Letteratura scientifica selezionata sul tema "Radical induced reactivity"

✓ Previous experiments have shown that, following experimental fluid-percussion brain injury, cyclo-oxygenase-dependent formation of oxygen radicals prevents arteriolar vasoconstriction in response to hyperventilation. The oxygen radical scavengers superoxide dismutase and catalase restore normal reactivity; however, they are not routinely available for clinical use. The present study tested whether n-acetylcysteine (Mucomyst), an agent currently available for acetaminophen toxicity, could be used as a radical scavenger to restore reactivity after brain injury. N-acetylcysteine (163 mg/kg) was given intraperitoneally prior to or 30 minutes after fluid-percussion brain injury (2.6 atm) in cats, and reactivity to hyperventilation was tested 1 hour after injury. The authors found either that pre- or postinjury administration led to normal reactivity. Additional experiments supported the hypothesis that n-acetylcysteine is an oxygen radical scavenger, since it reduced or prevented the free radical-dependent cerebral arteriolar dilation normally induced by the topical application of arachidonic acid or bradykinin. The mechanism by which n-acetylcysteine is effective in trauma may involve direct scavenging of radicals or stimulation of glutathione peroxidase activity. The results suggest that n-acetylcysteine may be useful for treatment of oxygen free radical-mediated brain injury.

Plasma-induced surface radicals formed on a variety of organic polymers have been studied by electron spin resonance (ESR), making it possible to provide a sound basis for future experimental design of polymer surface processing (i.e., plasma treatment). On the basis of the findings from such studies on the nature of radical formation and radical reactivity, several novel bioapplications in the field of biomedical and drug engineering have been developed. Applications derived from the nature of plasma-induced surface radical formation include the preparation of a reservoir-type drug delivery system (DDS) of sustained and delayed release, and a floating drug delivery system (FDDS) possessing gastric retention capabilities, the combined findings leading to preparation of a novel “patient-tailored DDS” administered under consideration of the fact that the environment (pH and transit time, etc.) in the gastrointestinal (GI) tract varies with each patient. Applications derived from the reactivity of plasma-induced surface radicals include the preparation of composite powders applicable to a matrix-type DDS by making a mechanical application to the surface radical-containing polymer powders with drug powders, plasma-assisted immobilization of oligo-nucleotides (DNA) onto polymer surfaces applicable to constructing a DNA diagnosis system, and basic study of plasma-assisted preparation of a novel functionalized chemo-embolic agent of non-crosslinked hydrogel, vinyl alcohol-sodium acrylate copolymer (PVA-PAANa).

Previous studies have shown that after experimental neural trauma or acute hypertension the brain produces superoxide anion radicals, and brain arterioles display endothelial lesions, dilation, and loss of normal reactivity in response to a decrease in CO2 tension. Because these abnormalities are prevented by pretreatment with free radical scavengers or inhibitors of the cyclooxygenase component of prostaglandin (PG) H synthase, arachidonic acid metabolism by PGH synthase with concomitant formation of tissue injuring oxygen radicals causes the vascular damage. The purpose of the present experiments was to determine whether kinins, which are known to stimulate arachidonate metabolism and to induce cerebral arteriolar dilation via production of superoxide anion, may be involved in initiating the cerebrovascular abnormalities produced by neural trauma in cats. The diameter and reactivity of untreated in vivo pial arterioles on one cerebral cortex was compared with the diameter and reactivity of pial arterioles on the contralateral cortex, which were pretreated topically with a competitive receptor antagonist, which is specific for kinins. Before fluid percussion neural trauma was induced, arterioles on both cerebral hemispheres constricted normally to a decrease in CO2 tension. After injury, the arterioles on the untreated cortex dilated and did not constrict in response to a decrease in arterial CO2 tension, whereas the arterioles pretreated with the kinin antagonist dilated less and displayed normal reactivity to CO2. These experiments demonstrate that a specific kinin receptor stimulates PGH synthase-dependent, free radical-mediated cerebrovascular injury. Given the ubiquitous distribution of the kallikrein-kinin system, we propose that kinins may be an important common mediator of systemic vascular injury and abnormal vascular reactivity.

