is a nitramine, a nitrosamine is formed along with the aminoxyl radical. Reactions of aminoxyl radicals can lead readily to the "oxy-s-triazine" product (as the s-triazine N-oxide) observed mass-spectrometrically by Behrens and co-workers. In addition to forming aminoxyl radicals, the initial aminyl radical can catalyze loss of HONO from RDX.

Temperature Effects on Free Radicals in Gamma-sterilized Beef

Science.gov (United States)

Pramanik, S. I.; Jahan, M. S.

1999-11-01

Gamma irradiation has become the method of choice for sterilizing frozen meat and their products to reduce levels of food-borne pathogens and to extend shelf life. In this report we have employed ESR technique for detection of free radicals in sterilized and non-sterilized dry beef without bone. We have also determined the heating effects on free radicals at temperatures 176^°C and 250^°C. Meat samples were dried in a food dehydrator at 60^°C and were packaged in dry N_2. They were then sterilized by γ-irradiation (2.5 MRad), ground into powder, and placed in ESR sample tubes. Non-sterilized powder samples were used as control. While all powder samples, sterilized or not, produced a broad single line in the ESR spectra with (Δ H_pp ~ 9 G) and g = 2.013, the radical concentration in the sterilized samples increased by a factor of five. Heat treatment at 176^°C produced similar radicals. But, when samples were heated 250^°C different radical species were formed which are characterized by narrow width (Δ H_pp ~ 6 G) and lower g-value (g =2.010). In contrast with previous work, where free radicals in chicken bones were reduced by heating [1], we observed an increase in concentration. Results of structural analyses of the radicals will be presented. Ref.[1]: Radiat. Phys. Chem., 49, 477-481, 1997. Work supported by Grants from the University of Memphis

Synthesis and Free Radical Scavenging Activity of New Hydroxybenzylidene Hydrazines.

Science.gov (United States)

Sersen, Frantisek; Gregan, Fridrich; Kotora, Peter; Kmetova, Jarmila; Filo, Juraj; Loos, Dusan; Gregan, Juraj

2017-05-29

Hydroxybenzylidene hydrazines exhibit a wide spectrum of biological activities. Here, we report synthesis and free radical scavenging activity of nine new N-(hydroxybenzylidene)-N'-[2,6-dinitro-4-(trifluoromethyl)]phenylhydrazines. The chemical structures of these compounds were confirmed by 1H-NMR, 13C-NMR, 19F-NMR, IR spectroscopy, LC-MS, and elemental analysis. The prepared compounds were tested for their activity to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH), galvinoxyl radical (GOR), and 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulphonic acid (ABTS) radicals. The free radical scavenging activity expressed as SC50 values of these compounds varied in a wide range, from a strong to no radical scavenging effect. The most effective radical scavengers were hydroxybenzylidene hydrazines containing three hydroxyl groups in the benzylidene part of their molecules. The prepared compounds were also tested for their activity to inhibit photosynthetic electron transport in spinach chloroplasts. IC50 values of these compounds varied in wide range, from an intermediate to no inhibitory effect.

ESR study on free radicals trapped in crosslinked polytetrafluoroethylene (PTFE)

International Nuclear Information System (INIS)

Oshima, Akihiro; Tabata, Yoneho; Seguchi, Tadao

1997-01-01

Free radicals in crosslinked PTFE which formed by 60 Co γ-rays irradiation at 77 K and at room temperature were studied by electron spin resonance (ESR) spectroscopy. The crosslinked PTFE specimens with different crosslinking density were prepared by electron beam irradiation in the molten state. The ESR spectra observed in the irradiated crosslinked PTFE are much different from those in non-crosslinked PTFE (virgin); a broad singlet component increases with increasing the crosslinking density, G-value of radicals is much higher in crosslinked PTFE than in non-crosslinked one. Free radicals related to the broad component are trapped in the non-crystalline region of crosslinked PTFE and rather stable at room temperature, whereas radicals trapped in amorphous non-crosslinked PTFE are unstable at room temperature. It is thought that most of free radicals trapped in the crosslinked PTFE are formed in the crosslinked amorphous region. The trapped radicals decays around 383 K (110 o C) due to the molecular motion of α-relaxation. (Author)

Free Radical Scavenging Activities of Methanol Extract and ...

African Journals Online (AJOL)

Michael Horsfall

fractions were subjected to in vitro antioxidant evaluation using the DPPH free radical scavenging ... The crude extract has IC-50 value for radical scavenging activity of 5μg/mL which was .... effective concentration of the sample that is required.

EPR assessment of the free radicals in irradiated foodstuffs

International Nuclear Information System (INIS)

Tencheva, S.; Katsareva, Ts.; Malinovski, A.; Kabasanov, K.

1985-01-01

In the hygienic assessment of radiation treated foodstuffs the study of free radicals formed during radiation exposure, their concentration and disintegration kinetics are of particular interest. In the work presented the concentration of the free radicals in irradiated prunes, nuts and corn is determined using EPR spectroscopy. The following doses are applied: 2, 10 and 20 kGy for prunes, 1, 10 and 20 kGy for nuts, and 0.75, 10 and 20 kGy for corn. EPR measurements are done immediately after the irradiation: 24 hours, and 3, 6, 9 and 15 days after the exposure. In the small radiation doses the formation of single radicals is observed. In doses of 10 kGy the spectra get complicated with the occurence of radicals R 1 , R 2 , R 3 and R 4 . The assessment of radicals proves to be a prospective method for the identification and determination of the preservation terms of foodstuffs

Thermochemical properties for isooctane and carbon radicals: computational study.

Science.gov (United States)

Snitsiriwat, Suarwee; Bozzelli, Joseph W

2013-01-17

Thermochemical properties for isooctane, its internal rotation conformers, and radicals with corresponding bond energies are determined by use of computational chemistry. Enthalpies of formation are determined using isodesmic reactions with B3LYP density function theory and composite CBS-QB3 methods. Application of group additivity with comparison to calculated values is illustrated. Entropy and heat capacities are determined using geometric parameters, internal rotor potentials, and frequencies from B3LYP/6-31G(d,p) calculations for the lowest energy conformer. Internal rotor potentials are determined for the isooctane parent and for the primary, secondary, and tertiary radicals in order to identify isomer energies. Intramolecular interactions are shown to have a significant effect on the enthalpy of formation of the isooctane parent and its radicals. The computed standard enthalpy of formation for the lowest energy conformers of isooctane from this study is -54.40 ± 1.60 kcal mol(-1), which is 0.8 kcal mol(-1) lower than the evaluated experimental value -53.54 ± 0.36 kcal mol(-1). The standard enthalpy of formation for the primary radical for a methyl on the quaternary carbon is -5.00 ± 1.69 kcal mol(-1), for the primary radical on the tertiary carbon is -5.18 ± 1.69 kcal mol(-1), for the secondary isooctane radical is -9.03 ± 1.84 kcal mol(-1), and for the tertiary isooctane radical is -12.30 ± 2.02 kcal mol(-1). Bond energy values for the isooctane radicals are 100.64 ± 1.73, 100.46 ± 1.73, 96.41 ± 1.88 and 93.14 ± 2.05 kcal mol(-1) for C3•CCCC2, C3CCCC2•, C3CC•CC2, and C3CCC•C2, respectively. Entropy and heat capacity values are reported for the lowest energy homologues.

The research progress of several kinds of free radical scavengers

International Nuclear Information System (INIS)

Qian Liren; Huang Yuecheng; Cai Jianming

2009-01-01

Ionization radiation can generate free radicals in biological system, which could induce lipid peroxi-dation, biomacromolecule and biomembrane damage, lost of cell function, cell cycle disturbance, genetic mutation and so on. The scavenging free radicals can protect organism from radiation damage. Many radio-protective agents, such as amylase, hydroxyl-benzene derivatives, hormone, vitamin, have great abilities to protect organism from radiation via scavenging free radicals. In this paper, we mainly review the free radical scavenging effects of several kinds of radio-protective agents. (authors)

Why Nature Uses Radical SAM Enzymes so Widely: Electron Nuclear Double Resonance Studies of Lysine 2,3-Aminomutase Show the 5'-dAdo• "Free Radical" Is Never Free.

Science.gov (United States)

Horitani, Masaki; Byer, Amanda S; Shisler, Krista A; Chandra, Tilak; Broderick, Joan B; Hoffman, Brian M

2015-06-10

Lysine 2,3-aminomutase (LAM) is a radical S-adenosyl-L-methionine (SAM) enzyme and, like other members of this superfamily, LAM utilizes radical-generating machinery comprising SAM anchored to the unique Fe of a [4Fe-4S] cluster via a classical five-membered N,O chelate ring. Catalysis is initiated by reductive cleavage of the SAM S-C5' bond, which creates the highly reactive 5'-deoxyadenosyl radical (5'-dAdo•), the same radical generated by homolytic Co-C bond cleavage in B12 radical enzymes. The SAM surrogate S-3',4'-anhydroadenosyl-L-methionine (anSAM) can replace SAM as a cofactor in the isomerization of L-α-lysine to L-β-lysine by LAM, via the stable allylic anhydroadenosyl radical (anAdo•). Here electron nuclear double resonance (ENDOR) spectroscopy of the anAdo• radical in the presence of (13)C, (2)H, and (15)N-labeled lysine completes the picture of how the active site of LAM from Clostridium subterminale SB4 "tames" the 5'-dAdo• radical, preventing it from carrying out harmful side reactions: this "free radical" in LAM is never free. The low steric demands of the radical-generating [4Fe-4S]/SAM construct allow the substrate target to bind adjacent to the S-C5' bond, thereby enabling the 5'-dAdo• radical created by cleavage of this bond to react with its partners by undergoing small motions, ∼0.6 Å toward the target and ∼1.5 Å overall, that are controlled by tight van der Waals contact with its partners. We suggest that the accessibility to substrate and ready control of the reactive C5' radical, with "van der Waals control" of small motions throughout the catalytic cycle, is common within the radical SAM enzyme superfamily and is a major reason why these enzymes are the preferred means of initiating radical reactions in nature.

Relacionismo substancial: a ontologia do comportamento à luz do behaviorismo radical

Directory of Open Access Journals (Sweden)

Diego Zilio

Full Text Available Sob a influência do pragmatismo e contextualismo pepperiano, analistas do comportamento extraíram do behaviorismo radical qualquer posição ontológica. Como resultado, há a defesa de um relacionismo radical no qual a única propriedade relevante para a existência do comportamento é a própria relação que o define. O objetivo deste ensaio é avaliar a pertinência dessa posição. Três questões guiram esse trabalho: (1 Por que a substância não é importante para o behaviorismo radical?; (2 Por que a substância é importante para o behaviorismo radical?; e (3 Qual seria, de fato, o posicionamento ontológico mais condizente com o behaviorismo radical? Argumenta-se que o relacionismo radical não reflete com acurácia a ontologia behaviorista radical e sugere-se que o relacionismo substancial seja a posição mais coerente.

Changes in free-radical scavenging ability of kombucha tea during fermentation.

Science.gov (United States)

Jayabalan, R; Subathradevi, P; Marimuthu, S; Sathishkumar, M; Swaminathan, K

2008-07-01

Kombucha tea is a fermented tea beverage produced by fermenting sugared black tea with tea fungus (kombucha). Free-radical scavenging abilities of kombucha tea prepared from green tea (GTK), black tea (BTK) and tea waste material (TWK) along with pH, phenolic compounds and reducing power were investigated during fermentation period. Phenolic compounds, scavenging activity on DPPH radical, superoxide radical (xanthine-xanthine oxidase system) and inhibitory activity against hydroxyl radical mediated linoleic acid oxidation (ammonium thiocyanate assay) were increased during fermentation period, whereas pH, reducing power, hydroxyl radical scavenging ability (ascorbic acid-iron EDTA) and anti-lipid peroxidation ability (thiobarbituric assay) were decreased. From the present study, it is obvious that there might be some chances of structural modification of components in tea due to enzymes liberated by bacteria and yeast during kombucha fermentation which results in better scavenging performance on nitrogen and superoxide radicals, and poor scavenging performance on hydroxyl radicals. Copyright © 2007 Elsevier Ltd. All rights reserved.

prepared via atom transfer radical polymerization, reverse atom

Indian Academy of Sciences (India)

Synthesis and characterization of poly(2-ethylhexyl acrylate) prepared via atom transfer radical polymerization, reverse atom transfer radical polymerization and ... Zydex Industries, 25-A Gandhi Oil Mill Compound, Gorwa, Vadodara 390 016, India; Rubber Technology Centre, Indian Institute of Technology Kharagpur, ...

Electronic states of aryl radical functionalized graphenes: Density functional theory study

Science.gov (United States)

Tachikawa, Hiroto; Kawabata, Hiroshi

2016-06-01

Functionalized graphenes are known as a high-performance molecular device. In the present study, the structures and electronic states of the aryl radical functionalized graphene have been investigated by the density functional theory (DFT) method to elucidate the effects of functionalization on the electronic states of graphene (GR). Also, the mechanism of aryl radical reaction with GR was investigated. The benzene, biphenyl, p-terphenyl, and p-quaterphenyl radicals [denoted by (Bz) n (n = 1-4), where n means numbers of benzene rings in aryl radical] were examined as aryl radicals. The DFT calculation of GR-(Bz) n (n = 1-4) showed that the aryl radical binds to the carbon atom of GR, and a C-C single bond was formed. The binding energies of aryl radicals to GR were calculated to be ca. 6.0 kcal mol-1 at the CAM-B3LYP/6-311G(d,p) level. It was found that the activation barrier exists in the aryl radical addition: the barrier heights were calculated to be 10.0 kcal mol-1. The electronic states of GR-(Bz) n were examined on the basis of theoretical results.

Free radical scavenging properties of some wine probes

International Nuclear Information System (INIS)

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

1999-01-01

There are preliminary results of investigation of scavenging properties of 8 probes of Slovak wines (consisting of one reference, 3 probes of white wine and 4 probes of red wine). According to the literature so far, wine probes contain paramagnetic species (Mn 2+ , characterised with sextet spectrum, and a singlet line around g=2,00). In our probes we observed Mn 2+ signals, but no significant evidence for a single line of free radical was found. We can conclude that Mn 2+ content in the red wines is generally higher than in the white ones. Further, we investigated the scavenging activities of the probes adding solution of dinitropicryl hydrazyl (DPPH-stable radical) to them. Their ability to terminate free radicals resulted in the decrease of the final DPPH concentrations in the probes. The red wines have significantly higher capability to scavenge free radicals than the probes of white wines. (authors)

Chemical determination of free radical-induced damage to DNA.

Science.gov (United States)

Dizdaroglu, M

1991-01-01

Free radical-induced damage to DNA in vivo can result in deleterious biological consequences such as the initiation and promotion of cancer. Chemical characterization and quantitation of such DNA damage is essential for an understanding of its biological consequences and cellular repair. Methodologies incorporating the technique of gas chromatography/mass spectrometry (GC/MS) have been developed in recent years for measurement of free radical-induced DNA damage. The use of GC/MS with selected-ion monitoring (SIM) facilitates unequivocal identification and quantitation of a large number of products of all four DNA bases produced in DNA by reactions with hydroxyl radical, hydrated electron, and H atom. Hydroxyl radical-induced DNA-protein cross-links in mammalian chromatin, and products of the sugar moiety in DNA are also unequivocally identified and quantitated. The sensitivity and selectivity of the GC/MS-SIM technique enables the measurement of DNA base products even in isolated mammalian chromatin without the necessity of first isolating DNA, and despite the presence of histones. Recent results reviewed in this article demonstrate the usefulness of the GC/MS technique for chemical determination of free radical-induced DNA damage in DNA as well as in mammalian chromatin under a vast variety of conditions of free radical production.

