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Sample records for two-hit model oxidative

  1. Preventive effect of α-lipoic acid on prepulse inhibition deficits in a juvenile two-hit model of schizophrenia.

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    Deslauriers, J; Racine, W; Sarret, P; Grignon, S

    2014-07-11

    Some pathophysiological models of schizophrenia posit that prenatal inflammation sensitizes the developing brain to second insults in early life and enhances brain vulnerability, thereby increasing the risk of developing the disorder during adulthood. We previously developed a two-hit animal model, based on the well-established prenatal immune challenge with poly-inosinic/cytidylic acid (polyI:C), followed by juvenile restraint stress (RS). We observed an additive disruption of prepulse inhibition (PPI) of acoustic startle in juvenile mice submitted to both insults. Previous studies have also reported that oxidative stress is associated with pathophysiological mechanisms of psychiatric disorders, including schizophrenia. We report here that PPI disruption in our two-hit animal model of schizophrenia is associated with an increase in oxidative stress. These findings led us to assess whether α-lipoic acid, an antioxidant, can prevent both increase in oxidative status and PPI deficits in our juvenile in vivo model of schizophrenia. In the offspring submitted to prenatal injection of polyI:C and to RS, treatment with α-lipoic acid prevented the development of PPI deficits 24h after the last period of RS. α-Lipoic acid also improved PPI performance in control mice. The reversal effect of α-lipoic acid pretreatment on these behavioral alterations was further accompanied by a normalization of the associated oxidative status and dopaminergic and GABAergic abnormalities in the prefrontal cortex. Based on our double insult paradigm, these results support the hypothesis that oxidative stress plays an important role in the development of PPI deficits, a well-known behavior associated with schizophrenia. These findings form the basis of future studies aiming to unravel mechanistic insights of the putative role of antioxidants in the treatment of schizophrenia, especially during the prodromal stage.

  2. A Two-Hit Model of Autism: Adolescence as the Second Hit

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    Picci, Giorgia; Scherf, K. Suzanne

    2015-01-01

    Adolescence brings dramatic changes in behavior and neural organization. Unfortunately, for some 30% of individuals with autism, there is marked decline in adaptive functioning during adolescence. We propose a two-hit model of autism. First, early perturbations in neural development function as a “first hit” that sets up a neural system that is “built to fail” in the face of a second hit. Second, the confluence of pubertal hormones, neural reorganization, and increasing social demands during adolescence provides the “second hit” that interferes with the ability to transition into adult social roles and levels of adaptive functioning. In support of this model, we review evidence about adolescent-specific neural and behavioral development in autism. We conclude with predictions and recommendations for empirical investigation about several domains in which developmental trajectories for individuals with autism may be uniquely deterred in adolescence. PMID:26609500

  3. Biophysics Representation of the Two-Hit Model of Alzheimer's Disease for the Exploration of Late CNS Risks from Space Radiation

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    Cucinotta, Francis A.; Ponomarev, Artem

    2009-01-01

    A concern for long-term space travel outside the Earth s magnetic field is the late effects to the central nervous system (CNS) from galactic cosmic ray (GCR) or solar particle events (SPE). Human epidemiology data is severely limited for making CNS risk estimates and it is not clear such effects occur following low LET exposures. We are developing systems biology models based on biological information on specific diseases, and experimental data for proton and heavy ion radiation. A two-hit model of Alzheimer s disease (AD) has been proposed by Zhu et al.(1), which is the framework of our model. Of importance is that over 50% of the US population over the age of 75-y have mild to severe forms of AD. Therefore we recommend that risk assessment for a potential AD risk from space radiation should focus on the projection of an earlier age of onset of AD and the prevention of this possible acceleration through countermeasures. In the two-hit model, oxidative stress and aberrant cell cycle-related abnormalities leading to amyloid-beta plaques and neurofibrillary tangles are necessary and invariant steps in AD. We have formulated a stochastic cell kinetics model of the two-hit AD model. In our model a population of neuronal cells is allowed to undergo renewal through neurogenesis and is susceptible to oxidative stress or cell cycle abnormalities with age-specific accumulation of damage. Baseline rates are fitted to AD population data for specific ages, gender, and for persons with an apolipoprotein 4 allele. We then explore how low LET or heavy ions may increase either of the two-hits or neurogenesis either through persistent oxidative stress, direct mutation, or through changes to the micro-environment, and suggest possible ways to develop accurate quantitative estimates of these processes for predicting AD risks following long-term space travel.

  4. A novel mouse model of cerebral cavernous malformations based on the two-hit mutation hypothesis recapitulates the human disease.

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    McDonald, David A; Shenkar, Robert; Shi, Changbin; Stockton, Rebecca A; Akers, Amy L; Kucherlapati, Melanie H; Kucherlapati, Raju; Brainer, James; Ginsberg, Mark H; Awad, Issam A; Marchuk, Douglas A

    2011-01-15

    Cerebral cavernous malformations (CCMs) are vascular lesions of the central nervous system appearing as multicavernous, blood-filled capillaries, leading to headache, seizure and hemorrhagic stroke. CCM occurs either sporadically or as an autosomal dominant disorder caused by germline mutation of one of the three genes: CCM1/KRIT1, CCM2/MGC4607 and CCM3/PDCD10. Surgically resected human CCM lesions have provided molecular and immunohistochemical evidence for a two-hit (germline plus somatic) mutation mechanism. In contrast to the equivalent human genotype, mice heterozygous for a Ccm1- or Ccm2-null allele do not develop CCM lesions. Based on the two-hit hypothesis, we attempted to improve the penetrance of the model by crossing Ccm1 and Ccm2 heterozygotes into a mismatch repair-deficient Msh2(-/-) background. Ccm1(+/-)Msh2(-/-) mice exhibit CCM lesions with high penetrance as shown by magnetic resonance imaging and histology. Significantly, the CCM lesions range in size from early-stage, isolated caverns to large, multicavernous lesions. A subset of endothelial cells within the CCM lesions revealed somatic loss of CCM protein staining, supporting the two-hit mutation mechanism. The late-stage CCM lesions displayed many of the characteristics of human CCM lesions, including hemosiderin deposits, immune cell infiltration, increased endothelial cell proliferation and increased Rho-kinase activity. Some of these characteristics were also seen, but to a lesser extent, in early-stage lesions. Tight junctions were maintained between CCM lesion endothelial cells, but gaps were evident between endothelial cells and basement membrane was defective. In contrast, the Ccm2(+/-)Msh2(-/-) mice lacked cerebrovascular lesions. The CCM1 mouse model provides an in vivo tool to investigate CCM pathogenesis and new therapies.

  5. Experimentally Approaching the ICU: Monitoring Outcome-Based Responses in the Two-Hit Mouse Model of Posttraumatic Sepsis

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    Susanne Drechsler

    2011-01-01

    Full Text Available To simulate and monitor the evolution of posttraumatic sepsis in mice, we combined a two-hit model of trauma/hemorrhage (TH followed by polymicrobial sepsis with repetitive blood sampling. Anesthetized mice underwent femur fracture/sublethal hemorrhage and cecal ligation and puncture (CLP 48 h later. To monitor outcome-dependent changes in circulating cells/biomarkers, mice were sampled daily (facial vein for 7 days and retrospectively divided into either dead (DIE or surviving (SUR by post-CLP day 7. Prior to CLP, AST was 3-fold higher in DIE, while all other post-TH changes were similar between groups. There was a significant post-CLP intergroup separation. In SUR, RBC and Hb were lower, platelets and neutrophils higher, and lymphocytes mixed compared to DIE. In DIE, all organ function markers except glucose (decrease were few folds higher compared to SUR. In summary, the combination of daily monitoring with an adequate two-hit model simulates the ICU setting, allows insight into outcome-based responses, and can identify biomarkers indicative of death in the acute posttraumatic sepsis in mice.

  6. Lung endothelial barrier protection by iloprost in the two-hit models of VILI involves inhibition of Rho signaling

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    Birukova, Anna A.; Fu, Panfeng; Xing, Junjie; Cokic, Ivan; Birukov, Konstantin G.

    2010-01-01

    Mechanical ventilation at high tidal volume may cause pulmonary capillary leakage and acute lung inflammation culminating in ventilator-induced lung injury. Iloprost is a stable synthetic analogue of prostaglandin I2 used for treatment of pulmonary hypertension, which also showed endothelium-dependent anti-edemagenic effects in the models of lung injury. To test the hypothesis that iloprost may attenuate lung inflammation and lung endothelial barrier disruption caused by pathologic lung distension and coagulation system component thrombin, we used cell and animal two-hit models of ventilator-induced lung injury. Mice received triple injection of iloprost (2 μg/kg, intravenous instillation) at 0, 40 and 80 min after onset of high tidal volume (HTV) mechanical ventilation (30 ml/kg, 4 hrs) combined with administration of thrombin receptor activating peptide 6 (TRAP6, 3 × 10−7 mol/mouse, intratracheal instillation). After 4 hrs of ventilation, bronchoalveolar lavage (BAL), histological analysis, and measurements of Evans blue accumulation in the lung tissue lung were performed. Effects of iloprost on endothelial barrier dysfunction were further assessed in pulmonary endothelial cells (EC) exposed to thrombin and pathologic (18%) cyclic stretch. Combination of HTV and TRAP6 enhanced accumulation of neutrophils in BAL fluid and lung parenchyma, increased BAL protein content and endothelial permeability judged by Evans blue extravasation in the lung tissue. These effects were markedly attenuated by iloprost. Application of 18% cyclic stretch to pulmonary EC enhanced thrombin-induced EC paracellular gap formation and Rho-GTPase-mediated phosphorylation of regulatory myosin light chains and myosin phosphatase. Iloprost markedly inhibited Rho-kinase mediated site-specific phosphorylation of myosin phosphatase, and prevented cyclic stretch- and thrombin-induced endothelial monolayer disruption. This study characterizes for the first time the protective effects of

  7. Reconciling the IPC and Two-Hit Models: Dissecting the Underlying Cellular and Molecular Mechanisms of Two Seemingly Opposing Frameworks.

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    Morris, Carlos F M; Tahir, Muhammad; Arshid, Samina; Castro, Mariana S; Fontes, Wagner

    2015-01-01

    Inflammatory cascades and mechanisms are ubiquitous during host responses to various types of insult. Biological models and interventional strategies have been devised as an effort to better understand and modulate inflammation-driven injuries. Amongst those the two-hit model stands as a plausible and intuitive framework that explains some of the most frequent clinical outcomes seen in injuries like trauma and sepsis. This model states that a first hit serves as a priming event upon which sequential insults can build on, culminating on maladaptive inflammatory responses. On a different front, ischemic preconditioning (IPC) has risen to light as a readily applicable tool for modulating the inflammatory response to ischemia and reperfusion. The idea is that mild ischemic insults, either remote or local, can cause organs and tissues to be more resilient to further ischemic insults. This seemingly contradictory role that the two models attribute to a first inflammatory hit, as priming in the former and protective in the latter, has set these two theories on opposing corners of the literature. The present review tries to reconcile both models by showing that, rather than debunking each other, each framework offers unique insights in understanding and modulating inflammation-related injuries.

  8. Sesame oil mitigates nutritional steatohepatitis via attenuation of oxidative stress and inflammation: a tale of two-hit hypothesis.

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    Periasamy, Srinivasan; Chien, Se-Ping; Chang, Po-Cheng; Hsu, Dur-Zong; Liu, Ming-Yie

    2014-02-01

    Nonalcoholic fatty liver disease, the most common chronic liver disorder worldwide, comprises conditions from steatosis to nonalcoholic steatohepatitis (NASH) and cirrhosis. NASH is associated with an increased risk of hepatocellular carcinoma. Sesame oil, a healthful food, increases resistance to oxidative stress, inflammation and protects against multiple organ injury in various animal models. We investigated the protective effect of sesame oil against nutritional steatohepatitis in mice. C57BL/6 J mice were fed with methionine-choline deficient (MCD) diet for 28 days to induce NASH. Sesame oil (1 and 2 ml/kg) was treated from 22nd to 28th day. Body weight, steatosis, triglycerides, aspartate transaminase, alanine transaminase, nitric oxide, malondialdehyde, tumor necrosis factor-α, interlukin-6, interleukin-1β, leptin, and transforming growth factor-β1 (TGF-β1) were assessed after 28 days. All tested parameters were higher in MCD-fed mice than in normal control mice. Mice fed with MCD diet for 4 weeks showed severe liver injury with steatosis, oxidative stress, and necrotic inflammation. In sesame-oil-treated mice, all tested parameters were significantly attenuated compared with MCD-alone mice. Sesame oil inhibited oxidative stress, inflammatory cytokines, leptin, and TGF-β1 in MCD-fed mice. In addition, histological analysis showed that sesame oil provided significant protection against fibrotic collagen. We conclude that sesame oil protects against steatohepatitic fibrosis by decreasing oxidative stress, inflammatory cytokines, leptin and TGF-β1. Copyright © 2014 Elsevier Inc. All rights reserved.

  9. Sex-specific disruptions in spatial memory and anhedonia in a "two hit" rat model correspond with alterations in hippocampal brain-derived neurotrophic factor expression and signaling.

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    Hill, Rachel A; Klug, Maren; Kiss Von Soly, Szerenke; Binder, Michele D; Hannan, Anthony J; van den Buuse, Maarten

    2014-10-01

    Post-mortem studies have demonstrated reduced expression of brain-derived neurotrophic factor (BDNF) in the hippocampus of schizophrenia and major depression patients. The "two hit" hypothesis proposes that two or more major disruptions at specific time points during development are involved in the pathophysiology of these mental illnesses. However, the role of BDNF in these "two hit" effects is unclear. Our aim was to behaviorally characterize a "two hit" rat model of developmental stress accompanied by an in-depth assessment of BDNF expression and signalling. Wistar rats were exposed to neonatal maternal separation (MS) stress and/or adolescent/young-adult corticosterone (CORT) treatment. In adulthood, models of cognitive and negative symptoms of mental illness were analyzed. The hippocampus was then dissected into dorsal (DHP) and ventral (VHP) regions and analyzed by qPCR for exon-specific BDNF gene expression or by Western blot for BDNF protein expression and downstream signaling. Male "two hit" rats showed marked disruptions in short-term spatial memory (Y-maze) which were absent in females. However, female "two hit" rats showed signs of anhedonia (sucrose preference test), which were absent in males. Novel object recognition and anxiety (elevated plus maze) were unchanged by either of the two "hits". In the DHP, MS caused a male-specific increase in BDNF Exons I, II, IV, VII, and IX mRNA but a decrease in mature BDNF and phosphorylated TrkB (pTrkB) protein expression in adulthood. In the VHP, BDNF transcript expression was unchanged; however, in female rats only, MS significantly decreased mature BDNF and pTrkB protein expression in adulthood. These data demonstrate that MS causes region-specific and sex-specific long-term effects on BDNF expression and signaling and, importantly, mRNA expression does not always infer protein expression. Alterations to BDNF signaling may mediate the sex-specific effects of developmental stress on anhedonic behaviors.

  10. Effects of vagus nerve stimulation and vagotomy on systemic and pulmonary inflammation in a two-hit model in rats.

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    Matthijs Kox

    Full Text Available Pulmonary inflammation contributes to ventilator-induced lung injury. Sepsis-induced pulmonary inflammation (first hit may be potentiated by mechanical ventilation (MV, second hit. Electrical stimulation of the vagus nerve has been shown to attenuate inflammation in various animal models through the cholinergic anti-inflammatory pathway. We determined the effects of vagotomy (VGX and vagus nerve stimulation (VNS on systemic and pulmonary inflammation in a two-hit model. Male Sprague-Dawley rats were i.v. administered lipopolysaccharide (LPS and subsequently underwent VGX, VNS or a sham operation. 1 hour following LPS, MV with low (8 mL/kg or moderate (15 mL/kg tidal volumes was initiated, or animals were left breathing spontaneously (SP. After 4 hours of MV or SP, rats were sacrificed. Cytokine and blood gas analysis was performed. MV with 15, but not 8 mL/kg, potentiated the LPS-induced pulmonary pro-inflammatory cytokine response (TNF-α, IL-6, KC: p<0.05 compared to LPS-SP, but did not affect systemic inflammation or impair oxygenation. VGX enhanced the LPS-induced pulmonary, but not systemic pro-inflammatory cytokine response in spontaneously breathing, but not in MV animals (TNF-α, IL-6, KC: p<0.05 compared to SHAM, and resulted in decreased pO(2 (p<0.05 compared to sham-operated animals. VNS did not affect any of the studied parameters in both SP and MV animals. In conclusion, MV with moderate tidal volumes potentiates the pulmonary inflammatory response elicited by systemic LPS administration. No beneficial effects of vagus nerve stimulation performed following LPS administration were found. These results questions the clinical applicability of stimulation of the cholinergic anti-inflammatory pathway in systemically inflamed patients admitted to the ICU where MV is initiated.

  11. A two-hit dog model for the study of multiple organ dysfunction syndrome%两次打击致犬多器官功能衰竭的实验研究

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    陈继红; 张振宇; 李玉芳; 刘健

    2010-01-01

    Objective Beagle dogs were subjected to hemorrhagic shock plus resuscitation and endotoxiemia (two-hit) to set up multiple organ dysfunction syndrome (MODS) model. In the study, this model can be used to monitor the responses of organ compensation and in compensation. Method Seven male Beagle dogs, weight ( 15 ± 2) kg, were provided by animal experiment centre of Xinjiang Medical University. MODS model was set up in 7 Beagle dogs. Hemorrhagic shock was produced according to the method of Wigger. After the resuscitation,Escherichia coli endotoxin was given via the femoral vein at a dose of 1.5 mg/kg. The criteria of MODS were defined as the presence of two or more of organ dysfunction. Clinical biochemical values were examined before making model and 0 h,3 h,6 h,9 h, 12 h after the establishment of model. The pathological change of the liver and the kidney were observed under the light microscopy. Results Significant differences of WBC,PaO2,LP,ALT, AST,Cr and BUN were observed after the establishment of model compared with those before the establishment of model ( P < 0.05). Severe pathological lesions were observed in tissues of the liver and kidney. Conclusions Hemorrhagic shock and endotoxemia,a two-hit method, can be used to set up a delayed animal model for MODS to study the responses of organ dysfunction caused by ischemic and infectious diseases.%目的 通过失血性休克加内毒素血症两次打击建立犬多器官功能障碍综合征(MODS)的动物模型,研究动物各器官代偿与失代偿的反应过程.方法 选择由新疆医科大学实验动物中心提供的体质量(15±2)kg雄性Beagle犬7只,采用Wiggers法造成失血性休克,复苏12 h后由静脉持续12 h滴入1.5 mg/kg内毒素,建立MODS模型.MODS诊断标准为出现两个或两个以上器官功能障碍者.在建模前、建模后0,3,6,9,12 h观察实验犬各脏器功能,及肝、肾病理组织学变化.采用SPSS12.0软件包,于各时间点行重复

  12. Anxiety vulnerability in women: a two-hit hypothesis.

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    Catuzzi, Jennifer E; Beck, Kevin D

    2014-09-01

    Females are twice as likely to develop an anxiety disorder compared to males, and thus, are believed to possess an innate vulnerability that increases their susceptibility to develop an anxiety disorder. However, studies using aversive learning paradigms to model anxiety disorders in humans and animals have revealed contradictory results. While females exhibit the ability to rapidly acquire stimulus-response associations, which may result from a greater attentional bias towards threat, females are also capable to readily extinguish these associations. Thus, there is little evidence to suggest that the female sex represents a vulnerability factor of anxiety, per se. However, if females are to possess a second vulnerability factor that increases the inflexibility of stimulus-response associations, then an anxiety disorder may be more likely to develop. Behavioral inhibition (BI) is a vulnerability factor associated with the formation of inflexible stimulus-response associations. In this "two hit" model of anxiety vulnerability, females possessing a BI temperament will rapidly acquire stimulus-response associations that are resistant to extinction, resulting in the development of an anxiety disorder. In this review we explore evidence for a "two-hit" hypothesis underlying anxiety vulnerability in females. We explore the literature for evidence of a sex difference in attentional bias towards threat that may lead to the facilitated acquisition of stimulus-response associations in females. We also provide evidence that BI is associated with inflexible stimulus-response association formation. We conclude with data generated from our laboratory that highlights the additive effect of the female sex and behavioral inhibition vulnerabilities using a model behavior for anxiety disorder-susceptibility, active avoidance.

  13. Duas classes de mutação na evolução de policitemia vera para leucemia mielóide aguda Two-hit model of leukemogenesis in the evolution of polycythemia vera to acute myeloid leukemia

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    Juliana C. C. Ribeiro

    2009-04-01

    case of PV with evolution to AML in which it was possible to demonstrate the two-hit model of leukemogenesis: one mutation confers proliferative advantage and another interferes with differentiation. Case: A 55-year-old female patient was diagnosed with PV in 2002 and treated with phlebotomies and hydroxyurea. In 2006, there was progression topost-polycythemic fibrosis with AML one year later. She presented the JAK2V617F mutation. The result of karyotyping performed at diagnosis was normal and at transformation, 46,XX,del(20(q13.1 was detected in 4/20 metaphases. FISH analysis of a stored sample for 20q13 showed the deletion in 20% of interphases confirming the earlier presence of a clonal abnormality that was not detected by karyotyping. The JAK2V617F mutation is sufficient to cause proliferation of hematopoietic cells and has been established as a primary pathogenetic mechanism in PV. However, the evolution of the disease is heterogeneous, suggesting the occurrence of additional phenomena contributing to leukemogenesis. This case demonstrates the two-hit model in the progression of PV to LMA, in which a class of mutation induces proliferative advantage and another blocks differentiation. Two events which contribute to proliferation and to maturation blockade were detected in this patient. Other mechanisms may be implicated and prospective studies should be encouraged in an attempt to elucidate the different steps involved in leukemogenesis.

  14. Inflammation and the two-hit hypothesis of schizophrenia.

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    Feigenson, Keith A; Kusnecov, Alex W; Silverstein, Steven M

    2014-01-01

    The high societal and individual cost of schizophrenia necessitates finding better, more effective treatment, diagnosis, and prevention strategies. One of the obstacles in this endeavor is the diverse set of etiologies that comprises schizophrenia. A substantial body of evidence has grown over the last few decades to suggest that schizophrenia is a heterogeneous syndrome with overlapping symptoms and etiologies. At the same time, an increasing number of clinical, epidemiological, and experimental studies have shown links between schizophrenia and inflammatory conditions. In this review, we analyze the literature on inflammation and schizophrenia, with a particular focus on comorbidity, biomarkers, and environmental insults. We then identify several mechanisms by which inflammation could influence the development of schizophrenia via the two-hit hypothesis. Lastly, we note the relevance of these findings to clinical applications in the diagnosis, prevention, and treatment of schizophrenia. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Inflammation and the Two-Hit Hypothesis of Schizophrenia

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    Feigenson, Keith A.; Kusnecov, Alex W.; Silverstein, Steven M.

    2014-01-01

    The high societal and individual cost of schizophrenia necessitates finding better, more effective treatment, diagnosis, and prevention strategies. One of the obstacles in this endeavor is the diverse set of etiologies that comprises schizophrenia. A substantial body of evidence has grown over the last few decades to suggest that schizophrenia is a heterogeneous syndrome with overlapping symptoms and etiologies. At the same time, an increasing number of clinical, epidemiological, and experimental studies have shown links between schizophrenia and inflammatory conditions. In this review, we analyze the literature on inflammation and schizophrenia, with a particular focus on comorbidity, biomarkers, and environmental insults. We then identify several mechanisms by which inflammation could influence the development of schizophrenia via the two-hit hypothesis. Lastly, we note the relevance of these findings to clinical applications in the diagnosis, prevention, and treatment of schizophrenia. PMID:24247023

  16. Mourning Dr. Alfred G. Knudson: the two-hit hypothesis, tumor suppressor genes, and the tuberous sclerosis complex.

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    Hino, Okio; Kobayashi, Toshiyuki

    2017-01-01

    On July 10, 2016, Alfred G. Knudson, Jr., MD, PhD, a leader in cancer research, died at the age of 93 years. We deeply mourn his loss. Knudson's two-hit hypothesis, published in 1971, has been fundamental for understanding tumor suppressor genes and familial tumor-predisposing syndromes. To understand the molecular mechanism of two-hit-initiated tumorigenesis, Knudson used an animal model of a dominantly inherited tumor, the Eker rat. From the molecular identification of Tsc2 germline mutations, the Eker rat became a model for tuberous sclerosis complex (TSC), a familial tumor-predisposing syndrome. Animal models, including the fly, have greatly contributed to TSC research. Because the product of the TSC2/Tsc2 gene (tuberin) together with hamartin, the product of another TSC gene (TSC1/Tsc1), suppresses mammalian/mechanistic target of rapamycin complex 1 (mTORC1), rapalogs have been used as therapeutic drugs for TSC. Although significant activity of these drugs has been reported, there are still problems such as recurrence of residual tumors and adverse effects. Recent studies indicate that there are mTORC1-independent signaling pathways downstream of hamartin/tuberin, which may represent new therapeutic targets. The establishment of cellular models, such as pluripotent stem cells with TSC2/Tsc2 gene mutations, will facilitate the understanding of new aspects of TSC pathogenesis and the development of novel treatment options. In this review, we look back at the history of Knudson and animal models of TSC and introduce recent progress in TSC research.

  17. Papilledema due to a permanent catheter for renal dialysis and an arteriovenous fistula: a "two hit" hypothesis.

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    Simon, Melissa A; Duffis, Ennis J; Curi, Michael A; Turbin, Roger E; Prestigiacomo, Charles J; Frohman, Larry P

    2014-03-01

    Elevated intracranial pressure in patients with chronic renal failure has several potential causes. Its rare occurrence secondary to the hemodynamic effects of hemodialysis is described and the findings support a multifactorial etiology ("two hits").

  18. The two-hit hypothesis for neuroinflammation: role of exogenous ATP in modulating inflammation in the brain

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    Bernd L. Fiebich

    2014-09-01

    Full Text Available Brain inflammation is a common occurrence following responses to varied insults such as bacterial infections, stroke, traumatic brain injury and neurodegenerative disorders. A common mediator for these varied inflammatory responses is prostaglandin E2 (PGE2, produced by the enzymatic activity of cyclooxygenases (COX 1 and 2. Previous attempts to reduce neuronal inflammation through COX inhibition, by use of nonsteroidal anti-inflammatory drugs (NSAIDs, have met with limited success. We are proposing the two-hit model for neuronal injury – an initial localized inflammation mediated by PGE2 (first hit and the simultaneous release of adenosine triphosphate (ATP by injured cells (second hit, which significantly enhances the inflammatory response through increased synthesis of PGE2. Several evidences on the role of exogenous ATP in inflammation have been reported, including contrary instances where extracellular ATP reduces inflammatory events. In this review, we will examine the current literature on the role of P2 receptors, to which ATP binds, in modulating inflammatory reactions during neurodegeneration. Targeting the P2 receptors, therefore, provides a therapeutic alternative to reduce inflammation in the brain. P2 receptor-based anti-inflammatory drugs (PBAIDs will retain the activities of essential COX enzymes, yet will significantly reduce neuroinflammation by decreasing the enhanced production of PGE2 by extracellular ATP.

  19. The danger signal plus DNA damage two-hit hypothesis for chronic inflammation in COPD.

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    Aoshiba, Kazutetsu; Tsuji, Takao; Yamaguchi, Kazuhiro; Itoh, Masayuki; Nakamura, Hiroyuki

    2013-12-01

    Inflammation in chronic obstructive pulmonary disease (COPD) is thought to originate from the activation of innate immunity by a danger signal (first hit), although this mechanism does not readily explain why the inflammation becomes chronic. Here, we propose a two-hit hypothesis explaining why inflammation becomes chronic in patients with COPD. A more severe degree of inflammation exists in the lungs of patients who develop COPD than in the lungs of healthy smokers, and the large amounts of reactive oxygen species and reactive nitrogen species released from inflammatory cells are likely to induce DNA double-strand breaks (second hit) in the airways and pulmonary alveolar cells, causing apoptosis and cell senescence. The DNA damage response and senescence-associated secretory phenotype (SASP) are also likely to be activated, resulting in the production of pro-inflammatory cytokines. These pro-inflammatory cytokines further stimulate inflammatory cell infiltration, intensifying cell senescence and SASP through a positive-feedback mechanism. This vicious cycle, characterised by mutually reinforcing inflammation and DNA damage, may cause the inflammation in COPD patients to become chronic. Our hypothesis helps explain why COPD tends to occur in the elderly, why the inflammation worsens progressively, why inflammation continues even after smoking cessation, and why COPD is associated with lung cancer.

  20. Evidence for Ancestral Programming of Resilience in a Two-Hit Stress Model

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    Jamshid Faraji

    2017-05-01

    Full Text Available In a continuously stressful environment, the effects of recurrent prenatal stress (PS may accumulate across generations and alter stress vulnerability and resilience. Here, we report in female rats that a family history of recurrent ancestral PS facilitates certain aspects of movement performance, and that these benefits are abolished by the experience of a second hit, induced by a silent ischemia during adulthood. Female F4-generation rats with and without a family history of cumulative multigenerational PS (MPS were tested for skilled motor function before and after the induction of a minor ischemic insult by endothelin-1 infusion into the primary motor cortex. MPS resulted in improved skilled motor abilities and blunted hypothalamic-pituitary-adrenal (HPA axis function compared to non-stressed rats. Deep sequencing revealed downregulation of miR-708 in MPS rats along with upregulation of its predicted target genes Mapk10 and Rasd2. Through miR-708 stress may regulate mitogen-activated protein kinase (MAPK pathway activity. Hair trace elemental analysis revealed an increased Na/K ratio, which suggests a chronic shift in adrenal gland function. The ischemic lesion activated the HPA axis in MPS rats only; the lesion, however, abolished the advantage of MPS in skilled reaching. The findings indicate that MPS generates adaptive flexibility in movement, which is challenged by a second stressor, such as a neuropathological condition. Thus, a second “hit” by a stressor may limit behavioral flexibility and neural plasticity associated with ancestral stress.

  1. Inherited 1q21.1q21.2 duplication and 16p11.2 deletion: a two-hit case with more severe clinical manifestations.

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    Brisset, Sophie; Capri, Yline; Briand-Suleau, Audrey; Tosca, Lucie; Gras, Domitille; Fauret-Amsellem, Anne-Laure; Pineau, Dominique; Saada, Julien; Ortonne, Valérie; Verloes, Alain; Goossens, Michel; Tachdjian, Gérard; Métay, Corinne

    2015-09-01

    We report paternally inherited duplication of 1q12q21.2 of 5.8 Mb associated with maternally inherited deletion of 16p11.2 of 545 Kb, this latter first identified in a fetus exhibiting an absent nasal bone detected during pregnancy. During the neonatal period, the young boy presented developmental delay, epilepsy, congenital anomalies and overweight. The clinical features of the proband with two rearrangements were more severe than in either of the parents carrying only one or the other mutation. Thus our data support a two-hit model in which the concomitant presence of these two copy-number variations exacerbates the neurodevelopmental phenotype.