Abstract. OH reactivity (k′OH) is the total pseudo-first-order loss rate coefficient describing the removal of OH radicals to all sinks in the atmosphere, and is the inverse of the chemical lifetime of OH. Measurements of ambient OH reactivity can be used to discover the extent to which measured OH sinks contribute to the total OH loss rate. Thus, OH reactivity measurements enable determination of the comprehensiveness of measurements used in models to predict air quality and ozone production, and, in conjunction with measurements of OH radical concentrations, to assess our understanding of OH production rates. In this work, we describe the design and characterisation of an instrument to measure OH reactivity using laser flash photolysis coupled to laser-induced fluorescence (LFP-LIF) spectroscopy. The LFP-LIF technique produces OH radicals in isolation, and thus minimises potential interferences in OH reactivity measurements owing to the reaction of HO2 with NO which can occur if HO2 is co-produced with OH in the instrument. Capabilities of the instrument for ambient OH reactivity measurements are illustrated by data collected during field campaigns in London, UK, and York, UK. The instrumental limit of detection for k′OH was determined to be 1.0 s−1 for the campaign in London and 0.4 s−1 for the campaign in York. The precision, determined by laboratory experiment, is typically < 1 s−1 for most ambient measurements of OH reactivity. Total uncertainty in ambient measurements of OH reactivity is ∼ 6 %. We also present the coupling and characterisation of the LFP-LIF instrument to an atmospheric chamber for measurements of OH reactivity during simulated experiments, and provide suggestions for future improvements to OH reactivity LFP-LIF instruments.

Abstract. Measurements of OH and HO2 radicals were conducted in a pine-dominated forest in southern Finland during the HUMPPA-COPEC-2010 (Hyytiälä United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) field campaign in summer 2010. Simultaneous side-by-side measurements of hydroxyl radicals were conducted with two instruments using chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF), indicating small systematic disagreement, OHLIF / OHCIMS = (1.31 ± 0.14). Subsequently, the LIF instrument was moved to the top of a 20 m tower, just above the canopy, to investigate the radical chemistry at the ecosystem–atmosphere interface. Comprehensive measurements including observations of many volatile organic compounds (VOCs) and the total OH reactivity were conducted and analysed using steady-state calculations as well as an observationally constrained box model. Production rates of OH calculated from measured OH precursors are consistent with those derived from the steady-state assumption and measured total OH loss under conditions of moderate OH reactivity. The primary photolytic sources of OH contribute up to one-third to the total OH production. OH recycling, which occurs mainly by HO2 reacting with NO and O3, dominates the total hydroxyl radical production in this boreal forest. Box model simulations agree with measurements for hydroxyl radicals (OHmod. / OHobs. = 1.00 ± 0.16), while HO2 mixing ratios are significantly under-predicted (HO2mod. / HO2obs. = 0.3 ± 0.2), and simulated OH reactivity does not match the observed OH reactivity. The simultaneous under-prediction of HO2 and OH reactivity in periods in which OH concentrations were simulated realistically suggests that the missing OH reactivity is an unaccounted-for source of HO2. Detailed analysis of the HOx production, loss, and recycling pathways suggests that in periods of high total OH reactivity there are additional recycling processes forming OH directly, not via reaction of HO2 with NO or O3, or unaccounted-for primary HOx sources. Under conditions of moderate observed OH reactivity and high actinic flux, an additional RO2 source of approximately 1 × 106 molec cm−3 s−1 would be required to close the radical budget. Nevertheless, a major fraction of the OH recycling occurs via the reaction of HO2 with NO and O3 in this terpene-dominated environment.

The role of endogenous radicals in the regulation of pulmonary vascular tone was evaluated by simultaneous measurement of pulmonary artery pressure and lung radical levels during exposure of isolated rat lungs to varying inspired O2 concentrations (0-95%) and angiotensin II. Lung radical levels, measured “on-line” using luminol and lucigenin-enhanced chemiluminescence, decreased in proportion to the degree of alveolar hypoxia. Radical levels fell during hypoxia before the onset of pulmonary vasoconstriction and promptly returned to basal levels with restoration of normoxic ventilation. Mild alveolar hypoxia (10% O2), which failed to decrease chemiluminescence, did not trigger pulmonary vasoconstriction. Although chemiluminescence tended to decrease more as the hypoxic response strengthened, there was not a simple correlation between the magnitude of the change in chemiluminescence induced by hypoxia and the strength of the hypoxic pressor response. Normoxic chemiluminescence was largely inhibited by superoxide dismutase but not catalase. Superoxide dismutase also increased normoxic pulmonary vascular tone and the strength of the pressor response to hypoxia and angiotensin II. Thus the predominant activated O2 species in the lung, during normoxia, was the superoxide anion or a closely related substance. Alteration of endogenous radical levels can result in changes in vascular tone. It remains uncertain whether the decrease in lung radical production during hypoxia caused pulmonary vasoconstriction or was merely associated with hypoxic ventilation.

Bleomycin–iron complexes cause lipidcis–transisomerisation through thiyl radical formation and reactivity with unsaturated phospholipids, revealing membranes as a relevant and novel site of drug effect.