Free radicals in cellulose containing food detected by ESR

International Nuclear Information System (INIS)

Abe, Aika; Yogo, Satsuki; Ichii, Akane; Ukai, Mitsuko

2003-01-01

Using electron spin resonance (ESR) spectroscopy, we revealed three radical species in cellulose containing foods, pepper and green tea. These are commercially available in Japan. The representative ESR spectrum is composed of a sextet centered at g=2.0, a singlet at the same g-value, and a singlet at g=4.0. The first one is attributable to a signal with hyperfine (hf) interactions of Mn 2+ ion (hf constant: 7.4 mT). The second one is due to an organic free radical, the third one may be originated from Fe 3+ ion. The progressive saturation behavior (PSB) of the ESR at various microwave power levels were indicated different relaxation behaviors of in those radicals. Namely, the peak intensity of the organic free radical component decreases in a monotonic fashion, whereas the Mn 2+ and Fe 3+ ESR signals substantially keep constant. This reflects the evidence of three independent radical species. The ESR spectrum of the cellulose containing foods shows the same spectral feature irrespective of the tea or pepper. Upon gamma irradiation, a new pair of signals appeared. The PSB of the pair peaks after the irradiation showed a quite different as compared with the free radical centered at g=2. (author)

In vitro free radical scavenging activity of platinum nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Watanabe, Aki; Kajita, Masashi; Kim, Juewon; Kanayama, Atsuhiro; Miyamoto, Yusei [Department of Integrated Biosciences, Graduate School of Frontier Sciences, University of Tokyo, Bioscience Building 402, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8562 (Japan); Takahashi, Kyoko; Mashino, Tadahiko, E-mail: yusei74@k.u-tokyo.ac.j [Department of Pharmaceutical Sciences, Faculty of Pharmacy, Keio University, 1-5-30 Shibakoen, Minato, Tokyo 105-8512 (Japan)

2009-11-11

A polyacrylic acid (PAA)-protected platinum nanoparticle species (PAA-Pt) was prepared by alcohol reduction of hexachloroplatinate. The PAA-Pt nanoparticles were well dispersed and homogeneous in size with an average diameter of 2.0 {+-} 0.4 nm (n = 200). We used electron spin resonance to quantify the residual peroxyl radical AOO. generated from 2,2-azobis (2-aminopropane) dihydrochloride (AAPH) by thermal decomposition in the presence of O{sub 2} and a spectrophotometric method to quantify the residual 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical. PAA-Pt scavenged these two radicals in a dose-dependent manner. Platinum was the functional component. PAA-Pt reduced the rate of oxygen consumption required for linoleic acid peroxidation initiated by AOO. generated from AAPH, indicating inhibition of the propagation of linolate peroxidation. A thiobarbituric acid test also revealed dose-dependent inhibition of the linolate peroxidation by PAA-Pt. Fifty micromolar platinum, as PAA-Pt, completely quenched 250 {mu}M DPPH radical for 5 min. Even when twice diluted in half, the PAA-Pt still quenched 100% of the 250 {mu}M DPPH radical. The scavenging activity of PAA-Pt is durable. These observations suggest that PAA-Pt is an efficient scavenger of free radicals.

La transformación del régimen de representación en provincia de Córdoba a partir de la aplicación de la ley Sáenz Peña

OpenAIRE

Loreta Giannone

2016-01-01

El presente trabajo analiza la influencia que tuvieron diversos actores políticos de Córdoba en la modificación del sistema electoral a partir de la aplicación en la provincia de la ley Sáenz Peña. En dicha provincia, las ideas de democracia liberal hicieron eco en todo el entramado social: la Unión Cívica Radical, la prensa y una facción liberal de la clase dirigente que desde la crisis del juarismo en 1890 se mantenía alejada del poder. Esta presión de cambio sobre el gobierno provinc...

Resveratrol products resulting by free radical attack

Energy Technology Data Exchange (ETDEWEB)

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

2008-06-15

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

Optimal pain management for radical prostatectomy surgery

DEFF Research Database (Denmark)

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

2015-01-01

BACKGROUND: Increase in the diagnosis of prostate cancer has increased the incidence of radical prostatectomy. However, the literature assessing pain therapy for this procedure has not been systematically evaluated. Thus, optimal pain therapy for patients undergoing radical prostatectomy remains...... controversial. METHODS: Medline, Embase, and Cochrane Central Register of Controlled Trials were searched for studies assessing the effects of analgesic and anesthetic interventions on pain after radical prostatectomy. All searches were conducted in October 2012 and updated in June 2015. RESULTS: Most...... treatments studied improved pain relief and/or reduced opioid requirements. However, there were significant differences in the study designs and the variables evaluated, precluding quantitative analysis and consensus recommendations. CONCLUSIONS: This systematic review reveals that there is a lack...

Test for antioxidant ability by scavenging long-lived mutagenic radicals in mammalian cells and by blood test with intentional radicals: an application of gallic acid

International Nuclear Information System (INIS)

Kumagai, Jun; Kawaura, Tomoko; Miyazaki, Tetsuo; Prost, Michel; Prost, Emmanuelle; Watanabe, Masami; Quetin-Leclercq, J.Joeelle

2003-01-01

Antioxidant ability of gallic acid (GA) are determined both by electron spin resonance measurement of long-lived radicals produced in γ-ray irradiated Syrian golden hamster embryo cells with GA and by hemolysis measurement with GA when blood cells are submitted to radicals. Scavenging properties of GA are determined by the reaction rate constant with long-lived mutagenic radicals in the cells while the blood test allows to analyze the global effects of this compound: radical scavenger+metal ion chelator+regeneration of intra- and extra-cellular antioxidant

Oxidation of spin-traps by chlorine dioxide (ClO2) radical in aqueous solutions: first ESR evidence of formation of new nitroxide radicals.

Science.gov (United States)

Ozawa, T; Miura, Y; Ueda, J

1996-01-01

The reactivities of the chlorine dioxide (ClO2), which is a stable free radical towards some water-soluble spin-traps were investigated in aqueous solutions by an electron spin resonance (ESR) spectroscopy. The ClO2 radical was generated from the redox reaction of Ti3+ with potassium chlorate (KClO3) in aqueous solutions. When one of the spin-traps, 5,5-dimethyl-1-pyrroline N-oxide (DMPO), was included in the Ti3+-KClO3 reaction system, ESR spectrum due to the ClO2 radical completely disappeared and a new ESR spectrum [aN(1) = 0.72 mT, aH(2) = 0.41 mT], which is different from that of DMPO-ClO2 adduct, was observed. The ESR parameters of this new ESR signal was identical to those of 5,5-dimethylpyrrolidone-(2)-oxyl-(1) (DMPOX), suggesting the radical species giving the new ESR spectrum is assignable to DMPOX. The similar ESR spectrum consisting of a triplet [aN(1) = 0.69 mT] was observed when the derivative of DMPO, 3,3,5,5-tetramethyl-1-pyrroline N-oxide (M4PO) was included in the Ti3+-KClO3 reaction system. This radical species is attributed to the oxidation product of M4PO, 3,3,5,5-tetramethylpyrrolidone-(2)-oxyl-(1) (M4POX). When another nitrone spin-trap, alpha-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN) was used as a spin-trap, the ESR signal intensity due to the ClO2 radical decreased and a new ESR signal consisting of a triplet [aN(1) = 0.76 mT] was observed. The similar ESR spectrum was observed when N-t-butyl-alpha- nitrone (PBN) was used as a spin-trap. This ESR parameter [a(N)(1) = 0.85 mT] was identical to the oxidation product of PBN, PBNX. Thus, the new ESR signal observed from POBN may be assigned to the oxidation product of POBN, POBNX. These results suggest that the ClO2, radical does not form the stable spin adducts with nitrone spin-traps, but oxidizes these spin-traps to give the corresponding nitroxyl radicals. On the other hand, nitroso spin-traps, 5,5-dibromo-4-nitrosobenzenesulfonate (DBNBS), and 2-methyl-2-nitrosopropane (MNP) did not trap

Effect of radiation sterilization on free radicals content in dry beverages

International Nuclear Information System (INIS)

Hidayati, Nur; Sudiro, Sutjipto; Maha, Munsiah

1998-01-01

This study was done to determine free radicals content in several dry beverages, namely instant coffee, milk powder, cane sugar, nutrisari, tea, and cacao powder after radiation-sterilization at 25 kGy and stored at room (24 o C) and freezing (-13 o C) temperatures. Each sample was vacuum-packed in Al foil laminate pouches, then irradiated at 25 kGy in dry ice temperature. Free radicals contents in some samples after being dissolved or soaked in hot water (73 o C) then freeze-dried were also measured. The free radicals content was measured using Electron Spin Resonance (ESR) Spectroscopy and expressed in spectrum area/g in arbitrary unit. The results showed that free radicals content increased after irradiation, but it decreased immediately after storage especially at room temperature. After about 5 months storage either at room or freezing temperature, free radicals contents of irradiated coffee, milk, powder and cacao powder were similar to those of the unirradiated control, while in tea sample stored at freezing temperature, the free radicals content was still a little bit higher than that stored at room temperature which was already similar to the control. Free radicals content of irradiated sugar as well as nutrisari was higher than the other samples, and the radicals were relatively stable either at room or freezing temperatures. However, after dissolving or soaking the samples in water, the ESR spectra or free radicals contents of the irradiated samples were found to be identical to the control. This indicates that free radicals formed by irradiation in the samples disappear because termination. (authors)

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

Science.gov (United States)

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The entry of free radicals into polystyrene latex particles

International Nuclear Information System (INIS)

Adams, M.E.; Trau, M.; Gilbert, R.C.; Napper, D.R.

1988-01-01

Mechanistic understanding of the processes governing the kinetics of emulsion polymerization has both scientific and technical interest. One component of this process that is poorly understood at present is that of free radical entry into latex particles. Measurements were made of the entry rate coefficient as a function of temperature for free radicals entering polystyrene latex particles in seeded emulsion polymerizations initiated by γ-rays. The activation energy for entry was found to be less than 24 ± 3 kJ mol -1 , consistent with entry being controlled by a physical (e.g. diffusional) rather than a chemical process. Measurement of the entry rate coefficient as a function of the γ-ray dose rate suggested that the factors that determine the entry rate when the primary free radicals are uncharged are similar to those that determine the entry rate for charged free radicals derived from chemical initiation by peroxydisulfate. This result was consistent with measurements of the entry rate coefficient of charged free radicals derived from peroxydisulfate; these data were found to be virtually independent of both the extent of the latex surface coverage by the anionic surfactant sodium dodecyl sulfate and the ionic strength of the continuous phase. The data refute several proposals given in the literature for the rate-determining step for entry, being inconsistent with control by collision of free radicals with the latex particles, surfactant desorption, and an electrostatic barrier arising from the colloidal nature of the entering free radical. The origin of the activation energy for entry remains obscure

Provocaciones teóricas para el siglo XXI: la experiencia del poema

OpenAIRE

Scarano, Laura

2008-01-01

Quisiera compartir pues en esta ponencia los derroteros críticos que impulsan mi curiosidad por entender los trazos de lo que un sujeto autoral llama su “experiencia” e “intimidad”, transpuestos a lenguaje poético. Y en el acto de esta “escritura del yo íntimo” proponen al lector –no ya su radical ajenidad­ sino un camino interpretativo para construir una experiencia análoga, dentro de las coordenadas de una estética de la proyección y el reconocimiento, que ponga en escena la “vivencia” ideo...

pi-Dimers of end-capped oligopyrrole cation radicals

NARCIS (Netherlands)

Haare, van J.A.E.H.; Groenendaal, L.; Havinga, E.E.; Janssen, R.A.J.; Meijer, E.W.

1996-01-01

In two consecutive one-electron oxidations, oligopyrroles substituted with phenyl capping groups (PhPynPh, n = 2–4) can be oxidized reversibly to give stable cation radicals and dications. Spectroelectrochemical studies give direct evidence that diamagnetic p-dimers of cation radicals are formed in

Robot-assisted radical prostatectomy is a safe procedure

DEFF Research Database (Denmark)

Thomsen, Frederik Birkebæk; Berg, Kasper Drimer; Hvarness, Helle

2013-01-01

We present our departmental experience with robot-assisted radical prostatectomy and describe complications and early results for the first 239 consecutive patients.......We present our departmental experience with robot-assisted radical prostatectomy and describe complications and early results for the first 239 consecutive patients....

Generation of radicals and antimalarial activity of dispiro-1,2,4-trioxolanes

Science.gov (United States)

Denisov, E. T.; Denisova, T. G.

2013-01-01

The kinetic schemes of the intramolecular oxidation of radicals generated from substituted dispiro-1,2,4-trioxolanes (seven compounds) in the presence of Fe2+ and oxygen were built. Each radical reaction was defined in terms of enthalpy, activation energy, and rate constant. The kinetic characteristics were calculated by the intersecting parabolas method. The competition between the radical reactions was considered. The entry of radicals generated by each compound into the volume was calculated. High antimalarial activity was found for 1,2,4-trioxolanes, which generated hydroxyl radicals. The structural features of trioxolanes responsible for the generation of hydroxyl radicals were determined.

Role of free radicals in radiation chemical aging

Energy Technology Data Exchange (ETDEWEB)

Greenstock, C L

1986-01-01

Ionizing radiation initiates chemical changes in DNA, phospholipid membranes and other critical cell targets, that, if allowed to accumulate unrepaired, may lead to aging and other chronic effects. The chemical effects are free radical mediated, the principal damaging species being radical OH and to a lesser extent O2-anion radical and the molecular product H/sub 2/O/sub 2/. Many compounds can act in combination with ionizing radiation, to amplify the potential oxidative stress. Chemicals, ultra-violet light, lipid peroxides and their breakdown products may increase the extent of acute and chronic radiobiological effects.

Homegrown religious radicalization and the quest for belonging

DEFF Research Database (Denmark)

Khawaja, Iram

this seemingly religious radicalization, from the point of view of the youngsters, by drawing on a study of young Muslims in religious communities in Copenhagen and combining it with existing blogs, twitter profiles etc. of youngsters sympathizing with Islamic radicalized movements. What are the youngsters...... framework based on a focus on belonging, self-construction and the sense of community will be proposed. The framework will be utilized in an analysis of narratives from youngsters who have chosen a radicalized path in life. The paper will shed light on how the sense of and yearning for belonging...

Transformations of dissolved organic matter induced by UV photolysis, Hydroxyl radicals, chlorine radicals, and sulfate radicals in aqueous-phase UV-Based advanced oxidation processes.