  2. Oxidative desulfurization: kinetic modelling.

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    Dhir, S; Uppaluri, R; Purkait, M K

    2009-01-30

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel.

  3. N-acetylcysteine attenuates progression of liver pathology in a rat model of nonalcoholic steatohepatitis

    Science.gov (United States)

    A "two-hit" model for non-alcoholic steatohepatitis (NASH) has been proposed in which steatosis constitutes the "first hit" and sensitizes the liver to potential "second hits" resulting in NASH. Oxidative stress is considered a candidate for the second hit. N-acetylcysteine (NAC), an antioxidant, ...

  4. Wet oxidation of a spacecraft model waste

    Science.gov (United States)

    Johnson, C. C.; Wydeven, T.

    1985-01-01

    Wet oxidation was used to oxidize a spacecraft model waste under different oxidation conditions. The variables studied were pressure, temperature, duration of oxidation, and the use of one homogeneous and three heterogeneous catalysts. Emphasis is placed on the final oxidation state of carbon and nitrogen since these are the two major components of the spacecraft model waste and two important plant nutrients.

  5. Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1992-02-03

    This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.

  6. Graphite oxidation modeling for application in MELCOR.

    Energy Technology Data Exchange (ETDEWEB)

    Gelbard, Fred

    2009-01-01

    The Arrhenius parameters for graphite oxidation in air are reviewed and compared. One-dimensional models of graphite oxidation coupled with mass transfer of oxidant are presented in dimensionless form for rectangular and spherical geometries. A single dimensionless group is shown to encapsulate the coupled phenomena, and is used to determine the effective reaction rate when mass transfer can impede the oxidation process. For integer reaction order kinetics, analytical expressions are presented for the effective reaction rate. For noninteger reaction orders, a numerical solution is developed and compared to data for oxidation of a graphite sphere in air. Very good agreement is obtained with the data without any adjustable parameters. An analytical model for surface burn-off is also presented, and results from the model are within an order of magnitude of the measurements of burn-off in air and in steam.

  7. Nonequilibrium Thermodynamic Model of Manganese Carbonate Oxidation

    Institute of Scientific and Technical Information of China (English)

    郝瑞霞; 彭省临

    1999-01-01

    Manganese carbonate can be converted to many kinds of manganese oxides when it is aerated in air and oxygen.Pure manganese carbonate can be changed into Mn3O4 and γ-MnOOH,and manganese carbonate ore can be converted to MnO2 under the air-aerating and oxygen-aerating circumstances.The oxidation process of manganese carbonate is a changing process of mineral association,and is also a converting process of valence of manganese itself.Not only equilibrium stat,but also nonequilibrium state are involved in this whole process,This process is an irreversible heterogeneous complex reaction,and oberys the nonequilibrium thermodynamic model,The oxidation rate of manganese cabonate is controlled by many factors,especially nonmanganese metallic ions which play an important role in the oxidation process of manganese carbonate.

  8. Advanced oxidation processes: overall models

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, M. [Univ. de los Andes, Escuela Basica de Ingenieria, La Hechicera, Merida (Venezuela); Curco, D.; Addardak, A.; Gimenez, J.; Esplugas, S. [Dept. de Ingenieria Quimica. Univ. de Barcelona, Barcelona (Spain)

    2003-07-01

    Modelling AOPs implies to consider all the steps included in the process, that means, mass transfer, kinetic (reaction) and luminic steps. In this way, recent works develop models which relate the global reaction rate to catalyst concentration and radiation absorption. However, the application of such models requires to know what is the controlling step for the overall process. In this paper, a simple method is explained which allows to determine the controlling step. Thus, it is assumed that reactor is divided in two hypothetical zones (dark and illuminated), and according to the experimental results, obtained by varying only the reaction volume, it can be decided if reaction occurs only in the illuminated zone or in the all reactor, including dark zone. The photocatalytic degradation of phenol, by using titania degussa P-25 as catalyst, is studied as reaction model. The preliminary results obtained are presented here, showing that it seems that, in this case, reaction only occurs in the illuminated zone of photoreactor. A model is developed to explain this behaviour. (orig.)

  9. A Self-Consistent Model for Thermal Oxidation of Silicon at Low Oxide Thickness

    Directory of Open Access Journals (Sweden)

    Gerald Gerlach

    2016-01-01

    Full Text Available Thermal oxidation of silicon belongs to the most decisive steps in microelectronic fabrication because it allows creating electrically insulating areas which enclose electrically conductive devices and device areas, respectively. Deal and Grove developed the first model (DG-model for the thermal oxidation of silicon describing the oxide thickness versus oxidation time relationship with very good agreement for oxide thicknesses of more than 23 nm. Their approach named as general relationship is the basis of many similar investigations. However, measurement results show that the DG-model does not apply to very thin oxides in the range of a few nm. Additionally, it is inherently not self-consistent. The aim of this paper is to develop a self-consistent model that is based on the continuity equation instead of Fick’s law as the DG-model is. As literature data show, the relationship between silicon oxide thickness and oxidation time is governed—down to oxide thicknesses of just a few nm—by a power-of-time law. Given by the time-independent surface concentration of oxidants at the oxide surface, Fickian diffusion seems to be neglectable for oxidant migration. The oxidant flux has been revealed to be carried by non-Fickian flux processes depending on sites being able to lodge dopants (oxidants, the so-called DOCC-sites, as well as on the dopant jump rate.

  10. Empirical Modeling of Metal Oxides Dissolution

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Seon-Byeong; Won, Hui-Jun; Park, Sang-Yoon; Moon, Jei-Kwon; Choi, Wang-Kyu [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2015-05-15

    There have been tons of studies to examine the dissolution of metal oxides in terms of dissolution kinetics, type of reactants, geometry, etc. However, most of previous studies is the observation of macroscopic dissolution characteristics and might not provide the atomic scale characteristics of dissolution reactions. Even the analysis of microscopic structure of metal oxide with SEM, XRD, etc. during the dissolution does not observe the microscopic characteristics of dissolution mechanism. Computational analysis with well-established dissolution model is the one of the best approaches to understand indirectly the microscopic dissolution behaviour. Various designs of experimental conditions are applied to the in-vitro methods interpreting the dissolution characteristics controlled by each influencing parameter.

  11. Modelling the Krebs cycle and oxidative phosphorylation.

    Science.gov (United States)

    Korla, Kalyani; Mitra, Chanchal K

    2014-01-01

    The Krebs cycle and oxidative phosphorylation are the two most important sets of reactions in a eukaryotic cell that meet the major part of the total energy demands of a cell. In this paper, we present a computer simulation of the coupled reactions using open source tools for simulation. We also show that it is possible to model the Krebs cycle with a simple black box with a few inputs and outputs. However, the kinetics of the internal processes has been modelled using numerical tools. We also show that the Krebs cycle and oxidative phosphorylation together can be combined in a similar fashion - a black box with a few inputs and outputs. The Octave script is flexible and customisable for any chosen set-up for this model. In several cases, we had no explicit idea of the underlying reaction mechanism and the rate determining steps involved, and we have used the stoichiometric equations that can be easily changed as and when more detailed information is obtained. The script includes the feedback regulation of the various enzymes of the Krebs cycle. For the electron transport chain, the pH gradient across the membrane is an essential regulator of the kinetics and this has been modelled empirically but fully consistent with experimental results. The initial conditions can be very easily changed and the simulation is potentially very useful in a number of cases of clinical importance.

  12. Modeling Nitrogen Oxides in the Lower Stratosphere

    Science.gov (United States)

    Kawa, S. Randy; Einaudi, Franco (Technical Monitor)

    2001-01-01

    This talk will focus on the status of current understanding (not a historical review) as regards modeling nitrogen oxides (NOy) in the lower stratosphere (LS). The presentation will be organized around three major areas of process understanding: 1) NOy sources, sinks, and transport to the LS, 2) NOy species partitioning, and 3) polar multiphase processes. In each area, process topics will be identified with an estimate of the degree of confidence associated with their representation in numerical models. Several exotic and/or speculative processes will also be discussed. Those topics associated with low confidence or knowledge gaps, weighted by their prospective importance in stratospheric chemical modeling, will be collected into recommendations for further study. Suggested approaches to further study will be presented for discussion.

  13. Simulation of wet oxidation of silicon based on the interfacial silicon emission model and comparison with dry oxidation

    OpenAIRE

    Uematsu, Masashi; Kageshima, Hiroyuki; Shiraishi, Kenji

    2001-01-01

    Silicon oxidation in wet ambients is simulated based on the interfacial silicon emission model and is compared with dry oxidation in terms of the silicon-atom emission. The silicon emission model enables the simulation of wet oxidation to be done using the oxidant self-diffusivity in the oxide with a single activation energy. The amount of silicon emission from the interface during wet oxidation is smaller than that during dry oxidation. The small emission rate for wet oxidation is responsibl...

  14. MARMOT update for oxide fuel modeling

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yongfeng [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schwen, Daniel [Idaho National Lab. (INL), Idaho Falls, ID (United States); Chakraborty, Pritam [Idaho National Lab. (INL), Idaho Falls, ID (United States); Jiang, Chao [Idaho National Lab. (INL), Idaho Falls, ID (United States); Aagesen, Larry [Idaho National Lab. (INL), Idaho Falls, ID (United States); Ahmed, Karim [Idaho National Lab. (INL), Idaho Falls, ID (United States); Jiang, Wen [Idaho National Lab. (INL), Idaho Falls, ID (United States); Biner, Bulent [Idaho National Lab. (INL), Idaho Falls, ID (United States); Bai, Xianming [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Tonks, Michael [Pennsylvania State Univ., University Park, PA (United States); Millett, Paul [Univ. of Arkansas, Fayetteville, AR (United States)

    2016-09-01

    This report summarizes the lower-length-scale research and development progresses in FY16 at Idaho National Laboratory in developing mechanistic materials models for oxide fuels, in parallel to the development of the MARMOT code which will be summarized in a separate report. This effort is a critical component of the microstructure based fuel performance modeling approach, supported by the Fuels Product Line in the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program. The progresses can be classified into three categories: 1) development of materials models to be used in engineering scale fuel performance modeling regarding the effect of lattice defects on thermal conductivity, 2) development of modeling capabilities for mesoscale fuel behaviors including stage-3 gas release, grain growth, high burn-up structure, fracture and creep, and 3) improved understanding in material science by calculating the anisotropic grain boundary energies in UO$_2$ and obtaining thermodynamic data for solid fission products. Many of these topics are still under active development. They are updated in the report with proper amount of details. For some topics, separate reports are generated in parallel and so stated in the text. The accomplishments have led to better understanding of fuel behaviors and enhance capability of the MOOSE-BISON-MARMOT toolkit.

  15. Kinetic Modelling of Macroscopic Properties Changes during Crosslinked Polybutadiene Oxidation

    Science.gov (United States)

    Audouin, Ludmila; Coquillat, Marie; Colin, Xavier; Verdu, Jacques; Nevière, Robert

    2008-08-01

    The thermal oxidation of additive free hydroxyl-terminated polybutadiene (HTPB) isocyanate crosslinked rubber bulk samples has been studied at 80, 100 and 120 °C in air. The oxidation kinetics has been monitored by gravimetry and thickness distribution of oxidation products was determined by FTIR mapping. Changes of elastic shear modulus G' during oxidation were followed during oxidation at the same temperatures. The kinetic model established previously for HTPB has been adapted for bulk sample oxidation using previously determined set of kinetic parameters. Oxygen diffusion control of oxidation has been introduced into the model. The mass changes kinetic curves and oxidation products profiles were simulated and adequate fit was obtained. Using the rubber elasticity theory the elastic modulus changes were simulated taking into account the elastically active chains concentration changes due to chain scission and crosslinking reactions. The reasonable fit of G' as a function of oxidation time experimental curves was obtained.

  16. Modeling Degradation in Solid Oxide Electrolysis Cells

    Energy Technology Data Exchange (ETDEWEB)

    Manohar S. Sohal; Anil V. Virkar; Sergey N. Rashkeev; Michael V. Glazoff

    2010-09-01

    Idaho National Laboratory has an ongoing project to generate hydrogen from steam using solid oxide electrolysis cells (SOECs). To accomplish this, technical and degradation issues associated with the SOECs will need to be addressed. This report covers various approaches being pursued to model degradation issues in SOECs. An electrochemical model for degradation of SOECs is presented. The model is based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic no equilibrium. It is shown that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential, , within the electrolyte. The within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just near the oxygen electrode/electrolyte interface, leading to oxygen electrode delamination. These predictions are in accordance with the reported literature on the subject. Development of high pressures may be avoided by introducing some electronic conduction in the electrolyte. By combining equilibrium thermodynamics, no equilibrium (diffusion) modeling, and first-principles, atomic scale calculations were performed to understand the degradation mechanisms and provide practical recommendations on how to inhibit and/or completely mitigate them.

  17. Simplified Modeling of Oxidation of Hydrocarbons

    Science.gov (United States)

    Bellan, Josette; Harstad, Kenneth

    2008-01-01

    A method of simplified computational modeling of oxidation of hydrocarbons is undergoing development. This is one of several developments needed to enable accurate computational simulation of turbulent, chemically reacting flows. At present, accurate computational simulation of such flows is difficult or impossible in most cases because (1) the numbers of grid points needed for adequate spatial resolution of turbulent flows in realistically complex geometries are beyond the capabilities of typical supercomputers now in use and (2) the combustion of typical hydrocarbons proceeds through decomposition into hundreds of molecular species interacting through thousands of reactions. Hence, the combination of detailed reaction- rate models with the fundamental flow equations yields flow models that are computationally prohibitive. Hence, further, a reduction of at least an order of magnitude in the dimension of reaction kinetics is one of the prerequisites for feasibility of computational simulation of turbulent, chemically reacting flows. In the present method of simplified modeling, all molecular species involved in the oxidation of hydrocarbons are classified as either light or heavy; heavy molecules are those having 3 or more carbon atoms. The light molecules are not subject to meaningful decomposition, and the heavy molecules are considered to decompose into only 13 specified constituent radicals, a few of which are listed in the table. One constructs a reduced-order model, suitable for use in estimating the release of heat and the evolution of temperature in combustion, from a base comprising the 13 constituent radicals plus a total of 26 other species that include the light molecules and related light free radicals. Then rather than following all possible species through their reaction coordinates, one follows only the reduced set of reaction coordinates of the base. The behavior of the base was examined in test computational simulations of the combustion of

  18. Mathematical Model of Silicon Oxidation in Microelectronics

    Directory of Open Access Journals (Sweden)

    V. A. Bondarev

    2006-01-01

    Full Text Available The paper involves analytical solutions and formulae for determination of the oxide film thickness in the silicon oxidation while using nitride mask. Calculations are based on solutions of a three-dimensional diffusion equation and new mathematical functions that are firstly defined by the author. Suitable analytical and numerical solutions based on the diffusion equation have not yet been obtained

  19. Modeling for CVD of Solid Oxide Electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Starr, T.L.

    2002-09-18

    Because of its low thermal conductivity, high thermal expansion and high oxygen ion conductivity yttria-stabilized zirconia (YSZ) is the material of choice for high temperature electrolyte applications. Current coating fabrication methods have their drawbacks, however. Air plasma spray (APS) is a relatively low-cost process and is suitable for large and relatively complex shapes. it is difficult to produce uniform, relatively thin coatings with this process, however, and the coatings do not exhibit the columnar microstructure that is needed for reliable, long-term performance. The electron-beam physical vapor deposition (EB-PVD) process does produce the desirable microstructure, however, the capital cost of these systems is very high and the line-of-sight nature of the process limits coating uniformity and the ability to coat large and complex shapes. The chemical vapor deposition (CVD) process also produces the desirable columnar microstructure and--under proper conditions--can produce uniform coatings over complex shapes. CVD has been used for many materials but is relatively undeveloped for oxides, in general, and for zirconia, in particular. The overall goal of this project--a joint effort of the University of Louisville and Oak Ridge National Laboratory (ORNL)--is to develop the YSZ CVD process for high temperature electrolyte applications. This report describes the modeling effort at the University of Louisville, which supports the experimental work at ORNL. Early work on CVD of zirconia and yttria used metal chlorides, which react with water vapor to form solid oxide. Because of this rapid gas-phase reaction the water generally is formed in-situ using the reverse water-gas-shift reaction or a microwave plasma. Even with these arrangements gas-phase nucleation and powder formation are problems when using these precursors. Recent efforts on CVD of zirconia and YSZ have focused on use of metal-organic precursors (MOCVD). These are more stable in the gas

  20. A Detailed Modeling Study of Propane Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Jayaweera, T M; Pitz, W J; Curran, H J

    2004-03-19

    A detailed chemical kinetic mechanism has been used to simulate ignition delay times recorded by a number of experimental shock tube studies over the temperature range 900 {le} T {le} 1800 K, in the pressure range 0.75-40 atm and in the equivalence ratio range 0.5 {le} {phi} {le} 2.0. Flame speed measurements at 1 atm in the equivalence ratio range 0.4 {le} {phi} {le} 1.8 have also been simulated. Both of these data sets, particularly those recorded at high pressure, are of particular importance in validating a kinetic mechanism, as internal combustion engines operate at elevated pressures and temperatures and rates of fuel oxidation are critical to efficient system operation. Experiments in which reactant, intermediate and product species were quantitatively recorded, versus temperature in a jet-stirred reactor (JSR) and versus time in a flow reactor are also simulated. This data provide a stringent test of the kinetic mechanism as it must reproduce accurate quantitative profiles for all reactant, intermediate and product species. The JSR experiments were performed in the temperature range 1000-1110 K, in the equivalence ratio range 0.5 {le} {phi} {le} 4.0, at a pressure of 5 atm. These experiments are complemented by those carried out in a flow reactor in the temperature range 660-820 K, at 10 atm and at an equivalence ratio of 0.4. In addition, burner stabilized flames were simulated, where chemical species profiles were measured at atmospheric pressure for two propane-air flat flames. Overall, reasonably good agreement is observed between the model simulations and the experimental results.

  1. Modeling Electronic Properties of Complex Oxides

    Science.gov (United States)

    Krishnaswamy, Karthik

    Complex oxides are a class of materials that have recently emerged as potential candidates for electronic applications owing to their interesting electronic properties. The goal of this dissertation is to develop a fundamental understanding of these electronic properties using a combination of first-principles approaches based on density functional theory (DFT), and Schr odinger-Poisson (SP) simulation (Abstract shortened by ProQuest.

  2. Advanced methods of solid oxide fuel cell modeling

    CERN Document Server

    Milewski, Jaroslaw; Santarelli, Massimo; Leone, Pierluigi

    2011-01-01

    Fuel cells are widely regarded as the future of the power and transportation industries. Intensive research in this area now requires new methods of fuel cell operation modeling and cell design. Typical mathematical models are based on the physical process description of fuel cells and require a detailed knowledge of the microscopic properties that govern both chemical and electrochemical reactions. ""Advanced Methods of Solid Oxide Fuel Cell Modeling"" proposes the alternative methodology of generalized artificial neural networks (ANN) solid oxide fuel cell (SOFC) modeling. ""Advanced Methods

  3. Air oxidation of Zircaloy, Part 2: New model for Zry-4 oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Stempniewicz, M.M., E-mail: stempniewicz@nrg.eu

    2016-05-15

    Highlights: • Recommended set of correlations proposed for air oxidation of Zircaloy-4. • New breakaway correlation for air oxidation of Zircaloy-4. • Improved accuracy of predicting air oxidation of Zircaloy-4. • Models applicable to analyses of accidents in Spent Fuel Pool. - Abstract: The accident in Fukushima brought up new issues in the area of safety of nuclear reactors. Among others, Spent Fuel Pool accidents gained new focus. The computer codes applicable for safety analyses of Nuclear Power Plants have limited verification and validation in this area and their applicability remains still to be proven. An important phenomenon occurring during loss of water in SFP is air oxidation of Zircaloy cladding material. Mathematical modeling of this phenomenon in computer codes has been under development during the last years. This document presents a review of models for air oxidation of Zircaloy, including: up to date models available in open literature, as well as models available in computer codes: ASTEC, MELCOR, and SPECTRA. The models were tested by performing simulations of a number air oxidation experiments from ANL, KIT, and IRSN. As a result of this work, a recommended set of correlations, applicable for wide range of temperatures, including pre- and post-breakaway reaction, has been selected. For the pre-breakaway (parabolic) regime the correlation of Benjamin et al. (Sandia National Laboratories, Albuquerque, NM, 1979) was selected for the low temperatures and a new correlation has been proposed for the high temperatures. For the post-breakaway (linear) regime, Boase and Vandergraaf (Nucl. Technol., 1977;32:60–71) were selected for the low temperatures and a new correlation has been proposed for the high temperatures. Furthermore, a new model for the breakaway transition has been proposed. The correlation set is applicable for Zircaloy-4, for practically the entire temperature range. The recommended set provides an improved accuracy of results

  4. Modeling oxidation damage of continuous fiber reinforced ceramic matrix composites

    Institute of Scientific and Technical Information of China (English)

    Cheng-Peng Yang; Gui-Qiong Jiao; Bo Wang

    2011-01-01

    For fiber reinforced ceramic matrix composites (CMCs), oxidation of the constituents is a very important damage type for high temperature applications. During the oxidizing process, the pyrolytic carbon interphase gradually recesses from the crack site in the axial direction of the fiber into the interior of the material. Carbon fiber usually presents notch-like or local neck-shrink oxidation phenomenon, causing strength degradation. But, the reason for SiC fiber degradation is the flaw growth mechanism on its surface. A micromechanical model based on the above mechanisms was established to simulate the mechanical properties of CMCs after high temperature oxidation. The statistic and shearlag theory were applied and the calculation expressions for retained tensile modulus and strength were deduced, respectively. Meanwhile, the interphase recession and fiber strength degradation were considered. And then, the model was validated by application to a C/SiC composite.

  5. Simplified kinetic models of methanol oxidation on silver

    DEFF Research Database (Denmark)

    Andreasen, Anders; Lynggaard, Hasse Harloff; Stegelmann, Carsten;

    2005-01-01

    Recently the authors developed a microkinetic model of methanol oxidation on silver [A. Andreasen, H. Lynggaard, C. Stegelmann, P. Stoltze, Surf. Sci. 544 (2003) 5–23]. The model successfully explains both surface science experiments and kinetic experiments at industrial conditions applying...

  6. Simplified kinetic models of methanol oxidation on silver

    DEFF Research Database (Denmark)

    Andreasen, A.; Lynggaard, H.; Stegelmann, C.;

    2005-01-01

    Recently the authors developed a microkinetic model of methanol oxidation on silver [A. Andreasen, H. Lynggaard, C. Stegelmann, P. Stoltze, Surf. Sci. 544 (2003) 5-23]. The model successfully explains both surface science experiments and kinetic experiments at industrial conditions applying...

  7. Modelling nitrous oxide emissions from organic soils in Europe

    Science.gov (United States)

    Leppelt, Thomas; Dechow, Rene; Gebbert, Sören; Freibauer, Annette

    2013-04-01

    The greenhouse gas emission potential of peatland ecosystems are mandatory for a complete annual emission budget in Europe. The GHG-Europe project aims to improve the modelling capabilities for greenhouse gases, e.g., nitrous oxide. The heterogeneous and event driven fluxes of nitrous oxide are challenging to model on European scale, especially regarding the upscaling purpose and certain parameter estimations. Due to these challenges adequate techniques are needed to create a robust empirical model. Therefore a literature study of nitrous oxide fluxes from organic soils has been carried out. This database contains flux data from boreal and temperate climate zones and covers the different land use categories: cropland, grassland, forest, natural and peat extraction sites. Especially managed crop- and grassland sites feature high emission potential. Generally nitrous oxide emissions increases significantly with deep drainage and intensive application of nitrogen fertilisation. Whereas natural peatland sites with a near surface groundwater table can act as nitrous oxide sink. An empirical fuzzy logic model has been applied to predict annual nitrous oxide emissions from organic soils. The calibration results in two separate models with best model performances for bogs and fens, respectively. The derived parameter combinations of these models contain mean groundwater table, nitrogen fertilisation, annual precipitation, air temperature, carbon content and pH value. Influences of the calibrated parameters on nitrous oxide fluxes are verified by several studies in literature. The extrapolation potential has been tested by an implemented cross validation. Furthermore the parameter ranges of the calibrated models are compared to occurring values on European scale. This avoid unknown systematic errors for the regionalisation purpose. Additionally a sensitivity analysis specify the model behaviour for each alternating parameter. The upscaling process for European peatland

  8. Developments in kinetic modelling of chalcocite particle oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Jaervi, J.; Ahokainen, T.; Jokilaakso, A. [Helsinki Univ. of Technology, Otaniemi (Finland). Lab. of Materials Processing and Powder Metallurgy

    1997-12-31

    A mathematical model for simulating chalcocite particle oxidation is presented. Combustion of pure chalcocite with oxygen is coded as a kinetic module which can be connected as a separate part of commercial CFD-package, PHOENICS. Heat transfer, fluid flow and combustion phenomena can be simulated using CFD-calculation together with the kinetic model. Interaction between gas phase and particles are taken into account by source terms. The aim of the kinetic model is to calculate the particle temperature, contents of species inside the particle, oxygen consumption and formation of sulphur dioxide. Four oxidation reactions are considered and the shrinking core model is used to describe the rate of the oxidation reactions. The model is verified by simulating the particle oxidation reactions in a laboratory scale laminar-flow furnace under different conditions and the model predicts the effects of charges correctly. In the future, the model validation will be done after experimental studies in the laminar flow-furnace. (author) 18 refs.

  9. Alternative model for the Great Oxidation Event

    Science.gov (United States)

    Bekker, A.

    2014-12-01

    Transition from the Archean, largely anoxic atmosphere and ocean to the Proterozoic oxidizing surface conditions has been inferred in Zimbabwe from the geochemical and geological evidence as early as 1927. Subsequent studies provided additional support for this interpretation, bracketed the transition between 2.45 and 2.32 Ga, and suggested temporal and cause-and-effect relationship with a series of the early Paleoproterozoic ice ages (including 4 discrete events). Recently recognized transient oxidation events of the Archean add texture to this pattern, but do not change it. The rise of atmospheric oxygen requires a misbalance between oxygen sinks and sources and most attention was focused on sinks. In contrast, change in oxygen supply related to low organic productivity in Archean oceans with limited nutrient contents are considered here. Although carbon isotope values of carbonates and organic carbon indicate substantial relative burial rate of organic carbon during the Archean, most of the earlier buried organic matter at that time was recycled to sediments during continental weathering, implying very low productivity and burial of 'new' organic carbon. Low contents of redox-sensitive elements, such as Mo, Cu, Zn, and V, in Archean seawater could have kept organic productivity and oxygen production at low levels. The GOE was immediately preceded by deposition of giant iron formations, accounting for more than 70% of world iron resources, and worldwide emplacement of a number of LIPs between 2.5 and 2.45 Ga, indicating enhanced delivery of nutrients and redox-sensitive elements to the oceans via submarine hydrothermal processes and continental weathering under CO2- and SO2-rich atmosphere and associated terrestrial acidic runoff. This enhanced emplacement of LIPs has been linked with the growth of continental crust, emergence of the first supercontinent, and mantle overturn at the Archean-Proterozoic boundary. The GOE could have thus been triggered by enhanced

  10. Subcritical and supercritical water oxidation of CELSS model wastes

    Science.gov (United States)

    Takahashi, Y.; Wydeven, T.; Koo, C.

    1989-01-01

    A mixture of ammonium hydroxide with acetic acid and a slurry of human feces, urine, and wipes were used as CELSS model wastes to be wet-oxidized at temperatures from 250 to 500 C, i.e. below and above the critical point of water (374 C and 218 kg/sq cm or 21.4 MPa). The effects of oxidation temperature ( 250-500 C) and residence time (0-120 mn) on carbon and nitrogen and on metal corrosion from the reactor material were studied. Almost all of the organic matter in the model wastes was oxidized in the temperature range from 400 to 500 C, above the critical conditions for water. In contrast, only a small portion of the organic matter was oxidized at subcritical conditions. A substantial amount of nitrogen remained in solution in the form of ammonia at temperatures ranging from 350 to 450 C suggesting that, around 400 C, organic carbon is completely oxidized and most of the nitrogen is retained in solution. The Hastelloy C-276 alloy reactor corroded during subcritical and supercritical water oxidation.

  11. Modeling the ignition of a copper oxide aluminum thermite

    Science.gov (United States)

    Lee, Kibaek; Stewart, D. Scott; Clemenson, Michael; Glumac, Nick; Murzyn, Christopher

    2017-01-01

    An experimental "striker confinement" shock compression experiment was developed in the Glumac-group at the University of Illinois to study ignition and reaction in composite reactive materials. These include thermitic and intermetallic reactive powders. Sample of materials such as a thermite mixture of copper oxide and aluminum powders are initially compressed to about 80 percent full density. Two RP-80 detonators simultaneously push steel bars into the reactive material and the resulting compression causes shock compaction of the material and rapid heating. At that point one observes significant reaction and propagation of fronts. But the fronts are peculiar in that they are comprised of reactive events that can be traced to the reaction of the initially separated reactants of copper oxide and aluminum that react at their mutual interfaces, that nominally make copper liquid and aluminum oxide products. We discuss our model of the ignition of the copper oxide aluminum thermite in the context of the striker experiment and how a Gibbs formulation model [1], that includes multi-components for liquid and solid phases of aluminum, copper oxide, copper and aluminum oxide, can predict the events observed at the particle scale in the experiments.

  12. Detailed Chemical Kinetic Modeling of Cyclohexane Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Silke, E J; Pitz, W J; Westbrook, C K; Ribaucour, M

    2006-11-10

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of cyclohexane at both low and high temperatures. Reaction rate constant rules are developed for the low temperature combustion of cyclohexane. These rules can be used for in chemical kinetic mechanisms for other cycloalkanes. Since cyclohexane produces only one type of cyclohexyl radical, much of the low temperature chemistry of cyclohexane is described in terms of one potential energy diagram showing the reaction of cyclohexyl radical + O{sub 2} through five, six and seven membered ring transition states. The direct elimination of cyclohexene and HO{sub 2} from RO{sub 2} is included in the treatment using a modified rate constant of Cavallotti et al. Published and unpublished data from the Lille rapid compression machine, as well as jet-stirred reactor data are used to validate the mechanism. The effect of heat loss is included in the simulations, an improvement on previous studies on cyclohexane. Calculations indicated that the production of 1,2-epoxycyclohexane observed in the experiments can not be simulated based on the current understanding of low temperature chemistry. Possible 'alternative' H-atom isomerizations leading to different products from the parent O{sub 2}QOOH radical were included in the low temperature chemical kinetic mechanism and were found to play a significant role.