Abstract. Measurements of OH and HO2 radicals were conducted in a~pine dominated forest in Southern Finland during the HUMPPA-COPEC-2010 (Hyytiälä United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) field campaign in summer 2010. Simultaneous side-by-side measurements of hydroxyl radicals were conducted with two instruments using chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF), indicating good agreement. Subsequently, the LIF instrument was moved to the top of a 20 m tower, just above the canopy, to investigate the radical chemistry at the ecosystem–atmosphere interface. Comprehensive measurements including observations of many VOCs and the total OH reactivity were conducted and analysed using steady-state calculations as well as an observationally constrained box model. Production rates of OH calculated from measured OH precursors are consistent with those derived from the steady state assumption and measured total OH loss under conditions of moderate OH reactivity. The primary photolytic sources of OH contribute up to one third to the total OH production. OH recycling, which occurs mainly by HO2 reacting with NO and O3, dominates the total hydroxyl radical production in this boreal forest. Box model simulations agree with measurements for hydroxyl radicals (OHmod./OHobs. = 1.04 ± 0.16), while HO2 mixing ratios are significantly underpredicted (HO2mod./HO2obs. = 0.3 ± 0.2) and simulated OH reactivity does not match the observed OH reactivity. The simultaneous underprediction of HO2 and OH reactivity in periods in which OH concentrations were simulated well, suggests that the missing OH reactivity is an unaccounted source of HO2. Detailed analysis of the HOx production, loss, and recycling pathways suggests that in periods of high total OH reactivity there are additional recycling processes forming OH directly, not via reaction of HO2 with NO or O3. Nevertheless, a major fraction of the OH recycling occurs via the reaction of HO2 with NO and O3 in this terpene dominated environment.

Nitrones have a well-recognized capacity as spin-traps and are considered powerful free radical scavengers, which are two important issues in hypoxia-induced oxidative stress and cell death in brain ischemia. Consequently, nitrones have been proposed as therapeutic agents in acute ischemic stroke (AIS). In this paper, we update the biological and pharmacological characterization of ISQ-201, a previously identified cholesteronitrone hybrid with antioxidant and neuroprotective activity. This study characterizes ISQ-201 as a neuroprotective agent against the hypoxia-induced ischemic injury. Transitory four-vessel occlusion and middle cerebral artery occlusion (tMCAO) were used to induce cerebral ischemia. Functional outcomes were determined using neurofunctional tests. Infarct area, neuronal death, and apoptosis induction were evaluated. In addition, ISQ-201 reactivity towards free radicals was studied in a theoretical model. ISQ-201 significantly decreased the ischemia-induced neuronal death and apoptosis, in a dose-dependent manner, showing its therapeutic effect when administered up until 6 h after post-ischemic reperfusion onset, effects that remained after 3 months from the ischemic episode. Furthermore, ISQ-201 significantly reduced infarct volume, leading to recovery of the motor function in the tMCAO model. Finally, the theoretical study confirmed the reactivity of ISQ-201 towards hydroxyl radicals. The results reported here prompted us to suggest ISQ-201 as a promising candidate for the treatment of AIS.

The combination of vinylcyclopropanes with an ester-activated vinyl sulfonate ester in a light-induced radical polymerization shows high reactivity accompanied by a significant increase in conversion and it leads to an enhanced reduction of polymerization-induced shrinkage stress.

Afin de mieux comprendre la chimie du milieu interstellaire (MIS), nous avons simulé au laboratoire les processus thermiques et énergétiques ayant lieu dans les zones de formation d’étoiles au moyen d’une expérience de physico-chimie, appelée RING (reactivity in iINterstellar grains), qui permet de générer des analogues de glaces interstellaires sur un doigt froid (11 K) et sous vide (10^-9 mbar). Nous utilisons une lampe à plasma d’hydrogène pour reproduire le rayonnement UV (Lyman-alpha : 121,6 nm) des étoiles environnantes et initier des processus de réactivité radicalaire au sein de l’échantillon. Trois techniques analytiques nous permettent de suivre l’évolution chimique de nos analogues de glaces interstellaires : les spectroscopies infrarouge et à résonance paramagnétique électronique et la spectrométrie de masse. Grâce à l’utilisation conjointe de ces techniques, de nombreux produits pertinents pour la chimie du MIS tels que des sucres (glycéraldéhyde), des polyols (glycérol), des acides carboxyliques (acide formique) ou encore des polymères (polyoxyméthylène) ont été caractérisés. Les schémas réactionnels précis conduisant à la formation de ces molécules ont également été étudiés, notamment par l’isolation des intermédiaires radicalaires en matrice cryogénique de gaz rares
In order to better understand the chemistry of the interstellar medium (ISM), we have simulated in the laboratory the thermal and energetic processes taking place in star-forming regions by means of a physical chemistry experiment, called RING (reactivity in INterstellar grains), which allows us to generate interstellar ice analogues on a cold finger (11 K) and under vacuum (10^-9 mbar). We use a hydrogen plasma lamp to reproduce the UV radiation (Lyman-alpha: 121.6 nm) of surrounding stars and to initiate radical reactivity processes within the sample. Three analytical techniques allow us to follow the chemical evolution of our interstellar ice analogues: infrared and electron paramagnetic resonance spectroscopies and mass spectrometry. Thanks to the joint use of these techniques, many products relevant to the ISM chemistry such as sugars (glyceraldehyde), polyols (glycerol), carboxylic acids (formic acid) and polymers (polyoxymethylene) have been characterized. The precise reaction schemes leading to the formation of these molecules were also studied, in particular by isolating the radical intermediates in cryogenic rare gas matrices