Science.gov (United States)

Varanasi, Lathika; Coscarelli, Erica; Khaksari, Maryam; Mazzoleni, Lynn R; Minakata, Daisuke

2018-05-15

Considering the increasing identification of trace organic contaminants in natural aquatic environments, the removal of trace organic contaminants from water or wastewater discharge is an urgent task. Ultraviolet (UV) and UV-based advanced oxidation processes (AOPs), such as UV/hydrogen peroxide (UV/H 2 O 2 ), UV/free chlorine and UV/persulfate, are attractive and promising approaches for the removal of these contaminants due to the high reactivity of active radical species produced in these UV-AOPs with a wide variety of organic contaminants. However, the removal efficiency of trace contaminants is greatly affected by the presence of background dissolved organic matter (DOM). In this study, we use ultrahigh resolution mass spectrometry to evaluate the transformation of a standard Suwanee River fulvic acid DOM isolate in UV photolysis and UV-AOPs. The use of probe compounds allows for the determination of the steady-state concentrations of active radical species in each UV-AOP. The changes in the H/C and O/C elemental ratios, double bond equivalents, and the low-molecular-weight transformation product concentrations of organic acids reveal that different DOM transformation patterns are induced by each UV-AOP. By comparison with the known reactivities of each radical species with specific organic compounds, we mechanistically and systematically elucidate the molecular-level DOM transformation pathways induced by hydroxyl, chlorine, and sulfate radicals in UV-AOPs. We find that there is a distinct transformation in the aliphatic components of DOM due to HO• in UV/H 2 O 2 and UV/free chlorine. Cl• induced transformation of olefinic species is also observed in the UV/free chlorine system. Transformation of aromatic and olefinic moieties by SO 4 •- are the predominant pathways in the UV/persulfate system. Copyright © 2018 Elsevier Ltd. All rights reserved.

Antioxidant Effects of Herbal Tea Leaves from Yacon (Smallanthus sonchifolius) on Multiple Free Radical and Reducing Power Assays, Especially on Different Superoxide Anion Radical Generation Systems.

Science.gov (United States)

Sugahara, Shintaro; Ueda, Yuto; Fukuhara, Kumiko; Kamamuta, Yuki; Matsuda, Yasushi; Murata, Tatsuro; Kuroda, Yasuhiro; Kabata, Kiyotaka; Ono, Masateru; Igoshi, Keiji; Yasuda, Shin

2015-11-01

Yacon (Smallanthus sonchifolius), a native Andean plant, has been cultivated as a crop and locally used as a traditional folk medicine for the people suffering from diabetes and digestive/renal disorders. However, the medicinal properties of this plant and its processed foods have not been completely established. This study investigates the potent antioxidative effects of herbal tea leaves from yacon in different free radical models and a ferric reducing model. A hot-water extract exhibited the highest yield of total polyphenol and scavenging effect on 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical among four extracts prepared with hot water, methanol, ethanol, and ethylacetate. In addition, a higher reducing power of the hot-water extract was similarly demonstrated among these extracts. Varying concentrations of the hot-water extract resulted in different scavenging activities in four synthetic free radical models: DPPH radical (EC50 28.1 μg/mL), 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) cation radical (EC50 23.7 μg/mL), galvinoxyl radical (EC50 3.06 μg/mL), and chlorpromazine cation radical (EC50 475 μg/mL). The yacon tea-leaf extract further demonstrated superoxide anion (O2(-)) radical scavenging effects in the phenazine methosulfate-NADH-nitroblue tetrazolium (EC50 64.5 μg/mL) and xanthine oxidase assay systems (EC50 20.7 μg/mL). Subsequently, incubating human neutrophilic cells in the presence of the tea-leaf extract could suppress the cellular O2(-) radical generation (IC50 65.7 μg/mL) in a phorbol 12-myristate 13-acetate-activated cell model. These results support yacon tea leaves may be a good source of natural antioxidants for preventing O2(-) radical-mediated disorders. Yacon has been considered to be a potent alternative food source for patients who require a dietary cure in regional area, while the leaf part has been provided and consumed as an herbal tea in local markets. We demonstrated here potent antioxidative effects of the tea

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

Science.gov (United States)

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...

Quantification of Radicals Generated in a Sonicator

Directory of Open Access Journals (Sweden)

Kassim Badmus

2016-06-01

Full Text Available The hydroxyl radical (OH• is a powerful oxidant produced as a consequence of cavitation in water. It can react nonspecifically in breaking down persistent organic pollutants in water into their mineral form. It can also recombine to form hydrogen peroxide which is very useful in water treatment. In this study, terephthalic acid (TA and potassium iodide dosimetry were used to quantify and investigate the behaviour of the generated OH radical in a laboratory scale sonicator. The 2-hydroxyl terephthalic acid (HTA formed during terephthalic acid dosimetry was determined by optical fibre spectrometer. The production rate of HTA served as a means of evaluating and characterizing the OH• generated over given time in a sonicator. The influence of sonicator power intensity, solution pH and irradiation time upon OH• generation were investigated. Approximately 2.2 ´ 10-9 M s-1 of OH radical was generated during the sonication process. The rate of generation of the OH radicals was established to be independent of the concentration of the initial reactant. Thus, the rate of generation of OH• can be predicted by zero order kinetics in a sonicator.

DISTRIBUCIÓN RADICAL DE ÁRBOLES DE LIMÓN PERSA (Citrus latifolia Tan.

Directory of Open Access Journals (Sweden)

E. Contreras-Morales

2008-01-01

Full Text Available Este estudio fue hecho para conocer la distribución radical de árboles de limón persa cultivados en un suelo arenoso y uno arcilloso en Martínez de la Torre, Ver. Se empleó el método de la pared del perfil del suelo, clasificando las raíces en cuatro categorías de acuerdo con su diámetro: R1 (>15 mm, R2 (5-15 mm, R3 (1-5 mm y R4 (<1 mm. Las dimensiones de la cepa fueron 4 m de largo, 1 m de profundidad y 0.8 m de ancho y se construyeron tres por cada árbol (a 50 cm del tronco, zona de goteo y la parte media entre las anteriores. En cada tipo de suelo se emplearon cuatro árboles homogéneos los cuales tenían 12 años de edad en suelo arenoso y 9 años de edad en el arcilloso. Las raíces se agruparon en tres estratos de profundidad (de 0 a 30 cm; 30-60 cm y de 60-100 cm. Se analizó el número de raíces con el programa SAS considerando a la profundidad y a la distancia como factores. La mayor cantidad de raíces se presentó, para ambos tipos de suelo, en el estrato de 0-30 cm de profundidad decreciendo hacia los estratos más profundos. Se observó la tendencia en el número de raíces, a descender conforme se incrementa la distancia desde el tronco. Las raíces más numerosas fueron las R4 o fibrosas seguidas en orden decreciente por R3, R2 y R1.

TRATAMIENTO QUIRÚRGICO DEL CANCER GÁSTRICO: UNA VISIÓN ACTUALIZADA

Directory of Open Access Journals (Sweden)

José Felix Patiño Restrepo

1984-09-01

Full Text Available

La conducta adoptada en el Hospital de La Samaritana coincide con algunos preceptos actualmente preconizados por la Clínica Lahey (54, uno de los centros que en una época promulgaron la extirpación radical y que mayor influencia produjeron en muchos países del mundo, así como con los preconizados por la Clínica Cleveland (55, institución que ha modificado muchos de los tradicionales principios de radicalidad en la cirugía del cáncer:

1. Todo paciente con cáncer gástrico es sometido a exploración quirúrgica;
2. Si la lesión es resecable, se emprende una operación "curativa", la cual comprende la
resección del tumor con márgenes suficientes, pero no excesivos, de tejido normal, tratando siempre de conservar un segmento de estómago proximal, y evitando la resección profiláctica del bazo, epiplones y órganos vecinos;
3. No se realiza la gastrectomía total sino en situaciones en las cuales ésta es la única forma de lograr la extirpación total del tumor, y nunca como terapia paliativa;
4. Se realizan grandes resecciones sólo para grandes cánceres, y se realizan pequeñas resecciones para tumores pequeños;
5. Cuando no es posible realizar una resección curativa, se procede con una resección paliativa si ésta es fácilmente realizable y no significa una resección heroica o masiva; específicamente se realizan resecciones paliativas para controlar hemorragia, obstrucción y dolor; nunca debe hacerse una gastrectomía total como procedimiento paliativo, y la gastroenterostomía, la gastrostomía o la yeyunostomía tienen muy escasa indicación en la paliación del cáncer gástrico.
6. Creemos que en última instancia el pronóstico del paciente depende del tipo y estado del tumor, de su rata de crecimiento y caracteristicas biológicas y de otros factores de la relación tumor/paciente, más que del tipo y la radicalidad del tratamiento quirúrgico empleado.

Reactions of carbon radicals generated by 1,5-transposition of reactive centers

Directory of Open Access Journals (Sweden)

ZIVORAD CEKOVIC

2005-03-01

Full Text Available Radical intermediates can undergo specific reactions, such as intramolecular rearrangements, i.e., the transpositions of radical centers, which are not known in classical ionic organic reactions. 1,5-Transposition of a radical center to a non-activated carbon atom are of great synthetic importance. It can be successfully applied for the introduction of different functional groups (oxygen, nitrogen, sulfur, halogens onto a carbon atom remote from the present functional group. In addition to functionalization of a remote non-activated carbon atom, the formation of new C-C bonds on the d-carbon atom have also been achieved. 1,5-Transposition of the radical centers takes place from alkoxyl, aminyl and carbon radicals to a remote carbon atom. Relocation of the radical centers preferentially involves 1,5-transfer of a hydrogen atom, although migrations of some other groups are known. The reactions of the carbon radical generated by 1,5-relocation of the radical center are presented and their synthetic applications are reviewed.

Synthesis and Free Radical Scavenging Activity of New Hydroxybenzylidene Hydrazines

Directory of Open Access Journals (Sweden)

Frantisek Sersen

2017-05-01

Full Text Available Hydroxybenzylidene hydrazines exhibit a wide spectrum of biological activities. Here, we report synthesis and free radical scavenging activity of nine new N-(hydroxybenzylidene-N′-[2,6-dinitro-4-(trifluoromethyl]phenylhydrazines. The chemical structures of these compounds were confirmed by 1H-NMR, 13C-NMR, 19F-NMR, IR spectroscopy, LC-MS, and elemental analysis. The prepared compounds were tested for their activity to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH, galvinoxyl radical (GOR, and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS radicals. The free radical scavenging activity expressed as SC50 values of these compounds varied in a wide range, from a strong to no radical scavenging effect. The most effective radical scavengers were hydroxybenzylidene hydrazines containing three hydroxyl groups in the benzylidene part of their molecules. The prepared compounds were also tested for their activity to inhibit photosynthetic electron transport in spinach chloroplasts. IC50 values of these compounds varied in wide range, from an intermediate to no inhibitory effect.

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

Science.gov (United States)

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

2018-06-04

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

Radiation-initiated free-radical fragmentation of biologically active glycerides

International Nuclear Information System (INIS)

Akhrem, A.A.; Kisel', M.A.; Shadyro, O.I.; Yurkova, I.L.

1993-01-01

Oxidation reactions of the free-radical type play a decisive role in the initial processes of radiation damage. The most suitable substrates for such reactions are lipids. Lipids are a basic structural element of biomembranes and are involved in the barrier function and biocatalytic activity of such membranes. Free-radical degradation of membrane lipids can lead to serious damage and ultimately to destruction of the living cell. A well-studied type of free-radical conversion of lipids is oxidation of polyunsaturated fatty acid residues, so-called peroxide oxidation of lipids. In this paper, using as examples dimyristoylphosphatidyl glycerol (DMPG), monoglycerides, and glycerophosphate, the authors investigated the possibility of free-radical degradation in compounds of a lipid nature containing the α,β-bifunctional group

Pertinent issues related to laparoscopic radical prostatectomy

Directory of Open Access Journals (Sweden)

Sidney C. Abreu

2003-12-01

Full Text Available PURPOSE: We describe the critical steps of the laparoscopic radical prostatectomy (LRP technique and discuss how they impact upon the pertinent issues regarding prostate cancer surgery: blood loss, potency and continence. RESULTS: A major advantage of LRP is the reduced operative blood loss. The precise placement of the dorsal vein complex stitch associated with the tamponading effect of the CO2 pneumoperitoneum significantly decrease venous bleeding, which is the main source of blood loss during radical prostatectomy. At the Cleveland Clinic, the average blood loss of our first 100 patients was 322.5 ml, resulting in low transfusion rates. The continuous venous bleeding narrowed pelvic surgical field and poor visibility can adversely impact on nerve preservation during open radical prostatectomy. Laparoscopy, with its enhanced and magnified vision in a relatively bloodless field allows for excellent identification and handling of the neurovascular bundles. During open retropubic radical prostatectomy, the pubic bone may impair visibility and access to the urethral stump, and the surgeon must tie the knots relying on tactile sensation alone. Consequently, open prostatectomy is associated with a prolonged catheterization period of 2 - 3 weeks. Comparatively, during laparoscopic radical prostatectomy all sutures are meticulously placed and each is tied under complete visual control, resulting in a precise mucosa-to-mucosa approximation. CONCLUSION: The laparoscopic approach may represent a reliable less invasive alternative to the conventional open approach. Despite the encouraging preliminary anatomical and functional outcomes, prospective randomized comparative trials are required to critically evaluate the role of laparoscopy for this sophisticated and delicate operation.

Rapid Hydrogen Shift Reactions in Acyl Peroxy Radicals

DEFF Research Database (Denmark)

Knap, Hasse Christian; Jørgensen, Solvejg

2017-01-01

-shift with X = 6, 7, 8, or 9) in the hydroperoxy acyl peroxy radicals, this H-shift is a reversible reaction and it scrambles between two peroxides, hydroperoxy acyl peroxy and peroxy peroxoic acid radicals. The forward reaction rate constants of the 1,X-OOH H-shift reactions are estimated to be above 103 s–1...... with transition state theory corrected with Eckart quantum tunnelling correction. The ratio between the forward and reverse reaction rate constant of the 1,X-OOH H-shift reactions is around ∼105. Therefore, the equilibrium is pushed toward the production of peroxy peroxoic acid radicals. These very fast 1,X-OOH H......We have used quantum mechanical chemical calculations (CCSD(T)-F12a/cc-pVDZ-F12//M06-2X/aug-cc-pVTZ) to investigate the hydrogen shift (H-shift) reactions in acyl peroxy and hydroperoxy acyl peroxy radicals. We have focused on the H-shift reactions from a hydroperoxy group (OOH) (1,X-OOH H...

Engineering radical polymer electrodes for electrochemical energy storage

Science.gov (United States)

Nevers, Douglas R.; Brushett, Fikile R.; Wheeler, Dean R.

2017-06-01

In principle a wide range of organic materials can store energy in the form of reversible redox conversions of stable radicals. Such chemistry holds great promise for energy storage applications due to high theoretical capacities, high rate capabilities, intrinsic structural tunability, and the possibility of low-cost "green" syntheses from renewable sources. There have been steady improvements in the design of organic radical polymers, in which radicals are incorporated into the backbone and/or as pendant groups. This review highlights opportunities for improved redox molecule and polymer design along with the key challenges (e.g., transport phenomena, solubility, and reaction mechanisms) to transitioning known organic radicals into high-performance electrodes. Ultimately, organic-based batteries are still a nascent field with many open questions. Further advances in molecular design, electrode engineering, and device architecture will be required for these systems to reach their full potential and meet the diverse and increasing demands for energy storage.