  13. Electrothermal model for complete metal-oxide surge arresters

    Energy Technology Data Exchange (ETDEWEB)

    Costa, E. Guedes da; Naidu, S.R. [UFPB, Dept. of Electrical Engineering, Campina Grande, PB (Brazil); Lima, A. Guedes de [CEFET-PB, Dept. of Mechanical Engineering, Joao Pessoa, PB (Brazil)

    2001-01-01

    A computational, electrothermal model for a complete metal-oxide surge arrester based on the implicit form of the finite-differences method is presented. The model is used to calculate the cooling curve after the application of overvoltages and the temperature variations during standard test. The model has been checked against experiments carried out on a test section and a complete surge arrester and the behaviour of a hypothetical surge arrester during standard tests simulated. (Author)

  14. Universal Responses of Cyclic-Oxidation Models Studied

    Science.gov (United States)

    Smialek, James L.

    2003-01-01

    Oxidation is an important degradation process for materials operating in the high-temperature air or oxygen environments typical of jet turbine or rocket engines. Reaction of the combustion gases with the component material forms surface layer scales during these oxidative exposures. Typically, the instantaneous rate of reaction is inversely proportional to the existing scale thickness, giving rise to parabolic kinetics. However, more realistic applications entail periodic startup and shutdown. Some scale spallation may occur upon cooling, resulting in loss of the protective diffusion barrier provided by a fully intact scale. Upon reheating, the component will experience accelerated oxidation due to this spallation. Cyclic-oxidation testing has, therefore, been a mainstay of characterization and performance ranking for high-temperature materials. Models simulate this process by calculating how a scale spalls upon cooling and regrows upon heating (refs. 1 to 3). Recently released NASA software (COSP for Windows) allows researchers to specify a uniform layer or discrete segments of spallation (ref. 4). Families of model curves exhibit consistent regularity and trends with input parameters, and characteristic features have been empirically described in terms of these parameters. Although much insight has been gained from experimental and model curves, no equation has been derived that can describe this behavior explicitly as functions of the key oxidation parameters.

  15. Modeling the viscosity of silicate melts containing manganese oxide

    Directory of Open Access Journals (Sweden)

    Kim Wan-Yi

    2013-01-01

    Full Text Available Our recently developed model for the viscosity of silicate melts is applied to describe and predict the viscosities of oxide melts containing manganese oxide. The model requires three pairs of adjustable parameters that describe the viscosities in three systems: pure MnO, MnO-SiO2 and MnO-Al2O3-SiO2. The viscosity of other ternary and multicomponent silicate melts containing MnO is then predicted by the model without any additional adjustable model parameters. Experimental viscosity data are reviewed for melts formed by MnO with SiO2, Al2O3, CaO, MgO, PbO, Na2O and K2O. The deviation of the available experimental data from the viscosities predicted by the model is shown to be within experimental error limits.

  16. Animation Model to Conceptualize ATP Generation: A Mitochondrial Oxidative Phosphorylation

    Science.gov (United States)

    Jena, Ananta Kumar

    2015-01-01

    Adenosine triphosphate (ATP) is the molecular unit of intracellular energy and it is the product of oxidative phosphorylation of cellular respiration uses in cellular processes. The study explores the growth of the misconception levels amongst the learners and evaluates the effectiveness of animation model over traditional methods. The data…

  17. Modelling toluene oxidation : Incorporation of mass transfer phenomena

    NARCIS (Netherlands)

    Hoorn, J.A.A.; van Soolingen, J.; Versteeg, G. F.

    2005-01-01

    The kinetics of the oxidation of toluene have been studied in close interaction with the gas-liquid mass transfer occurring in the reactor. Kinetic parameters for a simple model have been estimated on basis of experimental observations performed under industrial conditions. The conclusions for the m

  18. Modelling toluene oxidation : Incorporation of mass transfer phenomena

    NARCIS (Netherlands)

    Hoorn, J.A.A.; van Soolingen, J.; Versteeg, G. F.

    The kinetics of the oxidation of toluene have been studied in close interaction with the gas-liquid mass transfer occurring in the reactor. Kinetic parameters for a simple model have been estimated on basis of experimental observations performed under industrial conditions. The conclusions for the

  19. SUPERCRITICAL WATER OXIDATION MODEL DEVELOPMENT FOR SELECTED EPA PRIORITY POLLUTANTS

    Science.gov (United States)

    Supercritical Water Oxidation (SCWO) evaluated for five compounds: acetic acid, 2,4-dichlorophenol, pentachlorophenol, pyridine, 2,4-dichlorophenoxyacetic acid (methyl ester). inetic models were developed for acetic acid, 2,4-dichlorophenol, and pyridine. he test compounds were e...

  20. Modelling toluene oxidation : Incorporation of mass transfer phenomena

    NARCIS (Netherlands)

    Hoorn, J.A.A.; van Soolingen, J.; Versteeg, G. F.

    2005-01-01

    The kinetics of the oxidation of toluene have been studied in close interaction with the gas-liquid mass transfer occurring in the reactor. Kinetic parameters for a simple model have been estimated on basis of experimental observations performed under industrial conditions. The conclusions for the m

  1. Structure and properties of molybdenum oxide nitrides as model systems for selective oxidation catalysts

    Directory of Open Access Journals (Sweden)

    Lerch Martin

    2011-07-01

    Full Text Available Abstract Molybdenum oxide nitride (denoted as Mo(O,N3 was obtained by ammonolysis of α-MoO3 with gaseous ammonia. Electronic and geometric structure, reducibility, and conductivity of Mo(O,N3 were investigated by XRD, XAS, UV-Vis spectroscopy, and impedance measurements. Catalytic performance in selective propene oxidation was determined by online mass spectrometry und gas chromatography. Upon incorporation of nitrogen, Mo(O,N3 maintained the characteristic layer structure of α-MoO3. XRD analysis showed an increased structural disorder in the layers while nitrogen is removed from the lattice of Mo(O,N3 at temperatures above ~600 K. Compared to regular α-MoO3, Mo(O,N3 exhibited a higher electronic and ionic conductivity and an onset of reduction in propene at lower temperatures. Surprisingly, α-MoO3 and Mo(O,N3 exhibited no detectable differences in onset temperatures of propene oxidation and catalytic selectivity or activity. Apparently, the increased reducibility, oxygen mobility, and conductivity of Mo(O,N3 compared to α-MoO3 had no effect on the catalytic behavior of the two catalysts. The results presented confirm the suitability of molybdenum oxide nitrides as model systems for studying bulk contributions to selective oxidation.

  2. Ab initio and kinetic modeling studies of formic acid oxidation

    DEFF Research Database (Denmark)

    Marshall, Paul; Glarborg, Peter

    2015-01-01

    A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...... as the fate of HOCO, determines the oxidation rate of formic acid. At lower temperatures HO2, formed from HOCO + O2, is an important chain carrier and modeling predictions become sensitive to the HOCHO + HO2 reaction. © 2014 The Combustion Institute....... on calculations with the kinetic model. Formic acid is consumed mainly by reaction with OH, yielding OCHO, which dissociates rapidly to CO2 + H, and HOCO, which may dissociate to CO + OH or CO2 + H, or react with H, OH, or O2 to form more stable products. The branching fraction of the HOCHO + OH reaction, as well...

  3. European scale modeling of sulfur, oxidized nitrogen and photochemical oxidants. Model development and evaluation for the 1994 growing season

    Energy Technology Data Exchange (ETDEWEB)

    Langner, J.; Bergstroem, R. [Swedish Meteorological and Hydrological Inst., Norrkoeping (Sweden); Pleijel, K. [Swedish Environmental Research Inst., Goeteborg (Sweden)

    1998-09-01

    A chemical mechanism, including the relevant reactions leading to the production of ozone and other photochemical oxidants, has been implemented in the MATCH regional tracer transport/chemistry/deposition model. The aim has been to develop a model platform that can be used as a basis for a range of regional scale studies involving atmospheric chemistry, including assessment of the importance of different sources of pollutants to the levels of photochemical oxidants and air pollutant forecasting. Meteorological input data to the model were taken from archived output from the operational version of HIRLAM at SMHI. Evaluation of model calculations over Europe for a six month period in 1994 for a range of chemical components show good results considering known sources of error and uncertainties in input data and model formulation. With limited further work the system is sufficiently good to be applied for scenario studies and for regional scale air pollutant forecasts 42 refs, 24 figs, 17 tabs

  4. Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides. Progress report, August 1, 1991--January 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1992-02-03

    This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.

  5. Modeling and Simulations in Photoelectrochemical Water Oxidation: From Single Level to Multiscale Modeling

    NARCIS (Netherlands)

    Zhang, X.; Bieberle, A.

    2016-01-01

    This review summarizes recent developments, challenges, and strategies in the field of modeling and simulations of photoelectrochemical (PEC) water oxidation. We focus on water splitting by metal-oxide semiconductors and discuss topics such as theoretical calculations of light absorption, band gap/b

  6. Global atmospheric model for mercury including oxidation by bromine atoms

    Directory of Open Access Journals (Sweden)

    C. D. Holmes

    2010-12-01

    Full Text Available Global models of atmospheric mercury generally assume that gas-phase OH and ozone are the main oxidants converting Hg0 to HgII and thus driving mercury deposition to ecosystems. However, thermodynamic considerations argue against the importance of these reactions. We demonstrate here the viability of atomic bromine (Br as an alternative Hg0 oxidant. We conduct a global 3-D simulation with the GEOS-Chem model assuming gas-phase Br to be the sole Hg0 oxidant (Hg + Br model and compare to the previous version of the model with OH and ozone as the sole oxidants (Hg + OH/O3 model. We specify global 3-D Br concentration fields based on our best understanding of tropospheric and stratospheric Br chemistry. In both the Hg + Br and Hg + OH/O3 models, we add an aqueous photochemical reduction of HgII in cloud to impose a tropospheric lifetime for mercury of 6.5 months against deposition, as needed to reconcile observed total gaseous mercury (TGM concentrations with current estimates of anthropogenic emissions. This added reduction would not be necessary in the Hg + Br model if we adjusted the Br oxidation kinetics downward within their range of uncertainty. We find that the Hg + Br and Hg + OH/O3 models are equally capable of reproducing the spatial distribution of TGM and its seasonal cycle at northern mid-latitudes. The Hg + Br model shows a steeper decline of TGM concentrations from the tropics to southern mid-latitudes. Only the Hg + Br model can reproduce the springtime depletion and summer rebound of TGM observed at polar sites; the snowpack component of GEOS-Chem suggests that 40% of HgII deposited to snow in the Arctic is transferred to the ocean and land reservoirs, amounting to a net deposition flux to the Arctic of 60 Mg a−1. Summertime events of depleted Hg0 at Antarctic sites due to subsidence are much better simulated by

  7. Global atmospheric model for mercury including oxidation by bromine atoms

    Directory of Open Access Journals (Sweden)

    C. D. Holmes

    2010-08-01

    Full Text Available Global models of atmospheric mercury generally assume that OH and ozone are the main oxidants converting Hg0 to HgII and thus driving mercury deposition to ecosystems. However, thermodynamic considerations argue against the importance of these reactions. We demonstrate here the viability of atomic bromine (Br as an alternative Hg0 oxidant. We conduct a global 3-D simulation with the GEOS-Chem model assuming Br to be the sole Hg0 oxidant (Hg + Br model and compare to the previous version of the model with OH and ozone as the sole oxidants (Hg + OH/O3 model. We specify global 3-D Br concentration fields based on our best understanding of tropospheric and stratospheric Br chemistry. In both the Hg + Br and Hg + OH/O3 models, we add an aqueous photochemical reduction of HgII in cloud to impose a tropospheric lifetime for mercury of 6.5 months against deposition, as needed to reconcile observed total gaseous mercury (TGM concentrations with current estimates of anthropogenic emissions. This added reduction would not be necessary in the Hg + Br model if we adjusted the Br oxidation kinetics downward within their range of uncertainty. We find that the Hg + Br and Hg + OH/O3 models are equally capable of reproducing the spatial distribution of TGM and its seasonal cycle at northern mid-latitudes. The Hg + Br model shows a steeper decline of TGM concentrations from the tropics to southern mid-latitudes. Only the Hg + Br model can reproduce the springtime depletion and summer rebound of TGM observed at polar sites; the snowpack component of GEOS-Chem suggests that 40% of HgII deposited to snow in the Arctic is transferred to the ocean and land reservoirs, amounting to a net deposition flux of 60 Mg a−1. Summertime events of depleted Hg0 at Antarctic sites due to subsidence are much better simulated by the Hg + Br model. Model

  8. A microkinetic model of the methanol oxidation over silver

    DEFF Research Database (Denmark)

    Andreasen, A.; Lynggaard, H.; Stegelmann, C.

    2003-01-01

    , respectively. The model explains observed reaction orders, selectivity, apparent activation enthalpies and the choice of industrial reaction conditions. More interesting the model disproves the notion that the mechanism deduced from surface science in UHV cannot be responsible for formaldehyde synthesis......A simple microkinetic model for the oxidation of methanol on silver based on surface science studies at UHV and low temperatures has been formulated. The reaction mechanism is a simple Langmuir-Hinshelwood mechanism, with one type of active oxygen and one route to formaldehyde and carbon dioxide...

  9. Growth Model for Pulsed-Laser Deposited Perovskite Oxide Films

    Institute of Scientific and Technical Information of China (English)

    WANG Xu; FEI Yi-Yan; ZHU Xiang-Dong; Lu Hui-Bin; YANG Guo-Zhen

    2008-01-01

    We present a multi-level growth model that yields some of the key features of perovskite oxide film growth as observed in the reflection high energy electron diffraction(RHEED)and ellipsometry studies.The model describes the effect of deposition,temperature,intra-layer transport,interlayer transport and Ostwald ripening on the morphology of a growth surface in terms of the distribution of terraces and step edges during and after deposition.The numerical results of the model coincide well with the experimental observation.

  10. A modelling approach for the heterogeneous oxidation of elastomers

    Science.gov (United States)

    Herzig, A.; Sekerakova, L.; Johlitz, M.; Lion, A.

    2017-04-01

    The influence of oxygen on elastomers, known as oxidation, is one of the most important ageing processes and becomes more and more important for nowadays applications. The interaction with thermal effects as well as antioxidants makes oxidation of polymers a complex process. Based on the polymer chosen and environmental conditions, the ageing processes may behave completely different. In a lot of cases the influence of oxygen is limited to the surface layer of the samples, commonly referred to as diffusion-limited oxidation. For the lifetime prediction of elastomer components, it is essential to have detailed knowledge about the absorption and diffusion behaviour of oxygen molecules during thermo-oxidative ageing and how they react with the elastomer. Experimental investigations on industrially used elastomeric materials are executed in order to develop and fit models, which shall be capable of predicting the permeation and consumption of oxygen as well as changes in the mechanical properties. The latter are of prime importance for technical applications of rubber components. Oxidation does not occur homogeneously over the entire elastomeric component. Hence, material models which include ageing effects have to be amplified in order to consider heterogeneous ageing, which highly depends on the ageing temperature. The influence of elevated temperatures upon accelerated ageing has to be critically analysed, and influences on the permeation and diffusion coefficient have to be taken into account. This work presents phenomenological models which describe the oxygen uptake and the diffusion into elastomers based on an improved understanding of ongoing chemical processes and diffusion limiting modifications. On the one side, oxygen uptake is modelled by means of Henry's law in which solubility is a function of the temperature as well as the ageing progress. The latter is an irreversible process and described by an inner differential evolution equation. On the other side

  11. A modelling approach for the heterogeneous oxidation of elastomers

    Science.gov (United States)

    Herzig, A.; Sekerakova, L.; Johlitz, M.; Lion, A.

    2017-09-01

    The influence of oxygen on elastomers, known as oxidation, is one of the most important ageing processes and becomes more and more important for nowadays applications. The interaction with thermal effects as well as antioxidants makes oxidation of polymers a complex process. Based on the polymer chosen and environmental conditions, the ageing processes may behave completely different. In a lot of cases the influence of oxygen is limited to the surface layer of the samples, commonly referred to as diffusion-limited oxidation. For the lifetime prediction of elastomer components, it is essential to have detailed knowledge about the absorption and diffusion behaviour of oxygen molecules during thermo-oxidative ageing and how they react with the elastomer. Experimental investigations on industrially used elastomeric materials are executed in order to develop and fit models, which shall be capable of predicting the permeation and consumption of oxygen as well as changes in the mechanical properties. The latter are of prime importance for technical applications of rubber components. Oxidation does not occur homogeneously over the entire elastomeric component. Hence, material models which include ageing effects have to be amplified in order to consider heterogeneous ageing, which highly depends on the ageing temperature. The influence of elevated temperatures upon accelerated ageing has to be critically analysed, and influences on the permeation and diffusion coefficient have to be taken into account. This work presents phenomenological models which describe the oxygen uptake and the diffusion into elastomers based on an improved understanding of ongoing chemical processes and diffusion limiting modifications. On the one side, oxygen uptake is modelled by means of Henry's law in which solubility is a function of the temperature as well as the ageing progress. The latter is an irreversible process and described by an inner differential evolution equation. On the other side

  12. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

    Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, flat...... sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells....

  13. Advanced impedance modeling of solid oxide electrochemical cells

    DEFF Research Database (Denmark)

    Graves, Christopher R.; Hjelm, Johan

    2014-01-01

    Impedance spectroscopy is a powerful technique for detailed study of the electrochemical and transport processes that take place in fuel cells and electrolysis cells, including solid oxide cells (SOCs). Meaningful analysis of impedance measurements is nontrivial, however, because a large number o...... analysis methods and integrates the analysis process in a modular workflow – data validation (Kramers-Kronig), clean-up, visualization (DRT and others), modeling (nonlinear least-squares fitting), and final plotting for publication....

  14. Impedance Modeling of Solid Oxide Fuel Cell Cathodes

    DEFF Research Database (Denmark)

    Mortensen, Jakob Egeberg; Søgaard, Martin; Jacobsen, Torben

    2010-01-01

    A 1-dimensional impedance model for a solid oxide fuel cell cathode is formulated and applied to a cathode consisting of 50/50 wt% strontium doped lanthanum cobaltite and gadolinia doped ceria. A total of 42 impedance spectra were recorded in the temperature range: 555-852°C and in the oxygen...... physical parameters such as the cathode thickness. ©2010 COPYRIGHT ECS - The Electrochemical Society...

  15. Natural gas and blends oxidation and ignition: Experiments and modeling

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Y.; Dagaut, P.; Cathonnet, M.; Boettner, J.C. [CNRS, Orleans (France); Bachman, J.S.; Carlier, P. [Gaz de France, La Plaine-Saint-Denis (France)

    1994-12-31

    The kinetics of the oxidation of natural gas and blends (CH{sub 4}/C{sub 2}H{sub 6}, CH{sub 4}/C{sub 3}H{sub 8}, CH{sub 4}/C{sub 2}H{sub 6}/C{sub 3}H{sub 8}) has been studied in a jet-stirred reactor (800 {<=} T/K {<=} 1240, 1 {<=} P/atm {<=} 10, 0.1 {<=} equivalence ratio {<=} 1.5). The concentration profiles of reactants, intermediates, and products measured in a jet-stirred reactor (JSR) have been used to validate a detailed kinetic reaction mechanism. Literature ignition delay times measured in shock tube have also been modeled. A generally good agreement between the data and the model is found. The same mechanism has also been used to successfully represent the oxidation of methane, ethyne, ethene, ethane, propene, propane, n-butane, and 1-butene in various conditions including JSR, shock tube, and flame. The present study clearly shows the importance of trace hydrocarbons in the oxidation of methane. The computations indicate that the oxidation of methane is initiated by its reaction with O{sub 2} when no other hydrocarbon is present. In natural gas and blends, higher hydrocarbons react before methane, leading to the formation of OH, H, and O radicals, which in turn initiate methane oxidation. This work demonstrates that methane cannot be used safely to represent the kinetics of natural gas combustion. However, simple blends like methane-propane or methane-ethane-propane could be used.

  16. Assessment of the basis for modeling releases from plutonium oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Mahoney, L.A.; Mishima, J.

    1990-08-01

    Ideally, a model of the release of plutonium aerosols from plutonium during oxidation or combustion should begin from a description of the plutonium material and its surroundings and proceed unequivocally to a situation-dependent estimate of the amount of oxide released and its size distribution. Such a model would need to provide a description of the heat- and mass-transfer processes involved and link them directly to the rate of aerosol production. The first step, the description of heat and mass transfer, is more easily achieved from current information than the second, the aerosol release. The sections of this report titled Physical Fundamentals'' and Available Theoretical Information'' describe the approach that would be required for theoretical modeling. The Experimental Results'' section describes the information on aerosol releases, size distributions, peak temperatures, oxidation rates, and experimental conditions that we have gleaned from the existing experimental literature. The data is summarized and the bibliography lists the relevant literature that has and has not been reviewed. 42 refs., 10 figs., 6 tabs.

  17. Modeling toxic compounds from nitric oxide emission measurements

    Science.gov (United States)

    Vallero, Daniel A.; Peirce, Jeffrey; Cho, Ki Don

    Determining the amount and rate of degradation of toxic pollutants in soil and groundwater is difficult and often requires invasive techniques, such as deploying extensive monitoring well networks. Even with these networks, degradation rates across entire systems cannot readily be extrapolated from the samples. When organic compounds are degraded by microbes, especially nitrifying bacteria, oxides or nitrogen (NO x) are released to the atmosphere. Thus, the flux of nitric oxide (NO) from the soil to the lower troposphere can be used to predict the rate at which organic compounds are degraded. By characterizing and applying biogenic and anthropogenic processes in soils the rates of degradation of organic compounds. Toluene was selected as a representative of toxic aromatic compounds, since it is inherently toxic, it is a substituted benzene compound and is listed as a hazardous air pollutant under Section 12 of the Clean Air Act Amendments of 1990. Measured toluene concentrations in soil, microbial population growth and NO fluxes in chamber studies were used to develop and parameterize a numerical model based on carbon and nitrogen cycling. These measurements, in turn, were used as indicators of bioremediation of air toxic (i.e. toluene) concentrations. The model found that chemical concentration, soil microbial abundance, and NO production can be directly related to the experimental results (significant at P hydrocarbons and oxides of nitrogen. As such, the model may be a tool for decision makers in ozone non-attainment areas.

  18. Quantification of oxide particle composition in model oxide dispersion strengthened steel alloys

    Energy Technology Data Exchange (ETDEWEB)

    London, A.J., E-mail: andrew.london@materials.ox.ac.uk [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom); Lozano-Perez, S.; Moody, M.P. [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom); Amirthapandian, S.; Panigrahi, B.K.; Sundar, C.S. [Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, TN (India); Grovenor, C.R.M. [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom)

    2015-12-15

    Oxide dispersion strengthened ferritic steels (ODS) are being considered for structural components of future designs of fission and fusion reactors because of their impressive high-temperature mechanical properties and resistance to radiation damage, both of which arise from the nanoscale oxide particles they contain. Because of the critical importance of these nanoscale phases, significant research activity has been dedicated to analysing their precise size, shape and composition (Odette et al., Annu. Rev. Mater. Res. 38 (2008) 471–503 [1]; Miller et al., Mater. Sci. Technol. 29(10) (2013) 1174–1178 [2]). As part of a project to develop new fuel cladding alloys in India, model ODS alloys have been produced with the compositions, Fe–0.3Y{sub 2}O{sub 3}, Fe–0.2Ti–0.3Y{sub 2}O{sub 3} and Fe–14Cr–0.2Ti–0.3Y{sub 2}O{sub 3}. The oxide particles in these three model alloys have been studied by APT in their as-received state and following ion irradiation (as a proxy for neutron irradiation) at various temperatures. In order to adequately quantify the composition of the oxide clusters, several difficulties must be managed, including issues relating to the chemical identification (ranging and variable peak-overlaps); trajectory aberrations and chemical structure; and particle sizing. This paper presents how these issues can be addressed by the application of bespoke data analysis tools and correlative microscopy. A discussion follows concerning the achievable precision in these measurements, with reference to the fundamental limiting factors.

  19. Modeling of oxidation of structural materials in LBE systems

    Science.gov (United States)

    Steiner, H.; Schroer, C.; Voß, Z.; Wedemeyer, O.; Konys, J.

    2008-02-01

    In recent years, liquid metal alloys have been examined in the light of various applications in technical systems the most famous example is the sodium cooled Fast Breeder Reactor. One major problem in non-isothermal heavy liquid metal systems lies in the corrosion of their structural components. The formation of oxide scales on the structural components is considered as a viable measure in limiting the dissolution rates in the hot parts in lead and lead-bismuth loops. Models for oxide scale growth under the action of flowing liquid metals have been implemented in the newly developed code MATLIM, which allow calculating the evolution of the oxide scales on structural materials in multi-modular loops. There are thermo-hydraulic limitations on oxygen supply from the liquid metal to the structural materials, the oxygen mass transfer coefficient in the liquid metal, which depends on the flow conditions, being rate-determining. This seems to explain, for example, why in the first stage of oxidation of stainless steels slowly growing, dense single layer Fe/Cr spinel scales are formed.

  20. Growth model of lantern-like amorphous silicon oxide nanowires

    Science.gov (United States)

    Wu, Ping; Zou, Xingquan; Chi, Lingfei; Li, Qiang; Xiao, Tan

    2007-03-01

    Silicon oxide nanowire assemblies with lantern-like morphology were synthesized by thermal evaporation of the mixed powder of SnO2 and active carbon at 1000 °C and using the silicon wafer as substrate and source. The nano-lanterns were characterized by a scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), energy-dispersive spectroscope (EDS) and selective area electron diffraction (SAED). The results show that the nano-lantern has symmetrical morphology, with one end connecting with the silicon wafer and the other end being the tin ball. The diameter of the nano-lantern is about 1.5-3.0 µm. Arc silicon oxide nanowire assemblies between the two ends have diameters ranging from 70 to 150 nm. One single catalyst tin ball catalyzes more than one amorphous nanowires' growth. In addition, the growth mechanism of the nano-lantern is discussed and a growth model is proposed. The multi-nucleation sites round the Sn droplet's perimeter are responsible for the formation of many SiOx nanowires. The growing direction of the nanowires is not in the same direction of the movement of the catalyst tin ball, resulting in the bending of the nanowires and forming the lantern-like silicon oxide morphology. The controllable synthesis of the lantern-like silicon oxide nanostructure may have potential applications in the photoelectronic devices field.

  1. Growth model of lantern-like amorphous silicon oxide nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Wu Ping; Zou Xingquan; Chi Lingfei; Li Qiang; Xiao Tan [Department of Physics, Shantou University, Shantou 515063 (China)

    2007-03-28

    Silicon oxide nanowire assemblies with lantern-like morphology were synthesized by thermal evaporation of the mixed powder of SnO{sub 2} and active carbon at 1000 deg. C and using the silicon wafer as substrate and source. The nano-lanterns were characterized by a scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), energy-dispersive spectroscope (EDS) and selective area electron diffraction (SAED). The results show that the nano-lantern has symmetrical morphology, with one end connecting with the silicon wafer and the other end being the tin ball. The diameter of the nano-lantern is about 1.5-3.0 {mu}m. Arc silicon oxide nanowire assemblies between the two ends have diameters ranging from 70 to 150 nm. One single catalyst tin ball catalyzes more than one amorphous nanowires' growth. In addition, the growth mechanism of the nano-lantern is discussed and a growth model is proposed. The multi-nucleation sites round the Sn droplet's perimeter are responsible for the formation of many SiO{sub x} nanowires. The growing direction of the nanowires is not in the same direction of the movement of the catalyst tin ball, resulting in the bending of the nanowires and forming the lantern-like silicon oxide morphology. The controllable synthesis of the lantern-like silicon oxide nanostructure may have potential applications in the photoelectronic devices field.

  2. Evaluation of discrepancy between measured and modelled oxidized mercury species

    Directory of Open Access Journals (Sweden)

    G. Kos

    2013-05-01

    Full Text Available L. Zhang et al. (2012, in a recent report, compared model estimates with new observations of oxidized and particulate mercury species (Hg2+ and Hgp in the Great Lakes region and found that the sum of Hg2+ and Hgp varied between a factor of 2 to 10 between measurements and model. They suggested too high emission inputs as Hg2+ and too fast oxidative conversion of Hg0 to Hg2+ and Hgp as possible causes. This study quantitatively explores measurement uncertainties in detail. These include sampling efficiency, composition of sample, interfering species and calibration errors. Model (Global/Regional Atmospheric Heavy Metals Model – GRAHM sensitivity experiments are used to examine the consistency between various Hg measurements and speciation of Hg near emission sources to better understand the discrepancies between modelled and measured concentrations of Hg2+ and Hgp. We find that the ratio of Hg0, Hg2+ and Hgp in the emission inventories, measurements of surface air concentrations of oxidized Hg and measurements of wet deposition are currently inconsistent with each other in the vicinity of emission sources. Current speciation of Hg emissions suggests higher concentrations of Hg2+ in air and in precipitation near emission sources; however, measured air concentrations of Hg2+ and measured concentrations of Hg in precipitation are not found to be significantly elevated near emission sources compared to the remote regions. The averaged unbiased root mean square error (RMSE between simulated and observed concentrations of Hg2+ is found to be reduced by 42% and for Hgp reduced by 40% for 21 North American sites investigated, when a ratio for Hg0 : Hg2+ : Hgp in the emissions is changed from 50 : 40 : 10 (as specified in the original inventories to 90 : 8 : 2. Unbiased RMSE reductions near emissions sources in the eastern United States and Canada are found to be reduced by up to 58% for Hg2+. Significant improvement in the model simulated spatial

  3. Oxidative stress in toxicology: established mammalian and emerging piscine model systems.

    Science.gov (United States)

    Kelly, K A; Havrilla, C M; Brady, T C; Abramo, K H; Levin, E D

    1998-07-01

    Interest in the toxicological aspects of oxidative stress has grown in recent years, and research has become increasingly focused on the mechanistic aspects of oxidative damage and cellular responses in biological systems. Toxic consequences of oxidative stress at the subcellular level include lipid peroxidation and oxidative damage to DNA and proteins. These effects are often used as end points in the study of oxidative stress. Typically, mammalian species have been used as models to study oxidative stress and to elucidate the mechanisms underlying cellular damage and response, largely because of the interest in human health issues surrounding oxidative stress. However, it is becoming apparent that oxidative stress also affects aquatic organisms exposed to environmental pollutants. Research in fish has demonstrated that mammalian and piscine systems exhibit similar toxicological and adaptive responses to oxidative stress. This suggests that piscine models, in addition to traditional mammalian models, may be useful for further understanding the mechanisms underlying the oxidative stress response.