Doutoramento em Bioquímica
Os polissacarídeos são os componentes maioritários dos grãos de café verde e torrado e da bebida de café. Os mais abundantes são as galactomananas, seguindo-se as arabinogalactanas. Durante o processo de torra, as galactomananas e arabinogalactanas sofrem modificações estruturais, as quais estão longe de estar completamente elucidadas devido à sua diversidade e à complexidade estrutural dos compostos formados. Durante o processo de torra, as galactomananas e arabinogalactanas reagem com proteínas, ácidos clorogénicos e sacarose, originando compostos castanhos de alto peso molecular contendo nitrogénio, designados de melanoidinas. As melanoidinas do café apresentam diversas atividades biológicas e efeitos benéficos para a saúde. No entanto, a sua estrutura exata e os mecanismos envolvidos na sua formação permanecem desconhecidos, bem como a relação estrutura-atividade biológica. A utilização de sistemas modelo e a análise por espectrometria de massa permitem obter uma visão global e, simultaneamente, detalhada das modificações estruturais nos polissacarídeos do café promovidas pela torra, contribuindo para a elucidação das estruturas e mecanismos de formação das melanoidinas. Com base nesta tese, oligossacarídeos estruturalmente relacionados com a cadeia principal das galactomananas, (β1→4)-Dmanotriose (Man3), e as cadeias laterais das arabinogalactanas, (α1→5)-Larabinotriose (Ara3), isoladamente ou em misturas com ácido 5-Ocafeoilquínico (5-CQA), o ácido clorogénico mais abundante nos grãos de café verde, e péptidos compostos por tirosina e leucina, usados como modelos das proteínas, foram sujeitos a tratamento térmico a seco, mimetizando o processo de torra. A oxidação induzida por radicais hidroxilo (HO•) foi também estudada, uma vez que estes radicais parecem estar envolvidos na modificação dos polissacarídeos durante a torra. A identificação das modificações estruturais induzidas por tratamento térmico e oxidativo dos compostos modelo foi feita por estratégias analíticas baseadas principalmente em espectrometria de massa, mas também em cromatografia líquida. A cromatografia de gás foi usada na análise de açúcares neutros e ligações glicosídicas. Para validar as conclusões obtidas com os compostos modelo, foram também analisadas amostras de polissacarídeos do café obtidas a partir de resíduo de café e café instantâneo. Os resultados obtidos a partir dos oligossacarídeos modelo quando submetidos a tratamento térmico (seco), assim como à oxidação induzida por HO• (em solução), indicam a ocorrência de despolimerização, o que está de acordo com estudos anteriores que reportam a despolimerização das galactomananas e arabinogalactanas do café durante a torra. Foram ainda identificados outros compostos resultantes da quebra do anel de açúcares formados durante o tratamento térmico e oxidativo da Ara3. Por outro lado, o tratamento térmico a seco dos oligossacarídeos modelo (individualmente ou quando misturados) promoveu a formação de oligossacarídeos com um maior grau de polimerização, e também polissacarídeos com novos tipos de ligações glicosídicas, evidenciando a ocorrência de polimerização através reações de transglicosilação não enzimática induzidas por tratamento térmico a seco. As reações de transglicosilação induzidas por tratamento térmico a seco podem ocorrer entre resíduos de açúcares provenientes da mesma origem, mas também de origens diferentes com formação de estruturas híbridas, contendo arabinose e manose como observado nos casos dos compostos modelo usados. Os resultados obtidos a partir de amostras do resíduo de café e de café instantâneo sugerem a presença de polissacarídeos híbridos nestas amostras de café processado, corroborando a ocorrência de transglicosilação durante o processo de torra. Além disso, o estudo de misturas contendo diferentes proporções de cada oligossacarídeo modelo, mimetizando regiões do grão de café com composição distinta em polissacarídeos, sujeitos a diferentes períodos de tratamento térmico, permitiu inferir que diferentes estruturas híbridas e não híbridas podem ser formadas a partir das arabinogalactanas e galactomananas, dependendo da sua distribuição nas paredes celulares do grão e das condições de torra. Estes resultados podem explicar a heterogeneidade de estruturas de melanoidinas formadas durante a torra do café. Os resultados obtidos a partir de misturas modelo contendo um oligossacarídeo (Ara3 ou Man3) e 5-CQA sujeitas a tratamento térmico a seco, assim como de amostras provenientes do resíduo de café, mostraram a formação de compostos híbridos compostos por moléculas de CQA ligadas covalentemente a um número variável de resíduos de açúcar. Além disso, os resultados obtidos a partir da mistura contendo Man3 e 5-CQA mostraram que o CQA atua como catalisador das reações de transglicosilação. Por outro lado, nas misturas modelo contendo um péptido, mesmo contendo também 5-CQA e sujeitas ao mesmo tratamento, observou-se uma diminuição na extensão das reações transglicosilação. Este resultado pode explicar a baixa extensão das reações de transglicosilação não enzimáticas durante a torra nas regiões do grão de café mais ricas em proteínas, apesar dos polissacarídeos serem os componentes maioritários dos grãos de café. A diminuição das reações de transglicosilação na presença de péptidos/proteínas pode dever-se ao facto de os resíduos de açúcares redutores reagirem preferencialmente com os grupos amina de péptidos/proteínas por reação de Maillard, diminuindo o número de resíduos de açúcares redutores disponíveis para as reações de transglicosilação. Além dos compostos já descritos, uma diversidade de outros compostos foram formados a partir dos sistemas modelo, nomeadamente derivados de desidratação formados durante o tratamento térmico a seco. Em conclusão, a tipificação das modificações estruturais promovidas pela torra nos polissacarídeos do café abre o caminho para a compreensão dos mecanismos de formação das melanoidinas e da relação estrutura-atividade destes compostos.