J/{psi} production in {radical}(s)=7 TeV pp collisions

Energy Technology Data Exchange (ETDEWEB)

Kramer, Frederick

2012-07-01

In the first part of this work the inclusive cross section for J/{psi} production in inelastic {radical}(s) = 7 TeV pp collisions has been determined within vertical stroke y vertical stroke < 0.9 and in the decay channel J/{psi} {yields} e{sup +}e{sup -}. The result for the integrated value is: {sigma}{sub J/{psi}}(vertical stroke y vertical stroke < 0.9) = 10.7 {+-} 0.8 (stat.) {+-} 1.4 (syst.) {+-} 0.4 (lumi.) {mu}b. Together with the ALICE measurement in the {mu}{sup +}{mu}{sup -} decay channel at forward rapidities and data from other experiments this result fills the gap at mid-rapidity for a comprehensive measurement of the J/{psi} rapidity distribution. Furthermore, results of the differential analysis as a function of the J/{psi} transverse momentum were presented. Finally the data are shown together with various theoretical predictions representing the current status of the three most common theoretical approaches for the description of quarkonia production: the Color-Singlet Model, the Color-Evaporation Model and NRQCD.

Formation of radicals in coal pyrolysis examined by electron spin resonance

Directory of Open Access Journals (Sweden)

Tong Chang

2017-09-01

Full Text Available Electron spin resonance (ESR spectroscopy is used to study materials with unpaired electrons, such as organic radicals and metal complexes. This method can also be used to follow radical reactions during pyrolysis of carbonaceous materials. However, the temperature dependence of ESR measurement should be considered. To enable reasonable comparisons, results measured at different temperatures must be converted. In this study, we investigated the behavior of free radicals in the process of coal pyrolysis using in situ and ex situ ESR. The ESR data were collected at both pyrolysis and room temperatures, and apparent differences were analyzed. The differences were diminished when our data were converted to the same measurement temperature level based on the Boltzmann distribution law. Furthermore, we investigated the effects of process conditions on the behavior of free radicals in the solid phase of coal. We found that temperature is the most important factor determining the formation and behavior of free radicals in the solid phase, followed by the residence time. Relatively active radicals were quenched by hydrogen-donor solvents to some degree, while stable radicals remained.

Fluorophore-based sensor for oxygen radicals in processing plasmas

International Nuclear Information System (INIS)

Choudhury, Faraz A.; Shohet, J. Leon; Sabat, Grzegorz; Sussman, Michael R.; Nishi, Yoshio

2015-01-01

A high concentration of radicals is present in many processing plasmas, which affects the processing conditions and the properties of materials exposed to the plasma. Determining the types and concentrations of free radicals present in the plasma is critical in order to determine their effects on the materials being processed. Current methods for detecting free radicals in a plasma require multiple expensive and bulky instruments, complex setups, and often, modifications to the plasma reactor. This work presents a simple technique that detects reactive-oxygen radicals incident on a surface from a plasma. The measurements are made using a fluorophore dye that is commonly used in biological and cellular systems for assay labeling in liquids. Using fluorometric analysis, it was found that the fluorophore reacts with oxygen radicals incident from the plasma, which is indicated by degradation of its fluorescence. As plasma power was increased, the quenching of the fluorescence significantly increased. Both immobilized and nonimmobilized fluorophore dyes were used and the results indicate that both states function effectively under vacuum conditions. The reaction mechanism is very similar to that of the liquid dye

Fluorophore-based sensor for oxygen radicals in processing plasmas

Energy Technology Data Exchange (ETDEWEB)

Choudhury, Faraz A.; Shohet, J. Leon, E-mail: shohet@engr.wisc.edu [Plasma Processing and Technology Laboratory and Department of Electrical and Computer Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States); Sabat, Grzegorz; Sussman, Michael R. [Department of Biochemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States); Nishi, Yoshio [Department of Electrical Engineering, Stanford University, Stanford, California 94305 (United States)

2015-11-15

A high concentration of radicals is present in many processing plasmas, which affects the processing conditions and the properties of materials exposed to the plasma. Determining the types and concentrations of free radicals present in the plasma is critical in order to determine their effects on the materials being processed. Current methods for detecting free radicals in a plasma require multiple expensive and bulky instruments, complex setups, and often, modifications to the plasma reactor. This work presents a simple technique that detects reactive-oxygen radicals incident on a surface from a plasma. The measurements are made using a fluorophore dye that is commonly used in biological and cellular systems for assay labeling in liquids. Using fluorometric analysis, it was found that the fluorophore reacts with oxygen radicals incident from the plasma, which is indicated by degradation of its fluorescence. As plasma power was increased, the quenching of the fluorescence significantly increased. Both immobilized and nonimmobilized fluorophore dyes were used and the results indicate that both states function effectively under vacuum conditions. The reaction mechanism is very similar to that of the liquid dye.

Radical Left in Albania and Kosovo: Differences and Similarities

Directory of Open Access Journals (Sweden)

Këlliçi Klejd

2017-06-01

Full Text Available The main research question for this paper is: Are there radical left wing movements in Albania and Kosovo and what are their main traits? Through answering this question, we will explore the development (or lack thereof of radical left wing movements. With radical left we intend movements that reject the underlying socio-economic structure of contemporary capitalism and its values and practices without opposing democracy. Through a thorough desk research and several interviews with experts and activists both in Albania and Kosovo, we look at the two case Political Opportunity Structures to study the emergence, the strategies, success or failures of the radical left. In Albania the radical left has been in decline since 1992, with only a recent revival from 2009 on. In Kosovo, the Lëvizja Vetëvendojse! (Self-Determination Movement, a civil movement transformed in a party, has succeeded in imposing its left agenda. Both cases employ a new rhetoric unrelated to the past communist regimes thus changing the perspective of political debate in both countries.

X-band ESR study on evaluation of radicals induced in pasteurized pepper

International Nuclear Information System (INIS)

Matsuura, Masaaki; Ogawa, Satoko; Ukai, Mitsuko; Oowada, Shigeru

2007-01-01

The radical properties of pasteurized pepper were investigated by means of X-band ESR spectroscopy. Pasteurization process was done by irradiation or steam. There were three radicals in the specimens before and after pasteurization. Upon irradiation a new radical was found. ESR peak intensity of specimen before and after parturition with steam was almost same level. Peak intensity of radiated pepper showed almost 4 times as compare with that of non treated pepper. Radical activity of the specimens after pasteurization showed almost same value. We concluded that radicals were induced by irradiation. But the radical activity was not changed before and after pasteurization. (author)

Mechanism of protection of adenosine from sulphate radical anion ...

Indian Academy of Sciences (India)

Unknown

Keywords. Repair by caffeic acid; repair of adenosine radicals; oxidation by sulphate radical anions. ... known that hydroxycinnamic acids are natural anti- oxidants ... acid. 2. Experimental ..... ously and independently under kinetic conditions at.

Geoscientists and the Radical Middle

Science.gov (United States)

Tinker, S. W.

2015-12-01

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

Radiation chemistry of aromatic dimer radical cations

International Nuclear Information System (INIS)

Okamoto, Kazumasa; Tagawa, Seiichi

2009-01-01

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

Radical versus Social Constructivism: Dilemma, Dialogue, and Defense

Science.gov (United States)

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…

Radicals versus Moderates: A Critique of Gyekye's Moderate ...

African Journals Online (AJOL)

The communitarian conception of person is a widely accepted view in African thought. Kwame Gyekye thinks there is a distinction between what he calls radical communitarianism and his own version of moderate communitarianism. He is of the view that radical communitarianism is faced with insurmountable problems and ...

Characterization and DPPH Radical Scavenging Activity of Gallic ...

African Journals Online (AJOL)

Characterization and DPPH Radical Scavenging Activity of Gallic Acid-Lecithin Complex. C Liu, C Chen, H Ma, E Yuan, Q Li. Abstract. Purpose: To investigate the physicochemical properties and DPPH radical scavenging activity of gallic acid–lecithin complex. Methods: The complex of gallic acid with lecithin was prepared ...

EPR spectral investigation of radiation-induced radicals of gallic acid.

Science.gov (United States)

Tuner, Hasan

2017-11-01

In the present work, spectroscopic features of the radiation-induced radicals of gallic acid compounds were investigated using electron paramagnetic resonance (EPR) spectroscopy. While un-irradiated samples presented no EPR signal, irradiated samples exhibited an EPR spectrum consisting of an intense resonance line at the center and weak lines on both sides. Detailed microwave saturation investigations were carried out to determine the origin of the experimental EPR lines. It is concluded that the two side lines of the triplet satellite originate from forbidden "spin-flip" transitions. The spectroscopic and structural features of the radiation-induced radicals were determined using EPR spectrum fittings. The experimental EPR spectra of the two gallic acid compounds were consistent with the calculated EPR spectroscopic features of the proposed radicals. It is concluded that the most probable radicals are the cyclohexadienyl-type, [Formula: see text] radicals for both compounds.

Radical scavenging potentials of single and combinatorial herbal formulations in vitro

Directory of Open Access Journals (Sweden)

Okey A. Ojiako

2016-04-01

Full Text Available Reactive oxygen and nitrogen species (RONS are involved in deleterious/beneficial biological processes. The present study sought to investigate the capacity of single and combinatorial herbal formulations of Acanthus montanus, Emilia coccinea, Hibiscus rosasinensis, and Asystasia gangetica to act as superoxide radicals (SOR, hydrogen peroxide (HP, nitric oxide radical (NOR, hydroxyl radical (HR, and 2,2-diphenyl-1-picrylhydrazyl (DPPH radical antagonists using in vitro models. The herbal extracts were single herbal formulations (SHfs, double herbal formulations (DHfs, triple herbal formulations (THfs, and a quadruple herbal formulation (QHf. The phytochemical composition and radical scavenging capacity index (SCI of the herbal formulations were measured using standard methods. The flavonoids were the most abundant phytochemicals present in the herbal extracts. The SCI50 defined the concentration (μg/mL of herbal formulation required to scavenge 50% of the investigated radicals. The SHfs, DHfs, THfs, and QHf SCI50 against the radicals followed the order HR > SOR > DPPH radical > HP > NOR. Although the various herbal formulations exhibited ambivalent antioxidant activities in terms of their radical scavenging capabilities, a broad survey of the results of the present study showed that combinatorial herbal formulations (DHfs, THfs, and QHf appeared to exhibit lower radical scavenging capacities than those of the SHfs in vitro.

Effects of oxygen radical scavengers on the inactivation of SS phi X174 DNA by the semi-quinone free radical of the antitumor agent etoposide

NARCIS (Netherlands)

van Maanen, M.J.; Mans, D.R.A.; Lafleur, M.V.M.; Van Schaik, M A; de Vries, J; Vermeulen, N P; Retèl, J.; Lankelma, J

1990-01-01

We have studied the effects of oxygen radical scavengers on the inactivation of ss phi X174 DNA by the semi-quinone free radical of the antitumor agent etoposide (VP 16-213), which was generated from the ortho-quinone of etoposide at pH greater than or equal to 7.4. A semi-quinone free radical of

Free Radical Imaging Using In Vivo Dynamic Nuclear Polarization-MRI.

Science.gov (United States)

Utsumi, Hideo; Hyodo, Fuminori

2015-01-01

Redox reactions that generate free radical intermediates are essential to metabolic processes, and their intermediates can produce reactive oxygen species, which may promote diseases related to oxidative stress. The development of an in vivo electron spin resonance (ESR) spectrometer and its imaging enables us noninvasive and direct measurement of in vivo free radical reactions in living organisms. The dynamic nuclear polarization magnetic resonance imaging (DNP-MRI), also called PEDRI or OMRI, is also a new imaging method for observing free radical species in vivo. The spatiotemporal resolution of free radical imaging with DNP-MRI is comparable with that in MRI, and each of the radical species can be distinguished in the spectroscopic images by changing the frequency or magnetic field of ESR irradiation. Several kinds of stable nitroxyl radicals were used as spin probes to detect in vivo redox reactions. The signal decay of nitroxyl probes, which is determined with in vivo DNP-MRI, reflects the redox status under oxidative stress, and the signal decay is suppressed by prior administration of antioxidants. In addition, DNP-MRI can also visualize various intermediate free radicals from the intrinsic redox molecules. This noninvasive method, in vivo DNP-MRI, could become a useful tool for investigating the mechanism of oxidative injuries in animal disease models and the in vivo effects of antioxidant drugs. © 2015 Elsevier Inc. All rights reserved.

A muoniated radical in selenium

International Nuclear Information System (INIS)

Reid, I.D.; Cox, S.F.J.; Jayasooriya, U.A.; Zimmermann, U.

2003-01-01

We report new 0.3 T transverse-field μSR experiments in crystalline Se which show only a small, slowly relaxing muon signal at 300 K, accounting for about 30% of the incoming muon polarization. However, at 90 K signals are observed around 74 and 157 MHz, characteristic of a radical with a hyperfine coupling of 231 MHz. Very fast relaxation which increases with temperature makes these signals impossible to follow beyond 200 K. Above 400 K a quickly relaxing diamagnetic signal becomes visible, its relaxation falling with increasing temperature. In the melt (>490 K) just a single non-relaxing diamagnetic signal is seen. These observations may be explained by electron spin-exchange with a muoniated radical

Free radicals. High-resolution spectroscopy and molecular structure

International Nuclear Information System (INIS)

Hirota, E.

1983-01-01

High-resolution, high-sensitivity spectroscopy using CW laser and microwave sources has been applied to free radicals and transient molecules to establish their existence and to explore their properties in detail. The radicals studied were mainly generated by discharge-induced reactions. A few molecules are used as typical examples to illustrate the results so far obtained. The molecular and electronic structures of free radicals, intramolecular motions of large amplitudes in some labile molecules, and metastable electronic states of carbenes are given special emphasis. The significance of the present spectroscopic results in other related fields such as astronomy and atmospheric chemistry is stressed. 4 figures, 3 tables

Radical C-H functionalization to construct heterocyclic compounds.

Science.gov (United States)

Yu, Jin-Tao; Pan, Changduo

2016-02-07

Heterocyclic compounds are widely present in natural products, pharmaceuticals and bioactive molecules. Thus, organic and pharmaceutical chemists have been making extensive efforts to construct those heterocyclic frameworks through developing versatile and efficient synthetic strategies. The direct C-H functionalization via the radical pathway has emerged as a promising and dramatic approach towards heterocycles with high atom- and step-economy. Heterocyclic compounds such as coumarins, furans, benzofurans, xanthones, benzothiazoles, indoles, indolines, oxindoles, quinolines, isoquinolines, quinoxaline, and phenanthridines have been successfully synthesized by C-H functionalization through the radical pathway. In this review, recent advances on radical C-H functionalization to construct heterocyclic compounds are highlighted with discussions.