  4. Oxidative airway inflammation leads to systemic and vascular oxidative stress in a murine model of allergic asthma.

    Science.gov (United States)

    Al-Harbi, Naif O; Nadeem, A; Al-Harbi, Mohamed M; Imam, F; Al-Shabanah, Othman A; Ahmad, Sheikh F; Sayed-Ahmed, Mohamed M; Bahashwan, Saleh A

    2015-05-01

    Oxidant-antioxidant imbalance plays an important role in repeated cycles of airway inflammation observed in asthma. It is when reactive oxygen species (ROS) overwhelm antioxidant defenses that a severe inflammatory state becomes apparent and may impact vasculature. Several studies have shown an association between airway inflammation and cardiovascular complications; however so far none has investigated the link between airway oxidative stress and systemic/vascular oxidative stress in a murine model of asthma. Therefore, this study investigated the contribution of oxidative stress encountered in asthmatic airways in modulation of vascular/systemic oxidant-antioxidant balance. Rats were sensitized intraperitoneally with ovalbumin (OVA) in the presence of aluminum hydroxide followed by several intranasal (i.n.) challenges with OVA. Rats were then assessed for airway and vascular inflammation, oxidative stress (ROS, lipid peroxides) and antioxidants measured as total antioxidant capacity (TAC) and thiol content. Challenge with OVA led to increased airway inflammation and oxidative stress with a concomitant increase in vascular inflammation and oxidative stress. Oxidative stress in the vasculature was significantly inhibited by antioxidant treatment, N-acetyl cysteine; whereas hydrogen peroxide (H2O2) inhalation worsened it. Therefore, our study shows that oxidative airway inflammation is associated with vascular/systemic oxidative stress which might predispose these patients to increased cardiovascular risk.

  5. Evidence of Oxidative Stress in Autism Derived from Animal Models

    Directory of Open Access Journals (Sweden)

    Xue Ming

    2008-01-01

    Full Text Available Autism is a pervasive neurodevelopmental disorder that leads to deficits in social interaction, communication and restricted, repetitive motor movements. Autism is a highly heritable disorder, however, there is mounting evidence to suggest that toxicant-induced oxidative stress may play a role. The focus of this article will be to review our animal model of autism and discuss our evidence that oxidative stress may be a common underlying mechanism of neurodevelopmental damage. We have shown that mice exposed to either methylmercury (MeHg or valproic acid (VPA in early postnatal life display aberrant social, cognitive and motor behavior. Interestingly, early exposure to both compounds has been clinically implicated in the development of autism. We recently found that Trolox, a water-soluble vitamin E derivative, is capable of attenuating a number of neurobehavioral alterations observed in mice postnatally exposed to MeHg. In addition, a number of other investigators have shown that oxidative stress plays a role in neural injury following MeHg exposure both in vitro and in vivo. New data presented here will show that VPA-induced neurobehavioral deficits are attenuated by vitamin E as well and that the level of glial fibrillary acidic protein (GFAP, a marker of astrocytic neural injury, is altered following VPA exposure. Collectively, these data indicate that vitamin E and its derivative are capable of protecting against neurobehavioral deficits induced by both MeHg and VPA. This antioxidant protection suggests that oxidative stress may be a common mechanism of injury leading to aberrant behavior in both our animal model as well as in the human disease state.

  6. LG Solid Oxide Fuel Cell (SOFC) Model Development

    Energy Technology Data Exchange (ETDEWEB)

    Haberman, Ben [LG Fuel Cell Systems Inc., North Canton, OH (United States); Martinez-Baca, Carlos [LG Fuel Cell Systems Inc., North Canton, OH (United States); Rush, Greg [LG Fuel Cell Systems Inc., North Canton, OH (United States)

    2013-05-31

    This report presents a summary of the work performed by LG Fuel Cell Systems Inc. during the project LG Solid Oxide Fuel Cell (SOFC) Model Development (DOE Award Number: DE-FE0000773) which commenced on October 1, 2009 and was completed on March 31, 2013. The aim of this project is for LG Fuel Cell Systems Inc. (formerly known as Rolls-Royce Fuel Cell Systems (US) Inc.) (LGFCS) to develop a multi-physics solid oxide fuel cell (SOFC) computer code (MPC) for performance calculations of the LGFCS fuel cell structure to support fuel cell product design and development. A summary of the initial stages of the project is provided which describes the MPC requirements that were developed and the selection of a candidate code, STAR-CCM+ (CD-adapco). This is followed by a detailed description of the subsequent work program including code enhancement and model verification and validation activities. Details of the code enhancements that were implemented to facilitate MPC SOFC simulations are provided along with a description of the models that were built using the MPC and validated against experimental data. The modeling work described in this report represents a level of calculation detail that has not been previously available within LGFCS.

  7. Preservation engineering assets developed from an oxidation predictive model

    Directory of Open Access Journals (Sweden)

    Coutelieris Frank A.

    2016-01-01

    Full Text Available A previously developed model which effectively predicts the probability of olive oil reaching the end of its shelf-life within a certain time frame was tested for its response when the convective diffusion of oxygen through packaging material is taken in account. Darcy’s Law was used to correlate the packaging permeability with the oxygen flow through the packaging materials. Mass transport within the food-packaging system was considered transient and the relative one-dimensional differential equations along with appropriate initial and boundary conditions were numerically solved. When the Peclet (Pe number was used to validate the significance of the oxygen transport mechanism through packaging, the model results confirmed the Arrhenius type dependency of diffusion, where the slope of the line per material actually indicated their –Ea/R. Furthermore, Pe could not be correlated to the hexanal produced in samples stored under light. Photo-oxidation has a significant role in the oxidative degradation of olive oil confirmed by the shelf-assessing test. The validity of our model for the oxygen diffusion driven systems, was also confirmed, for that reason the predictive boundaries were set. Results safely indicated the significance of applying a self-assessing process to confirm the packaging selection process for oxygen sensitive food via this model.

  8. Macro Level Modeling of a Tubular Solid Oxide Fuel Cell

    Directory of Open Access Journals (Sweden)

    Farshid Zabihian

    2010-11-01

    Full Text Available This paper presents a macro-level model of a solid oxide fuel cell (SOFC stack implemented in Aspen Plus® for the simulation of SOFC system. The model is 0-dimensional and accepts hydrocarbon fuels such as reformed natural gas, with user inputs of current density, fuel and air composition, flow rates, temperature, pressure, and fuel utilization factor. The model outputs the composition of the exhaust, work produced, heat available for the fuel reformer, and electrochemical properties of SOFC for model validation. It was developed considering the activation, concentration, and ohmic losses to be the main over-potentials within the SOFC, and mathematical expressions for these were chosen based on available studies in the literature. The model also considered the water shift reaction of CO and the methane reforming reaction. The model results were validated using experimental data from Siemens Westinghouse. The results showed that the model could capture the operating pressure and temperature dependency of the SOFC performance successfully in an operating range of 1–15 atm for pressure and 900 °C–1,000 °C for temperature. Furthermore, a sensitivity analysis was performed to identify the model constants and input parameters that impacted the over-potentials.

  9. Oxidative stress in toxicology: established mammalian and emerging piscine model systems.

    OpenAIRE

    Kelly, K.A.; Havrilla, C M; Brady, T C; Abramo, K H; Levin, E.D.

    1998-01-01

    Interest in the toxicological aspects of oxidative stress has grown in recent years, and research has become increasingly focused on the mechanistic aspects of oxidative damage and cellular responses in biological systems. Toxic consequences of oxidative stress at the subcellular level include lipid peroxidation and oxidative damage to DNA and proteins. These effects are often used as end points in the study of oxidative stress. Typically, mammalian species have been used as models to study o...

  10. Mechanical modeling of porous oxide fuel pellet A Test Problem

    Energy Technology Data Exchange (ETDEWEB)

    Nukala, Phani K [ORNL; Barai, Pallab [ORNL; Simunovic, Srdjan [ORNL; Ott, Larry J [ORNL

    2009-10-01

    A poro-elasto-plastic material model has been developed to capture the response of oxide fuels inside the nuclear reactors under operating conditions. Behavior of the oxide fuel and variation in void volume fraction under mechanical loading as predicted by the developed model has been reported in this article. The significant effect of void volume fraction on the overall stress distribution of the fuel pellet has also been described. An important oxide fuel issue that can have significant impact on the fuel performance is the mechanical response of oxide fuel pellet and clad system. Specifically, modeling the thermo-mechanical response of the fuel pellet in terms of its thermal expansion, mechanical deformation, swelling due to void formation and evolution, and the eventual contact of the fuel with the clad is of significant interest in understanding the fuel-clad mechanical interaction (FCMI). These phenomena are nonlinear and coupled since reduction in the fuel-clad gap affects thermal conductivity of the gap, which in turn affects temperature distribution within the fuel and the material properties of the fuel. Consequently, in order to accurately capture fuel-clad gap closure, we need to account for fuel swelling due to generation, retention, and evolution of fission gas in addition to the usual thermal expansion and mechanical deformation. Both fuel chemistry and microstructure also have a significant effect on the nucleation and growth of fission gas bubbles. Fuel-clad gap closure leading to eventual contact of the fuel with the clad introduces significant stresses in the clad, which makes thermo-mechanical response of the clad even more relevant. The overall aim of this test problem is to incorporate the above features in order to accurately capture fuel-clad mechanical interaction. Because of the complex nature of the problem, a series of test problems with increasing multi-physics coupling features, modeling accuracy, and complexity are defined with the

  11. Lithium ion transport in a model of amorphous polyethylene oxide.

    Energy Technology Data Exchange (ETDEWEB)

    Boinske, P. T.; Curtiss, L.; Halley, J. W.; Lin, B.; Sutjianto, A.; Chemical Engineering; Univ. of Minnesota

    1996-01-01

    We have made a molecular dynamics study of transport of a single lithium ion in a previously reported model of amorphous polyethylene oxide. New ab initio calculations of the interaction of the lithium ion with 1,2-dimethoxyethane and with dimethyl ether are reported which are used to determine force fields for the simulation. We report preliminary calculations of solvation energies and hopping barriers and a calculation of the ionic conductivity which is independent of any assumptions about the mechanism of ion transport. We also report some details of a study of transport of the trapped lithium ion on intermediate time and length scales.

  12. Modelling of the partial oxidation of {alpha}, {beta}-unsaturated aldehydes on Mo-V-oxides based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Boehnke, H.; Petzoldt, J.C.; Stein, B.; Weimer, C.; Gaube, J.W. [Technische Univ. Darmstadt (Germany). Inst. fuer Chemische Technologie

    1998-12-31

    A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)

  13. Model studies with gold: a versatile oxidation and hydrogenation catalyst.

    Science.gov (United States)

    Pan, Ming; Gong, Jinlong; Dong, Guangbin; Mullins, C Buddie

    2014-03-18

    Historically, scientists have considered gold an inert catalyst constituent. However, in recent decades, chemists have discovered that nanoscale gold shows exceptional activity for many chemical reactions. They have investigated model gold surfaces in order to obtain fundamental understanding of catalytic properties. In this Account, we present our current understanding of oxidation and hydrogenation reactions on the Au(111) single crystal as a planar representative of gold catalysts, revealing the interesting surface chemistry of gold. We begin by comparing two inverse reactions, alcohol oxidation and aldehyde hydrogenation, on a Au(111) surface. Beyond the expected different chemistry, we observe intriguing similarities since the same surface is employed. First, both molecular oxygen and hydrogen have high barriers to dissociation on Au(111), and frequently chemists study reactions here by using atomic O and H to populate the surfaces. Recombinative desorption features of oxygen and hydrogen are apparent at ∼500 and ∼110 K, lower than other transition metals. These results indicate that oxygen and hydrogen have low desorption activation energies and weakly chemisorb on the surface, likely leading to selective reactions. On the oxygen-precovered Au(111) surface, alcohols are selectively oxidized to aldehydes. Similarly, weakly bound hydrogen atoms on Au(111) also show chemoselective reactivity for hydrogenation of propionaldehyde and acetone. The second similarity is that the gold surface activates self-coupling of alcohol or aldehyde with oxygen or hydrogen, resulting in the formation of esters and ethers, respectively, in alcohol oxidation and aldehyde hydrogenation. During these two reactions, both alkoxy groups and alcohol-like species show up as intermediates, which likely play a key role in the formation of coupling products. In addition, the cross coupling reaction between alcohol and aldehyde occurs on both O- and H-modified surfaces, yielding the

  14. A Simple Hydraulic Analog Model of Oxidative Phosphorylation.

    Science.gov (United States)

    Willis, Wayne T; Jackman, Matthew R; Messer, Jeffrey I; Kuzmiak-Glancy, Sarah; Glancy, Brian

    2016-06-01

    Mitochondrial oxidative phosphorylation is the primary source of cellular energy transduction in mammals. This energy conversion involves dozens of enzymatic reactions, energetic intermediates, and the dynamic interactions among them. With the goal of providing greater insight into the complex thermodynamics and kinetics ("thermokinetics") of mitochondrial energy transduction, a simple hydraulic analog model of oxidative phosphorylation is presented. In the hydraulic model, water tanks represent the forward and back "pressures" exerted by thermodynamic driving forces: the matrix redox potential (ΔGredox), the electrochemical potential for protons across the mitochondrial inner membrane (ΔGH), and the free energy of adenosine 5'-triphosphate (ATP) (ΔGATP). Net water flow proceeds from tanks with higher water pressure to tanks with lower pressure through "enzyme pipes" whose diameters represent the conductances (effective activities) of the proteins that catalyze the energy transfer. These enzyme pipes include the reactions of dehydrogenase enzymes, the electron transport chain (ETC), and the combined action of ATP synthase plus the ATP-adenosine 5'-diphosphate exchanger that spans the inner membrane. In addition, reactive oxygen species production is included in the model as a leak that is driven out of the ETC pipe by high pressure (high ΔGredox) and a proton leak dependent on the ΔGH for both its driving force and the conductance of the leak pathway. Model water pressures and flows are shown to simulate thermodynamic forces and metabolic fluxes that have been experimentally observed in mammalian skeletal muscle in response to acute exercise, chronic endurance training, and reduced substrate availability, as well as account for the thermokinetic behavior of mitochondria from fast- and slow-twitch skeletal muscle and the metabolic capacitance of the creatine kinase reaction.

  15. An experimental and modeling study of diethyl carbonate oxidation

    KAUST Repository

    Nakamura, Hisashi

    2015-04-01

    Diethyl carbonate (DEC) is an attractive biofuel that can be used to displace petroleum-derived diesel fuel, thereby reducing CO2 and particulate emissions from diesel engines. A better understanding of DEC combustion characteristics is needed to facilitate its use in internal combustion engines. Toward this goal, ignition delay times for DEC were measured at conditions relevant to internal combustion engines using a rapid compression machine (RCM) and a shock tube. The experimental conditions investigated covered a wide range of temperatures (660-1300K), a pressure of 30bar, and equivalence ratios of 0.5, 1.0 and 2.0 in air. To provide further understanding of the intermediates formed in DEC oxidation, species concentrations were measured in a jet-stirred reactor at 10atm over a temperature range of 500-1200K and at equivalence ratios of 0.5, 1.0 and 2.0. These experimental measurements were used to aid the development and validation of a chemical kinetic model for DEC.The experimental results for ignition in the RCM showed near negative temperature coefficient (NTC) behavior. Six-membered alkylperoxy radical (RO˙2) isomerizations are conventionally thought to initiate low-temperature branching reactions responsible for NTC behavior, but DEC has no such possible 6- and 7-membered ring isomerizations. However, its molecular structure allows for 5-, 8- and 9-membered ring RO˙2 isomerizations. To provide accurate rate constants for these ring structures, ab initio computations for RO˙2⇌Q˙OOH isomerization reactions were performed. These new RO˙2 isomerization rate constants have been implemented in a chemical kinetic model for DEC oxidation. The model simulations have been compared with ignition delay times measured in the RCM near the NTC region. Results of the simulation were also compared with experimental results for ignition in the high-temperature region and for species concentrations in the jet-stirred reactor. Chemical kinetic insights into the

  16. Modeling of sulfur oxide removal in circulating fluidized bed absorbers

    Energy Technology Data Exchange (ETDEWEB)

    Mao, D.; Edwards, J.R.; Kuznetsov, A.V. [North Carolina State Univ., Raleigh, NC (United States). Dept. of Mechanical and Aerospace Engineering; Srivastava, R. [U.S. Environmental Protection Agency, Research Triangle Park, NC (United States). Air Pollution Prevention and Control Division

    2002-07-01

    This paper presents a model to simulate a circulating fluidized bed absorber (CFBA) that combines flow, mixing, and reaction through residence time distribution (RTD). These parameters are often overlooked in existing simulation models. In addition, the paper presents a newly developed gas-solid reaction model for sulphur dioxide removal by limestone. For the reaction model that considers RTD inside the core and annulus regions of CFBA, the macrochemical reaction is simulated according to microchemical reaction dynamics. The proposed model can predict sulphur dioxide and limestone distributions inside the CFBA and calculate how much limestone is needed to remove an appropriate amount of sulphur dioxide. Sulphur dioxide concentration at the outlet of the CFBA decreases as the distance of the CFBA increases from the bottom of the core region. Limestone concentration varies only very slightly in the core region, suggesting that limestone in the CFBA is efficiently utilized to remove sulphur oxide. Sulphur dioxide partial pressure at the exit of the CFBA decreases as fresh limestone increases at the inlet to the CFBA. 16 refs., 8 figs.

  17. Photosynthetic water oxidation: insights from manganese model chemistry.

    Science.gov (United States)

    Young, Karin J; Brennan, Bradley J; Tagore, Ranitendranath; Brudvig, Gary W

    2015-03-17

    Catalysts for light-driven water oxidation are a critical component for development of solar fuels technology. The multielectron redox chemistry required for this process has been successfully deployed on a global scale in natural photosynthesis by green plants and cyanobacteria using photosystem II (PSII). PSII employs a conserved, cuboidal Mn4CaOX cluster called the O2-evolving complex (OEC) that offers inspiration for artificial O2-evolution catalysts. In this Account, we describe our work on manganese model chemistry relevant to PSII, particularly the functional model [Mn(III/IV)2(terpy)2(μ-O)2(OH2)2](NO3)3 complex (terpy = 2,2';6',2″-terpyridine), a mixed-valent di-μ-oxo Mn dimer with two terminal aqua ligands. In the presence of oxo-donor oxidants such as HSO5(-), this complex evolves O2 by two pathways, one of which incorporates solvent water in an O-O bond-forming reaction. Deactivation pathways of this catalyst include comproportionation to form an inactive Mn(IV)Mn(IV) dimer and also degradation to MnO2, a consequence of ligand loss when the oxidation state of the complex is reduced to labile Mn(II) upon release of O2. The catalyst's versatility has been shown by its continued catalytic activity after direct binding to the semiconductor titanium dioxide. In addition, after binding to the surface of TiO2 via a chromophoric linker, the catalyst can be oxidized by a photoinduced electron-transfer mechanism, mimicking the natural PSII process. Model oxomanganese complexes have also aided in interpreting biophysical and computational studies on PSII. In particular, the μ-oxo exchange rates of the Mn-terpy dimer have been instrumental in establishing that the time scale for μ-oxo exchange of high-valent oxomanganese complexes with terminal water ligands is slower than O2 evolution in the natural photosynthetic system. Furthermore, computational studies on the Mn-terpy dimer and the OEC point to similar Mn(IV)-oxyl intermediates in the O-O bond

  18. Validation of the chloramine-T induced oxidation of human serum albumin as a model for oxidative damage in vivo.

    Science.gov (United States)

    Anraku, Makoto; Kragh-Hansen, Ulrich; Kawai, Keiichi; Maruyama, Toru; Yamasaki, Yasuomi; Takakura, Yoshinobu; Otagiri, Masaki

    2003-04-01

    The validity of using chloramine-T as a model compound for mimicing oxidative stress was examined using human serum albumin (HSA) as a model. Important sites of oxidation were studied by mild treatment with chloramine-T and by mutating 34Cys for a serine (C34S). High-performance liquid chromatography (HPLC) combined with fluorescence detection to confirm the validity of chloramine-T as an oxidizing agent was used. Oxidized amino acid residues were detected by reaction with 5,5'-dithiobis(2-nitro benzoic acid), digestion with cyanogen bromide, followed by capillary electrophoresis. Protein conformation was examined by spectroscopic techniques. From the HPLC analysis of human serum, the validity of using chloramine-T as an oxidizing agent was confirmed. At low chloramine-T concentrations (CT0.1-HSA, CT1-HSA), 34Cys and Met residues were oxidized, at medium concentrations (CT10-HSA), the tryptophan residue also appeared to be oxidized, and at the highest concentration (CT50-HSA), the net charge of Site II of HSA was found to be more negative. The two highest levels of oxidation of HSA (CT10-HSA, CT50-HSA) resulted in conformational changes with an increased exposure of hydrophobic regions, decreased high-affinity bindings of warfarin and ketoprofen and a reduced esterase-like activity. The latter protein also has a shorter plasma half-life and an increased liver clearance. We succeeded in imitating oxidative damage to HSA using chloramine-T and the findings show that Site II is more affected than Site I and 34Cys, when HSA is exposed to oxidative stress.

  19. Modelling of diffusion and conductivity relaxation of oxide ceramics

    Science.gov (United States)

    Preis, Wolfgang

    2016-12-01

    A two-dimensional square grain model has been applied to simulate simultaneously the diffusion process and relaxation of the dc conduction of polycrystalline oxide materials due to a sudden change of the oxygen partial pressure of the surrounding gas phase. The numerical calculations are performed by employing the finite element approach. The grains are squares of equal side length (average grain size) and the grain boundaries may consist of thin slabs of uniform thickness. An additional (space charge) layer adjacent to the grain boundary cores (thin slabs) either blocking (depletion layer) or highly conductive for electronic charge carriers may surround the grains. The electronic transport number of the mixed ionic-electronic conducting oxide ceramics may be close to unity (predominant electronic conduction). If the chemical diffusion coefficient of the neutral mobile component (oxygen) of the grain boundary core regions is assumed to be higher by many orders of magnitude than that in the bulk, the simulated relaxation curves for mass transport (diffusion) and dc conduction can deviate remarkably from each other. Deviations between the relaxation of mass transport and dc conduction are found in the case of considerably different electronic conductivities of grain boundary core regions, space charge layers, and bulk. On the contrary, the relaxation curves of mass transport and electronic conductivity are in perfect coincidence, when either effective medium diffusion occurs or the effective conductivity is unaffected by the individual conductivities of core regions and possible space charge layers, i.e. the grain boundary resistivity is negligible.

  20. The role of lager beer yeast in oxidative stability of model beer

    DEFF Research Database (Denmark)

    Berner, Torben Sune; Arneborg, Nils

    2012-01-01

    AIMS: In this study, we investigated the relationship between the ability of lager brewing yeast strains to tolerate oxidative stress and their ability to produce oxidative stable model beer. METHODS AND RESULTS: Screening of 21 lager brewing yeast strains against diamide and paraquat showed...... that the oxidative stress resistance was strain dependent. Fermentation of model wort in European Brewing Convention tubes using three yeast strains with varying oxidative stress resistances resulted in three model beers with different rates of radical formation as measured by electron spin resonance in forced...... in the model beers. CONCLUSIONS: A more oxidative stable beer is not obtained by a more-oxidative-stress-tolerant lager brewing yeast strain, exhibiting a higher secretion of thioredoxin, but rather by a less-oxidative-stress-tolerant strain, exhibiting a higher iron uptake. SIGNIFICANCE AND IMPACT...

  1. Modeling Degradation in Solid Oxide Electrolysis Cells - Volume II

    Energy Technology Data Exchange (ETDEWEB)

    Manohar Motwani

    2011-09-01

    Idaho National Laboratory has an ongoing project to generate hydrogen from steam using solid oxide electrolysis cells (SOECs). To accomplish this, technical and degradation issues associated with the SOECs will need to be addressed. This report covers various approaches being pursued to model degradation issues in SOECs. An electrochemical model for degradation of SOECs is presented. The model is based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic non-equilibrium. It is shown that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential,, within the electrolyte. The within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just near the oxygen electrode/electrolyte interface, leading to oxygen electrode delamination. These predictions are in accordance with the reported literature on the subject. Development of high pressures may be avoided by introducing some electronic conduction in the electrolyte. By combining equilibrium thermodynamics, non-equilibrium (diffusion) modeling, and first-principles, atomic scale calculations were performed to understand the degradation mechanisms and provide practical recommendations on how to inhibit and/or completely mitigate them.

  2. Demethyleneberberine attenuates non-alcoholic fatty liver disease with activation of AMPK and inhibition of oxidative stress.

    Science.gov (United States)

    Qiang, Xiaoyan; Xu, Lulu; Zhang, Miao; Zhang, Pengcheng; Wang, Yinhang; Wang, Yongchen; Zhao, Zheng; Chen, Huan; Liu, Xie; Zhang, Yubin

    2016-04-15

    Non-alcoholic fatty liver disease (NAFLD) has reached an epidemic level globally, which is recognized to form non-alcoholic steatohepatitis (NASH) by the "two-hit" model, including oxidative stress and inflammation. AMP-activated protein kinase (AMPK) has long been regarded as a key regulator of energy metabolism, which is recognized as a critical target for NAFLD treatment. Here we introduce a natural product, demethyleneberberine (DMB), which potentially ameliorated NAFLD by activating AMPK pathways. Our study showed that the intraperitoneal injection of DMB (20 or 40 mg/kg body weight) decreased hepatic lipid accumulation in methionine and choline deficient (MCD) high-fat diet feeding mice and db/db mice. The further investigation demonstrated that DMB activated AMPK by increasing its phosphorylation in vitro and in vivo. Accompanied with AMPK activation, the expression of lipogenic genes were significantly reduced while genes responsible for the fatty acid β-oxidation were restored in DMB-treated NAFLD mice. In addition, the remarkable oxidative damage and inflammation induced by NAFLD were both attenuated by DMB treatment, which is reflected by decreased lipid oxidative product, malonaldehyde (MDA) and inflammatory factors, tumor necrosis factor α (TNFα) and interleukin 1β (IL-1β). Based on all above, DMB could serve as a novel AMPK activator for treating NAFLD and preventing the pathologic progression from NAFLD to NASH by inhibiting the oxidative stress and inflammation.

  3. Inflammation and the Two-Hit Hypothesis of Schizophrenia

    OpenAIRE

    Feigenson, Keith A.; Kusnecov, Alex W.; Silverstein, Steven M

    2013-01-01

    The high societal and individual cost of schizophrenia necessitates finding better, more effective treatment, diagnosis, and prevention strategies. One of the obstacles in this endeavor is the diverse set of etiologies that comprises schizophrenia. A substantial body of evidence has grown over the last few decades to suggest that schizophrenia is a heterogeneous syndrome with overlapping symptoms and etiologies. At the same time, an increasing number of clinical, epidemiological, and experime...

  4. Reactor modeling and process analysis for partial oxidation of natural gas

    NARCIS (Netherlands)

    Albrecht, Bogdan Alexandru

    2004-01-01

    This thesis analyses a novel process of partial oxidation of natural gas and develops a numerical tool for the partial oxidation reactor modeling. The proposed process generates syngas in an integrated plant of a partial oxidation reactor, a syngas turbine and an air separation unit. This is called

  5. Modeling and Simulations in Photoelectrochemical Water Oxidation: From Single Level to Multiscale Modeling.

    Science.gov (United States)

    Zhang, Xueqing; Bieberle-Hütter, Anja

    2016-06-08

    This review summarizes recent developments, challenges, and strategies in the field of modeling and simulations of photoelectrochemical (PEC) water oxidation. We focus on water splitting by metal-oxide semiconductors and discuss topics such as theoretical calculations of light absorption, band gap/band edge, charge transport, and electrochemical reactions at the electrode-electrolyte interface. In particular, we review the mechanisms of the oxygen evolution reaction, strategies to lower overpotential, and computational methods applied to PEC systems with particular focus on multiscale modeling. The current challenges in modeling PEC interfaces and their processes are summarized. At the end, we propose a new multiscale modeling approach to simulate the PEC interface under conditions most similar to those of experiments. This approach will contribute to identifying the limitations at PEC interfaces. Its generic nature allows its application to a number of electrochemical systems.

  6. Experimental and modeling study of the oxidation of xylenes

    CERN Document Server

    Battin-Leclerc, F; Glaude, P A; Belmekki, N; Battin-Leclerc, Fr\\'{e}d\\'{e}rique; Bounaceur, Roda; Glaude, Pierre-Alexandre; Belmekki, Najib

    2006-01-01

    This paper describes an experimental and modeling study of the oxidation of the three isomers of xylene (ortho-, meta- and para-xylenes). For each compound, ignition delay times of hydrocarbon-oxygen-argon mixtures with fuel equivalence ratios from 0.5 to 2 were measured behind reflected shock waves for temperatures from 1330 to 1800 K and pressures from 6.7 to 9 bar. The results show a similar reactivity for the three isomers. A detailed kinetic mechanism has been proposed, which reproduces our experimental results, as well as some literature data obtained in a plug flow reactor at 1155 K showing a clear difference of reactivity between the three isomers of xylene. The main reaction paths have been determined by sensitivity and flux analyses and have allowed the differences of reactivity to be explained.

  7. A physiologically based kinetic model for bacterial sulfide oxidation

    NARCIS (Netherlands)

    Klok, J.B.; Graaff, M. de; Bosch, P.L. van den; Boelee, N.C.; Keesman, K.J.; Janssen, A.J.W.M.

    2013-01-01

    In the biotechnological process for hydrogen sulfide removal from gas streams, a variety of oxidation products can be formed. Under natron-alkaline conditions, sulfide is oxidized by haloalkaliphilic sulfide oxidizing bacteria via flavocytochrome c oxidoreductase. From previous studies, it was concl

  8. An approach to modeling of silicon oxidation in a wet ultra-diluted ambient

    NARCIS (Netherlands)

    Kovalgin, A.Y.; Hof, A.J.; Schmitz, J.

    2005-01-01

    In this work, we make steps towards developing a new wet-oxidation model of silicon based on electron-stimulated dissociation of H2O molecules. The need for a new model arises from the fact that existing physical models are inadequate to describe the thin-oxide regime. Two regimes of silicon oxidati

  9. Photocatalytic Oxidation of Lignin Model Systems by Merging Visible-Light Photoredox and Palladium Catalysis.

    Science.gov (United States)

    Kärkäs, Markus D; Bosque, Irene; Matsuura, Bryan S; Stephenson, Corey R J

    2016-10-07

    Lignin valorization has long been recognized as a sustainable solution for the renewable production of aromatic compounds. Two-step oxidation/reduction strategies, whereby the first oxidation step is required to "activate" lignin systems for controlled fragmentation reactions, have recently emerged as viable routes toward this goal. Herein we describe a catalytic protocol for oxidation of lignin model systems by combining photoredox and Pd catalysis. The developed dual catalytic protocol allowed the efficient oxidation of lignin model substrates at room temperature to afford the oxidized products in good to excellent yields.