Polysaccharides are the major components of green and roasted coffee beans, and coffee brew. The most abundant ones are galactomannans, followed by arabinogalactans. During the roasting process, galactomannans and arabinogalactans undergo structural modifications that are far to be completely elucidated due to their diversity and complexity of the compounds formed. During the roasting process, galactomannans and arabinogalactans react with proteins, chlorogenic acids, and sucrose, originating high molecular weight brown compounds containing nitrogen, known as melanoidins. Several biological activities and beneficial health effects have been attributed to coffee melanoidins. However, their exact structures and the mechanisms involved in their formation remain unknown, as well as the structure-biological activity relationship. The use of model systems and mass spectrometry analysis allow to obtain an overall view and, simultaneously, detailed, of the structural modifications in coffee polysaccharides promoted by roasting, contributing to the elucidation of the structures and formation mechanisms of melanoidins. Based on this thesis, oligosaccharides structurally related to the backbone of galactomannans, (β1→4)-D-mannotriose, and the side chains of arabinogalactans, (α1→5)-Larabinotriose, alone or in mixtures with 5-O-caffeoylquinic acid, the most abundant chlorogenic acid in green coffee beans, and dipeptides composed by tyrosine and leucine, used as models of proteins, were submitted to dry thermal treatments, mimicking the coffee roasting process. The oxidation induced by hydroxyl radicals (HO•) was also studied, since these radicals seem to be involved in the modification of the polysaccharides during roasting. The identification of the structural modifications induced by thermal and oxidative treatment of the model compounds was performed mostly by mass spectrometry-based analytical strategies, but also using liquid chromatography. Gas chromatography was used in the analysis of neutral sugars and glycosidic linkages. To validate the conclusions achieved with the model compounds, coffee polysaccharide samples obtained from spent coffee grounds and instant coffee were also analysed. The results obtained from the model oligosaccharides when submitted to thermal treatment (dry) or oxidation induced by HO• (in solution) indicate the occurrence of depolymerization, which is in line with previous studies reporting the depolymerization of coffee galactomannans and arabinogalactans during roasting. Compounds resulting from sugar ring cleavage were also formed during thermal treatment and oxidative treatment of Ara3. On the other hand, the dry thermal treatment of the model oligosaccharides (alone or when mixed) promoted the formation of oligosaccharides with a higher degree of polymerization, and also polysaccharides with new type of glycosidic linkages, evidencing the occurrence of polymerization via non-enzymatic transglycosylation reactions induced by dry thermal treatment. The transglycosylation reactions induced by dry thermal treatment can occur between sugar residues from the same origin, but also of different origins, with formation of hybrid structures, containing arabinose and mannose in the case of the model compounds used. The results obtained from spent coffee grounds and instant coffee samples suggest the presence of hybrid polysaccharides in these processed coffee samples, corroborating the occurrence of transglycosylation during the roasting process. Furthermore, the study of mixtures containing different proportions of each model oligosaccharide, mimicking coffee bean regions with distinct polysaccharide composition, subjected to different periods of thermal treatment, allowed to infer that different hybrid and non-hybrid structures may be formed from arabinogalactans and galactomannans, depending on their distribution in the bean cell walls and on roasting conditions. These results may explain the heterogeneity of melanoidins structures formed during coffee roasting. The results obtained from model mixtures containing an oligosaccharide (Ara3 or Man3) and 5-CQA and subjected to dry thermal treatment, as well as samples derived from spent coffee grounds, showed the formation of hybrid compounds composed by CQA molecules covalently linked to a variable number of sugar residues. Moreover, the results obtained from the mixture containing Man3 and 5-CQA showed that CQA acts as catalyst of transglycosylation reactions. On the other hand, in the model mixtures containing a peptide, even if containing 5-CQA and subjected to the same treatment, it was observed a decrease in the extent of transglycosylation reactions. This outcome can explain the low extent of non-enzymatic transglycosylation reactions during roasting in coffee bean regions enriched in proteins, although polysaccharides are the major components of the coffee beans. The decrease of transglycosylation reactions in the presence of peptides/proteins can be related with the preferential reactivity of reducing residues with the amino groups of peptides/proteins by Maillard reaction, decreasing the number of reducing residues available to be directly involved in the transglycosylation reactions. In addition to the compounds already described, a diversity of other compounds were formed from model systems, namely dehydrated derivatives formed during dry thermal treatment. In conclusion, the identification of the structural modifications in coffee polysaccharides promoted by roasting pave the way to the understanding of the mechanisms of formation of melanoidins and structure-activity relationship of these compounds.