LOS DESTINOS DEL ZAPATISMO Y LA CUESTIÓN DE LA AUTONOMÍA

Directory of Open Access Journals (Sweden)

Rafael Miranda Redondo

2017-08-01

Full Text Available En el artículo a continuación abordamos la cuestión de los destinos del zapatismo como movimiento social a la luz de la cuestión de la autonomía. Ese cometido lo trabajamos a la luz de hipótesis de Castoriadis en el sentido de que el punto clave, en lo que a la autonomía se refiere, no es la resistencia, la identidad o el comunitarismo, mucho menos el relativismo o el supuesto universalismo y si la relación respecto a la institución que está en el propio origen. En este sentido la prueba de fuego respecto al aporte de los movimientos sociales en el sentido del proyecto de autonomía pasa por la negativa de ocultar el poder instituyente que resignifica el propio origen, sometiendo dicha tendencia a la autoalteración y en ese sentido no respecto de lo que es y si respecto de lo que va a ser. Dos instituciones están en el origen del zapatismo contemporáneo, el marxismo y la teología de la liberación, que en versión tercermundista mesiánica, en boca del fanonísmo y el foquísmo, permean los ambientes del activismo político y de la academia, gracias al ultimo recurso de la identidad como algo esencial. En seguimiento a un prolongado ejercicio de dialogo con esa cultura política adelantamos en el cierre del presente escrito una tendencia al cuestionamiento radical en lo que a la teología de la liberación se refiere por un lado y una asignatura pendiente, un duelo congelado diríamos, respecto al marxismo.

Fast Resonance Raman Spectroscopy of Short-Lived Radicals

DEFF Research Database (Denmark)

Pagsberg, Palle Bjørn; Wilbrandt, Robert Walter; Hansen, Karina Benthin

1976-01-01

We report the first application of pulsed resonance Raman spectroscopy to the study of short-lived free radicals produced by pulse radiolysis. A single pulse from a flash-lamp pumped tunable dye laser is used to excite the resonance Raman spectrum of the p-terphenyl anion radical with an initial...

Method for recovering or recirculating stable nitroxide radicals

NARCIS (Netherlands)

Heeres, Andre; Van Doren, Hendrik Arend; Bleeker, Ido Pieter; Gotlieb, Kornelis Fester.

1996-01-01

The invention relates fo a method for recovering stable nitroxide radicals, wherein at least a part of a reaction mixt. consisting of a soln. or suspension, or a filtrate or supernatant of a suspension, in which stable nitroxide radicals are present in non-solid form, is subjected to an azeotropic

Crossed-beam studies of the dynamics of radical reactions

Energy Technology Data Exchange (ETDEWEB)

Liu, K. [Argonne National Laboratory, IL (United States)

1993-12-01

The objective of this program is to characterize the detailed dynamics of elementary radical reactions and to provide a better understanding of radical reactivity in general. The radical beam is typically generated by a laser photolysis method. After colliding with the reacting molecule in a crossed-beam apparatus, the reaction product state distribution is interrogated by laser spectroscopic techniques. Several radicals of combustion significance, such as O, CH, OH, CN and NCO have been successfully generated and their collisional behavior at the state-to-state integral cross section level of detail has been studied in this manner. During the past year, the detection system has been converted from LIF to REMPI schemes, and the emphasis of this program shifted to investigate the product angular distributions. Both inelastic and reactive processes have been studied.

Some aspects of radiation-induced free-radical chemistry of biologically important molecules

International Nuclear Information System (INIS)

Sonntag, C. von

1992-01-01

Biologically relevant material is usually associated with considerable amounts of water. When ionizing radiation interacts with such material one must consider two modes of energy deposition: the direct effect (ionizing radiation is absorbed by the biomolecules) and the indirect effect (ionizing radiation is absorbed by the surrounding water). In the direct effect, radical cations plus electrons, and excited states of the biomolecules are formed. In the indirect effect the water is decomposed resulting in the formation of the water radicals OH,H and e aq - . These reactive intermediates then interact with the biomolecules. When such systems are irradiated oxygen is often present. As a result of this, the radicals formed in the biomolecules by the various routes are converted into the corresponding peroxyl radicals. In certain cases, e.g. with the nucleobases of DNA, radical cations can be produced in dilute aqueous solutions by radiation-generated SO 4 - radicals, and the fate of these nucleobase radical cations studied by pulse radiolysis and product analysis. Attention will be drawn to the fact that frequently some of the reaction products of the radical cations with water are identical to those formed by OH radical attack, but that there are also marked differences. Similarly, protonation of radical anions (formed by the reaction of solvated electrons with the biomolecules) and the reaction of H-atoms with these molecules can lead to radical intermediates with considerably differing characteristics. Our present knowledge of the variety of reactions of the peroxyl radicals occurring in aqueous solutions will be briefly discussed, emphasizing the large variety of HO 2 /O 2 - elimination reactions and pointing to the reversibility of the oxygen addition (RO 2 →R + O 2 ) in some systems recently studied. (author)

Generation and detection of the cyclohexadienyl radical in phosphonium ionic liquids.

Science.gov (United States)

Lauzon, J M; Arseneau, D J; Brodovitch, J C; Clyburne, J A C; Cormier, P; McCollum, B; Ghandi, K

2008-10-21

The formation of the cyclohexadienyl radical, C(6)H(6)Mu, in ionic and molecular solvents has been compared. This is the first time that a muoniated free radical is reported in an ionic liquid. In marked contrast to molecular liquids, free radical generation in ionic liquids is significantly enhanced. Comparison of the hyperfine interactions in the ionic liquid and in molecular solvents and with theoretical calculations, suggests significant and unforeseen solvent interaction with the cyclohexadienyl radical.

The free radical process for the polymer surface treated by radio frequency plasma

International Nuclear Information System (INIS)

Ma Yuguang; Yang Meiling; Shen Jiacong; Zheng Yingguang

1992-01-01

The formation and translation of the free radicals on the polymer surface treated by plasmas were studied and observed by ESR measurement. The results show that C-C bond split was main reaction in the process of the polymer irradiated by plasma, by which a stable alkyl free radical was formed. When alkyl free radical contacted with air, they translate into peroxide radical instantaneously. The peroxide radical was not as stable as radical in vacuum, they can react each other to form some polar-groups on polymer surface. The interaction between the peroxide free radical and polymer chain was correlative not only to the structure of polymer but also to the molecular motion of the polymer chain. The nature of plasma treating polymer surface was that the peroxide radicals were led onto polymer surface

Quenching of photoluminescence of colloidal ZnO nanocrystals by nitronyl nitroxide radicals

Energy Technology Data Exchange (ETDEWEB)

Stroyuk, Oleksandr L., E-mail: stroyuk@inphyschem-nas.kiev.ua [L.V. Pysarzhevsky Institute of Physical Chemistry of National Academy of Sciences of Ukraine, 31 Nauky avenue, 03028 Kyiv (Ukraine); Yakovenko, Anastasiya V.; Raevskaya, Oleksandra E. [L.V. Pysarzhevsky Institute of Physical Chemistry of National Academy of Sciences of Ukraine, 31 Nauky avenue, 03028 Kyiv (Ukraine); Plyusnin, Victor F. [Institute of Chemical Kinetics and Combustion of Siberian Branch of Russian Academy of Sciences, Novosibirsk (Russian Federation)

2014-11-15

Quenching of the photoluminescence of colloidal zinc oxide nanocrystals by a series of stable nitronyl nitroxide radicals was studied by means of stationary and time-resolved luminescence spectroscopy. Among the studied radicals the most efficient quenchers of the ZnO luminescence are the carboxyl-substituted species. The meta-substituted radical was found to be a more active quencher, than para-substituted one due to a closer proximity of the radical center to the nanocrystals surface. The PL quenching has a complex dynamic/static character. The dynamic quenching arises from photocatalytic radical reduction by ZnO conduction band electrons, while the static quenching is caused by adsorption of the photoreduction products on the nanocrystal surface. The non-substituted and OH-substituted radicals are inferior to the products of their photoreduction in capability of adsorption of the ZnO surface, and the quenching is dominated by interactions between the nanocrystals and photoreduced hydroxylamines. In case of COOH-substituted radicals, however, the radicals compete with the photoreduction products for the surface sites of ZnO nanocrystals resulting in a dynamic character of photoluminescence quenching.

Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere

Science.gov (United States)

Wennberg, P. O.; Hanisco, T. F.; Jaegle, L.; Jacob, D. J.; Hintsa, E. J.; Lanzendorf, E. J.; Anderson, J. G.; Gao, R.-S.; Keim, E. R.; Donnelly, S. G.;

Endoscopic extraperitoneal radical prostatectomy after radical resection of pT1-pT2 rectal cancer: a report of thirty cases.

Science.gov (United States)

Liu, Zhuo; Li, Dechuan; Chen, Yinbo

2017-01-01

Endoscopic extraperitoneal radical prostatectomy (EERPE) has gained popularity for the treatment of localized prostate cancer. However, prior complex lower abdominal or pelvic surgery can complicate subsequent EERPE. To date, there have been few reports on patients who underwent EERPE after radical resection of pT1-pT2 rectal cancer. To present our experience with EERPE in patients after radical resection of pT1-pT2 rectal carcinoma and introduce a simple and effective way to create an extraperitoneal working space. Thirty patients after radical resection of pT1-pT2 rectal carcinoma were treated with EERPE for biopsy-proven localized prostate cancer. Operation time, estimated blood loss, conversion to open surgery rate, transfusion rate and transurethral catheter time were recorded. Meanwhile, functional outcome (continence and potency) and oncological outcome were reviewed. The average operative time was 168 min. Mean blood loss was 195 ml. There was no need for conversion to open surgery or transfusion. The catheter was removed on postoperative day (POD) 7.8. After a mean follow-up time of 53.1 months, 3 patients had a prostate-specific antigen level relapse over 0.1 ng/ml. At the follow-up time, 26 patients were completely continent, and 4 needed 1-2 pads/day. Of the 6 patients who underwent neurovascular bundle preservation, none have experienced return of erections at the last follow-up time. Endoscopic extraperitoneal radical prostatectomy after radical resection of rectal carcinoma appears promising, with feasibility in experienced hands. The operative data, postoperative urinary incontinence and oncological outcomes appear encouraging, but the rate of erectile dysfunction seems to be disappointing.

Reactions of linoleic acid peroxyl radicals with phenolic antioxidants: a pulse radiolysis study

International Nuclear Information System (INIS)

Erben-Russ, Michael; Bors, Wolf; Saran, Manfred

1987-01-01

Linoleic acid peroxyl radicals (LOO) can be viewed as model intermediates occurring during lipid peroxidation processes. Formation and reactions of these species were investigated in aqueous alkaline solution using pulse radiolysis combined with kinetic spectroscopy. Irradiation of linoleic acid in N 2 O/O 2 -saturated solutions leads to a mixture of peroxyl radical isomers; reaction of 13-hydroperoxylinoleic acid (13-LOOH) with azide radicals in N 2 O-saturated solution produces 13-LOO radicals specifically. These peroxyl radicals cannot be observed directly, but their reactions with kaempferol and quercetin, acting as radical-scavenging antioxidants, produced strongly absorbing aroxyl radicals (ArO). The same aroxyl radicals were generated by OH and N 3 with rate constants exceeding 10 9 dm 3 mol -1 s -1 . Applying a reaction scheme that includes competing generation and decay reactions of both LOO and ArO radicals, individual rate constants were derived for LOO reactions with the phenols (> 10 7 dm 3 mol -1 s-? 1 ), with aroxyl radicals to form covalent adducts (> 10 8 dm 3 mol -1 s -1 ), as well as for their bimilecular decay (3.0 x 10 8 dm 3 mol -1 s -1 ). These results demonstrate high reactivity of fatty acid peroxyl radicals and flavone antioxidants in aqueous solution. (author)

Transients observed in the low temperature photolysis of alkyl radicals and divalent sulfur substrates

International Nuclear Information System (INIS)

Adam, F.C.

1976-01-01

The 253.7 nm photolysis of the isometric butyl radicals is described. These radicals are produced by electron capture during the γ-radiolysis of the corresponding butyl chlorides diluted in a rigid glass of 3-methylpentane-d14 at 77K. Thus t-butyl gives an equilibrium mixture of i-butyl and methyl radicals. Solvent radicals, M, are also produced and these obscure the former species in 3-MP-h14. Likewise sec-butyl radicals give rise to the ethyl, n-butyl, methyl and small amounts of the i-butyl radicals. Solvent radicals also rearrange and degrade in the photolytic beam, and the mechanism by which these processes occur is discussed. The procedure has also been used to study the formation and photolability of the alkyl thinyl and perthyl radicals occuring in the photolysis of RSH, RSR and RSSR. The thinyl radical is found to be unstable and gives the alkyl radical and atomic sulfur while the perthiyl radical is stable to radiation > 240 nm. (author)

La vida humana como principio interpretativo radical en la filosofía de Ortega y Gasset

Directory of Open Access Journals (Sweden)

Antonio Gutiérrez-Pozo

2012-12-01

Full Text Available En este artículo presentamos el concepto de vida humana como texto eterno en el pensamiento de Ortega y sus consecuencias para el problema de la interpretación. La filosofía de la razón vital de Ortega se fundamenta en el concepto de vida humana como realidad radical y principio interpretativo universal, y por esta razón se presenta desde el principio como una filosofía hermenéutica de la vida y no como una reducción hacia la conciencia trascendental. Esta hermenéutica se practica especialmente en el ámbito del arte. Pero para Ortega todo texto es hermenéutico y necesita por tanto la interpretación, porque ningún texto posee en sí mismo su verdad.

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

International Nuclear Information System (INIS)

Liu Weihua; Wang Mouhua; Xing Zhe; Wu Guozhong

2012-01-01

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

Effect of Azospirillum brasilense on the harvest and radical development of sugar cane plants, variety C86 - 456, obtained by in vitro culture in normal conditions and under overhumidity of soil

Directory of Open Access Journals (Sweden)

Sergio Rodríguez Rodríguez

2005-01-01

Full Text Available In order to know the influence of the bacteria Azospirillum brasilense on plants of sugar cane, cultivar C86-456, from tissue culture under normal conditions and flooded soil in a Vertisol from El Valle del Cauto, an experiment was carried out using an at random blocks design. The main crop variables (pol in cane, t. caña.ha-1 and t. pol.ha-1 at the twelve months of age were taken, as stump of spring of the year and the development reached by the radical system in its more active area to achieve this experiment. The best results in the crop variables and development of the radical system were obtained it the treatments where the bacteria was present, although non significant under both conditions, evidencing that the stress due to excess of water in the soil affects the normal development of the sugar cane in general by modifying the kindness that the rhizospheric microorganism provides. Key words: biofertilizer, radical system, Saccharum, yield

Kinetics of free radical reactions in irradiated crystalline L-leucine

International Nuclear Information System (INIS)

Dole, M.; Mahdavi, M.

1983-01-01

Four aspects of the radiation chemistry of crystalline L-leucine are presented. They are as follows: the transformation of one type of free radical into another as observed by following the ESR spectrum of individual peaks in the initial stages of the free radical decay at room or higher temperatures after a gamma irradiation at 77K; the catalytic effect of hydrogen gas in significantly accelerating the free radical decay; the unexpected effect of argon gas in decreasing the rate of the free radical decay; and the accurate agreement of the decay data with the diffusion controlled second order Waite equation when the latter is expressed in the linear form. The major free radical which exists in irradiated L-leucine gives rise to a spectrum of 8 Doublets for a total of 16 lines. Numbering the peaks from the least intense to the strongest, peaks numbers 3, 4, 6, and 7, initially increase in intensity before decreasing while peak number 5 rapidly decreases. However, during this initial period the total free radical concentration as measured by the total moment of the ESR spectrum decreases. The kinetics of these effects are discussed. (author)

Redox potentials of free radicals. III. Reevaluation of the method

International Nuclear Information System (INIS)

Rao, P.S.; Hayon, E.