  10. Ultrasound assisted synthesis of nanocrystalline zinc oxide: Experiments and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Hosni, Mongia [Laboratoire des Sciences des Procédés et des Matériaux, LSPM-CNRS, Université Paris 13, 99 av. J.B. Clément, 93430 Villetaneuse (France); Farhat, Samir, E-mail: farhat@lspm.cnrs.fr [Laboratoire des Sciences des Procédés et des Matériaux, LSPM-CNRS, Université Paris 13, 99 av. J.B. Clément, 93430 Villetaneuse (France); Schoenstein, Frederic; Karmous, Farah; Jouini, Noureddine [Laboratoire des Sciences des Procédés et des Matériaux, LSPM-CNRS, Université Paris 13, 99 av. J.B. Clément, 93430 Villetaneuse (France); Viana, Bruno [LCMCP Chimie-Paristech, UPMC, Collège de France, 11 Rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France); Mgaidi, Arbi [Laboratoire de chimie minérale industrielle université Tunis el Manar (Tunisia)

    2014-12-05

    Highlights: • ZnO nanospheres and nanowires were grown using ultrasound and thermal activation techniques. • The growth uses forced hydrolysis of zinc acetate in diethylene glycol (DEG). • A thermochemical model was developed based on thermodynamic equilibrium calculations. • We estimate species distribution in the bubble in temperature range from 5000 K to ambient. • We propose a new mechanism for ZnO growth assisted by ultrasound irradiation. - Abstract: A fast and green approach is proposed for the preparation of nanocrystalline zinc oxide (ZnO) via ultrasonic (US) irradiation in polyol medium. The process uses forced hydrolysis of zinc acetate in diethylene glycol (DEG). The protocol is compared to thermal activation under the same chemical environment. The activation method is found to be playing a critical role in the selective synthesis of morphologically distinct nanostructures. As compared to thermally activated conventional polyol process, (US) permits to considerably reduce reaction time as well as size of particles. In addition, the shape of these nanoparticles was changed from long nanowires to small nanospheres, indicating different reaction mechanisms. To explain this difference, a thermochemical model was developed based on thermodynamic equilibrium calculations. The model estimate species distribution in the bubble in temperature range from 5000 K to ambient simulating quenching process during bubble formation and collapse. Our results indicate the presence of high density of zinc atoms that could be responsible of a high density of nucleation as compared to thermal activation.

  11. A comprehensive experimental and modeling study of isobutene oxidation

    KAUST Repository

    Zhou, Chong-Wen

    2016-03-17

    Isobutene is an important intermediate in the pyrolysis and oxidation of higher-order branched alkanes, and it is also a component of commercial gasolines. To better understand its combustion characteristics, a series of ignition delay time (IDT) and laminar flame speed (LFS) measurements have been performed. In addition, flow reactor speciation data recorded for the pyrolysis and oxidation of isobutene is also reported. Predictions of an updated kinetic model described herein are compared with each of these data sets, as well as with existing jet-stirred reactor (JSR) species measurements. IDTs of isobutene oxidation were measured in four different shock tubes and in two rapid compression machines (RCMs) under conditions of relevance to practical combustors. The combination of shock tube and RCM data greatly expands the range of available validation data for isobutene oxidation models to pressures of 50 atm and temperatures in the range 666–1715 K. Isobutene flame speeds were measured experimentally at 1 atm and at unburned gas temperatures of 298–398 K over a wide range of equivalence ratios. For the flame speed results, there was good agreement between different facilities and the current model in the fuel-rich region. Ab initio chemical kinetics calculations were carried out to calculate rate constants for important reactions such as H-atom abstraction by hydroxyl and hydroperoxyl radicals and the decomposition of 2-methylallyl radicals. A comprehensive chemical kinetic mechanism has been developed to describe the combustion of isobutene and is validated by comparison to the presently considered experimental measurements. Important reactions, highlighted via flux and sensitivity analyses, include: (a) hydrogen atom abstraction from isobutene by hydroxyl and hydroperoxyl radicals, and molecular oxygen; (b) radical–radical recombination reactions, including 2-methylallyl radical self-recombination, the recombination of 2-methylallyl radicals with

  12. Modeling the chemical evolution of nitrogen oxides near roadways

    Science.gov (United States)

    Wang, Yan Jason; DenBleyker, Allison; McDonald-Buller, Elena; Allen, David; Zhang, K. Max

    2011-01-01

    The chemical evolution of nitrogen dioxide (NO 2) and nitrogen monoxide (NO) in the vicinity of roadways is numerically investigated using a computational fluid dynamics model, CFD-VIT-RIT and a Gaussian-based model, CALINE4. CFD-VIT-RIT couples a standard k- ɛ turbulence model for turbulent mixing and the Finite-Rate model for chemical reactions. CALINE4 employs a discrete parcel method, assuming that chemical reactions are independent of the dilution process. The modeling results are compared to the field measurement data collected near two roadways in Austin, Texas, State Highway 71 (SH-71) and Farm to Market Road 973 (FM-973), under parallel and perpendicular wind conditions during the summer of 2007. In addition to ozone (O 3), other oxidants and reactive species including hydroperoxyl radical (HO 2), organic peroxyl radical (RO 2), formaldehyde (HCHO) and acetaldehyde (CH 3CHO) are considered in the transformation from NO to NO 2. CFD-VIT-RIT is shown to be capable of predicting both NO x and NO 2 profiles downwind. CALINE4 is able to capture the NO x profiles, but underpredicts NO 2 concentrations under high wind velocity. Our study suggests that the initial NO 2/NO x ratios have to be carefully selected based on traffic conditions in order to assess NO 2 concentrations near roadways. The commonly assumed NO 2/NO x ratio by volume of 5% may not be suitable for most roadways, especially those with a high fraction of heavy-duty truck traffic. In addition, high O 3 concentrations and high traffic volumes would lead to the peak NO 2 concentration occurring near roadways with elevated concentrations persistent over a long distance downwind.

  13. The role of lager beer yeast in oxidative stability of model beer.

    Science.gov (United States)

    Berner, T S; Arneborg, N

    2012-03-01

    In this study, we investigated the relationship between the ability of lager brewing yeast strains to tolerate oxidative stress and their ability to produce oxidative stable model beer. Screening of 21 lager brewing yeast strains against diamide and paraquat showed that the oxidative stress resistance was strain dependent. Fermentation of model wort in European Brewing Convention tubes using three yeast strains with varying oxidative stress resistances resulted in three model beers with different rates of radical formation as measured by electron spin resonance in forced ageing experiments. Interestingly, the strain with the lowest oxidative stress resistance and lowest secretion of thioredoxin, as measured by Western blotting, resulted in the highest uptake of iron, as measured by inductively coupled plasma-mass spectrometry, and the slowest formation of radicals in the model beers. A more oxidative stable beer is not obtained by a more-oxidative-stress-tolerant lager brewing yeast strain, exhibiting a higher secretion of thioredoxin, but rather by a less-oxidative-stress-tolerant strain, exhibiting a higher iron uptake. To obtain lager beers with enhanced oxidative stability, yeast strains should be screened for their low oxidative stress tolerance and/or high ability to take up iron rather than for their high oxidative stress tolerance and/or high ability to secrete thioredoxin. © 2011 The Authors. Letters in Applied Microbiology © 2011 The Society for Applied Microbiology.

  14. Modeling of structural effects in biomedical elements after titanium oxidation in fluidized bed

    Directory of Open Access Journals (Sweden)

    Mendzik K.

    2010-06-01

    Full Text Available Oxidation is one of the most employed methods to improve titanium and its alloys properties especially due to medical application. This process like most of the thermochemical treatment processes substantially influences on the characteristic of surface layers and the same on its mechanical and useful properties. Oxide coatings produced during titanium oxidation were examined due to their composition identification. Titanium was oxidized in fluidized bed in temperature range between 500÷700°C. Microstructures of titanium with a visible oxide coating on its surface after thermochemical treatment and changes of grain size in core of titanium samples are described. Moreover Xray phase analysis of obtained oxides coatings was made as well as microhardness measurements of titanium surface layers after oxidation process. Finally, the surfaces of titanium after oxidation in fluidized bed were measured by Auger electron spectroscopy. All research results are used to built numerical model of oxidation process in fluidized. Titanium oxidation process in fluidized bed is very complicated, because changes of parameters are non linear characteristics. This fact and lack of mathematical algorithms describing this process makes modeling properties of titanium elements by traditional numerical methods difficult or even impossible. In this case it is possible to try using artificial neural network. Using neural networks for modeling oxidizing in fluidized bed is caused by several nets' features: non linear character, ability to generalize the results of calculations for data out of training set, no need for mathematical algorithms describing influence changes input parameters on modeling materials properties.

  15. Transgenic Mouse Model for Reducing Oxidative Damage in Bone

    Science.gov (United States)

    Schreurs, A.-S.; Torres, S.; Truong, T.; Kumar, A.; Alwood, J. S.; Limoli, C. L.; Globus, R. K.

    2014-01-01

    Exposure to musculoskeletal disuse and radiation result in bone loss; we hypothesized that these catabolic treatments cause excess reactive oxygen species (ROS), and thereby alter the tight balance between bone resorption by osteoclasts and bone formation by osteoblasts, culminating in bone loss. To test this, we used transgenic mice which over-express the human gene for catalase, targeted to mitochondria (MCAT). Catalase is an anti-oxidant that converts the ROS hydrogen peroxide into water and oxygen. MCAT mice were shown previously to display reduced mitochondrial oxidative stress and radiosensitivity of the CNS compared to wild type controls (WT). As expected, MCAT mice expressed the transgene in skeletal tissue, and in marrow-derived osteoblasts and osteoclast precursors cultured ex vivo, and also showed greater catalase activity compared to wildtype (WT) mice (3-6 fold). Colony expansion in marrow cells cultured under osteoblastogenic conditions was 2-fold greater in the MCAT mice compared to WT mice, while the extent of mineralization was unaffected. MCAT mice had slightly longer tibiae than WT mice (2%, P less than 0.01), although cortical bone area was slightly lower in MCAT mice than WT mice (10%, p=0.09). To challenge the skeletal system, mice were treated by exposure to combined disuse (2 wk Hindlimb Unloading) and total body irradiation Cs(137) (2 Gy, 0.8 Gy/min), then bone parameters were analyzed by 2-factor ANOVA to detect possible interaction effects. Treatment caused a 2-fold increase (p=0.015) in malondialdehyde levels of bone tissue (ELISA) in WT mice, but had no effect in MCAT mice. These findings indicate that the transgene conferred protection from oxidative damage caused by treatment. Unexpected differences between WT and MCAT mice emerged in skeletal responses to treatment.. In WT mice, treatment did not alter osteoblastogenesis, cortical bone area, moment of inertia, or bone perimeter, whereas in MCAT mice, treatment increased these

  16. Modeling of Alkane Oxidation Using Constituents and Species

    Science.gov (United States)

    Bellan, Jasette; Harstad, Kenneth G.

    2010-01-01

    It is currently not possible to perform simulations of turbulent reactive flows due in particular to complex chemistry, which may contain thousands of reactions and hundreds of species. This complex chemistry results in additional differential equations, making the numerical solution of the equation set computationally prohibitive. Reducing the chemical kinetics mathematical description is one of several important goals in turbulent reactive flow modeling. A chemical kinetics reduction model is proposed for alkane oxidation in air that is based on a parallel methodology to that used in turbulence modeling in the context of the Large Eddy Simulation. The objective of kinetic modeling is to predict the heat release and temperature evolution. This kinetic mechanism is valid over a pressure range from atmospheric to 60 bar, temperatures from 600 K to 2,500 K, and equivalence ratios from 0.125 to 8. This range encompasses diesel, HCCI, and gas-turbine engines, including cold ignition. A computationally efficient kinetic reduction has been proposed for alkanes that has been illustrated for n-heptane using the LLNL heptane mechanism. This model is consistent with turbulence modeling in that scales were first categorized into either those modeled or those computed as progress variables. Species were identified as being either light or heavy. The heavy species were decomposed into defined 13 constituents, and their total molar density was shown to evolve in a quasi-steady manner. The light species behave either in a quasi-steady or unsteady manner. The modeled scales are the total constituent molar density, Nc, and the molar density of the quasi-steady light species. The progress variables are the total constituent molar density rate evolution and the molar densities of the unsteady light species. The unsteady equations for the light species contain contributions of the type gain/loss rates from the heavy species that are modeled consistent with the developed mathematical

  17. Effects of aerosols on tropospheric oxidants: A global model study

    Science.gov (United States)

    Tie, Xuexi; Brasseur, Guy; Emmons, Louisa; Horowitz, Larry; Kinnison, Douglas

    2001-10-01

    The global distributions of sulfate and soot particles in the atmosphere are calculated, and the effect of aerosol particles on tropospheric oxidants is studied using a global chemical/transport/aerosol model. The model is developed in the framework of the National Center for Atmospheric Research (NCAR) global three-dimensional chemical/transport model (Model for Ozone and Related Chemical Tracers (MOZART)). In addition to the gas-phase photochemistry implemented in the MOZART model, the present study also accounts for the formation of sulfate and black carbon aerosols as well as for heterogeneous reactions on particles. The simulated global sulfate aerosol distributions and seasonal variation are compared with observations. The seasonal variation of sulfate aerosols is in agreement with measurements, except in the Arctic region. The calculated vertical profiles of sulfate aerosol agree well with the observations over North America. In the case of black carbon the calculated surface distribution is in fair agreement with observations. The effects of aerosol formation and heterogeneous reactions on the surface of sulfate aerosols are studied. The model calculations show the following: (1) The concentration of H2O2 is reduced when sulfate aerosols are formed due to the reaction of SO2 + H2O2 in cloud droplets. The gas-phase reaction SO2 + OH converts OH to HO2, but the reduction of OH and enhancement of HO2 are insignificant (<3%). (2) The heterogeneous reaction of HO2 on the surface of sulfate aerosols produces up to 10% reduction of hydroperoxyl radical (HO2) with an uptake coefficient of 0.2. However, this uptake coefficient could be overestimated, and the results should be regard as an upper limit estimation. (3) The N2O5 reaction on the surface of sulfate aerosols leads to an 80% reduction of NOx at middle to high latitudes during winter. Because ozone production efficiency is low in winter, ozone decreases by only 10% as a result of this reaction. However

  18. Stoichiometric modeling of oxidation of reduced inorganic sulfur compounds (Riscs) in Acidithiobacillus thiooxidans.

    Science.gov (United States)

    Bobadilla Fazzini, Roberto A; Cortés, Maria Paz; Padilla, Leandro; Maturana, Daniel; Budinich, Marko; Maass, Alejandro; Parada, Pilar

    2013-08-01

    The prokaryotic oxidation of reduced inorganic sulfur compounds (RISCs) is a topic of utmost importance from a biogeochemical and industrial perspective. Despite sulfur oxidizing bacterial activity is largely known, no quantitative approaches to biological RISCs oxidation have been made, gathering all the complex abiotic and enzymatic stoichiometry involved. Even though in the case of neutrophilic bacteria such as Paracoccus and Beggiatoa species the RISCs oxidation systems are well described, there is a lack of knowledge for acidophilic microorganisms. Here, we present the first experimentally validated stoichiometric model able to assess RISCs oxidation quantitatively in Acidithiobacillus thiooxidans (strain DSM 17318), the archetype of the sulfur oxidizing acidophilic chemolithoautotrophs. This model was built based on literature and genomic analysis, considering a widespread mix of formerly proposed RISCs oxidation models combined and evaluated experimentally. Thiosulfate partial oxidation by the Sox system (SoxABXYZ) was placed as central step of sulfur oxidation model, along with abiotic reactions. This model was coupled with a detailed stoichiometry of biomass production, providing accurate bacterial growth predictions. In silico deletion/inactivation highlights the role of sulfur dioxygenase as the main catalyzer and a moderate function of tetrathionate hydrolase in elemental sulfur catabolism, demonstrating that this model constitutes an advanced instrument for the optimization of At. thiooxidans biomass production with potential use in biohydrometallurgical and environmental applications.

  19. Cellular Automata Modelling of Photo-Induced Oxidation Processes in Molecularly Doped Polymers

    Directory of Open Access Journals (Sweden)

    David M. Goldie

    2016-11-01

    Full Text Available The possibility of employing cellular automata (CA to model photo-induced oxidation processes in molecularly doped polymers is explored. It is demonstrated that the oxidation dynamics generated using CA models exhibit stretched-exponential behavior. This dynamical characteristic is in general agreement with an alternative analysis conducted using standard rate equations provided the molecular doping levels are sufficiently low to prohibit the presence of safe-sites which are impenetrable to dissolved oxygen. The CA models therefore offer the advantage of exploring the effect of dopant agglomeration which is difficult to assess from standard rate equation solutions. The influence of UV-induced bleaching or darkening upon the resulting oxidation dynamics may also be easily incorporated into the CA models and these optical effects are investigated for various photo-oxidation product scenarios. Output from the CA models is evaluated for experimental photo-oxidation data obtained from a series of hydrazone-doped polymers.

  20. Asparagine decarboxylation by lipid oxidation products in model systems.

    Science.gov (United States)

    Hidalgo, Francisco J; Delgado, Rosa M; Navarro, José L; Zamora, Rosario

    2010-10-13

    The decarboxylation of asparagine in the presence of alkanals, alkenals, and alkadienals, among other lipid derivatives, was studied in an attempt to understand the reaction pathways by which some lipid oxidation products are able to convert asparagine into acrylamide. Asparagine was converted into 3-aminopropionamide in the presence of lipid derivatives as a function of reaction conditions (pH, water content, time, and temperature), as well as the type and amount of lipid compound involved. Alkadienals (and analogous ketodienes) were the most reactive lipids followed by hydroperoxides and alkenals. Saturated carbonyls and polyunsaturated fatty acids, or other polyunsaturated derivatives, also exhibited some reactivity. On the other hand, saturated lipids or monounsaturated alcohols did not degrade asparagine. A mechanism for the decarboxylation of asparagine in the presence of alkadienals based on the deuteration results obtained when asparagine/2,4-decadienal model systems were heated in the presence of deuterated water was proposed. The activation energy (E(a)) of asparagine decarboxylation by 2,4-decadienal was 81.0 kJ/mol, which is higher than that found for the conversion of 3-aminopropionamide into acrylamide in the presence of 2,4-decadienal. This result points to the decarboxylation step as the key step in the conversion of asparagine into acrylamide in the presence of alkadienals. Therefore, any inhibiting strategy for suppressing the formation of acrylamide by alkadienals should be mainly directed to the inhibition of this step.

  1. Copper Oxide Nanoparticles for Advanced Refrigerant Thermophysical Properties: Mathematical Modeling

    Directory of Open Access Journals (Sweden)

    S. A. Fadhilah

    2014-01-01

    Full Text Available In modern days, refrigeration systems are important for industrial and domestic applications. The systems consume more electricity as compared to other appliances. The refrigeration systems have been investigated thoroughly in many ways to reduce the energy consumption. Hence, nanorefrigerant which is one kind of nanofluids has been introduced as a superior properties refrigerant that increased the heat transfer rate in the refrigeration system. Many types of materials could be used as the nanoparticles to be suspended into the conventional refrigerants. In this study, the effect of the suspended copper oxide (CuO nanoparticles into the 1,1,1,2-tetrafluoroethane, R-134a is investigated by using mathematical modeling. The investigation includes the thermal conductivity, dynamic viscosity, and heat transfer rate of the nanorefrigerant in a tube of evaporator. The results show enhanced thermophysical properties of nanorefrigerant compared to the conventional refrigerant. These advanced thermophysical properties increased the heat transfer rate in the tube. The nanorefrigerant could be a potential working fluid to be used in the refrigeration system to increase the heat transfer characteristics and save the energy usage.

  2. Energy dependent model of a metal oxide surge arrester. Sanka aengata hiraiki no energy izon model

    Energy Technology Data Exchange (ETDEWEB)

    Kojima, S.; Kan, M.; Masuzawa, K. (Toshiba Corp., Tokyo (Japan))

    1994-03-20

    This paper reports on modeling a zinc-oxide lightning arrester. The paper indicates that it is difficult to model the zinc-oxide elements by using non-linear resistance and inductance only, based on results of measuring hysteresis curves of restriction voltage on dual peak discharge of the elements. The paper then proposes a model (of numerical expression) that incorporates a concept that the restriction voltage decreases in response to energy absorbed by the elements from the discharge current. The paper explains a method for deciding on constants contained in the proposed expression, and a method to calculate the restriction voltage according to the proposed expression by using TACS of the program EMTP for circuit analysis. Further, it is indicated that the measured values of the restriction voltage on the dual-peak discharge current agree well with the calculated values from the proposed expression. A comparison was made on effects of this model and the conventional non-linear resistance model on the results of analyzing lightning surge responses in a 500-kV model system. 6 refs., 14 figs., 1 tab.

  3. Observations and Model Analysis of Enhanced Oxidized Mercury in the Free Troposphere during NOMADSS

    Science.gov (United States)

    Gratz, L.; Shah, V.; Ambrose, J. L., II; Jaffe, D. A.; Jaegle, L.; Selin, N. E.; Song, S.; Festa, J.; Stutz, J.

    2014-12-01

    Mercury (Hg) is a hazardous neurotoxic pollutant with complex atmospheric speciation and chemistry. It exists in the atmosphere primarily as gaseous elemental Hg (GEM), with a lifetime on the order of months, while oxidized Hg is more water soluble and deposits readily. Thus, Hg is considered both a local and a global pollutant. There are significant limitations in our understanding of global Hg cycling, including the sources and chemical mechanisms producing enhanced oxidized Hg in the free troposphere. Ground-based and airborne studies have associated free tropospheric oxidized Hg with GEM oxidation and atmospheric subsidence. Chemical transport models suggest that free tropospheric GEM oxidation is largely attributable to bromine (Br) atoms. During the 2013 Nitrogen Oxidants Mercury and Aerosol Distributions Sources and Sinks (NOMADSS) campaign, we sought to quantify the distribution and chemical transformation of Hg species in the free troposphere over the southeastern US. Enhanced oxidized Hg over North Texas was associated with long-range transport and subsidence from the sub-tropical Pacific free troposphere, where GEOS-Chem predicts air enriched in oxidized Hg. Bromine oxide (BrO) concentrations were also elevated over North Texas, perhaps supporting halogen oxidation as a source of free tropospheric oxidized Hg. Over the Atlantic Ocean, oxidized Hg up to 680 pg m-3 was associated with GEM oxidation and subsidence within the Atlantic high pressure system. The standard GEOS-Chem model underestimates free tropospheric oxidized Hg in these locations by a factor of three to ten, possibly due to underestimation of Br concentrations and/or uncertainty in the Hg+Br rate constant. We investigate GEOS-Chem's improved ability to reproduce the observed concentrations by tripling free tropospheric Br in the tropics and implementing a faster Hg+Br oxidation mechanism. Results have important implications for our understanding of global-scale atmospheric Hg chemistry and

  4. Towards a Predictive Thermodynamic Model of Oxidation States of Uranium Incorporated in Fe (hydr) oxides

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S. [Univ. of North Texas, Denton, TX (United States)

    2013-01-01

    -Level Excited States: Consequences For X-Ray Absorption Spectroscopy”, J. Elec. Spectros. and Related Phenom., 200, 174 (2015) describes our first application of these methods. As well as applications to problems and materials of direct interest for our PNNL colleagues, we have pursued applications of fundamental theoretical significance for the analysis and interpretation of XPS and XAS spectra. These studies are important for the development of the fields of core-level spectroscopies as well as to advance our capabilities for applications of interest to our PNNL colleagues. An excellent example is our study of the surface core-level shifts, SCLS, for the surface and bulk atoms of an oxide that provides a new approach to understanding how the surface electronic of oxides differs from that in the bulk of the material. This work has the potential to lead to a new key to understanding the reactivity of oxide surfaces. Our theoretical studies use cluster models with finite numbers of atoms to describe the properties of condensed phases and crystals. This approach has allowed us to focus on the local atomistic, chemical interactions. For these clusters, we obtain orbitals and spinors through the solution of the Hartree-Fock, HF, and the fully relativistic Dirac HF equations. These orbitals are used to form configuration mixing wavefunctions which treat the many-body effects responsible for the open shell angular momentum coupling and for the satellites of the core-level spectra. Our efforts have been in two complementary directions. As well as the applications described above, we have placed major emphasis on the enhancement and extension of our theoretical and computational capabilities so that we can treat complex systems with a greater range of many-body effects. Noteworthy accomplishments in terms of method development and enhancement have included: (1) An improvement in our treatment of the large matrices that must be handled when many-body effects are treated. (2

  5. Modeling of hydrogen sulfide oxidation in concrete corrosion products from sewer pipes.

    Science.gov (United States)

    Jensen, Henriette Stokbro; Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes

    2009-04-01

    Abiotic and biotic oxidation of hydrogen sulfide related to concrete corrosion was studied in corrosion products originating from a sewer manhole. The concrete corrosion products were suspended in an acidic solution, mimicking the conditions in the pore water of corroded concrete. The removal of hydrogen sulfide and dissolved oxygen was measured in parallel in the suspension, upon which the suspension was sterilized and the measurement repeated. The results revealed the biotic oxidation to be fast compared with the abiotic oxidation. The stoichiometry of the hydrogen sulfide oxidation was evaluated using the ratio between oxygen and hydrogen sulfide uptake. The ratio for the biotic oxidation pointed in the direction of elemental sulfur being formed as an intermediate in the oxidation of hydrogen sulfide to sulfuric acid. The experimental results were applied to suggest a hypothesis and a mathematical model describing the hydrogen sulfide oxidation pathway in a matrix of corroded concrete.

  6. Model-based evaluation of the role of Anammox on nitric oxide and nitrous oxide productions in membrane aerated biofilm reactor

    DEFF Research Database (Denmark)

    Ni, Bing-Jie; Smets, Barth F.; Yuan, Zhiguo;

    2013-01-01

    A multispecies one-dimensional biofilm model considering nitric oxide (NO) and nitrous oxide (N2O) productions for membrane aerated biofilm reactor (MABR) that remove nitrogen autotrophically through aerobic ammonia oxidation followed by Anammox is used to study the role of Anammox activity on th...

  7. Quantitative Mapping of Reversible Mitochondrial Complex I Cysteine Oxidation in a Parkinson Disease Mouse Model*

    OpenAIRE

    Danielson, Steven R.; Held, Jason M.; Oo, May; Riley, Rebeccah; Gibson, Bradford W.; Andersen, Julie K.

    2011-01-01

    Differential cysteine oxidation within mitochondrial Complex I has been quantified in an in vivo oxidative stress model of Parkinson disease. We developed a strategy that incorporates rapid and efficient immunoaffinity purification of Complex I followed by differential alkylation and quantitative detection using sensitive mass spectrometry techniques. This method allowed us to quantify the reversible cysteine oxidation status of 34 distinct cysteine residues out of a total 130 present in muri...

  8. A kinetic model of municipal sludge degradation during non-catalytic wet oxidation.

    Science.gov (United States)

    Prince-Pike, Arrian; Wilson, David I; Baroutian, Saeid; Andrews, John; Gapes, Daniel J

    2015-12-15

    Wet oxidation is a successful process for the treatment of municipal sludge. In addition, the resulting effluent from wet oxidation is a useful carbon source for subsequent biological nutrient removal processes in wastewater treatment. Owing to limitations with current kinetic models, this study produced a kinetic model which predicts the concentrations of key intermediate components during wet oxidation. The model was regressed from lab-scale experiments and then subsequently validated using data from a wet oxidation pilot plant. The model was shown to be accurate in predicting the concentrations of each component, and produced good results when applied to a plant 500 times larger in size. A statistical study was undertaken to investigate the validity of the regressed model parameters. Finally the usefulness of the model was demonstrated by suggesting optimum operating conditions such that volatile fatty acids were maximised.

  9. Modelling nitrous oxide emissions from cropland at the regional scale

    Directory of Open Access Journals (Sweden)

    Gabrielle Benoît

    2006-11-01

    Full Text Available Arable soils are a large source of nitrous oxide (N2O emissions, making up half of the biogenic emissions worldwide. Estimating their source strength requires methods capable of capturing the spatial and temporal variability of N2O emissions, along with the effects of crop management. Here, we applied a process-based model, CERES, with geo-referenced input data on soils, weather, and land use to map N2O emissions from wheat-cropped soils in three agriculturally intensive regions in France. Emissions were mostly controlled by soil type and local climate conditions, and only to a minor extent by the doses of fertilizer nitrogen applied. As a result, the direct emission factors calculated at the regional level were much smaller (ranging from 0.0007 to 0.0033 kg N2O-N kg–1 N than the value of 0.0125 kg N2O-N kg–1 N currently recommended in the IPCC Tier 1 methodology. Regional emissions were far more sensitive to the soil microbiological parameter s governing denitrification and its fraction evolved as N2O, soil bulk density, and soil initial inorganic N content. Mitigation measures should therefore target a reduction in the amount of soil inorganic N upon sowing of winter crops, and a decrease of the soil N2O production potential itself. From a general perspective, taking into account the spatial variability of soils and climate thereby appears necessary to improve the accuracy of national inventories, and to tailor mitigation strategies to regional characteristics. The methodology and results presented here may easily be transferred to winter oilseed rape, whose has growing cycle and fertilser requirements are similar.

  10. Global modelling of the ClNO2 production impact on tropospheric nitrogen oxides and main oxidants

    Science.gov (United States)

    Cuevas Rodríguez, Carlos Alberto; Brown, Steven S.; Lamarque, Jean-Francoise; Saiz-Lopez, Alfonso; Kinnison, Douglas E.; Lopez-Hilfiker, Felipe; Thornton, Joel A.; Jaegle, Lyatt; Fibiger, Dorothy; McDuffie, Erin E.; Sullivan, Amy P.; Weber, Rodney J.; Dibb, Jack

    2016-04-01

    Heterogeneous uptake of dinitrogen pentoxide, N2O5, to aerosol is one of the most important reactions controlling the global budget of nitrogen oxides, with subsequent impacts on oxidants such as ozone and hydroxyl radical. Most chemistry global models assume that this uptake proceeds through hydrolysis to produce nitric acid, effectively a terminal sink for nitrogen oxides. However, recent field studies have shown that the yield of nitryl chloride, ClNO2, from N2O5 uptake is significant in many locations. Because ClNO2 photolyzes subsequent to its nighttime production to recycle NO2 and produce atomic chlorine, a potent oxidant, the impact of heterogeneous N2O5 uptake and the role of ClNO2 on the scale distribution of oxidants need to be re-assessed. Here we present global simulations using the chemistry-climate model CAM-Chem, including a state of the art halogen chemistry scheme and different assumptions for the magnitude and spatial distribution of ClNO2 yields from N2O5. The model shows a significant effect of ClNO2 production on tropospheric ozone, hydroxyl radical and peroxyacyl nitrates (PAN) during northern hemisphere late winter and early spring. Simulations are compared to observations from recent field campaigns, including ClNO2 and N2O5 from the Wintertime INvestigation of Transport, Emissions and Reactivity (WINTER) study on the NSF / NCAR C-130 aircraft on the U.S. East Coast in February and March of 2015.

  11. Evaluation and Model of Performance of A Tubular Solid Oxide Fuel Cell

    Institute of Scientific and Technical Information of China (English)

    JIA Jun-xi; SHEN Sheng-qiang

    2005-01-01

    A simulation model was developed to analyze the steady state and transient operation of a tubular solid oxide fuel cell. The model covers both the electrochemical and the heat transfer models. The electrochemical model deals with the Nernst potential, ohmic polarization, activation polarization, and concentration polarization, while the heat transfer model concerns the heat transfer by conduction, convection and radiation. The numerical results show that the ohmic loss is the dominant one among the three polarizations in a cathode-supported solid oxide fuel cell and in the middle part of a solid oxide fuel cell the temperature is higher than those at both the ends. When the inlet temperature and the flow rates of the fuel and the oxidant are kept constantly, the temperature of the solid structure of the cell will increase due to the increase of power output of the cell from the initial state to the new one.