AbstractOxygen-centered radicals (R1O•) are reactive intermediates in organic synthesis, with versatile synthetic utilities in processes such as hydrogen-atom transfer (HAT), β-fragmentation, radical addition to unsaturated carbon–carbon bonds, and rearrangement reactions. In this review, we focus on recent advances in the generation and transformation of oxygen-centered radicals, including (alkyl-, α-oxo-, aryl-) carboxyl, alkoxyl, aminoxyl, phenoxyl, and vinyloxyl radicals, and compare the reactivity of oxygen-centered radicals under traditional reaction conditions with their reactivity under visible-light-induced reaction conditions.

AbstractThe field of organic electron donors is large and diverse, both in terms of the structures of the donors and the structures of the acceptors. In the past 15 years, organic donors have been developed that show remarkable strength, with ground-state or excited-state oxidation potentials rivalling even the most reactive metals. At the other end of the scale of reactivity, highly reactive oxidizing agents are now available upon photoactivation of a number of organic structures. The first part of this chapter reviews organic electron donors that are based upon an alkene that is activated by strongly electron-releasing substituents; these donors can be active in the ground and/or excited states. The chapter also covers anionic organic donors that emerged in the field of SRN1 and base-induced homolytic aromatic substitution (BHAS) reactions, as well as substrate-based anionic donors including borates and silicates. The use of photoexcited organic dyes as electron donors is described and, finally, some of the recent research with very weak organic donors is highlighted.

The effects of H2 enrichment on the ignition and propagation of laminar CH4-air flames in axisymmetric coflowing jets are numerically investigated. A comprehensive, time-dependent computational model, which employs a detailed description of chemistry and transport, is used to simulate the transient ignition and flame propagation phenomena. Because fuel-air mixtures can potentially be ignited due to the presence of either a high-temperature zone or a radical pool, we explore temperature-induced ignition and radical-pool-induced ignition. It is observed overall that radical-pool-induced ignition is more effective than temperature-induced ignition for igniting any H2-CH4-air mixture. With increasing the radical-pool concentration ignition is facilitated and the total ignition time for the mixture to reach the ignition conditions is significantly reduced. In addition, as H2 mole fraction in the fuel jet increases, the mixture is more easily ignited. To study the propagation characteristics of these flames only radical-induced ignition is used since it is more effective. Following ignition, a well-defined triple flame, containing a rich premixed, a nonpremixed, and a lean premixed reaction zone, is formed that propagates upstream with nearly constant flame displacement speed towards the burner. As the flame approaches the burner, it transitions to a double flame, and subsequently to a burner-stabilized nonpremixed flame. Predictions are validated using measurements of the flame displacement speed. Detailed simulations are used to examine the effects of H2 enrichment on the propagation characteristics of CH4-air triple flames. As H2 concentration in the fuel blend is increased, the flame displacement and propagation speeds increase progressively due to the enhanced chemical reactivity, diffusivity, and preferential diffusion caused by H2 addition. In addition, the flammability limits associated with the triple flames are progressively extended with the increase in H2 concentration. The flame structure and flame dynamics are also markedly modified by H2 enrichment, which substantially increases the flame curvature and mixture fraction gradient. For all the H2-enriched methane-air flames investigated in this study, there is a negative correlation between flame speed and stretch, with the flame speed decreasing almost linearly with stretch, consistent with previous studies. The effect of H2 addition is to modify the flame sensitivity to stretch, as it decreases the Markstein number (Ma) and increases the flame tendency towards diffusive-thermal instability (i.e. Ma→0). These results are consistent with the previously reported experimental results for outwardly propagating spherical flames burning a mixture of natural gas and hydrogen.