1974-01-01

A reevaluation of the method described in ref 1 and 2 to determine the redox potentials of free radicals (.RH) in water using the techniques of pulse radiolysis and absorption spectrophotometry is presented. This method is based on the dependence of the percentage efficiency for the one-electron oxidation (or reduction) of .RH radicals on the redox potentials E 01 of the electron acceptors, A. The reaction .RH + A → .A - + R + H + (kappa/sub ox/) is not reversible for most radicals under the experimental conditions used, and the derived potentials are, therefore, not thermodynamic values. A reinterpretation of the results is made on the basis of the kinetic competition between the above reaction and .RH + A → .RHA (kappa/sub add/) (radical adducts). Based on kappa/ sub ox/ and kappa/sub add/, it is concluded that the observed experimental ''titration'' curves do represent a measure of the redox property of the free radicals. From the midpoint on the curves, the kinetic potential, E/sub kappa/ 01 : of the free radicals can be derived based on the known two-electron redox potentials of the electron acceptors. These and other questions are discussed. (U.S.)

Saul Alinsky, community organizing and rules for Radicals

OpenAIRE

Seal, Mike

2012-01-01

Saul Alinsky's work is an important reference point for thinking about community organizing and community development. His books Reveille for Radicals (1946) and Rules for Radicals (1971) were both classic explorations of organizing and remain popular today. Mike Seal examines Alinsky's continuing relevance to the activities of informal educators, community organizers and animateurs.

Flow Giese reaction using cyanoborohydride as a radical mediator

Directory of Open Access Journals (Sweden)

Takahide Fukuyama

2013-09-01

Full Text Available Tin-free Giese reactions, employing primary, secondary, and tertiary alkyl iodides as radical precursors, ethyl acrylate as a radical trap, and sodium cyanoborohydride as a radical mediator, were examined in a continuous flow system. With the use of an automated flow microreactor, flow reaction conditions for the Giese reaction were quickly optimized, and it was found that a reaction temperature of 70 °C in combination with a residence time of 10–15 minutes gave good yields of the desired addition products.

The mechanisms of radical formation in L-α-alanine

International Nuclear Information System (INIS)

Bugay, A.A.; Onischuk, V.A.; Petrenko, T.L.; Teslenko, V.V.

2000-01-01

Modeling of radical transformations in L-α-alanine after irradiation was performed for isolated radicals and for clusters. Special attention was devoted to the explanation of the experimental results concerning selective proton transfer and behavior of cation-radicals because a unique interpretation of the corresponding experiments is very difficult. Both semi-empirical and ab initio methods were used depending on the size of system under investigation. The results obtained show the usefulness of the computer simulation for processes in rather complex materials used in dosimetry

EPR detection of free radicals in UV-irradiated skin: mouse versus human

International Nuclear Information System (INIS)

Jurkiewicz, B.A.; Buettner, G.R.

1996-01-01

Ultraviolet radiation produces free radicals in Skh-1 mouse skin, contributing to photoaging and carcinogenesis. If a mouse model is a general indicator of free radical processes in human skin photobiology, then radical production observed in mouse and human skin should be directly comparative. In this work we show that UV radiation (λ > 300 nm, 14 μW/cm 2 UVB; 3.5 mW/cm 2 UVA) increases the ascorbate free radical (Asc) electron paramagnetic resonance (EPR) signal in both Skh-1 mouse skin (45%) and human facial skin biopsies (340%). Visible light (λ > 400 nm; 0.23 mW/cm 2 UVA) also increased the Ascsignal in human skin samples (45%) but did not increase baseline mouse Asc, indicating that human skin is more susceptible to free radical formation and that a chromophore for visible light may be present. Using EPR spin-trapping techniques, UV radiation produced spin adducts consistent with trapping lipid alkyl radicals in mouse skin (α-[4-pyridyl 1-oxide]-N-tert-butyl nitrone/alkyl radical adduct; a N = 15.56 G and a H 2.70 G) and lipid alkoxyl radicals in human skin (5,5-dimethylpyrroline -1-oxide/alkoxyl radical adduct; a N = 14.54 G and a H = 16.0 G). Topical application of the iron chelator Desferal to human skin significantly decreases these radicals (∼50%), indicating a role for iron in lipid peroxidation. (Author)

Spin relaxation of radicals in cryptochrome and its role in avian magnetoreception

Energy Technology Data Exchange (ETDEWEB)

Worster, Susannah; Kattnig, Daniel R.; Hore, P. J., E-mail: peter.hore@chem.ox.ac.uk [Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ (United Kingdom)

2016-07-21

Long-lived spin coherence and rotationally ordered radical pairs have previously been identified as key requirements for the radical pair mechanism of the avian magnetic compass sense. Both criteria are hard to meet in a biological environment, where thermal motion of the radicals creates dynamic disorder and drives efficient spin relaxation. This has long been cited as a major stumbling block of the radical pair hypothesis. Here we combine Redfield relaxation theory with analytical solutions to a rotational diffusion equation to assess the impact of restricted rotational motion of the radicals on the operation of the compass. The effects of such motions are first investigated generally in small, model systems and are then critically examined in the magnetically sensitive flavin-tryptophan radical pair that is formed photochemically in the proposed magnetoreceptor protein, cryptochrome. We conclude that relaxation is slowest when rotational motion of the radicals within the protein is fast and highly constrained; that in a regime of slow relaxation, the motional averaging of hyperfine interactions has the potential to improve the sensitivity of the compass; and that consideration of motional effects can significantly alter the design criteria for an optimal compass. In addition, we demonstrate that motion of the flavin radical is likely to be compatible with its role as a component of a functioning radical-pair compass, whereas the motion of the tryptophan radical is less ideal, unless it is particularly fast.

Customers as Partners in Radical Service Innovation

DEFF Research Database (Denmark)

Scupola, Ada; Nicolajsen, Hanne Westh

2009-01-01

  Purpose- The main purpose of this paper is to investigate customer involvement and related challenges in radical service innovations in engineering consulting services Design/methodology/approach - The paper uses a case study approach and so called rich descriptions to investigate customer...... involvement, roles and related challenges and conditions in radical service innovations.Findings- One main finding is that customers can engage in radical service innovations in engineering consultancy services and may play a decisive role. In doing this they most likely take on all the three user involvement...... roles defined in the literature of New Service and New Product Development. Also a number of conditions are found to be necessary in order for this collaboration to succeed. The conclusion is that another understanding and handling of the customer/supplier relation is needed along with a need...

Formation of stable radicals during perfluoroalkane radiolysis

International Nuclear Information System (INIS)

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

1984-01-01

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

Effect of flavoring chemicals on free radical formation in electronic cigarette aerosols.

Science.gov (United States)

Bitzer, Zachary T; Goel, Reema; Reilly, Samantha M; Elias, Ryan J; Silakov, Alexey; Foulds, Jonathan; Muscat, Joshua; Richie, John P

2018-05-20

Flavoring chemicals, or flavorants, have been used in electronic cigarettes (e-cigarettes) since their inception; however, little is known about their toxicological effects. Free radicals present in e-cigarette aerosols have been shown to induce oxidative stress resulting in damage to proliferation, survival, and inflammation pathways in the cell. Aerosols generated from e-liquid solvents alone contain high levels of free radicals but few studies have looked at how these toxins are modulated by flavorants. We investigated the effects of different flavorants on free radical production in e-cigarette aerosols. Free radicals generated from 49 commercially available e-liquid flavors were captured and analyzed using electron paramagnetic resonance (EPR). The flavorant composition of each e-liquid was analyzed by gas chromatography mass spectroscopy (GCMS). Radical production was correlated with flavorant abundance. Ten compounds were identified and analyzed for their impact on free radical generation. Nearly half of the flavors modulated free radical generation. Flavorants with strong correlations included β-damascone, δ-tetradecalactone, γ-decalactone, citral, dipentene, ethyl maltol, ethyl vanillin, ethyl vanillin PG acetal, linalool, and piperonal. Dipentene, ethyl maltol, citral, linalool, and piperonal promoted radical formation in a concentration-dependent manner. Ethyl vanillin inhibited the radical formation in a concentration dependent manner. Free radical production was closely linked with the capacity to oxidize biologically-relevant lipids. Our results suggest that flavoring agents play an important role in either enhancing or inhibiting the production of free radicals in flavored e-cigarette aerosols. This information is important for developing regulatory strategies aimed at reducing potential harm from e-cigarettes. Copyright © 2018 Elsevier Inc. All rights reserved.

Ultrasound-induced radical polymerization

NARCIS (Netherlands)

Kuijpers, M.W.A.; Kemmere, M.F.; Keurentjes, J.T.F.

2004-01-01

Sonochemistry comprises all chemical effects that are induced by ultrasound. Most of these effects are caused by cavitations, ie, the collapse of microscopic bubbles in a liquid. The chemical effects of ultrasound include the formation of radicals and the enhancement of reaction rates at ambient

Laccase catalyzed grafting of-N-OH type mediators to lignin via radical-radical coupling

DEFF Research Database (Denmark)

Munk, Line; Punt, A. M.; Kabel, M. A.

2017-01-01

Lignin is an underexploited resource in biomass refining. Laccases (EC 1.10.3.2) catalyze oxidation of phenolic hydroxyls using O2 as electron acceptor and may facilitate lignin modification in the presence of mediators. This study assessed the reactivity of four different synthetic mediators...... better than HBT (1-hydroxybenzotriazole). Three different mechanisms are suggested to explain the grafting of HPI and HBT, all involving radical-radical coupling to produce covalent bonding to lignin. Lignin from exhaustive cellulase treatment of wheat straw was more susceptible to grafting than beech...... organosolv lignin with the relative abundance of grafting being 35% vs. 11% for HPI and 5% vs. 1% for HBT on these lignin substrates. The data imply that lignin can be functionalized via laccase catalysis with-N-OH type mediators....

Contro la tirannia del Progresso. DeLillo e Sebald, alcuni esercizi di resistenza

Directory of Open Access Journals (Sweden)

Arturo Mazzarella

2015-11-01

Full Text Available Il saggio si propone di contribuire a un’ulteriore revisione critica della categoria di “progresso”: termine decisivo nel lessico teorico-politico della modernità, il quale ancor oggi conserva interamente il proprio valore. Troppo spesso si dimentica, però – come ha messo in luce Nietzsche nel corso di tutta la sua opera –, la profonda radice nichilistica su cui si innesta la categoria di progresso: proiettata in un orizzonte temporale che, in vista di un interminabile perfezionamento individuale e collettivo, finisce per svuotare, annullare, la dimensione del presente. In questo senso resistere (proprio nell’accezione adoperata da Foucault alle tentazioni del progresso significa impegnarsi nella costruzione di un immaginario che individui nel presente, appunto, nelle sue imprevedibili metamorfosi, l’unico tempo storico in grado di generare un reale mutamento. Proprio come dimostrano esemplarmente i due romanzi – di rilevante spessore concettuale – su cui si sofferma il saggio: Austerlitz, di Sebald e Punto omega, di DeLillo.

Radical constructivism and radical constructedness: Luhmann's sociology of semantics, organizations, and self-organization

NARCIS (Netherlands)

Leydesdorff, L.

2012-01-01

Context: Using radical constructivism, society can be considered from the perspective of asking the question, "Who conceives of society?" In Luhmann’s social systems theory, this question itself is considered as a construct of the communication among reflexive agents. Problem: Structuration of

A new face of phenalenyl-based radicals in the transition metal-free C-H arylation of heteroarenes at room temperature: trapping the radical initiator via C-C σ-bond formation.

Science.gov (United States)

Ahmed, Jasimuddin; P, Sreejyothi; Vijaykumar, Gonela; Jose, Anex; Raj, Manthan; Mandal, Swadhin K

2017-11-01

The radical-mediated transition metal-free approach for the direct C-H bond functionalization of arenes is considered as a cost effective alternative to transition metal-based catalysis. An organic ligand-based radical plays a key role by generating an aryl radical which undergoes a subsequent functionalization process. The design principle of the present study takes advantage of a relatively stable odd alternant hydrocarbon-based phenalenyl (PLY) radical. In this study, the first transition metal-free catalyzed direct C-H arylation of a variety of heteroarenes such as azoles, furan, thiophene and pyridine at room temperature has been reported using a phenalenyl-based radical without employing any photoactivation step. This protocol has been successfully applied to the gram scale synthesis of core moieties of bioactive molecules. The phenalenyl-based radical initiator has been characterized crystallographically by trapping it via the formation of a C-C σ-bond between the phenalenyl radical and solvent-based radical species.

Missing Peroxy Radical Sources Within a Rural Forest Canopy

Science.gov (United States)

Wolfe, G. M.; Cantrell, C.; Kim, S.; Mauldin, R. L., III; Karl, T.; Harley, P.; Turnipseed, A.; Zheng, W.; Flocke, F.; Apel, E. C.;

Western radicalization: rethinking the psychology of terrorism

OpenAIRE

Pierson, Vern

2017-01-01

Approved for public release; distribution is unlimited The U.S. strategy to counter violent extremism relies heavily on the expert consensus that terrorists are engaging in political group speak and are by nature psychologically normal. Thus, anyone is susceptible to radicalization. To counter radicalization, finding answers is like finding a needle in a haystack. However, in the psychologically similar phenomenon of arson by firefighter—when a firefighter deliberately sets and then exting...

Absolute photoionization cross-section of the methyl radical.

Science.gov (United States)

Taatjes, Craig A; Osborn, David L; Selby, Talitha M; Meloni, Giovanni; Fan, Haiyan; Pratt, Stephen T

2008-10-02

The absolute photoionization cross-section of the methyl radical has been measured using two completely independent methods. The CH3 photoionization cross-section was determined relative to that of acetone and methyl vinyl ketone at photon energies of 10.2 and 11.0 eV by using a pulsed laser-photolysis/time-resolved synchrotron photoionization mass spectrometry method. The time-resolved depletion of the acetone or methyl vinyl ketone precursor and the production of methyl radicals following 193 nm photolysis are monitored simultaneously by using time-resolved synchrotron photoionization mass spectrometry. Comparison of the initial methyl signal with the decrease in precursor signal, in combination with previously measured absolute photoionization cross-sections of the precursors, yields the absolute photoionization cross-section of the methyl radical; sigma(CH3)(10.2 eV) = (5.7 +/- 0.9) x 10(-18) cm(2) and sigma(CH3)(11.0 eV) = (6.0 +/- 2.0) x 10(-18) cm(2). The photoionization cross-section for vinyl radical determined by photolysis of methyl vinyl ketone is in good agreement with previous measurements. The methyl radical photoionization cross-section was also independently measured relative to that of the iodine atom by comparison of ionization signals from CH3 and I fragments following 266 nm photolysis of methyl iodide in a molecular-beam ion-imaging apparatus. These measurements gave a cross-section of (5.4 +/- 2.0) x 10(-18) cm(2) at 10.460 eV, (5.5 +/- 2.0) x 10(-18) cm(2) at 10.466 eV, and (4.9 +/- 2.0) x 10(-18) cm(2) at 10.471 eV. The measurements allow relative photoionization efficiency spectra of methyl radical to be placed on an absolute scale and will facilitate quantitative measurements of methyl concentrations by photoionization mass spectrometry.