  12. Phenolic mediators enhance the manganese peroxidase catalyzed oxidation of recalcitrant lignin model compounds and synthetic lignin.

    Science.gov (United States)

    Nousiainen, Paula; Kontro, Jussi; Manner, Helmiina; Hatakka, Annele; Sipilä, Jussi

    2014-11-01

    Fungal oxidative enzymes, such as peroxidases and laccases, are the key catalysts in lignin biodegradation in vivo, and consequently provide an important source for industrial ligninolytic biocatalysts. Recently, it has been shown that some syringyl-type phenolics have potential as industrial co-oxidants or mediators, in laccase-catalyzed modification of lignocellulosic material. We have now studied the effect of such mediators with ligninolytic peroxidases on oxidation of the most recalcitrant lignin model compounds. We found that they are able to enhance the manganese peroxidase (MnP) catalyzed oxidation reactions of small non-phenolic compounds, veratryl alcohol and veratrylglycerol β-guaiacyl ether (adlerol), which are not usually oxidized by manganese peroxidases alone. In these experiments we compared two peroxidases from white-rot fungi, MnP from Phlebia sp. Nf b19 and versatile peroxidase (VP) from Bjerkandera adusta under two oxidation conditions: (i) the Mn(III) initiated mediated oxidation by syringyl compounds and (ii) the system involving MnP-dependent lipid peroxidation, both with production of (hydrogen) peroxides in situ to maintain the peroxidase catalytic cycle. It was found that both peroxidases produced α-carbonyl oxidation product of veratryl alcohol in clearly higher yields in reactions mediated by phenoxy radicals than in lipid-peroxyl radical system. The oxidation of adlerol, on the other hand, was more efficient in lipid-peroxidation-system. VP was more efficient than MnP in the oxidation of veratryl alcohol and showed its lignin peroxidase type activity in the reaction conditions indicated by some cleavage of Cα-Cβ-bond of adlerol. Finally, the mediator assisted oxidation conditions were applied in the oxidation of synthetic lignin (DHP) and the structural analysis of the oxidized polymers showed clear modifications in the polymer outcome, e.g. the oxidation resulted in reduced amount of aliphatic hydroxyls indicated by (31)P NMR

  13. Oxidative Damage in the Aging Heart: an Experimental Rat Model

    Science.gov (United States)

    Marques, Gustavo Lenci; Neto, Francisco Filipak; Ribeiro, Ciro Alberto de Oliveira; Liebel, Samuel; de Fraga, Rogério; Bueno, Ronaldo da Rocha Loures

    2015-01-01

    Introduction: Several theories have been proposed to explain the cause of ‘aging’; however, the factors that affect this complex process are still poorly understood. Of these theories, the accumulation of oxidative damage over time is among the most accepted. Particularly, the heart is one of the most affected organs by oxidative stress. The current study, therefore, aimed to investigate oxidative stress markers in myocardial tissue of rats at different ages. Methods: Seventy-two rats were distributed into 6 groups of 12 animals each and maintained for 3, 6, 9, 12, 18 and 24 months. After euthanasia, the heart was removed and the levels of non-protein thiols, lipid peroxidation, and protein carbonylation, as well as superoxide dismutase and catalase activities were determined. Results: Superoxide dismutase, catalase activity and lipid peroxidation were reduced in the older groups of animals, when compared with the younger group. However, protein carbonylation showed an increase in the 12-month group followed by a decrease in the older groups. In addition, the levels of non-protein thiols were increased in the 12-month group and not detected in the older groups. Conclusion: Our data showed that oxidative stress is not associated with aging in the heart. However, an increase in non-protein thiols may be an important factor that compensates for the decrease of superoxide dismutase and catalase activity in the oldest rats, to maintain appropriate antioxidant defenses against oxidative insults. PMID:27006709

  14. In vitro model suggests oxidative stress involved in keratoconus disease

    Science.gov (United States)

    Karamichos, D.; Hutcheon, A. E. K.; Rich, C. B.; Trinkaus-Randall, V.; Asara, J. M.; Zieske, J. D.

    2014-04-01

    Keratoconus (KC) affects 1:2000 people and is a disorder where cornea thins and assumes a conical shape. Advanced KC requires surgery to maintain vision. The role of oxidative stress in KC remains unclear. We aimed to identify oxidative stress levels between human corneal keratocytes (HCKs), fibroblasts (HCFs) and keratoconus cells (HKCs). Cells were cultured in 2D and 3D systems. Vitamin C (VitC) and TGF-β3 (T3) were used for 4 weeks to stimulate self-assembled extracellular matrix (ECM). No T3 used as controls. Samples were analyzed using qRT-PCR and metabolomics. qRT-PCR data showed low levels of collagen I and V, as well as keratocan for HKCs, indicating differentiation to a myofibroblast phenotype. Collagen type III, a marker for fibrosis, was up regulated in HKCs. We robustly detected more than 150 metabolites of the targeted 250 by LC-MS/MS per condition and among those metabolites several were related to oxidative stress. Lactate levels, lactate/malate and lactate/pyruvate ratios were elevated in HKCs, while arginine and glutathione/oxidized glutathione ratio were reduced. Similar patterns found in both 2D and 3D. Our data shows that fibroblasts exhibit enhanced oxidative stress compared to keratocytes. Furthermore the HKC cells exhibit the greatest level suggesting they may have a myofibroblast phenotype.

  15. Effect of dexmedetomidine sedation on acute lung injury induced by trauma and endotoxemia "two-hit" in rats%右美托咪定镇静对创伤-内毒素“二次打击”诱发大鼠急性肺损伤的影响

    Institute of Scientific and Technical Information of China (English)

    陈功; 陈绪贵

    2014-01-01

    目的 评价右美托咪定镇静对创伤-内毒素“二次打击”诱发大鼠急性肺损伤的影响.方法 清洁级SD雄性大鼠24只,6~8周龄,体重150~ 200 g,采用随机数字表法,将其分为3组(n=8):对照组(C组)、二次打击组(T组)和右美托咪定组(D组).T组和D组采用钳夹法造成双侧股骨中段闭合骨折,骨折后即刻D组静脉输注右美托咪定2.5 μg·kg-1 ·h-1,C组和T组输注等容量生理盐水,输注8h.骨折后4h时T组和D组静脉注射脂多糖2.5 mg/kg.腹腔皮下接动态血糖监测系统感应探头,用于监测组织间液葡萄糖浓度,记录骨折后24 h内血糖浓度,计算日内平均血糖波动幅度(MAGE).于骨折后24h时采集动脉血样,进行血气分析,然后取肺组织,测定肺组织TNF-α和IL-6的含量,并进行肺损伤评分.结果 与C组比较,T组和D组MAGE、PaCO2、肺组织TNF-α和IL-6含量及肺损伤评分升高,pH值和PaO2降低(P<0.01);与T组比较,D组MAGE、肺组织TNF-α和IL-6含量及肺损伤评分降低,pH值和Pa02升高(P<0.05),PaCO2差异无统计学意义(P>0.05).结论 右美托咪定镇静可减轻创伤-内毒素“二次打击”诱发大鼠急性肺损伤,其机制与减轻应激反应及炎性反应有关.%Objective To evaluate the effect of dexmedetomidine sedation on acute lung injury induced by trauma and endotoxemia "two-hit" in rats.Methods Twenty-four adult male Sprague-Dawley rats,aged 6-8 weeks,weighing 150-200 g,were randomized into 3 groups (n =8 each) using a random number table:control group (group C),"two-hit" group (group T) and dexmedetomidine group (group D).Bilateral middle femoral shaft fractures were produced using hemostatic forceps.In group D,dexmedetomidine 2.5 tμg· kg-1· h-1 was infused via the caudal vein immediately after fractures,while the equal volume of normal saline was infused for 8 h in C and T groups.Lipopolysaccharide 2.5 mg/kg was injected via the caudal vein at 4 h after fractures in T and D

  16. Metal Oxide Nanomaterial QNAR Models: Available Structural Descriptors and Understanding of Toxicity Mechanisms

    Directory of Open Access Journals (Sweden)

    Jiali Ying

    2015-10-01

    Full Text Available Metal oxide nanomaterials are widely used in various areas; however, the divergent published toxicology data makes it difficult to determine whether there is a risk associated with exposure to metal oxide nanomaterials. The application of quantitative structure activity relationship (QSAR modeling in metal oxide nanomaterials toxicity studies can reduce the need for time-consuming and resource-intensive nanotoxicity tests. The nanostructure and inorganic composition of metal oxide nanomaterials makes this approach different from classical QSAR study; this review lists and classifies some structural descriptors, such as size, cation charge, and band gap energy, in recent metal oxide nanomaterials quantitative nanostructure activity relationship (QNAR studies and discusses the mechanism of metal oxide nanomaterials toxicity based on these descriptors and traditional nanotoxicity tests.

  17. Models for solid oxide fuel cell systems exploitation of models hierarchy for industrial design of control and diagnosis strategies

    CERN Document Server

    Marra, Dario; Polverino, Pierpaolo; Sorrentino, Marco

    2016-01-01

    This book presents methodologies for optimal design of control and diagnosis strategies for Solid Oxide Fuel Cell systems. A key feature of the methodologies presented is the exploitation of modelling tools that balance accuracy and computational burden.

  18. Arsenate and phosphate adsorption in relation to oxides composition in soils: LCD modeling.

    Science.gov (United States)

    Cui, Yanshan; Weng, Liping

    2013-07-02

    The pH dependent solid-solution distribution of arsenate and phosphate in five Dutch agricultural soil samples was measured in the pH range 4-8, and the results were interpreted using the LCD (ligand and charge distribution) adsorption modeling. The pH dependency is similar for both oxyanions, with a minimum soluble concentration observed around pH 6-8. This pH dependency can be successfully described with the LCD model and it is attributed mainly to the synergistic effects from Ca adsorption. The solubility of phosphate is much lower than that of arsenate. This big difference cannot be sufficiently explained by the reduction of small amount of As(V) into As(III), neither by slow desorption/adsorption. The difference between phosphate and arsenate in their solid-solution distribution becomes larger with the increase of aluminum (hydr)oxides (Al-oxides) contribution to the total amount of metal (Al and Fe) (hydr)oxides. The influence of Al-oxides is much larger than its relative amount extracted from the soils. When Al-oxides account for >40% of the soil oxides, the whole adsorbents behave apparently similarly to that of pure Al-oxides. These results indicated that surface coating and substitution may have modified significantly oxyanion adsorption to Fe-oxides in soils, and how to account for this complexity is a challenge for geochemical modeling.

  19. Activity Calculation by Application of Sub-Regular Solution Model in Binary Oxide Systems

    Institute of Scientific and Technical Information of China (English)

    HOU Yan-qing; XIE Gang; TAO Dong-ping; LI Rong-xing; YU Xiao-hua

    2012-01-01

    To confirm sub-regular solution model valid for predicting the activity of component in binary oxide systems, seven systems in the whole concentration and twelve systems presenting saturation concentration have been studied. The total average relative errors of component 1 and 2 are 3.2 % and 4.1% respectively by application of the sub-regular solution model into the systems within the whole concentration. However, the total average relative errors are 16 % and 1088 % in the systems presenting saturation concentration. The results show that sub-regular solu- tion model is not good for predicting the systems presenting saturation concentration, especially for the systems con- taining acidic or neutral oxide. The reason may be that the influence of the two types of oxide on the configuration is greater in binary oxide systems. These oxides can be present in the form of complex anion partly, Si-O, Al-O, Ti-O and so on, for example (SiO4)4-. That is contrary to sub-regular solution model which is supposed that the oxide systems consist of cation and O2-. But compared with regular solution model and quasi-regular solution model, sub- regular solution model is closer to the characteristics of actual solution and the calculated results are superior.

  20. Pulmonary oxidative stress, inflammation and dysregulated iron homeostatis in rat models of cardiovascular disease

    Science.gov (United States)

    Underlying cardiovascular disease (CVD) is considered a risk factor for the exacerbation of air pollution health effects. Therefore, rodent models of CVD are increasingly used to examine mechanisms ofvariation in susceptibility. Pulmonary oxidative stress, inflammation and altere...

  1. Modeling of autoignition and NO sensitization for the oxidation of IC engine surrogate fuels

    CERN Document Server

    Anderlohr, Jörg; Da Cruz, A Pires; Battin-Leclerc, Frédérique; 10.1016/j.combustflame.2008.09.009

    2009-01-01

    This paper presents an approch for modeling with one single kinetic mechanism the chemistry of the autoignition and combustion processes inside an internal combustion engine, as well as the chemical kinetics governing the post-oxidation of unburned hydrocarbons in engine exhaust gases. Therefore a new kinetic model was developed, valid over a wide range of temperatures including the negative temperature coefficient regime. The model simulates the autoignition and the oxidation of engine surrogate fuels composed of n-heptane, iso-octane and toluene, which are sensitized by the presence of nitric oxides. The new model was obtained from previously published mechanisms for the oxidation of alkanes and toluene where the coupling reactions describing interactions between hydrocarbons and NOx were added. The mechanism was validated against a wide range of experimental data obtained in jet-stirred reactors, rapid compression machines, shock tubes and homogenous charge compression ignition engines. Flow rate and sensi...

  2. Temperature Dependent Residual Stress Models for Ultra-High-Temperature Ceramics on High Temperature Oxidation

    Science.gov (United States)

    Wang, Ruzhuan; Li, Weiguo

    2016-11-01

    The strength of SiC-depleted layer of ultra-high-temperature ceramics on high temperature oxidation degrades seriously. The research for residual stresses developed within the SiC-depleted layer is important and necessary. In this work, the residual stress evolutions in the SiC-depleted layer and the unoxidized substrate in various stages of oxidation are studied by using the characterization models. The temperature and oxidation time dependent mechanical/thermal properties of each phase in SiC-depleted layer are considered in the models. The study shows that the SiC-depleted layer would suffer from large tensile stresses due to the great temperature changes and the formation of pores on high temperature oxidation. The stresses may lead to the cracking and even the delamination of the oxidation layer.

  3. A model for thermal oxidation of Si and SiC including material expansion

    Energy Technology Data Exchange (ETDEWEB)

    Christen, T., E-mail: thomas.christen@ch.abb.com; Ioannidis, A. [ABB Corporate Research, Segelhofstrasse 1K, CH-5405 Baden (Switzerland); Winkelmann, C. [ETH Zürich, Seminar for Applied Mathematics, Rämistrasse 101, CH-8092 Zürich (Switzerland)

    2015-02-28

    A model based on drift-diffusion-reaction kinetics for Si and SiC oxidation is discussed, which takes the material expansion into account with an additional convection term. The associated velocity field is determined self-consistently from the local reaction rate. The approach allows a calculation of the densities of volatile species in an nm-resolution at the oxidation front. The model is illustrated with simulation results for the growth and impurity redistribution during Si oxidation and for carbon and silicon emission during SiC oxidation. The approach can be useful for the prediction of Si and/or C interstitial distribution, which is particularly relevant for the quality of metal-oxide-semiconductor electronic devices.

  4. Temperature Dependent Residual Stress Models for Ultra-High-Temperature Ceramics on High Temperature Oxidation

    Science.gov (United States)

    Wang, Ruzhuan; Li, Weiguo

    2017-08-01

    The strength of SiC-depleted layer of ultra-high-temperature ceramics on high temperature oxidation degrades seriously. The research for residual stresses developed within the SiC-depleted layer is important and necessary. In this work, the residual stress evolutions in the SiC-depleted layer and the unoxidized substrate in various stages of oxidation are studied by using the characterization models. The temperature and oxidation time dependent mechanical/thermal properties of each phase in SiC-depleted layer are considered in the models. The study shows that the SiC-depleted layer would suffer from large tensile stresses due to the great temperature changes and the formation of pores on high temperature oxidation. The stresses may lead to the cracking and even the delamination of the oxidation layer.

  5. Efficacy of chitosan in inhibiting the oxidation of (+)-catechin in white wine model solutions.

    Science.gov (United States)

    Chinnici, Fabio; Natali, Nadia; Riponi, Claudio

    2014-10-08

    The efficacy of chitosan and sulfites in inhibiting the oxidation of (+)-catechin in aerated model white wines has been compared by monitoring the browning development and the generation of oxidized phenolic compounds. In addition, the protecting effects of these two additives toward the oxidative decay of varietal thiols were investigated. Chitosan effectively contrasted the browning onset in model solutions all along the entire duration of the experimentation. Color development was limited and comparable in both the sulfite and chitosan added samples. Thanks to its polyelectrolyte behavior, chitosan adsorbed up to 80% of the more hydrophilic oxidized phenolic species and chelated 70 and 30% of Fe and Cu added to the solutions, respectively. Thiol oxidation was significantly lowered by chitosan, suggesting that this additive could contribute to maintain the varietal character of wines coming from aromatic grapes and vinified with reduced sulfite amounts.

  6. Modelling the change in the oxidation coefficient during the aerobic ...

    African Journals Online (AJOL)

    2013-01-20

    Jan 20, 2013 ... aerobic degradation of phenol by acclimated activated sludge. Cintia C Lobo1, Nora C ... hazardous environmental pollutants. Several industries ... wastes, and in decomposing organic material, and are produced from the metabolism ... enzymatic peroxide wet oxidation, electrochemical and photo- catalytic ...

  7. Ab Initio Thermodynamic Modeling of Electrified Metal-Oxide Interfaces

    DEFF Research Database (Denmark)

    Zeng, Zhenhua; Hansen, Martin Hangaard; Greeley, Jeff

    2015-01-01

    Solid oxide fuel cells are attractive devices in a sustainable energy context because of their fuel flexibility and potentially highly efficient conversion of chemical to electrical energy. The performance of the device is to a large extent determined by the atomic structure of the electrode-elec...

  8. Metal oxide surge arrester model with active V-I characteristics; Sanka aenkei hiraiki dotokusei model

    Energy Technology Data Exchange (ETDEWEB)

    Hagiwara, T.; Funabashi, T.; Watanabe, H.; Takeuchi, N. [Meidensha Corporation, Tokyo (Japan); Ueda, T. [Chubu Electric Power Co. Inc., Nagoya (Japan)

    1996-11-20

    Generally a model of Metal Oxide Surge Arrester (MOSA) for numerical analysis uses a non-linear resistance. But actual Voltage-Current (V-I) characteristics of MOSA have hysteresis loop in time domain like i-{Phi} characteristic of a transformer and frequency dependency. The authors have investigated relation between the actual V-I hysteresis characteristics obtained by some current waveforms and static V-I characteristics. From the voltage difference between above two characteristics, an equation was derived and a new model of MOSA was developed. This model consists of a non-linear resistance representing fundamental V-I characteristic, a linear inductance and voltage source which depends on the absorbed energy. The calculated results by the proposed model are compared with measurement results by using the waveform of standard impulse current, steep front current and oscillated current. And the accuracy of the model has been confirmed to be satisfactory. The model is expected to be useful to investigate insulation coordination of power systems. 11 refs., 11 figs., 2 tabs.

  9. Mathematical Modelling to Predict Oxidative Behaviour of Conjugated Linoleic Acid in the Food Processing Industry

    Directory of Open Access Journals (Sweden)

    Aitziber Ojanguren

    2013-06-01

    Full Text Available Industrial processes that apply high temperatures in the presence of oxygen may compromise the stability of conjugated linoleic acid (CLA bioactive isomers. Statistical techniques are used in this study to model and predict, on a laboratory scale, the oxidative behaviour of oil with high CLA content, controlling the limiting factors of food processing. This modelling aims to estimate the impact of an industrial frying process (140 °C, 7 L/h air on the oxidation of CLA oil for use as frying oil instead of sunflower oil. A factorial design was constructed within a temperature (80–200 °C and air flow (7–20 L/h range. Oil stability index (Rancimat method was used as a measure of oxidation. Three-level full factorial design was used to obtain a quadratic model for CLA oil, enabling the oxidative behaviour to be predicted under predetermined process conditions (temperature and air flow. It is deduced that temperatures applied in food processes affect the oxidation of CLA to a greater extent than air flow. As a result, it is estimated that the oxidative stability of CLA oil is less resistant to industrial frying than sunflower oil. In conclusion, thanks to the mathematical model, a good choice of the appropriate industrial food process can be selected to avoid the oxidation of the bioactive isomers of CLA, ensuring its functionality in novel applications.

  10. The NASA Lightning Nitrogen Oxides Model (LNOM): Application to Air Quality Modeling

    Science.gov (United States)

    Koshak, William; Peterson, Harold; Khan, Maudood; Biazar, Arastoo; Wang, Lihua

    2011-01-01

    Recent improvements to the NASA Marshall Space Flight Center Lightning Nitrogen Oxides Model (LNOM) and its application to the Community Multiscale Air Quality (CMAQ) modeling system are discussed. The LNOM analyzes Lightning Mapping Array (LMA) and National Lightning Detection Network(TradeMark)(NLDN) data to estimate the raw (i.e., unmixed and otherwise environmentally unmodified) vertical profile of lightning NO(x) (= NO + NO2). The latest LNOM estimates of lightning channel length distributions, lightning 1-m segment altitude distributions, and the vertical profile of lightning NO(x) are presented. The primary improvement to the LNOM is the inclusion of non-return stroke lightning NOx production due to: (1) hot core stepped and dart leaders, (2) stepped leader corona sheath, K-changes, continuing currents, and M-components. The impact of including LNOM-estimates of lightning NO(x) for an August 2006 run of CMAQ is discussed.

  11. Influence of Heterogeneous OH Oxidation on the Evaporation Behavior and Composition of a Model Organic Aerosol

    Science.gov (United States)

    Kolesar, K. R.; Cappa, C. D.; Wilson, K. R.

    2011-12-01

    Heterogeneously oxidized squalane particles are used here as a model system to investigate the interplay between chemical composition and particle volatility. Reaction of squalane particles by OH radicals leads to the production of oxygenated products. Here we use the vacuum ultra-violet Aerosol Mass Spectrometer (VUV-AMS) at beamline 9.0.2 at the Advanced Light Source to monitor the evolution of specific oxidation products that result from increasing OH exposures, and how the composition changes as the oxidized particles evaporate. The soft ionization in the VUV-AMS allows us to uniquely track the parent squalane molecule and the various oxidation products over multiple generations of oxidation. Compositional changes of the oxidized particles resulting from evaporation have been measured in three sets of laboratory experiments. In the first set, a thermodenuder at varying temperatures was used to induce evaporation of particles at a fixed OH exposure. Second, the OH exposure was varied along with temperature to create a cross-sectional observation of particle composition at 50% mass fraction remaining for ten different oxidation levels. The combination of these two experiments provides information as to the compositional changes that occur during evaporation due to heating. In the third set of experiments, VUV-AMS spectra of oxidized squalane particles following dilution-induced evaporation were measured for comparison with the thermodenuder experiments. These experiments provide insights into the relationships between particle oxidation, composition and evaporation kinetics.

  12. Optimization of a new flow design for solid oxide cells using computational fluid dynamics modelling

    DEFF Research Database (Denmark)

    Duhn, Jakob Dragsbæk; Jensen, Anker Degn; Wedel, Stig;

    2016-01-01

    Design of a gas distributor to distribute gas flow into parallel channels for Solid Oxide Cells (SOC) is optimized, with respect to flow distribution, using Computational Fluid Dynamics (CFD) modelling. The CFD model is based on a 3d geometric model and the optimized structural parameters include...

  13. Generalized molybdenum oxide surface chemical state XPS determination via informed amorphous sample model

    Energy Technology Data Exchange (ETDEWEB)

    Baltrusaitis, Jonas, E-mail: job314@lehigh.edu [Department of Chemical Engineering, Lehigh University, B336 Iacocca Hall, 111 Research Drive, Bethlehem, PA 18015 (United States); PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Mendoza-Sanchez, Beatriz [CRANN, Chemistry School, Trinity College Dublin, Dublin (Ireland); Fernandez, Vincent [Institut des Matériaux Jean Rouxel, 2 rue de la Houssinière, BP 32229, F-44322 Nantes Cedex 3 (France); Veenstra, Rick [PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Dukstiene, Nijole [Department of Physical and Inorganic Chemistry, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas (Lithuania); Roberts, Adam [Kratos Analytical Ltd, Trafford Wharf Road, Wharfside, Manchester, M17 1GP (United Kingdom); Fairley, Neal [Casa Software Ltd, Bay House, 5 Grosvenor Terrace, Teignmouth, Devon TQ14 8NE (United Kingdom)

    2015-01-30

    Highlights: • We analyzed and modeled spectral envelopes of complex molybdenum oxides. • Molybdenum oxide films of varying valence and crystallinity were synthesized. • MoO{sub 3} and MoO{sub 2} line shapes from experimental data were created. • Informed amorphous sample model (IASM) developed. • Amorphous molybdenum oxide XPS envelopes were interpreted. - Abstract: Accurate elemental oxidation state determination for the outer surface of a complex material is of crucial importance in many science and engineering disciplines, including chemistry, fundamental and applied surface science, catalysis, semiconductors and many others. X-ray photoelectron spectroscopy (XPS) is the primary tool used for this purpose. The spectral data obtained, however, is often very complex and can be subject to incorrect interpretation. Unlike traditional XPS spectra fitting procedures using purely synthetic spectral components, here we develop and present an XPS data processing method based on vector analysis that allows creating XPS spectral components by incorporating key information, obtained experimentally. XPS spectral data, obtained from series of molybdenum oxide samples with varying oxidation states and degree of crystallinity, were processed using this method and the corresponding oxidation states present, as well as their relative distribution was elucidated. It was shown that monitoring the evolution of the chemistry and crystal structure of a molybdenum oxide sample due to an invasive X-ray probe could be used to infer solutions to complex spectral envelopes.

  14. Increased pulmonary arteriolar tone associated with lung oxidative stress and nitric oxide in a mouse model of Alzheimer's disease.

    Science.gov (United States)

    Roberts, Andrew M; Jagadapillai, Rekha; Vaishnav, Radhika A; Friedland, Robert P; Drinovac, Robert; Lin, Xingyu; Gozal, Evelyne

    2016-09-01

    Vascular dysfunction and decreased cerebral blood flow are linked to Alzheimer's disease (AD). Loss of endothelial nitric oxide (NO) and oxidative stress in human cerebrovascular endothelium increase expression of amyloid precursor protein (APP) and enhance production of the Aβ peptide, suggesting that loss of endothelial NO contributes to AD pathology. We hypothesize that decreased systemic NO bioavailability in AD may also impact lung microcirculation and induce pulmonary endothelial dysfunction. The acute effect of NO synthase (NOS) inhibition on pulmonary arteriolar tone was assessed in a transgenic mouse model (TgAD) of AD (C57BL/6-Tg(Thy1-APPSwDutIowa)BWevn/Mmjax) and age-matched wild-type controls (C57BL/6J). Arteriolar diameters were measured before and after the administration of the NOS inhibitor, L-NAME Lung superoxide formation (DHE) and formation of nitrotyrosine (3-NT) were assessed as indicators of oxidative stress, inducible NOS (iNOS) and tumor necrosis factor alpha (TNF-α) expression as indicators of inflammation. Administration of L-NAME caused either significant pulmonary arteriolar constriction or no change from baseline tone in wild-type (WT) mice, and significant arteriolar dilation in TgAD mice. DHE, 3-NT, TNF-α, and iNOS expression were higher in TgAD lung tissue, compared to WT mice. These data suggest L-NAME could induce increased pulmonary arteriolar tone in WT mice from loss of bioavailable NO In contrast, NOS inhibition with L-NAME had a vasodilator effect in TgAD mice, potentially caused by decreased reactive nitrogen species formation, while significant oxidative stress and inflammation were present. We conclude that AD may increase pulmonary microvascular tone as a result of loss of bioavailable NO and increased oxidative stress. Our findings suggest that AD may have systemic microvascular implications beyond central neural control mechanisms.

  15. Molecular modeling studies of oleate adsorption on iron oxides

    Energy Technology Data Exchange (ETDEWEB)

    Rath, Swagat S. [CSIR-Institute of Minerals and Materials Technology, Bhubaneswar (India); Sinha, Nishant [Accelrys K.K, Bengaluru (India); Sahoo, Hrushikesh [CSIR-Institute of Minerals and Materials Technology, Bhubaneswar (India); Das, Bisweswar, E-mail: bdas@immt.res.in [CSIR-Institute of Minerals and Materials Technology, Bhubaneswar (India); Mishra, Barada Kanta [CSIR-Institute of Minerals and Materials Technology, Bhubaneswar (India)

    2014-03-01

    Graphical abstract: - Highlights: • Plane wave periodic DFT study of oleate-iron oxide interaction. • Magnetite-oleate complex is more stable than hematite and goethite. • Flotation recovery of magnetite is more compared to the other two oxides. - Abstract: Comparative studies of oleate interaction with hematite, magnetite and goethite using density functional calculations are presented. The approach is illustrated by carrying out geometric optimization of oleate on the stable and most exposed planes of hematite, magnetite, and goethite. Interaction energies for oleate-mineral surface have been determined, based on which, magnetite is found to be forming the most stable complex with oleate. Trend as obtained from the quantum chemical calculations has been validated by contact angle measurements and flotation studies on hematite, magnetite and goethite with sodium oleate at different pH and collector concentrations.

  16. Nitric oxide synthase and nitric oxide alterations in chronically stressed rats: a model for nitric oxide in major depressive disorder.

    Science.gov (United States)

    Gao, Shang-Feng; Lu, Yun-Rong; Shi, Li-Gen; Wu, Xue-Yan; Sun, Bo; Fu, Xin-Yan; Luo, Jian-Hong; Bao, Ai-Min

    2014-09-01

    Nitric oxide (NO) and NO synthase-1 (NOS1) are involved in the stress response and in depression. We compared NOS-NO alterations in rats exposed to chronic unpredictable stress (CUS) with alterations in major depressive disorder (MDD) in humans. In the hypothalamus of male CUS rats we determined NOS activity, and in the paraventricular nucleus (PVN) we determined NOS1-immunoreactive (ir) cell densities and co-localization of NOS1 with stress-related neuropeptides corticotropin-releasing hormone (CRH), vasopressin (AVP) or oxytocin (OXT). We measured plasma NO levels and cortisol in male medicine-naïve MDD patients and plasma NO and corticosterone (CORT) in CUS rats. In the CUS rat total NOS activity in the hypothalamus (P=0.018) and NOS1-ir cell density in the PVN were both significantly decreased (P=0.018), while NOS1 staining was mainly expressed in OXT-ir neurons in this nucleus. Interestingly, plasma NO levels were significantly increased both in male CUS rats (P=0.001) and in male MDD patients (Pdepression.