In liquid-metal-cooled fast reactors, the temperature rise and its gradients over the core region, sometimes with an addition of the accumulated irradiation creep and swelling, result in a radial core expansion and the bowing of subassemblies, both of which lead to the radial displacements of fuel and reflector materials. In spite of the small magnitude of such displacements, the reactivity change due to radial core expansion and bowing of subassemblies during a transient, such as unprotected loss-of-flow (ULOF), is significant in magnitude and plays one of the most important roles among all inherent safety features; the focus is on the change of the power-to-flow ratio (P/F) from 1.0 to 2.0, during which a large temperature gradient is induced. A 3-D code, named PERMOV, is developed for the calculation of such reactivity feedback, at present as a part of the Neutronics Analysis System (NAS); NAS is a 3-D nodal code, independently developed by researchers in China Experimental Fast Reactor; and at the same time, the code PERMOV has a high portability, making it available to run with other mature core physics codes.

In addition to mostly H2 and CO, syngas also contains reasonable amounts of light hydrocarbons, CO2, H2O, N2, and Ar. Impurities such as NH3, HCN, COS, H2S, and NOx (NO, NO2, N2O) are also commonly found in syngas. The presence of these impurities, even in very low concentrations, can induce some large changes in combustion properties. Although they introduce potential design and operational issues for gas turbines, these changes in combustion properties due to the presence of impurities are still not well characterized. The aim of this work was therefore to investigate numerically the effect of the presence of impurities in realistic syngas compositions on some fundamental combustion properties of premixed systems such as laminar flame speed and ignition delay time, at realistic engine operating conditions. To perform this study, a state-of-the-art C0–C3 detailed kinetics mechanism was used. This mechanism was combined with recent, optimized sub-mechanisms for impurities which can impact the combustion properties of the syngas such as nitrogenous species (i.e., N2O, NO2, NH3, and HCN) and sulfur-based species such as H2S, SO2 and COS. Several temperatures, pressures, and equivalence ratios were investigated. The results of this study showed that the addition of some impurities modifies notably the reactivity of the mixture. The ignition delay time is decreased by the addition of NO2 and H2S at the temperatures and pressures for which the HO2 radical dominates the H2 combustion. However, while NO2 has no effect when OH is dominating, H2S increases the ignition delay time in such conditions for pressures above 1 atm. The amplitude of these effects is however dependent on the impurity concentration. Laminar flame speeds are not sensitive to NO2 addition but they are to NH3 and HCN, inducing a small reduction of the laminar flame speed at fuel rich conditions. H2S exhibits some inhibiting effects on the laminar flame speed but only for high concentrations. The inhibiting effects of NH3, HCN, and H2S are due to the OH radical consumption by these impurities, leading to the formation of radicals that are less reactive.

Abstract In hypothetical steam generator tube rupture (SGTR) accident scenario of pool-type liquid metal cooled fast breeder reactor, water is injected from SG into primary circuit through the break and flash. The injected steam bubbles may transport into the core region and insert positive reactivity, which threaten the reactor safety. To accurately predict the void fraction for evaluation of accident consequence, drift flux model applied to gas-liquid metal two-phase flow is useful and need to be developed. In this contribution, an algebraic model aimed at bubble induced turbulence (BIT) is introduced to improve the underestimation of turbulent viscosity calculated by Clark’s force balance model to accurately predict the one-dimensional liquid velocity distribution along radial direction in flow channel. On this basis, the distribution parameter is calculated. Analysis result shows that distribution parameter is assuming very high values at low Re number. With Froude number increase, distribution parameter tends to decrease. At lower void factions, distribution parameter is also assumed to be high values. It indicates that the pipe size, flow rate and void fraction can all influence distribution parameter. Considering the quantitative laws of above influence factors obtained by theoretical analysis and fitting test data, a new correlation for gas-liquid metal two-phase flow is developed and evaluated.

The fuel rods of pressurized water reactors operate under complex radioactive, thermal and mechanical conditions. Multiphysics has to be taken into account in order to evaluate their performance. Many existing fuel rod codes make great simplifications on analyzing the behavior of fuel rods. The present study develops a three dimensional module within the framework of a general-purpose finite element solver, i.e. ABAQUS, for modeling the thermo-mechanical performance of the fuel rods. A typical fuel rod is modeled and the temperature as well as the stress within the pellets are computed. The results show that the burnup levels have an important influence on the fuel temperature. The swelling of fission products cause dramatically increasing of pellet strain. The change of the cladding stress and radial displacement with the axial length can be reasonably predicted. It is shown that a quick power ramp or a reactivity insertion accident can induce high tensile stress to the outer regime of the pellet and may cause further fragmentation to the pellets.