La superaci??n del modelo del ??ngel del hogar:

OpenAIRE

Hurtado Mu??oz, M??nica

2012-01-01

La Tesis Doctoral titulada "La superaci??n del modelo del "??ngel del hogar". Recuperaci??n de la escritora Leonor Canalejas y Fustegueras (1869-1945)" aborda, en primer lugar, un an??lisis sociol??gico de las circunstancias que rodearon a la mujer espa??ola en el cambio de siglo en el ??mbito social y educativo, en un intento de esclarecer las caracter??sticas propias del contexto en el que la mujer accede a la intelectualidad en general y a la literatura en particular. Esta parte concluye q...

Comparison between Two Bromine Containing Free Radical Initiators in PRESAGE®

Energy Technology Data Exchange (ETDEWEB)

Park, Hyeonsuk; Ryu, Dongmin; Ye, Sung-Joon [Seoul National University, Seoul (Korea, Republic of)

2016-10-15

PRESAGE® is an optically clear 3-D polyurethane dosimeter which contains a halogenated carbon as a free radical initiator and leucomalachite dye. The change of the optical density is known to be linear with respect to the absorbed dose and the sensitivity is related to the carbon–halogen bond dissociation energy of the free radical initiator. Although there are some studies regarding free radical initiators and dye materials, there’s a lack of reports about the effect of other elements like LMG solvent which can be added when there’s a difficulty mixing materials. Also, there are some studies about comparison between free radicals with different kind of halogen atoms but there’s a lack of studies of comparison between initiators with the same halogen atom. In this experiments, two kinds of halocarbon free radical initiator with the same halogen atom (bromine) as well as the effect of the LMG solvent were studied to use the dosimeter as a therapeutic purpose. Effective atomic numbers were also calculated. The initiators with the same halogen atom, CBr{sub 4} and C{sub 2}H{sub 2}Br{sub 4}, reacted totally differently. CBr{sub 4} was more sensitive to the radiation and emitted maximum 4 times more free radicals upon irradiation with no additional effective atomic number but the absorbance after irradiation was highly variable with time. For stable measurement, C{sub 2}H{sub 2}Br{sub 4} would be more appropriate as a free radical initiator.

Learning curve of robot-assisted laparoscopic radical prostatectomy for a single experienced surgeon: comparison with simultaneous laparoscopic radical prostatectomy.

Science.gov (United States)

Ku, Ja Yoon; Ha, Hong Koo

2015-04-01

Despite the large number of analytical reports regarding the learning curve in the transition from open to robot-assisted radical prostatectomy (RARP), few comparative results with laparoscopic radical prostatectomy (LRP) have been reported. Thus, we evaluated operative and postoperative outcomes in RARP versus 100 simultaneously performed LRPs. A single surgeon had performed more than 1,000 laparoscopic operations, including 415 cases of radical nephrectomy, 85 radical cystectomies, 369 radical prostatectomies, and treatment of 212 other urological tumors, since 2009. We evaluated operative (operation time, intraoperative transfusion, complications, hospital stay, margin status, pathological stage, Gleason score) and postoperative (continence and erectile function) parameters in initial cases of RARP without tutoring compared with 100 recently performed LRPs. Mean operation time and length of hospital stay for RARP and LRP were 145.5±43.6 minutes and 118.1±39.1 minutes, and 6.4±0.9 days and 6.6±1.1 days, respectively (p=0.003 and p=0.721). After 17 cases, the mean operation time for RARP was similar to LRP (less than 2 hours). Positive surgical margins in localized cancer were seen in 11.1% and 8.9% of cases in RARP and LRP, respectively (p=0.733). At postoperative 3 months, sexual intercourse was reported in 14.0% and 12.0%, and pad-free continence in 96.0% and 81.0% in patients with RARP and LRP, respectively (p=0.796 and p=0.012). Previous large-volume experience of LRPs may shorten the learning curve for RARP in terms of oncological outcome. Additionally, previous experience with laparoscopy may improve the functional outcomes of RARP.

Electron transfer oxidation of DNA radicals by paranitroacetophenone

Energy Technology Data Exchange (ETDEWEB)

Whillans, D W; Adams, G E [Mount Vernon Hospital, Northwood (UK)

1975-12-01

The reaction of a typical electron-affinic sensitizer, paranitroacetophenone (PNAP) with the model compounds thymine, thymidine, thymidylic acid, deoxyribose and single and double-stranded DNA has been investigated by pulse radiolysis. Radicals formed by one-electron reduction of the bases and of DNA reacted rapidly and efficiently with PNAP by electron transfer. A small yield of transfer (< 10 per cent) was also observed arising from oxidation of the radicals formed by the small proportion of OH which reacted at the sugar moieties in DNA. In contrast, electron transfer oxidation by PNAP of radicals formed by the addition of OH to the base moieties, e.g. thymine, was not an efficient process. Further, addition of the sensitizer to the thymine OH-adduct proceeded at a rate that was too low to measure the pulse radiolysis. We conclude that, since the major sites of OH reaction by DNA are the heterocyclic bases (> 80 per cent), oxidation of the resultant radicals is unlikely to be a major step in the mechanism of sensitization by this typical hypoxic-cell sensitizer.

Reactions of linoleic acid peroxyl radicals with phenolic antioxidants: a pulse radiolysis study

Energy Technology Data Exchange (ETDEWEB)

Erben-Russ, M.; Bors, W.; Saran, M.

1987-09-01

Linoleic acid peroxyl radicals (LOO) can be viewed as model intermediates occurring during lipid peroxidation processes. Formation and reactions of these species were investigated in aqueous alkaline solution using pulse radiolysis combined with kinetic spectroscopy. Irradiation of linoleic acid in N/sub 2/O/O/sub 2/-saturated solutions leads to a mixture of peroxyl radical isomers; reaction of 13-hydroperoxylinoleic acid (13-LOOH) with azide radicals in N/sub 2/O-saturated solution produces 13-LOO radicals specifically. These peroxyl radicals cannot be observed directly, but their reactions with kaempferol and quercetin, acting as radical-scavenging antioxidants, produced strongly absorbing aroxyl radicals (ArO). The same aroxyl radicals were generated by OH and N/sub 3/ with rate constants exceeding 10/sup 9/ dm/sup 3/ mol/sup -1/ s/sup -1/. Applying a reaction scheme that includes competing generation and decay reactions of both LOO and ArO radicals, individual rate constants were derived for LOO reactions with the phenols (> 10/sup 7/ dm/sup 3/ mol/sup -1/ s-./sup 1/), with aroxyl radicals to form covalent adducts (> 10/sup 8/ dm/sup 3/ mol/sup -1/ s/sup -1/), as well as for their bimilecular decay (3.0 x 10/sup 8/ dm/sup 3/ mol/sup -1/ s/sup -1/). These results demonstrate high reactivity of fatty acid peroxyl radicals and flavone antioxidants in aqueous solution.

Production of free radical by magnetized sheet plasma with vertical gas-flow

International Nuclear Information System (INIS)

Tonegawa, Akira; Takatori, Masahiko; Kawamura, Kazutaka

1995-01-01

Free radicals play an important role in plasma processing, environment problem, and space plasma and so on because of their outstanding physical properties. Although much work has been done on the free radicals in the reactive plasma, very little is known about the production mechanism of the free radicals against various plasma parameters. To overcome this problem, we have proposed to do a new system of a magnetized sheet plasma with vertical gas-flow. The sheet plasma is a special type of strongly magnetized highly ionized slab plasma. This system is controlled to the parameters of radicals and plasma independently. Therefore, it is possible to make a quantitative analysis of free radicals as the simple one. In this paper, we describe the magnetized sheet plasma with vertical gas-flow system and report the preliminary results of production of the free radical. In particular, we show to produce and control the OH free radical which has been the most commonly studied combustion species

Insight into the Reaction Mechanism of Graphene Oxide with Oxidative Free Radical

Institute of Scientific and Technical Information of China (English)

ZHOU Xuejiao; XU Liangyou

2017-01-01

Graphene oxide(GO),as an important derivative of graphene,could be considered as a super aromatic molecule decorated with a range of reactive oxygen-containing groups on its surface,which endows graphene high reactivity with other molecules.In our previous work,we demonstrated that GO sheets were cut into small pieces(graphene quantum dots,GQDs) by oxidative free radicals(hydroxyl radical HO or oxygen radical [O]) under UV irradiation.It is notable that reactions involving free radicals are influenced by reaction conditions pronouncedly.However,researches on details about reactions of GO with free radicals have not been reported thus far.In this work,the effects of different factors on the photo-Fenton reaction of GO were studied.It is demonstrated that the reaction rate is closely related to the concentration of free radicals.It is speculated that through the optimization of reaction conditions,the reaction of graphene with free radicals could carry out efficiently for further applications.

FUNCTIONAL RESULTS OF ENDOSCOPIC EXTRAPERITONEAL RADICAL INTRAFASCIAL PROSTATECTOMY

Directory of Open Access Journals (Sweden)

D. V. Perlin

2014-01-01

Full Text Available Introduction. Endoscopic radical prostatectomy is a highly effective treatment for localized prostate cancer. Intrafascial prostate dissection ensures early recovery of urine continence function and erectile function. This article sums up our own experience of performing intrafascial endoscopic prostatectomy.Materials and methods. 25 patients have undergone this procedure. 12 months after surgery 88.2 % of the patients were fully continent, 11.7 % had symptoms of minimal stress urinary incontinence. We encountered no cases of positive surgical margins and one case of bio-chemical recurrence of the disease.Conclusion. Oncologically, intrafascial endoscopic radical prostatectomy is as effective as other modifications of radical prostatectomy and has the benefits of early recovery of urine continence function and erectile function. 

Robotic radical hysterectomy in the management of gynecologic malignancies.

Science.gov (United States)

Pareja, Rene; Ramirez, Pedro T

2008-01-01

Robotic surgery is being used with increasing frequency in gynecologic oncology. To date, 44 cases were reported in the literature of radical hysterectomy performed with robotic surgery. When comparing robotic surgery with laparoscopy or laparotomy in performing a radical hysterectomy, the literature shows that robotic surgery offers an advantage over the other 2 surgical approaches with regard to operative time, blood loss, and length of hospitalization. Future studies are needed to further elucidate the equivalence or superiority of robotic surgery to laparoscopy or laparotomy in performing a radical hysterectomy.

Intramolecular addition of benzylic radicals onto ketenimines. Synthesis of 2-alkylindoles.

Science.gov (United States)

Alajarín, Mateo; Vidal, Angel; Ortín, María-Mar

2003-12-07

The inter- and intramolecular addition of free radicals onto ketenimines is studied. All the attempts to add intermolecularly several silicon, oxygen or carbon centered radicals to N-(4-methylphenyl)-C,C-diphenyl ketenimine were unsuccessful. In contrast, the intramolecular addition of benzylic radicals, generated from xanthates, onto the central carbon of a ketenimine function with its N atom linked to the ortho position of the aromatic ring occurred under a variety of reaction conditions. These intramolecular cyclizations provide a novel radical-mediated synthesis of 2-alkylindoles.

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

Directory of Open Access Journals (Sweden)

Cohn Corey A

2008-02-01

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

EPR spectral investigation of radiation-induced radicals of gallic acid

Energy Technology Data Exchange (ETDEWEB)

Tuner, Hasan [Balikesir University, Department of Physics, Faculty of Art and Science, Balikesir (Turkey)

2017-11-15

In the present work, spectroscopic features of the radiation-induced radicals of gallic acid compounds were investigated using electron paramagnetic resonance (EPR) spectroscopy. While un-irradiated samples presented no EPR signal, irradiated samples exhibited an EPR spectrum consisting of an intense resonance line at the center and weak lines on both sides. Detailed microwave saturation investigations were carried out to determine the origin of the experimental EPR lines. It is concluded that the two side lines of the triplet satellite originate from forbidden ''spin-flip'' transitions. The spectroscopic and structural features of the radiation-induced radicals were determined using EPR spectrum fittings. The experimental EPR spectra of the two gallic acid compounds were consistent with the calculated EPR spectroscopic features of the proposed radicals. It is concluded that the most probable radicals are the cyclohexadienyl-type, O(OH){sub 2}C{sub 6}H{sub 2}COOH radicals for both compounds. (orig.)

EPR spectral investigation of radiation-induced radicals of gallic acid

International Nuclear Information System (INIS)

Tuner, Hasan

2017-01-01

In the present work, spectroscopic features of the radiation-induced radicals of gallic acid compounds were investigated using electron paramagnetic resonance (EPR) spectroscopy. While un-irradiated samples presented no EPR signal, irradiated samples exhibited an EPR spectrum consisting of an intense resonance line at the center and weak lines on both sides. Detailed microwave saturation investigations were carried out to determine the origin of the experimental EPR lines. It is concluded that the two side lines of the triplet satellite originate from forbidden ''spin-flip'' transitions. The spectroscopic and structural features of the radiation-induced radicals were determined using EPR spectrum fittings. The experimental EPR spectra of the two gallic acid compounds were consistent with the calculated EPR spectroscopic features of the proposed radicals. It is concluded that the most probable radicals are the cyclohexadienyl-type, O(OH) 2 C 6 H 2 COOH radicals for both compounds. (orig.)

Oxidation of benzene by radiolytically produced OH radicals. [x rays

Energy Technology Data Exchange (ETDEWEB)

Klein, G W; Schuler, R H [Carnegie-Mellon Univ., Pittsburgh, Pa. (USA)

1978-01-01

The radiolysis of N/sub 2/O saturated-aqueous solutions of benzene-/sup 14/C has been examined using radio-liquid chromatographic methods to follow the quantitative aspects of the reactions of hydroxycyclohexadienyl radicals. In the absence of a radical oxidant, at least five important products are produced. The total yield of 5.8 observed for the incorporation of benzene into products accounts for essentially all of the radicals initially produced from the water. Dimeric products predominate with a total yield of 4.1. Phenol is produced with a yield of only 0.8 indicating a disproportionation/combination ratio for hydroxycyclohexadienyl radicals of < = 0.4. In the presence of 2mM ferricyanide the hydroxycyclohexadienyl radicals are quantitatively oxidized to phenol with no trace (< 1%) remaining of dimeric or other high molecular weight products. The initial yield for phenol formation (6.0 molecules/100 eV) provides a measure for OH production in N/sub 2/O saturated aqueous solutions.

Efficiency of radical yield in alkylthymine and alkyluracil by high-LET irradiation

International Nuclear Information System (INIS)

Nakagawa, Seiko; Ohta, Nobuaki; Murakami, Takeshi

2010-01-01

Penthylthymines and hexyl-, nonyl-, and decyl- uracils were irradiated by C-ion (3.5 GeV) and γ-ray at 77 K. ESR spectra were measured to study radiation induced radicals in the temperature range from 108 to 273 K. A dihydro-5-yl (5-yl) radical formed by H addition to C6 carbon and a secondary alkyl radical by C-H bond fission at the second carbon from the end of the alkyl group were produced at 108 K. A dihydrouracil-6-yl (6-yl) radical formed by H addition to C5 carbon increased with increasing temperature for alkyluracils. The spectral feature obtained by C-ion irradiation was coincident with that by γ-irradiation. Total radical yields increased by alkylation and with increasing the length of alkyl chain. Yields of both 5-yl and secondary alkyl radicals irradiated by C-ion were less than those by γ-ray for penthylthymines and hexyluracil. On the contrary, radical yields were almost the same between ion and γ-ray irradiation for nonyl- and decyl-uracil. Mechanism of radical formation and effect of high-LET irradiation were discussed.