  17. Kinetic Modeling of C3H6 Inhibition on NO Oxidation over Pt Catalyst

    Directory of Open Access Journals (Sweden)

    Muhammad Mufti Azis

    2016-03-01

    Full Text Available Exhaust after treatment for lean burn and diesel engine is a complex catalytic system that consists of a number of catalytic units. Pt/Al2O3 is often used as a model Diesel Oxidation Catalyst (DOC that plays an important role to facilitate oxidation of NO to NO2. In the present study, we proposed a detailed kinetic model of NO oxidation as well as low temperature C3H6 inhibition to simulate temperature-programmed reaction (TPR data for NO oxidation over Pt/Al2O3. A steady-state microkinetic model based on Langmuir-Hinshelwood mechanism for NO oxidation was proposed. In addition, low temperature C3H6 inhibition was proposed as a result of site blocking as well as surface nitrite consumption. The model can explain the experimental data well over the studied temperature range. Copyright © 2016 BCREC GROUP. All rights reserved Received: 10th November 2015; Revised: 1st February 2016; Accepted: 1st February 2016 How to Cite: Azis, M.M., Creaser, D. (2016. Kinetic Modeling of C3H6 Inhibition on NO Oxidation over Pt Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 27-33. (doi:10.9767/bcrec.11.1.403.27-33 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.403.27-33

  18. Detailed Multi-dimensional Modeling of Direct Internal Reforming Solid Oxide Fuel Cells.

    Science.gov (United States)

    Tseronis, K; Fragkopoulos, I S; Bonis, I; Theodoropoulos, C

    2016-06-01

    Fuel flexibility is a significant advantage of solid oxide fuel cells (SOFCs) and can be attributed to their high operating temperature. Here we consider a direct internal reforming solid oxide fuel cell setup in which a separate fuel reformer is not required. We construct a multidimensional, detailed model of a planar solid oxide fuel cell, where mass transport in the fuel channel is modeled using the Stefan-Maxwell model, whereas the mass transport within the porous electrodes is simulated using the Dusty-Gas model. The resulting highly nonlinear model is built into COMSOL Multiphysics, a commercial computational fluid dynamics software, and is validated against experimental data from the literature. A number of parametric studies is performed to obtain insights on the direct internal reforming solid oxide fuel cell system behavior and efficiency, to aid the design procedure. It is shown that internal reforming results in temperature drop close to the inlet and that the direct internal reforming solid oxide fuel cell performance can be enhanced by increasing the operating temperature. It is also observed that decreases in the inlet temperature result in smoother temperature profiles and in the formation of reduced thermal gradients. Furthermore, the direct internal reforming solid oxide fuel cell performance was found to be affected by the thickness of the electrochemically-active anode catalyst layer, although not always substantially, due to the counter-balancing behavior of the activation and ohmic overpotentials.

  19. Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

    Directory of Open Access Journals (Sweden)

    J. Lee-Taylor

    2012-06-01

    Full Text Available The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere. Gas phase oxidation schemes are generated for the C8–C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA formation for various preexisting organic aerosol concentration (COA. As expected, simulation results show that (i SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii SOA yield decreases with decreasing COA, (iii SOA production rates increase with increasing COA and (iv the number of oxidation steps (i.e. generations needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA, suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA with large yields. The limitations of the model are discussed.

  20. Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

    Directory of Open Access Journals (Sweden)

    J. Lee-Taylor

    2012-08-01

    Full Text Available The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere. Gas phase oxidation schemes are generated for the C8–C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA formation for various preexisting organic aerosol concentration (COA. As expected, simulation results show that (i SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii SOA yield decreases with decreasing COA, (iii SOA production rates increase with increasing COA and (iv the number of oxidation steps (i.e. generations needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA, suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA with large yields. The limitations of the model are discussed.

  1. Modelling of composition and phase changes in multiphase alloys due to growth of an oxide layer

    Energy Technology Data Exchange (ETDEWEB)

    Nijdam, T.J. [Materials Innovation Institute (M2i) and Department of Materials Science and Engineering, Delft University of Technology, Mekelweg 2, 2628 CD Delft (Netherlands); Sloof, W.G. [Materials Innovation Institute (M2i) and Department of Materials Science and Engineering, Delft University of Technology, Mekelweg 2, 2628 CD Delft (Netherlands)], E-mail: w.g.sloof@tudelft.nl

    2008-10-15

    A coupled thermodynamic-kinetic oxidation model is presented for the selective, external oxidation of the most reactive alloy constituent of a multicomponent multiphase alloy. The model computes the composition depth profiles of the alloy constituents in the alloy as well as the evolution in the phase fractions in the alloy as function of oxidation time. The applicability of the model is illustrated through several examples. For the isothermal and cyclic oxidation of single- and two-phase binary alloys excellent agreement was obtained between the numerical calculations and the corresponding analytical solutions. For the isothermal oxidation of two {gamma}+{beta} NiCrAl alloys with different initial volume fractions of the {beta} phase, very good agreement was obtained between experimentally and calculated composition depth profiles. Finally, the effect of alloying additions on the phase evolution in the alloy was studied for the isothermal oxidation of freestanding MCrAlY (M = Ni, Co) coatings. It is shown that for a similar bulk Al and Cr content in the coating, the concentration profiles of Al in the coating after oxidation can be significantly affected by alloying with elements like Co, Ta and Re. Consequently, the multicomponent and multiphase character of the MCrAlY coating has to be taken into account when performing lifetime studies.

  2. Modeling of evaporation and oxidation phenomena in plasma spraying of metal powders

    Science.gov (United States)

    Zhang, Hanwei

    Plasma spraying of metals in air is usually accompanied by evaporation and oxidation of the sprayed material. Optimization of the spraying process must ensure that the particles are fully molten during their short residence time in the plasma jet and prior to hitting the substrate, but not overheated to minimize evaporation losses. In atmospheric plasma spraying (ASP), it is also clearly desirable to be able to control the extent of oxide formation. The objective of this work to develop an overall mathematical model of the oxidization and volatilization phenomena involved in the plasma-spraying of metallic particles in air atmosphere. Four models were developed to simulate the following aspects of the atmospheric plasma spraying (APS) process: (a) the particle trajectories and the velocity and temperature profiles in an Ar-H 2 plasma jet, (b) the heat and mass transfer between particles and plasma jet, (c) the interaction between the evaporation and oxidation phenomena, and (d) the oxidation of liquid metal droplets. The resulting overall model was generated by adapting the computational fluid dynamics code FIDAP and was validated by experimental measurements carried out at the collaborating plasma laboratory of the University of Limoges. The thesis also examined the environmental implications of the oxidization and volatilization phenomena in the plasma spraying of metals. The modeling results showed that the combination of the standard k-s model of turbulence and the Boussinesq eddy-viscosity model provided a more accurate prediction of plasma gas behavior. The estimated NOx generation levels from APS were lower than the U.S.E.P.A. emission standard. Either enhanced evaporation or oxidation can occur on the surface of the metal particles and the relative extent is determined by the process parameters. Comparatively, the particle size has the greatest impact on both evaporation and oxidation. The extent of particle oxidation depends principally on gas

  3. Egg white hydrolysate inhibits oxidation in mayonnaise and a model system.

    Science.gov (United States)

    Kobayashi, Hideaki; Sasahara, Ryou; Yoda, Shoichi; Kotake-Nara, Eiichi

    2017-06-01

    The flavor deterioration of mayonnaise is induced by iron, which is released from egg yolk phosvitin under acidic conditions and promotes lipid oxidation. To prevent oxidative deterioration, natural components, rather than synthetic chemicals such as ethylenediaminetetraacetic acid have been required by consumers. In the present study, we evaluated the inhibitory effects of three egg white components with the same amino acid composition, namely egg white protein, hydrolysate, and the amino acid mixture, on lipid oxidation in mayonnaise and an acidic egg yolk solution as a model system. We found that the hydrolysate had the strongest inhibitory effect on lipid oxidation among the three components. The mechanism underlying the antioxidant effect was associated with Fe(2+)-chelating activity. Thus, egg white hydrolysate may have the potential as natural inhibitors of lipid oxidation in mayonnaise.

  4. Development of 3D Oxide Fuel Mechanics Models

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, B. W. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Casagranda, A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Pitts, S. A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Jiang, W. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2017-07-27

    This report documents recent work to improve the accuracy and robustness of the mechanical constitutive models used in the BISON fuel performance code. These developments include migration of the fuel mechanics models to be based on the MOOSE Tensor Mechanics module, improving the robustness of the smeared cracking model, implementing a capability to limit the time step size based on material model response, and improving the robustness of the return mapping iterations used in creep and plasticity models.

  5. Fatty acid oxidation changes and the correlation with oxidative stress in different preeclampsia-like mouse models.

    Directory of Open Access Journals (Sweden)

    Xiaoyan Ding

    Full Text Available BACKGROUND: Long-chain 3-hydroxyacyl-CoA dehydrogenase (LCHAD expression is decreased in placenta of some cases of preeclampsia (PE which may result in free fatty acid (FFA increased. High FFA level will induce oxidative stress, so abnormal long-chain fatty acid-oxidation may participate in the pathogenesis of PE through oxidative stress pathway. METHODS: PE-like groups were ApoC3 transgenic mice with abnormal fatty acid metabolism, classical PE-like models with injection of Nw-nitro-L-arginine-methyl ester (L-NA or lipopolysaccharide (LPS and the antiphospholipid syndrome (APS mouse model with β2GPI injection (ApoC3+NS, ApoC3+L-NA, L-NA, LPS and β2GPI groups. The control group was wild-type mice with normal saline injection. Except for β2GPI mice, the other mice were subdivided into pre-implantation (Pre and mid-pregnancy (Mid subgroups by injection time. RESULTS: All PE-like groups showed hypertension and proteinuria except ApoC3+NS mice only showed hypertension. Serum FFA levels increased significantly except in LPS group compared to controls (P<0.05. LCHAD mRNA and protein expression in the liver and placenta was significantly higher for ApoC3+NS, ApoC3+L-NA and β2GPI mice and lower for L-NA mice than controls (P<0.05 but did not differ between LPS mice and controls. P47phox mRNA and protein expression in the liver significantly increased in all PE-like groups except LPS group, while P47phox expression in the placenta only significantly increased in L-NA and β2GPI groups. CONCLUSIONS: Abnormal long-chain fatty acid-oxidation may play a different role in different PE-like models and in some cases participate in the pathogenesis of PE through oxidative stress pathway.

  6. Optical modeling of nickel-base alloys oxidized in pressurized water reactor

    Energy Technology Data Exchange (ETDEWEB)

    Clair, A. [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS, Universite de Bourgogne, 9 avenue Alain Savary, BP 47870, 21078 Dijon cedex (France); Foucault, M.; Calonne, O. [Areva ANP, Centre Technique Departement Corrosion-Chimie, 30 Bd de l' industrie, BP 181, 71205 Le Creusot (France); Finot, E., E-mail: Eric.Finot@u-bourgogne.fr [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS, Universite de Bourgogne, 9 avenue Alain Savary, BP 47870, 21078 Dijon cedex (France)

    2012-10-01

    The knowledge of the aging process involved in the primary water of pressurized water reactor entails investigating a mixed growth mechanism in the corrosion of nickel-base alloys. A mixed growth induces an anionic inner oxide and a cationic diffusion parallel to a dissolution-precipitation process forms the outer zone. The in situ monitoring of the oxidation kinetics requires the modeling of the oxide layer stratification with the full knowledge of the optical constants related to each component. Here, we report the dielectric constants of the alloys 600 and 690 measured by spectroscopic ellipsometry and fitted to a Drude-Lorentz model. A robust optical stratification model was determined using focused ion beam cross-section of thin foils examined by transmission electron microscopy. Dielectric constants of the inner oxide layer depleted in chromium were assimilated to those of the nickel thin film. The optical constants of both the spinels and extern layer were determined. - Highlights: Black-Right-Pointing-Pointer Spectroscopic ellipsometry of Ni-base alloy oxidation in pressurized water reactor Black-Right-Pointing-Pointer Measurements of the dielectric constants of the alloys Black-Right-Pointing-Pointer Optical simulation of the mixed oxidation process using a three stack model Black-Right-Pointing-Pointer Scattered crystallites cationic outer layer; linear Ni-gradient bottom layer Black-Right-Pointing-Pointer Determination of the refractive index of the spinel and the Cr{sub 2}O{sub 3} layers.

  7. Analytical model of LDMOS with a single step buried oxide layer

    Science.gov (United States)

    Yuan, Song; Duan, Baoxing; Cao, Zhen; Guo, Haijun; Yang, Yintang

    2016-09-01

    In this paper, a two-dimensional analytical model is established for the Single-Step Buried Oxide SOI structure proposed by the authors. Based on the two-dimensional Poisson equation, the analytic expression of the surface electric field and potential distributions for the device is achieved. In the SBOSOI (Single-Step Buried Oxide Silicon On Insulator) structure, the buried oxide layer thickness changes stepwise along the drift region, and the electric field in the oxide layer also varies with the different buried oxide layer thickness. These variations will modulate the surface electric field distribution through the electric field modulation effects, which makes the surface electric field distribution more uniform. As a result, the breakdown voltage of the device is improved by 60% compared with the conventional SOI structure. To verify the accuracy of the analytical model, the device simulation software ISE TCAD is utilized, the analytical values are in good agreement with the simulation results by the simulation software. The results verified the established two-dimensional analytical model for SBOSOI structure is valid, and it also illustrates the breakdown voltage enhancement by the electric field modulation effect sufficiently. The established analytical models will provide the physical and mathematical basis for further analysis of the new power devices with the patterned buried oxide layer.

  8. SO2 oxidation catalyst model systems characterized by thermal methods

    DEFF Research Database (Denmark)

    Hatem, G; Eriksen, Kim Michael; Gaune-Escard, M;

    2002-01-01

    The molten salts M2S2O7 and MHSO4, the binary molten salt Systems M2S2O7-MHSO4 and the molten salt-gas systems M2S2O7 V2O5 and M2S2O7-M2SO4 V2O5 (M = Na, K, Rb, Cs) in O-2, SO2 and At atmospheres have been investigated by thermal methods like calorimetry, Differential Enthalpic Analysis (DEA) and...... to the mechanism Of SO2 oxidation by V2O5 based industrial catalysts....

  9. Modeling Oxidation Kinetics of SiC-Containing Refractory Diborides

    Science.gov (United States)

    2012-01-01

    K. E. Spear, R. E. Tressler, and C. F. Ram- berg, “Passive-Oxidation Kinetics of High - Purity Silicon Carbide from 800 to 1100 C,” J. Am. Ceram. Soc...investigations47–53 in pure oxygen; there is a large scatter in the data. Figure 2 includes data collected on high purity SiC by Ramberg et al.,47 and...mechanism. Data reported for pure SiC in air/oxygen, for ZrB2 containing varying volume fractions of SiC , and for SiC –HfB2 ultra- high temperature

  10. Effect of metal chelators on the oxidative stability of model wine.

    Science.gov (United States)

    Kreitman, Gal Y; Cantu, Annegret; Waterhouse, Andrew L; Elias, Ryan J

    2013-10-02

    Oxidation is a major problem with respect to wine quality, and winemakers have few tools at their disposal to control it. In this study, the effect of exogenous Fe(II) (bipyridine; Ferrozine) and Fe(III) chelators (ethylenediaminetetraacetic acid, EDTA; phytic acid) on nonenzymatic wine oxidation was examined. The ability of these chelators to affect the formation of 1-hydroxyethyl radicals (1-HER) and acetaldehyde was measured using a spin trapping technique with electron paramagnetic resonance (EPR) and by HPLC-PDA, respectively. The chelators were then investigated for their ability to prevent the oxidative loss of an important aroma-active thiol, 3-mercaptohexan-1-ol (3MH). The Fe(II)-specific chelators were more effective than the Fe(III) chelators with respect to 1-HER inhibition during the early stages of oxidation and significantly reduced oxidation markers compared to a control during the study. However, although the addition of Fe(III) chelators was less effective or even showed an initial pro-oxidant activity, the Fe(III) chelators proved to be more effective antioxidants compared to Fe(II) chelators after 8 days of accelerated oxidation. In addition, it is shown for the first time that Fe(II) and Fe(III) chelators can significantly inhibit the oxidative loss of 3MH in model wine.

  11. Modeling Nitrous Oxide Production during Biological Nitrogen Removal via Nitrification and Denitrification: Extensions to the General ASM Models

    DEFF Research Database (Denmark)

    Ni, Bing-Jie; Ruscalleda, Maël; Pellicer i Nàcher, Carles

    2011-01-01

    Nitrous oxide (N2O) can be formed during biological nitrogen (N) removal processes. In this work, a mathematical model is developed that describes N2O production and consumption during activated sludge nitrification and denitrification. The well-known ASM process models are extended to capture N2O...... dynamics during both nitrification and denitrification in biological N removal. Six additional processes and three additional reactants, all involved in known biochemical reactions, have been added. The validity and applicability of the model is demonstrated by comparing simulations with experimental data...... on N2O production from four different mixed culture nitrification and denitrification reactor study reports. Modeling results confirm that hydroxylamine oxidation by ammonium oxidizers (AOB) occurs 10 times slower when NO2– participates as final electron acceptor compared to the oxic pathway. Among...

  12. Configurational Model for Conductivity of Stabilized Fluorite Structure Oxides

    DEFF Research Database (Denmark)

    Poulsen, Finn Willy

    1981-01-01

    The formalism developed here furnishes means by which ionic configurations, solid solution limits, and conductivity mechanisms in doped fluorite structures can be described. The present model differs markedly from previous models but reproduces qualitatively reality. The analysis reported...

  13. Oxidation kinetics of model compounds of metabolic waste in supercritical water

    Science.gov (United States)

    Webley, Paul A.; Holgate, Henry R.; Stevenson, David M.; Tester, Jefferson W.

    1990-01-01

    In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

  14. Submicro-battery effect and selective bio-oxidation model of gold-bearing arsenopyrite by Thiobacillus ferrooxidans

    Institute of Scientific and Technical Information of China (English)

    杨洪英; 杨立; 赵玉山; 陈刚; 吕久吉; 范有静

    2002-01-01

    Through the study by electronic probe it was found that many new cracks and holes appear on the surface of gold-bearing arsenopyrite crystal oxidized by Thiobacillus ferrooxidans, which are along with some directions. Then the selective bio-oxidation model of gold-bearing arsenopyrite was set up. The selective bio-oxidation resulting from the submicro-battery effect of gold/ arsenopyrite mineral pairs naturally forms in the gold-bearing arsenopyrite crystal. Thiobacillus ferrooxidans has priority to oxidize the place of gold-rich and oxidizes selectedly along with the crystal border, crystal face and crack. The bacteria oxidation process of gold-bearing arsenopyrite is divided into three stages: the first stage is the surface oxidation, the second stage is restraining oxidation and the third stage is the filament oxidation, bacteria oxidize along with cracks of arsenopyrite.

  15. Oxidative Stress Associated with Neuronal Apoptosis in Experimental Models of Epilepsy

    Directory of Open Access Journals (Sweden)

    Marisela Méndez-Armenta

    2014-01-01

    Full Text Available Epilepsy is considered one of the most common neurological disorders worldwide. Oxidative stress produced by free radicals may play a role in the initiation and progression of epilepsy; the changes in the mitochondrial and the oxidative stress state can lead mechanism associated with neuronal death pathway. Bioenergetics state failure and impaired mitochondrial function include excessive free radical production with impaired synthesis of antioxidants. This review summarizes evidence that suggest what is the role of oxidative stress on induction of apoptosis in experimental models of epilepsy.

  16. THERMODYNAMIC MODELING OF THE SURFACE LAYER STRUCTURE ON INCONEL 600 OXIDIZED IN A CONTROLLED ATMOSPHERE

    Directory of Open Access Journals (Sweden)

    Abdallah Haouam

    2012-03-01

    Full Text Available Samples of Inconel 600 were isothermally oxidized in a controlled atmosphere with a special mounting at high-temperature oxidation. Along with this experimental study, a simulation of thermodynamic behavior of the material in the same oxidation conditions was carried out using the Thermo-Calc code. The thermodynamic modeling is able to predict the phase nature and its distribution in the structure of the surface layer resulting from the corrosion of the material in thermodynamic equilibrium in the absence of mechanical stress. The results of this simulation are supplemented to results obtained from the analysis by glow discharge spectrometry (GDS which is performed on the samples tested.

  17. Oxidatively Robust Monophenolate-Copper(II) Complexes as Potential Models of Galactose Oxidation

    NARCIS (Netherlands)

    Koten, G. van; Klein Gebbink, R.J.M.; Watanabe, M.; Pratt, R.C.; Stack, D.P.

    2003-01-01

    Cupric complexes of a novel phenanthroline-phenolate ligand have strongly distorted coordination geometries and electrochemical properties conducive to modeling the spectroscopy and reactivity of the enzyme galactose oxidase.

  18. Kinetic Model of Hypophosphite Oxidation on a Nickel Electrode in D2O Solution

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Kinetic model of hypophosphite oxidation on a nickel electrode was studied in D2Osolution in order to reach a better understanding of the oxidation mechanism. In the model the electrooxidation of hypophosphite undergo a H abstraction of hypophosphite from the P-H bond to form the phosphorus-centered radical PHO2-, which subsequently is electrochemically reacted with water to form the final product, phosphite. The kinetic equations were derived, and the kinetic parameters were obtained from a comparison of experimental results and the kinetic equations. The process of hypophosphite electrooxidation could be well simulated by this model

  19. A simple model to estimate the optimal doping of p - Type oxide superconductors

    Directory of Open Access Journals (Sweden)

    Adir Moysés Luiz

    2008-12-01

    Full Text Available Oxygen doping of superconductors is discussed. Doping high-Tc superconductors with oxygen seems to be more efficient than other doping procedures. Using the assumption of double valence fluctuations, we present a simple model to estimate the optimal doping of p-type oxide superconductors. The experimental values of oxygen content for optimal doping of the most important p-type oxide superconductors can be accounted for adequately using this simple model. We expect that our simple model will encourage further experimental and theoretical researches in superconducting materials.

  20. Modelling of Physical, Chemical, and Material Properties of Solid Oxide Fuel Cells

    Directory of Open Access Journals (Sweden)

    Jakub Kupecki

    2015-01-01

    Full Text Available This paper provides a review of modelling techniques applicable for system-level studies to account for physical, chemical, and material properties of solid oxide fuel cells. Functionality of 0D to 3D models is discussed and selected examples are given. Author provides information on typical length scales in evaluation of power systems with solid oxide fuel cells. In each section, proper examples of previous studies done in the field of 0D–3D modelling are recalled and discussed.

  1. Modeling of methane oxidation in landfill cover soil using an artificial neural network.

    Science.gov (United States)

    Abushammala, Mohammed F M; Basri, Noor Ezlin Ahmad; Elfithri, Rahmah; Younes, Mohammad K; Irwan, Dani

    2014-02-01

    Knowing the fraction of methane (CH4) oxidized in landfill cover soils is an important step in estimating the total CH4 emissions from any landfill. Predicting CH4 oxidation in landfill cover soils is a difficult task because it is controlled by a number of biological and environmental factors. This study proposes an artificial neural network (ANN) approach using feedforward backpropagation to predict CH4 oxidation in landfill cover soil in relation to air temperature, soil moisture content, oxygen (O2) concentration at a depth of 10 cm in cover soil, and CH4 concentration at the bottom of cover soil. The optimum ANN model giving the lowest mean square error (MSE) was configured from three layers, with 12 and 9 neurons at the first and the second hidden layers, respectively, log-sigmoid (logsig) transfer function at the hidden and output layers, and the Levenberg-Marquardt training algorithm. This study revealed that the ANN oxidation model can predict CH4 oxidation with a MSE of 0.0082, a coefficient of determination (R2) between the measured and predicted outputs of up to 0.937, and a model efficiency (E) of 0.8978. To conclude, further developments of the proposed ANN model are required to generalize and apply the model to other landfills with different cover soil properties.

  2. Chemometrics models for assessment of oxidative stress risk in chrome-electroplating workers.

    Science.gov (United States)

    Zendehdel, Rezvan; Shetab-Boushehri, Seyed Vahid; Azari, Mansoor R; Hosseini, Vajihe; Mohammadi, Hamidreza

    2015-04-01

    Oxidative stress is the main cause of hexavalant chromium-induced damage in chrome electroplating workers. The main goal of this study is toxicity analysis and the possibility of toxicity risk categorizing in the chrome electroplating workers based on oxidative stress parameters as prognostic variables. We assessed blood chromium levels and biomarkers of oxidative stress such as lipid peroxidation, thiol (SH) groups and antioxidant capacity of plasma. Data were subjected to principle component analysis (PCA) and artificial neuronal network (ANN) to obtain oxidative stress pattern for chrome electroplating workers. Blood chromium levels increased from 4.42 ppb to 10.6 ppb. Induction of oxidative stress was observed by increased in lipid peroxidation (22.38 ± 10.47 μM versus 14.74 ± 4.82 μM, p < 0.0008), decreased plasma antioxidant capacity (3.17 ± 1.35 μM versus 7.74 ± 4.45 μM, p < 0.0001) and plasma total thiol (SH groups) (0.21 ± 0.07 μM versus 0.45 ± 0.41 μM, p < 0.0042) in comparison to controls. Based on the oxidative parameters, two groups were identified by PCA methods. One category is workers with the risk of oxidative stress and second group is subjects with probable risk of oxidative stress induction. ANN methods can predict oxidative-risk category for assessment of toxicity induction in chrome electroplaters. The result showed multivariate modeling can be interpreted as the induced biochemical toxicity in the workers exposed to hexavalent chromium. Different occupation groups were assessed on the basis of risk level of oxidative stress which could further justify proceeding engineering control measures.

  3. Validation of membrane protein topology models by oxidative labeling and mass spectrometry.

    Science.gov (United States)

    Pan, Yan; Ruan, Xiang; Valvano, Miguel A; Konermann, Lars

    2012-05-01

    Computer-assisted topology predictions are widely used to build low-resolution structural models of integral membrane proteins (IMPs). Experimental validation of these models by traditional methods is labor intensive and requires modifications that might alter the IMP native conformation. This work employs oxidative labeling coupled with mass spectrometry (MS) as a validation tool for computer-generated topology models. ·OH exposure introduces oxidative modifications in solvent-accessible regions, whereas buried segments (e.g., transmembrane helices) are non-oxidizable. The Escherichia coli protein WaaL (O-antigen ligase) is predicted to have 12 transmembrane helices and a large extramembrane domain (Pérez et al., Mol. Microbiol. 2008, 70, 1424). Tryptic digestion and LC-MS/MS were used to map the oxidative labeling behavior of WaaL. Met and Cys exhibit high intrinsic reactivities with ·OH, making them sensitive probes for solvent accessibility assays. Overall, the oxidation pattern of these residues is consistent with the originally proposed WaaL topology. One residue (M151), however, undergoes partial oxidation despite being predicted to reside within a transmembrane helix. Using an improved computer algorithm, a slightly modified topology model was generated that places M151 closer to the membrane interface. On the basis of the labeling data, it is concluded that the refined model more accurately reflects the actual topology of WaaL. We propose that the combination of oxidative labeling and MS represents a useful strategy for assessing the accuracy of IMP topology predictions, supplementing data obtained in traditional biochemical assays. In the future, it might be possible to incorporate oxidative labeling data directly as constraints in topology prediction algorithms.

  4. Effect of glutathione on brain nitric oxide levels in an experimental epilepsy mouse model

    Institute of Scientific and Technical Information of China (English)

    Aylin Akcali; Sadrettin Pence; Naciye Kurtul; Mehmet Bosnak; Munife Neyal

    2009-01-01

    BACKGROUND: Oxidative stress plays an important role in the pathophysiology of epilepsy. Glutathione, known as one of the compounds of antioxidant defense, has been shown to inhibit convulsions. Nitric oxide has a proconvulsant effect on a pentylenetetrazole-induced animal model. OBJECTIVE: To evaluate the effects of glutathione administration on nitric oxide levels in brain regions of convulsive and kindling pentylenetetrazole-induced seizure models. DESIGN, TIME, AND SETTING: A randomized, controlled, animal experiment. The study was performed at the Department of Physiology, Gaziantep University and Department of Chemistry-Biochemistry, Kahramamaras Sutcu Imam University in 2006.MATERIALS: Pentylenetetrazole and glutathione were purchased from Sigma, USA. METHODS: A total of 80 mice were assigned to 8 groups (n=10): normal control, saline control (1 mL normal saline), convulsive pentylenetetrazole (single intraperitoneal administration of pentylenetetrazole, 60 mg/kg), convulsive pentylenetrazole plus glutathione (single administration of 60 mg/kg pentylenetetrazole and 200 mg/kg glutathione), five-dose glutathione (intraperitoneal injection of 200 mg/kg glutathione respectively at 1, 3, 5, 7, and 10 days), single-dose glutathione (single administration of 200 mg/kg glutathione), pentylenetetrazole kindling (intraperitoneal administration of pentylenetetrazole of 40 mg/kg at 1, 3, 5, 7, and 10 days), and pentylenetetrazole kindling plus glutathione group (intraperitoneal injection of 40 mg/kg pentylenetetrazole and 200 mg/kg glutathione respectively at 1, 3, 5, 7, and 10 days). MAIN OUTCOME MEASURES: All mice were sacrificed 1 hour after the last administration. Brain nitric oxide levels were determined by spectrophotometry. RESULTS: There were no significant differences in nitric oxide levels between the normal control, saline control, five-dose glutathione, and single-dose glutathione groups (P>0.05). Nitric oxide levels in the cerebral hemisphere and

  5. Simplified kinetic models of methanol oxidation on silver

    DEFF Research Database (Denmark)

    Andreasen, Anders; Lynggaard, Hasse Harloff; Stegelmann, Carsten

    2005-01-01

    reaction intermediate (MARI) approximation and the irreversible step (IS) approximation. This leads to further reduction in model complexity and in number of parameters. Computations verify that the performance of the model is preserved despite the reduction of the vast amount of parameters....

  6. Effects of glucocorticoid dexamethasone on serum nitric oxide synthase activity and nitric oxide levels in a rat model of lung disease-induced brain injury

    Institute of Scientific and Technical Information of China (English)

    Huajun Li; Ligang Jiang; Meng Xia; Haiping Li; Fanhua Meng; Wei Li; Lifeng Liu; Zhaohui Wang

    2011-01-01

    In this study, we investigated the effects of dexamethasone, pertussis toxin (a Gi protein inhibitor), and actinomycin (a transcription inhibitor) on serum nitric oxide synthase activity and nitric oxide content in a rat model of lung disease-induced brain injury. High-dose dexamethasone (13 mg/kg) and dexamethasone + actinomycin reduced lung water content, increased serum nitric oxide synthase activity and nitric oxide content, diminished inflammatory cell infiltration in pulmonary alveolar interstitium, attenuated meningeal vascular hyperemia, reduced glial cell infiltration, and decreased cerebral edema. These results demonstrate that high-dose glucocorticoid treatment can reduce the severity of lung disease-induced brain injury by increasing nitric oxide synthase activity and nitric oxide levels.