Flame radicals are fragments of molecules with high reactivity and control the process of combustion to a high degree. Therefore, the knowledge of accurate number densities of these species is very important, e.g. when modelling flames. Because of the relative large cross sections compared to other optical methods, laser-induced fluorescence (LIF) spectroscopy is one of the most sensitive techniques for accurate determination of concentrations and temperatures [1]. However, when LIF is applied for quantitative diagnostics at high pressures (10 bar >p> 1 bar) and high temperatures, which is typical for industrial combustions, several problems associated with the LIF-method itself appear, and limit the accuracy of the method. The laser excites an upper level population of the molecule or atom under investigation, which decays by spontaneous emission and radiationless by collisional induced processes (quenching). The latter one reduces the fluorescence yield considerably, two or three orders of magnitude are typical for atmospheric pressure. If the measurements are performed with a time resolution better than the quenching rates, the LIF-intensities can be used to extract absolute number densities. However, this requires a laser and a detection system with picosecond time resolution. Since important atomic radicals like O, C, N, H or diatomic molecules like NO, CO and OH can only be excited from the ground state via two- or one photon absorption in the spectral range between 200 and 300 nm [2] a powerful ultraviolet laser system is required in these experiments. However, the quantitative interpretation of the picosecond LIF-intensity measurements still needs accurate quenching rate data for the relevant pressures and temperatures and the species that are present in the combustion process. In the data analysis also systematic influences like photodissociation effects by the strong uv-laser pulses have to be considered. Therefore, in this paper improved quenching rate measurements of NO with NO, N2 and O2 for pressures up to p=10 bar, and photodissociation effects of NO are reported.

Stability and bifurcation analyses of nuclear-coupled thermal hydraulic instability in BWR has been performed using a semi-analytical method. The BWR model used in this study consists of three parts: neutron kinetics, fuel rod heat conduction and single and two-phase heated channel thermal hydraulics. Point reactor model is currently being used for neutron kinetics and will be extended in the future to higher order lambda or omega-mode. In the heat conduction part, a piecewise quadratic approximation to radial temperature distribution in fuel pellet and cladding is assumed. ODEs for the expansion coefficients of the quadratic spatial profiles are developed by applying variational principle. Similar to the heat conduction model, the spatial enthalpy distribution in the single phase region and steam quality in the two-phase region in the BWR core are approximated by quadratic polynomials. Two-phase flow is modeled using the homogeneous equilibrium model. A bifurcation analysis code, BIFDD, is then used to perform the analysis for the stability boundary (SB) and the nature of Poincare´-Andronov-Hopf bifurcation (PAH-B). Results in control-rod-induced-reactivity—inlet-subcooling-number space show that both super or sub-critical bifurcation can occur along the SB—the subcritical bifurcation occurs for very small or very large subcooling number values; super-critical PAH-B occurs for intermediate values of subcooling number.

Abstract Nuclear reactor designs are governed by postulated accident events that may occur during their operational lifetime. One type of incident is a reactivity-initiated accident (RIA), during which a sudden surge of power in the fuel components within the core may result in the latter exceeding its cooling capabilities. This could lead to a departure from nucleate boiling (DNB) event which results in a significant decrease in heat transfer capabilities. Preventing the occurrence of a DNB crisis requires a fundamental understanding of the cladding-to-coolant heat transfer under fast transient conditions, as well as the governing hydrodynamic and design parameters that influence when the critical heat flux (CHF) will be exceeded. Presently, large uncertainties in computer models used to predict CHF have led to conservative safety limits governing light-water reactor (LWR) designs. The Idaho National Laboratory (INL) is currently leading a combined effort that takes advantage of the restart of the Transient Reactor Test (TREAT) facility, to better understand the mechanism of CHF under in-pile pool boiling conditions. The goal of this laboratory directed project is to use the unique capabilities of TREAT coupled with a non-fueled nuclear heated borated stainless-steel 304 tube experiment within an experimental capsule. The borated tube will induce CHF in the surrounding coolant when subjected to a power pulse within the TREAT. The impacts of rapid surface heating effects as well as radiation-induced surface activation (RISA) will be experimentally investigated. This feature is a continuation to previous thermal hydraulics analysis that was conducted to inform on a test matrix for the design of the borated heater experiment. The borated tube was used in place of a solid rod so that the center axial region can be instrumented to allow for better experimental analysis. Therefore, it is desirable to design this rodlet so that the maximum heat flux occurs at the center of the axial length of the rod. The work presented here analyzes the potential to integrate axial boron gradients within this tube to shape its power curve. Several generic axial power shapes were initially considered. Natural boron concentrations between 0.1–2.0 wt.% were analyzed and a power coupling factor (PCF) was calculated for each. A self-shielding study was conducted to develop radial power profiles for several boron concentrations. These were then applied to three different power pulses to determine how these two parameters influence the chosen axial heat flux curve. Variations in the initial coolant temperature were investigated. Lastly, how the shape of the generic curve is affected following a DNB event was also studied. Two different CHF cases were included within the scope of this analyses; one during which CHF was exceeding along the entire axial region of the rod, and another where the former occurred at the center region only. The behavior of the curve overtime was investigated.