Reactions of Hydroxyalkyl Radicals with Cysteinyl Peptides in a NanoESI Plume

Science.gov (United States)

Stinson, Craig A.; Xia, Yu

2014-07-01

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

Radiolytic production and thermal decay kinetics of free radicals in n-alkoxyazoxybenzenes

International Nuclear Information System (INIS)

Tria, J.J.

1977-01-01

Free radical production and decay over several temperature ranges have been studied by ESR for three members of the series of n-alkoxyazoxybenzenes, those with one, two and seven carbon atoms respectively in the alkoxy chain: p,p'-azoxydianisole (PAA), p,p'-azoxydiphenetole (PAP) and 4,4'-bis-heptyloxyazoxybenzene (HAB). Radical yields per 100 ev absorbed at room temperature were: PAA 0.018, 0.019; PAP 0.033, 0.046; HAB 0.10, 0.14 for powder and single crystal samples respectively. Radicals present at room temperature and above are believed to be formed by loss of hydrogen from the benzene rings and the alkoxy groups, with more of the latter (probably α-alkoxy radicals) occurring as the alkoxy group becomes longer, based on the poorly resolved powder spectra. No cyclohexadienyl radicals or alkoxy radicals were seen. Decay of radicals between room temperature and the first liquid crystal phase transition occurred in a ''stepwise'' manner without radical conversions and was analyzed according to a model due to Waite (Phys. Rev., 107, 463 (1957) for diffusion-controlled reaction of randomly distributed reactants with a significant activation energy for the reaction step. Thermodynamic data are included for PAA powder samples and for toluene-grown single crystals. Reactions are postulated for the higher radical yields in powder samples of the three compounds irradiated at 77 0 K

Enantioselective conjugate radical addition to alpha'-hydroxy enones.

Science.gov (United States)

Lee, Sunggi; Lim, Chae Jo; Kim, Sunggak; Subramaniam, Rajesh; Zimmerman, Jake; Sibi, Mukund P

2006-09-14

Enantioselective conjugate radical addition to alpha'-hydroxy alpha,beta-unsaturated ketones, compounds containing bidentate donors, has been investigated. It has been found that radical additions to alpha'-hydroxy alpha,beta-unsaturated ketones in the presence of Mg(NTf2)2 and bisoxazoline ligand 5a proceeded cleanly, yielding the addition products in high chemical yields and good enantiomeric excesses.

Resonance ionization detection of combustion radicals

Energy Technology Data Exchange (ETDEWEB)

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

1993-12-01

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

Radical Change by Entrepreneurial Design

National Research Council Canada - National Science Library

Roberts, Nancy C

1998-01-01

.... Radical change by entrepreneurial design then becomes the focal point, in order to acquaint the reader with the strategies and tactics of well-known entrepreneurs who have been successful in molding...

Sexuality Following Radical Prostatectomy

DEFF Research Database (Denmark)

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

2017-01-01

incontinence in relation to sexual activity after surgery. This can present at the time of orgasm (ie, climacturia) or arise during arousal. In general, the problem subsides with time and pelvic floor training and tension penile loops can be used as treatments. Orgasmic disturbances after radical prostatectomy...

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

International Nuclear Information System (INIS)

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

2005-01-01

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

Sugar Radical Formation by a Proton Coupled Hole Transfer in 2′-Deoxyguanosine Radical Cation (2′-dG•+): A Theoretical Treatment

Science.gov (United States)

Kumar, Anil; Sevilla, Michael D.

2009-01-01

Previous experimental and theoretical work has established that electronic excitation of a guanine cation radical in nucleosides or in DNA itself leads to sugar radical formation by deprotonation from the dexoxyribose sugar. In this work we investigate a ground electronic state pathway for such sugar radical formation in a hydrated one electron oxidized 2′-deoxyguanosine (dG•+ + 7H2O), using density functional theory (DFT) with the B3LYP functional and the 6-31G* basis set. We follow the stretching of the C5′-H bond in dG•+ to gain an understanding of the energy requirements to transfer the hole from the base to sugar ring and then to deprotonate to proton acceptor sites in solution and on the guanine ring. The geometries of reactant (dG•+ + 7H2O), transition state (TS) for deprotonation of C5′ site and product (dG(•C5′, N7-H+) + 7 H2O) were fully optimized. The zero point energy (ZPE) corrected activation energy (TS) for the proton transfer (PT) from C5′ is calculated to be 9.0 kcal/mol and is achieved by stretching the C5′-H bond by 0.13 Å from its equilibrium bond distance (1.099 Å). Remarkably, this small bond stretch is sufficient to transfer the “hole” (positive charge and spin) from guanine to the C5′ site on the deoxyribose group. Beyond the TS, the proton (H+) spontaneously adds to water to form a hydronium ion (H3O+) as an intermediate. The proton subsequently transfers to the N7 site of the guanine (product). The 9 kcal/mol barrier suggests slow thermal conversion of the cation radical to the sugar radical but also suggests that localized vibrational excitations would be sufficient to induce rapid sugar radical formation in DNA base cation radicals. PMID:19754084

Polar-Nonpolar Radical Copolymerization under Li+ Catalysis

Science.gov (United States)

2008-09-21

bonds or aromatic rings. Thus, we propose that a transfer of a methyl radical from CB11Me12C to IB triggers a radical polymerization chain that yields ...b-PIB and the resulting CB11Me11 byproduct concurrently triggers a cationic polymerization chain that yields l-PIB terminated with a carborate anion...tetrahydrofuran and passed through a column of alumina about five times to remove the bulk of the catalyst. A Soxhlet apparatus was used to recover

Radical chemistry of epigallocatechin gallate and its relevance to protein damage

DEFF Research Database (Denmark)

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

2003-01-01

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

Free radical interactions between raw materials in dry soup powder.

Science.gov (United States)

Raitio, Riikka; Orlien, Vibeke; Skibsted, Leif H

2011-12-01

Interactions at the free radical level were observed between dry ingredients in cauliflower soup powder, prepared by dry mixing of ingredients and rapeseed oil, which may be of importance for quality deterioration of such dry food products. The free radical concentrations of cauliflower soup powder, obtained by electron spin resonance (ESR) spectroscopy, rapidly become smaller during storage (40°C and relative humidity of 75%) than the calculated concentrations of free radicals based on the free radical concentrations of the powder ingredients used to make the soup powder and stored separately under similar conditions. Similarly, free radical concentrations decreased faster when any combination of two powder ingredients (of the three major ingredients of the soup powder) were mixed together and stored at 50°C for 1week than when each powder component was stored separately. Furthermore, yeast extract powder was found to play a key role when free radical interactions between powder ingredients occurred. The incubation of rapeseed oil with powder ingredients at 45°C for 24h, indicated the ability of cauliflower powder to increase the concentration of hydroperoxides in rapeseed oil, while yeast extract powder was found to prevent this hydroperoxide formation. Copyright © 2011 Elsevier Ltd. All rights reserved.

Bergenin Content and Free Radical Scavenging Activity of Bergenia Extracts. .

Science.gov (United States)

Hendrychová, Helena; Martin, Jan; Tůmová, Lenka; Kočevar-Glavač, Nina

2015-07-01

Our research was focused on the evaluation of bergenin content and free radical scavenging activity of extracts prepared from three different species of Bergenia - B. crassifolia (L.) Fritsch., B. ciliata (Haw.) Sternb. and B. x ornata Stein. collected during different seasons. Using an HPLC method, the highest total amount of bergenin was revealed in the leaves of B. x ornata and B. crassifolia (4.9 - 5.1 mg x g(-1)). Free radical scavenging power was determined by two methods--FRAP and NADH. The best free radical scavengers were B. crassifolia (FRAP: 6.7 - 15.9 mg GAE. 100g(-1); NADH: 20.3 - 50.9%) and B. ornata (FRAP: 13.7 - 15.2 mg GAE. 100g(-1); NADH: 29.3 - 31.1%). The lowest content of bergenin and the weakest radical scavenger was B. ciliata (bergenin: 3.1 mg x g(-1); FRAP: 5.5 - 11.0 mg GAE.100g(-1); NADH: 23.2 - 25.6%). The presence of a large percentage of bergenin is responsible for the radical scavenging activity, as shown by the results from the FRAP and NADH assays. Significant, positive correlation was found between bergenin content and radical scavenging activity in both methods.

Formation and determination of perinaphthenyl radical and PCAH in combustion processes

Energy Technology Data Exchange (ETDEWEB)

Franceschi, A [Univ., Pisa, Italy; Gerbaz, G P; Mangolini, S

1976-09-01

The concentration profiles of polycyclic aromatic hydrocarbons (PCAH) and perinaphthenyl radical along a vertical flow reactor have been determined for fuel rich premixed flames of n-heptane with small fractions of other hydrocarbons, methanol, and nitrogen oxide. It has been found that there is a strict relation between the concentrations of the higher molecular weight PCAH, which are the main components of soluble fraction of soot, and the perinaphthenyl radical. The aromatic ring of the fuel supplying the reactor plays the most significant role in the formation of PCAH and perinaphthenyl radical. Furthermore their concentrations increase passing from benzene toluene and, lastly, to mesitylene, because the energy of the C(arom)--C(alif) bond is lower than that of the C(arom)--C(arom) bond. The promoting action of methanol, when added to benzene, in the formation of PCAH and perinaphthenyl radical could be explained by the increased presence of CH/sub 3/ . radicals, which, can overcome the inhibiting action of OH. radicals. The contrary happens when methanol is added to toluene, because CH/sub 3/. coming from alcohol represents only a small fraction of the overall concentration, while the oxidant activity of OH. is prevailing. Finally the strong action of NO in reducing the free radical concentration has been pointed out.

Electron spin resonance of spin-trapped radicals of amines and polyamines

International Nuclear Information System (INIS)

Mossoba, M.M.; Rosenthal, Ionel; Riesz, Peter

1982-01-01

The reactions of hydroxyl radicals with methylamine, dimethylamine, trimethylamine, diethylamine, sec-butylamine, ethylene-diamine, 1,3-diaminopropane, putrescine, cadaverine, 1,7-diaminoheptane, ornithine, spermidine, spermine, agmatine, and arcaine in aqueous solutions have been investigated by spin-trapping and esr. Hydroxyl radicals were generated by the uv photolysis of H 2 O 2 and 2-methyl-2-nitrosopropane (MNP) was used as the spin-trap. The effects of ionizing radiation on the same polyamines in the polycrystalline state were also investigated. The free radicals produced by ν-radiolysis of these solids at room temperature in the absence of air were identified by dissolution in aqueous solutions of MNP. The predominant reaction of OH radicals with amines and polyamines below pH 7 was the abstraction of hydrogen atoms from a carbon that is not adjacent to the protonated amino group. For agmatine and arcaine which contain guanidinium groups abstraction occurred from the α-CH. Dimethylamine was oxidized to the dimethylnitroxyl radical by H 2 O 2 in the dark. ν-Radiolysis of polyamines in the polycrystalline state generated radicals due to H-abstraction from either the α-Ch or from a carbon atom in the middle of the alkyl chain. The deamination radical was obtained from ornithine

La formación personal del futuro profesor: Un estudio desde el enfoque radical e inclusivo y la ontología del lenguaje

OpenAIRE

Campusano Varas, Rosa Inés

2016-01-01

Tesis doctoral inédita leída en la Universidad Autónoma de Madrid, Facultad de Formación de Profesorado y Educación, Departamento de Didáctica y Teoría de la Educación. Fecha de lectura: 19 de febrero de 2016 Esta investigación analiza la formación del profesorado en Chile desde una perspectiva de la persona, y la necesidad de repensar los programas de formación inicial tomando en consideración los actuales requerimientos sociales, que nos indican que las competencias técnicas de los...

Radical-induced oxidation of RAFT agents : a kinetic study

NARCIS (Netherlands)

Li, Changxi; He, Junpo; Zhou, Yanwu; Gu, Yuankai; Yang, Yuliang

2011-01-01

Radical-induced oxidn. of reversible addn.-fragmentation chain transfer (RAFT) agents is studied with respect to the effect of mol. structure on oxidn. rate. The radicals are generated by homolysis of either azobisisobutyronitrile or alkoxyamine and transformed in situ immediately into peroxy

Identification of Radical Scavengers in Sweet Grass (Hierochloe odorata)

NARCIS (Netherlands)

Pukalskas, A.; Beek, van T.A.; Venskutonis, R.P.; Linssen, J.P.H.; Veldhuizen, van A.; Groot, de Æ.

2002-01-01

Extracts from aerial parts of sweet grass (Hierochloe odorata) were active DPPH free radical scavengers, The active compounds were detected in extract fractions using HPLC with on-line radical scavenging detection. After multistep fractionation of the extract, two new natural products possessing

Enantioselective cyclizations and cyclization cascades of samarium ketyl radicals

Science.gov (United States)

Kern, Nicolas; Plesniak, Mateusz P.; McDouall, Joseph J. W.; Procter, David J.

2017-12-01

The rapid generation of molecular complexity from simple starting materials is a key challenge in synthesis. Enantioselective radical cyclization cascades have the potential to deliver complex, densely packed, polycyclic architectures, with control of three-dimensional shape, in one step. Unfortunately, carrying out reactions with radicals in an enantiocontrolled fashion remains challenging due to their high reactivity. This is particularly the case for reactions of radicals generated using the classical reagent, SmI2. Here, we demonstrate that enantioselective SmI2-mediated radical cyclizations and cascades that exploit a simple, recyclable chiral ligand can convert symmetrical ketoesters to complex carbocyclic products bearing multiple stereocentres with high enantio- and diastereocontrol. A computational study has been used to probe the origin of the enantioselectivity. Our studies suggest that many processes that rely on SmI2 can be rendered enantioselective by the design of suitable ligands.

Radical quenching by rosmarinic acid from Lavandula vera MM cell culture.

Science.gov (United States)

Kovacheva, Elena; Georgiev, Milen; Pashova, Svetlana; Angelova, Maria; Ilieva, Mladenka

2006-01-01

This study was conducted to evaluate the radical scavenging capacities of extracts and preparations from a Lavandula vera MM plant cell culture with different rosmarinic acid content and to compare them with pure rosmarinic and caffeic acids as well. The methods, which were used are superoxide anion and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt radicals scavenging assays. Results showed that extracts and preparations from Lavandula vera MM possess strong radical scavengers, as the best both radical scavengers appeared to be the fractions with enriched rosmarinic acid content, obtained after ethylacetate fractioning (47.7% inhibition of superoxide radicals and 14.2 microM 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid equivalents, respectively). These data reveal the possibilities for application of these preparations as antioxidants.

Functionalised Oximes: Emergent Precursors for Carbon-, Nitrogen- and Oxygen-Centred Radicals