  7. A functional group oxidation model (FGOM for SOA formation and aging

    Directory of Open Access Journals (Sweden)

    X. Zhang

    2013-06-01

    Full Text Available Secondary organic aerosol (SOA formation from a volatile organic compound (VOC involves multiple generations of oxidation that include functionalization and fragmentation of the parent carbon backbone and likely particle-phase oxidation and/or accretion reactions. Despite the typical complexity of the detailed molecular mechanism of SOA formation and aging, a relatively small number of functional groups characterize the oxidized molecules that constitute SOA. Given the carbon number and set of functional groups, the volatility of the molecule can be estimated. We present here a functional group oxidation model (FGOM that represents the process of SOA formation and aging. The FGOM contains a set of parameters that are to be determined by fitting of the model to laboratory chamber data: total organic aerosol concentration, and O : C and H : C atomic ratios. The sensitivity of the model prediction to variation of the adjustable parameters allows one to assess the relative importance of various pathways involved in SOA formation. An analysis of SOA formation from the high- and low-NOx photooxidation of four C12 alkanes (n-dodecane, 2-methylundecane, hexylcyclohexane, and cyclododecane using the FGOM is presented, and comparison with the statistical oxidation model (SOM of Cappa et al. (2013 is discussed.

  8. A Functional Group Oxidation Model (FGOM for SOA formation and aging

    Directory of Open Access Journals (Sweden)

    X. Zhang

    2012-12-01

    Full Text Available Secondary organic aerosol (SOA formation from a volatile organic compound (VOC involves multiple generations of oxidation that include functionalization and fragmentation of the parent carbon backbone and, likely, particle-phase oxidation and/or accretion reactions. Despite the typical complexity of the detailed molecular mechanism of SOA formation and aging, a relatively small number of functional groups characterize the oxidized molecules that constitute SOA. Given the carbon number and set of functional groups, the volatility of the molecule can be estimated. We present here a Functional Group Oxidation Model (FGOM that represents the process of SOA formation and aging. The FGOM contains a set of parameters that are to be determined by fitting of the model to laboratory chamber data: total organic aerosol concentration, and O:C and H:C atomic ratios. The sensitivity of the model prediction to variation of the adjustable parameters allows one to assess the relative importance of various pathways involved in SOA formation. An analysis of SOA formation from the high- and low-NOx photooxidation of four C12 alkanes (n-dodecane, 2-methylundecane, hexylcyclohexane, and cyclododecane using the FGOM is presented, and comparison with the Statistical Oxidation Model (SOM of Cappa et al. (2012 is discussed.

  9. Analytical model of LDMOS with a double step buried oxide layer

    Science.gov (United States)

    Yuan, Song; Duan, Baoxing; Cao, Zhen; Guo, Haijun; Yang, Yintang

    2016-09-01

    In this paper, a two-dimensional analytical model is established for the Buried Oxide Double Step Silicon On Insulator structure proposed by the authors. Based on the two-dimensional Poisson equation, the analytic expressions of the surface electric field and potential distributions for the device are achieved. In the BODS (Buried Oxide Double Step Silicon On Insulator) structure, the buried oxide layer thickness changes stepwise along the drift region, and the positive charge in the drift region can be accumulated at the corner of the step. These accumulated charge function as the space charge in the depleted drift region. At the same time, the electric field in the oxide layer also varies with the different drift region thickness. These variations especially the accumulated charge will modulate the surface electric field distribution through the electric field modulation effects, which makes the surface electric field distribution more uniform. As a result, the breakdown voltage of the device is improved by 30% compared with the conventional SOI structure. To verify the accuracy of the analytical model, the device simulation software ISE TCAD is utilized, the analytical values are in good agreement with the simulation results by the simulation software. That means the established two-dimensional analytical model for BODS structure is valid, and it also illustrates the breakdown voltage enhancement by the electric field modulation effect sufficiently. The established analytical models will provide the physical and mathematical basis for further analysis of the new power devices with the patterned buried oxide layer.

  10. Surface reaction network of CO oxidation on CeO2/Au(110) inverse model catalysts.

    Science.gov (United States)

    Ding, Liangbing; Xiong, Feng; Jin, Yuekang; Wang, Zhengming; Sun, Guanghui; Huang, Weixin

    2016-11-30

    CeO2/Au(110) inverse model catalysts were prepared and their activity toward the adsorption and co-adsorption of O2, CO, CO2 and water was studied by means of X-ray photoelectron spectroscopy, low energy electron diffraction, thermal desorption spectra and temperature-programmed reaction spectra. The Au surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs CO, CO2 and water, and the polycrystalline CeO2 surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs O2, and molecularly and reactively adsorbs CO, CO2 and water. By controllably preparing co-adsorbed surface species on CeO2/Au(110) inverse model catalysts, we successfully identified various surface reaction pathways of CO oxidation to produce CO2 with different barriers both on the CeO2 surface and at the Au-CeO2 interface, including CO oxidation by various oxygen species, and water/hydroxyl group-involved CO oxidation. These results establish a surface reaction network of CO oxidation catalyzed by Au/CeO2 catalysts, greatly advancing the fundamental understandings of catalytic CO oxidation reactions.

  11. A many-body potential approach to modelling the thermomechanical properties of actinide oxides.

    Science.gov (United States)

    Cooper, M W D; Rushton, M J D; Grimes, R W

    2014-03-12

    A many-body potential model for the description of actinide oxide systems, which is robust at high temperatures, is reported for the first time. The embedded atom method is used to describe many-body interactions ensuring good reproduction of a range of thermophysical properties (lattice parameter, bulk modulus, enthalpy and specific heat) between 300 and 3000 K for AmO2, CeO2, CmO2, NpO2, ThO2, PuO2 and UO2. Additionally, the model predicts a melting point for UO2 between 3000 and 3100 K, in close agreement with experiment. Oxygen-oxygen interactions are fixed across the actinide oxide series because it facilitates the modelling of oxide solid solutions. The new potential is also used to predict the energies of Schottky and Frenkel pair disorder processes.

  12. Integrative Model of Oxidative Stress Adaptation in the Fungal Pathogen Candida albicans.

    Directory of Open Access Journals (Sweden)

    Chandrasekaran Komalapriya

    Full Text Available The major fungal pathogen of humans, Candida albicans, mounts robust responses to oxidative stress that are critical for its virulence. These responses counteract the reactive oxygen species (ROS that are generated by host immune cells in an attempt to kill the invading fungus. Knowledge of the dynamical processes that instigate C. albicans oxidative stress responses is required for a proper understanding of fungus-host interactions. Therefore, we have adopted an interdisciplinary approach to explore the dynamical responses of C. albicans to hydrogen peroxide (H2O2. Our deterministic mathematical model integrates two major oxidative stress signalling pathways (Cap1 and Hog1 pathways with the three major antioxidant systems (catalase, glutathione and thioredoxin systems and the pentose phosphate pathway, which provides reducing equivalents required for oxidative stress adaptation. The model encapsulates existing knowledge of these systems with new genomic, proteomic, transcriptomic, molecular and cellular datasets. Our integrative approach predicts the existence of alternative states for the key regulators Cap1 and Hog1, thereby suggesting novel regulatory behaviours during oxidative stress. The model reproduces both existing and new experimental observations under a variety of scenarios. Time- and dose-dependent predictions of the oxidative stress responses for both wild type and mutant cells have highlighted the different temporal contributions of the various antioxidant systems during oxidative stress adaptation, indicating that catalase plays a critical role immediately following stress imposition. This is the first model to encapsulate the dynamics of the transcriptional response alongside the redox kinetics of the major antioxidant systems during H2O2 stress in C. albicans.

  13. Integrative Model of Oxidative Stress Adaptation in the Fungal Pathogen Candida albicans.

    Science.gov (United States)

    Komalapriya, Chandrasekaran; Kaloriti, Despoina; Tillmann, Anna T; Yin, Zhikang; Herrero-de-Dios, Carmen; Jacobsen, Mette D; Belmonte, Rodrigo C; Cameron, Gary; Haynes, Ken; Grebogi, Celso; de Moura, Alessandro P S; Gow, Neil A R; Thiel, Marco; Quinn, Janet; Brown, Alistair J P; Romano, M Carmen

    2015-01-01

    The major fungal pathogen of humans, Candida albicans, mounts robust responses to oxidative stress that are critical for its virulence. These responses counteract the reactive oxygen species (ROS) that are generated by host immune cells in an attempt to kill the invading fungus. Knowledge of the dynamical processes that instigate C. albicans oxidative stress responses is required for a proper understanding of fungus-host interactions. Therefore, we have adopted an interdisciplinary approach to explore the dynamical responses of C. albicans to hydrogen peroxide (H2O2). Our deterministic mathematical model integrates two major oxidative stress signalling pathways (Cap1 and Hog1 pathways) with the three major antioxidant systems (catalase, glutathione and thioredoxin systems) and the pentose phosphate pathway, which provides reducing equivalents required for oxidative stress adaptation. The model encapsulates existing knowledge of these systems with new genomic, proteomic, transcriptomic, molecular and cellular datasets. Our integrative approach predicts the existence of alternative states for the key regulators Cap1 and Hog1, thereby suggesting novel regulatory behaviours during oxidative stress. The model reproduces both existing and new experimental observations under a variety of scenarios. Time- and dose-dependent predictions of the oxidative stress responses for both wild type and mutant cells have highlighted the different temporal contributions of the various antioxidant systems during oxidative stress adaptation, indicating that catalase plays a critical role immediately following stress imposition. This is the first model to encapsulate the dynamics of the transcriptional response alongside the redox kinetics of the major antioxidant systems during H2O2 stress in C. albicans.

  14. Oxidative damage to macromolecules in human Parkinson disease and the rotenone model.

    Science.gov (United States)

    Sanders, Laurie H; Greenamyre, J Timothy

    2013-09-01

    Parkinson disease (PD), the most common neurodegenerative movement disorder, is associated with selective degeneration of nigrostriatal dopamine neurons. Although the underlying mechanisms contributing to neurodegeneration in PD seem to be multifactorial, mitochondrial impairment and oxidative stress are widely considered to be central to many forms of the disease. Whether oxidative stress is a cause or a consequence of dopaminergic death, there is substantial evidence for oxidative stress both in human PD patients and in animal models of PD, especially using rotenone, a complex I inhibitor. There are many indices of oxidative stress, but this review covers the recent evidence for oxidative damage to nucleic acids, lipids, and proteins in both the brain and the peripheral tissues in human PD and in the rotenone model. Limitations of the existing literature and future perspectives are discussed. Understanding how each particular macromolecule is damaged by oxidative stress and the interplay of secondary damage to other biomolecules may help us design better targets for the treatment of PD. Copyright © 2013 Elsevier Inc. All rights reserved.

  15. Modeling of thermo-mechanical and irradiation behavior of mixed oxide fuel for sodium fast reactors

    Science.gov (United States)

    Karahan, Aydın; Buongiorno, Jacopo

    2010-01-01

    An engineering code to model the irradiation behavior of UO2-PuO2 mixed oxide fuel pins in sodium-cooled fast reactors was developed. The code was named fuel engineering and structural analysis tool (FEAST-OXIDE). FEAST-OXIDE has several modules working in coupled form with an explicit numerical algorithm. These modules describe: (1) fission gas release and swelling, (2) fuel chemistry and restructuring, (3) temperature distribution, (4) fuel-clad chemical interaction and (5) fuel-clad mechanical analysis. Given the fuel pin geometry, composition and irradiation history, FEAST-OXIDE can analyze fuel and cladding thermo-mechanical behavior at both steady-state and design-basis transient scenarios. The code was written in FORTRAN-90 program language. The mechanical analysis module implements the LIFE algorithm. Fission gas release and swelling behavior is described by the OGRES and NEFIG models. However, the original OGRES model has been extended to include the effects of joint oxide gain (JOG) formation on fission gas release and swelling. A detailed fuel chemistry model has been included to describe the cesium radial migration and JOG formation, oxygen and plutonium radial distribution and the axial migration of cesium. The fuel restructuring model includes the effects of as-fabricated porosity migration, irradiation-induced fuel densification, grain growth, hot pressing and fuel cracking and relocation. Finally, a kinetics model is included to predict the clad wastage formation. FEAST-OXIDE predictions have been compared to the available FFTF, EBR-II and JOYO databases, as well as the LIFE-4 code predictions. The agreement was found to be satisfactory for steady-state and slow-ramp over-power accidents.

  16. Modelling and engineering of stress based controlled oxidation effects for silicon nanostructure patterning

    Science.gov (United States)

    Han, Xiang-Lei; Larrieu, Guilhem; Krzeminski, Christophe

    2013-12-01

    Silicon nanostructure patterning with tight geometry control is an important challenge at the bottom level. In that context, stress based controlled oxidation appears to be an efficient tool for precise nanofabrication. Here, we investigate the stress-retarded oxidation phenomenon in various silicon nanostructures (nanobeams, nanorings and nanowires) at both the experimental and the theoretical levels. Different silicon nanostructures have been fabricated by a top-down approach. Complex dependence of the stress build-up on the nano-object’s dimension, shape and size has been demonstrated experimentally and physically explained by modelling. For the oxidation of a two-dimensional nanostructure (nanobeam), relative independence to size effects has been observed. On the other hand, radial stress increase with geometry downscaling of a one-dimensional nanostructure (nanowire) has been carefully emphasized. The study of shape engineering by retarded oxidation effects for vertical silicon nanowires is finally discussed.

  17. Protective effects of MCI-186 on oxidative damage in a cell model of Alzheimer's disease

    Institute of Scientific and Technical Information of China (English)

    Ming Yu; Shujuan Li; Wenhui Leng; Han Chen; Yingquan Wu; Lirong Yan

    2010-01-01

    Oxidative stress has an important role in the development of Alzheimer's disease(AD).Beta amyloid protein 25 35(Aβ25-35)can generate oxygen free radicals,and MCI-186(3-methyl-1-phenyl-2-pyrazolin-5-one,edaravone)can specifically eliminate hydroxyl radicals.The present study introduced Aβ25-35 into PC12 cells to establish a cell model of AD,and investigated the neuroprotective effects of MCI-186 on AD.Results showed that MCI-186 had a positive effect on the prevention and treatment of AD by inhibiting protein oxidative products,advanced glycation end products,lipid oxidative end products and DNA oxidative damage in PC12 cells induced by Aβ25-35.

  18. Integrated modeling of nitrogen oxides formation in diesel engines

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    To account for the effects of both chemistry and flow turbulence,the present study proposes an integrated NO sub-model that combines the extended Zel'dovich mechanism and engine CFD computations to simulate the NO histories in a diesel engine.NOx sub-model parameters and pollutant formation mechanisms can be more easily investigated by solving the NOx sub-model.The new NO formation model incorporating the effects of hoth chemical kinetics and turbulent mixing was applied to simulate a diesel engine with a quiescent combustion chamber,and one with a re-entrant combustion chamber;the premise of the model being the reaction rate is mainlv determined by a kinetic timescale and a turbulent timescale.The results indicate that the predicted NO formulation from the new model agrees well with the measured data.As the utilization of fossil fuels continues to increase,the control of NOx emissions is a worldwide concern;and it is imperative to understand fully the NOx reaction processes in combustion systems.This technology has the Dotential to enhance the application of various combustion techniques used to reduce NOx emissions from practical combustion systems.

  19. Radiolytic modelling of spent fuel oxidative dissolution mechanism. Development of the model and testing with experimental data

    Energy Technology Data Exchange (ETDEWEB)

    Merino, J.; Cera, E.; Bruno, J. [ENVIROS, Passeig de Rubi, 29-31, 08197 Valldoreix, Barcelona (Spain); Casas, I.; Clarens, F.; Gimenez, J.; de Pablo, J.; Rovira, M. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, ETSEIB, Diagonal 647 H-4, 08028, Barcelona (Spain); Quinones, J. [Ciemat, Av. Complutense 22, 28040 Madrid (Spain); Martinez-Esparza, A. [Enresa, C/ Emilio Vargas 7, 28043 Madrid (Spain)

    2005-07-01

    Full text of publication follows: Assessing the performance of spent nuclear fuel in a potential future geological disposal system requires the understanding and quantification of the important time-dependent phenomena influencing its behaviour on a time-scale up to millions of years. In this work we present the development and testing of a matrix alteration model using recently obtained experimental data. The conceptual model assumes that water will enter in contact with the fuel surface, and then the first process we may expect is the radiolysis of water. Water radiolysis will generate reductants and oxidants and we may expect local oxidising conditions. Because of these local conditions, the surface of the fuel will oxidize. The oxidation of the matrix and the attachment of aqueous ligands able to form strong complexes with its major component will favour the dissolution of the matrix. The oxygen mediated oxidation of the UO{sub 2} matrix is a surface oxidation via a mechanism of electron transfer with the oxygen molecule adsorbed onto the surface of the matrix. Hydrogen peroxide oxidation occurs by radical formation with very high oxidation potentials, and with the radical hydroxyl (.OH) as one of the main species generated in this process. On the other hand, the bicarbonate may act as scavenger of the .OH to form the radical .CO{sub 3}{sup -}. The dissolution processes once the surface sites are oxidised are based on two dissolution steps: surface co-ordination of U(VI) by the aqueous ligands (H{sup +}, H{sub 2}O or HCO{sub 3}{sup -}), and detachment (dissolution) of the product species. All the above processes have been included in the mathematical model and their kinetic constants calibrated with unirradiated UO{sub 2} leaching experiments. Furthermore, testing of the model has been carried out by applying it to a range of leaching experiments available in the framework of the European SFS (Spent Fuel Stability) project. These experiments include both static

  20. Spectroscopic and catalytic investigations of VxOy/SBA-15 and magnesium vanadate model catalysts for selective propene oxidation

    OpenAIRE

    Walter, Anke

    2011-01-01

    The objective of the present work was elucidating structure-activity relationships concerning the individual role of vanadium sites in selective propene oxidation. Two suitable vanadium oxide model catalyst systems were employed: vanadium oxides supported on SBA-15, “VxOy/SBA-15”, and various magnesium vanadate phases. Detailed investigations on the preparation, thermal stability, structure, and structural evolution under reducing and propene oxidizing condition were conducted. Various in sit...

  1. A General Mechanistic Model of Solid Oxide Fuel Cells

    Institute of Scientific and Technical Information of China (English)

    SHI Yixiang; CAI Ningsheng

    2006-01-01

    A comprehensive model considering all forms of polarization was developed. The model considers the intricate interdependency among the electrode microstructure, the transport phenomena, and the electrochemical processes. The active three-phase boundary surface was expressed as a function of electrode microstructure parameters (porosity, coordination number, contact angle, etc.). The exchange current densities used in the simulation were obtained by fitting a general formulation to the polarization curves proposed as a function of cell temperature and oxygen partial pressure. A validation study shows good agreement with published experimental data. Distributions of overpotentials, gas component partial pressures, and electronic/ionic current densities have been calculated. The effects of a porous electrode structure and of various operation conditions on cell performance were also predicted. The mechanistic model proposed can be used to interpret experimental observations and optimize cell performance by incorporating reliable experimental data.

  2. Experimental and modeling study of the oxidation of n- and iso-butanal

    KAUST Repository

    Veloo, Peter S.

    2013-09-01

    Understanding the kinetics of large molecular weight aldehydes is essential in the context of both conventional and alternative fuels. For example, they are key intermediates formed during the low-temperature oxidation of hydrocarbons as well as during the high-temperature oxidation of oxygenated fuels such as alcohols. In this study, an experimental and kinetic modeling investigation of n-butanal (. n-butyraldehyde) and iso-butanal (. iso-butyraldehyde or 2-methylpropanal) oxidation kinetics was performed. Experiments were performed in a jet stirred reactor and in counterflow flames over a wide range of equivalence ratios, temperatures, and pressures. The jet stirred reactor was utilized to observe the evolution of stable intermediates and products for the oxidation of n- and iso-butanal at elevated pressures and low to intermediate temperatures. The counterflow configuration was utilized for the determination of laminar flame speeds. A detailed chemical kinetic interpretative model was developed and validated consisting of 244 species and 1198 reactions derived from a previous study of the oxidation of propanal (propionaldehyde). Extensive reaction pathway and sensitivity analysis was performed to provide detailed insight into the mechanisms governing low-, intermediate-, and high-temperature reactivity. The simulation results using the present model are in good agreement with the experimental laminar flame speeds and well within a factor of two of the speciation data obtained in the jet stirred reactor. © 2013 The Combustion Institute.

  3. Detailed kinetic modeling study of n-pentanol oxidation

    KAUST Repository

    Heufer, Karl Alexander

    2012-10-18

    To help overcome the world\\'s dependence upon fossil fuels, suitable biofuels are promising alternatives that can be used in the transportation sector. Recent research on internal combustion engines shows that short alcoholic fuels (e.g., ethanol or n-butanol) have reduced pollutant emissions and increased knock resistance compared to fossil fuels. Although higher molecular weight alcohols (e.g., n-pentanol and n-hexanol) exhibit higher reactivity that lowers their knock resistance, they are suitable for diesel engines or advanced engine concepts, such as homogeneous charge compression ignition (HCCI), where higher reactivity at lower temperatures is necessary for engine operation. The present study presents a detailed kinetic model for n-pentanol based on modeling rules previously presented for n-butanol. This approach was initially validated using quantum chemistry calculations to verify the most stable n-pentanol conformation and to obtain C-H and C-C bond dissociation energies. The proposed model has been validated against ignition delay time data, speciation data from a jet-stirred reactor, and laminar flame velocity measurements. Overall, the model shows good agreement with the experiments and permits a detailed discussion of the differences between alcohols and alkanes. © 2012 American Chemical Society.

  4. Electrochemical Impedance Modeling of a Solid Oxide Fuel Cell Anode

    DEFF Research Database (Denmark)

    Mohammadi, R.; Søgaard, Martin; Ramos, Tania

    2014-01-01

    (TLM), which is suitably modified to account for the electrode microstructural details, is used for modeling the impedance arising from the electrochemical reactions. In order to solve the system of nonlinear equations, an in-house code based on the finite difference method was developed. Some...

  5. Modeling selenate adsorption behavior on oxides, clay minerals, and soils using the triple layer model

    Science.gov (United States)

    Selenate adsorption behavior was investigated on amorphous aluminum oxide, amorphous iron oxide, goethite, clay minerals: kaolinites, montmorillonites, illite, and 18 soil samples from Hawaii, and the Southwestern and the Midwestern regions of the US as a function of solution pH. Selenate adsorpti...

  6. Analysis of Residual Performance of UD-CMC in Oxidation Atmosphere Based on a Notch-like Oxidation Model

    Science.gov (United States)

    Sun, Zhigang; Shao, Hongyan; Chen, Xihui; Song, Yingdong

    2016-10-01

    Experimental observation indicates unidirectional ceramic matrix composites (UD-CMC) will react with oxygen under high-temperature atmosphere inhomogeneous. As a result of the oxidation on fiber surface, fiber shows a notch-like morphology. Stress concentration near by the fiber notch causes a decline of the mechanic performance of UD-CMC. In this paper, the change rule of fiber notch depth is fitted by circular function. Based on this formula the residual strength and modulus of UD-CMC under 400-900 °C atmosphere are derived. The mechanical performance of unidirectional C/SiC composite is simulated by finite element method. The stress distribution of fiber, matrix and interface are obtained. The residual properties of unidirectional C/SiC composite are predicted by theoretical method and finite element method. And the predicting results are compared with the experiment data. The predicting results show a good accordance with experiment data, which means the notch-like oxidation model can analyze the mechanic performance of UD-CMC efficiently.

  7. Physical model for trap-assisted inelastic tunneling in metal-oxide-semiconductor structures

    Science.gov (United States)

    Jiménez-Molinos, F.; Palma, A.; Gámiz, F.; Banqueri, J.; López-Villanueva, J. A.

    2001-10-01

    A physical model for trap-assisted inelastic tunnel current through potential barriers in semiconductor structures has been developed. The model is based on the theory of multiphonon transitions between detrapped and trapped states and the only fitting parameters are those of the traps (energy level and concentration) and the Huang-Rhys factor. Therefore, dependences of the trapping and detrapping processes on the bias, position, and temperature can be obtained with this model. The results of the model are compared with experimental data of stress induced leakage current in metal-oxide-semiconductor devices. The average energy loss has been obtained and an interpretation is given of the curves of average energy loss versus oxide voltage. This allows us to identify the entrance of the assisted tunnel current in the Fowler-Nordheim regime. In addition, the dependence of the tunnel current and average energy loss on the model parameters has been studied.

  8. Thermal conductivity modeling of water containing metal oxide nanoparticles

    Institute of Scientific and Technical Information of China (English)

    Ahmad Azari

    2015-01-01

    The nano particles have demonstrated great potential to improve the heat transfer characteristics of heat transfer fluids. Possible parameters responsible for this increase were studied. The heat transfer profile in the nanolayer region was combined with other parameters such as volume fraction, particle radius thermal conductivity of the fluid, particle and nanolayer, to formulate a thermal conductivity model. Results predicting the thermal conductivity of nanofluids using the model were compared with experimental results as well as studies by other researchers. The comparison of the results obtained for the CuO/water and TiO2/water nanofluids studied shows that the correlation proposed is in closest proximity in predicting the experimental results for the thermal conductivity of a nanofluid. Also, a parametric study was performed to understand how a number of factors affect the thermal conductivity of nanofluids using the developed correlation.

  9. Model for solid oxide fuel cell cathodes prepared by infiltration

    DEFF Research Database (Denmark)

    Samson, Alfred Junio; Søgaard, Martin; Hendriksen, Peter Vang

    2017-01-01

    A 1-dimensional model of a cathode has been developed in order to understand and predict the performance of cathodes prepared by infiltration of La0.6Sr0.4Co1.05O3-δ (LSC) into porous backbones of Ce0.9Gd0.1O1.95 (CGO). The model accounts for the mixed ionic and electronic conductivity of LSC......, ionic conductivity of CGO, gas transport in the porous cathode, and the oxygen reduction reaction at the surface of percolated LSC. Geometrical variations are applied to reflect a changing microstructure of LSC under varying firing temperatures. Using microstructural parameters obtained from detailed...... parameter variations are presented and discussed with the aim of presenting specific guidelines for optimizing the microstructure of cathodes prepared by infiltration....

  10. Extending the models for iron and sulfur oxidation in the extreme Acidophile Acidithiobacillus ferrooxidans

    Directory of Open Access Journals (Sweden)

    Holmes David S

    2009-08-01

    Full Text Available Abstract Background Acidithiobacillus ferrooxidans gains energy from the oxidation of ferrous iron and various reduced inorganic sulfur compounds at very acidic pH. Although an initial model for the electron pathways involved in iron oxidation has been developed, much less is known about the sulfur oxidation in this microorganism. In addition, what has been reported for both iron and sulfur oxidation has been derived from different A. ferrooxidans strains, some of which have not been phylogenetically characterized and some have been shown to be mixed cultures. It is necessary to provide models of iron and sulfur oxidation pathways within one strain of A. ferrooxidans in order to comprehend the full metabolic potential of the pangenome of the genus. Results Bioinformatic-based metabolic reconstruction supported by microarray transcript profiling and quantitative RT-PCR analysis predicts the involvement of a number of novel genes involved in iron and sulfur oxidation in A. ferrooxidans ATCC23270. These include for iron oxidation: cup (copper oxidase-like, ctaABT (heme biogenesis and insertion, nuoI and nuoK (NADH complex subunits, sdrA1 (a NADH complex accessory protein and atpB and atpE (ATP synthetase F0 subunits. The following new genes are predicted to be involved in reduced inorganic sulfur compounds oxidation: a gene cluster (rhd, tusA, dsrE, hdrC, hdrB, hdrA, orf2, hdrC, hdrB encoding three sulfurtransferases and a heterodisulfide reductase complex, sat potentially encoding an ATP sulfurylase and sdrA2 (an accessory NADH complex subunit. Two different regulatory components are predicted to be involved in the regulation of alternate electron transfer pathways: 1 a gene cluster (ctaRUS that contains a predicted iron responsive regulator of the Rrf2 family that is hypothesized to regulate cytochrome aa3 oxidase biogenesis and 2 a two component sensor-regulator of the RegB-RegA family that may respond to the redox state of the quinone pool

  11. Extending the models for iron and sulfur oxidation in the extreme Acidophile Acidithiobacillus ferrooxidans

    Science.gov (United States)

    2009-01-01

    Background Acidithiobacillus ferrooxidans gains energy from the oxidation of ferrous iron and various reduced inorganic sulfur compounds at very acidic pH. Although an initial model for the electron pathways involved in iron oxidation has been developed, much less is known about the sulfur oxidation in this microorganism. In addition, what has been reported for both iron and sulfur oxidation has been derived from different A. ferrooxidans strains, some of which have not been phylogenetically characterized and some have been shown to be mixed cultures. It is necessary to provide models of iron and sulfur oxidation pathways within one strain of A. ferrooxidans in order to comprehend the full metabolic potential of the pangenome of the genus. Results Bioinformatic-based metabolic reconstruction supported by microarray transcript profiling and quantitative RT-PCR analysis predicts the involvement of a number of novel genes involved in iron and sulfur oxidation in A. ferrooxidans ATCC23270. These include for iron oxidation: cup (copper oxidase-like), ctaABT (heme biogenesis and insertion), nuoI and nuoK (NADH complex subunits), sdrA1 (a NADH complex accessory protein) and atpB and atpE (ATP synthetase F0 subunits). The following new genes are predicted to be involved in reduced inorganic sulfur compounds oxidation: a gene cluster (rhd, tusA, dsrE, hdrC, hdrB, hdrA, orf2, hdrC, hdrB) encoding three sulfurtransferases and a heterodisulfide reductase complex, sat potentially encoding an ATP sulfurylase and sdrA2 (an accessory NADH complex subunit). Two different regulatory components are predicted to be involved in the regulation of alternate electron transfer pathways: 1) a gene cluster (ctaRUS) that contains a predicted iron responsive regulator of the Rrf2 family that is hypothesized to regulate cytochrome aa3 oxidase biogenesis and 2) a two component sensor-regulator of the RegB-RegA family that may respond to the redox state of the quinone pool. Conclusion

  12. Hydrogen oxidation at high pressure and intermediate temperatures: experiments and kinetic modeling

    DEFF Research Database (Denmark)

    Hashemi, Hamid; Christensen, Jakob Munkholt; Gersen, Sander

    2015-01-01

    Hydrogen oxidation at 50 bar and temperatures of 700–900 K was investigated in a high pressure laminar flow reactor under highly diluted conditions. The experiments provided information about H 2 oxidation at pressures above the third explosion limit. The fuel–air equivalence ratio of the reactants...... was varied from very oxidizing to strongly reducing conditions. The results supplement high-pressure data from RCM (900–1100 K) and shock tubes (900–2200 K). At the reducing conditions ( U = 12), oxidation started at 748–775 K while it was shifted to 798–823 K for stoichiometric and oxidizing conditions ( U...... = 1.03 and 0.05). At very oxidizing conditions (O 2 atmosphere, U = 0.0009), the temperature for onset of reaction was reduced to 775–798 K. The data were interpreted in terms of a detailed chemical kinetic model, drawn mostly from work of Burke and coworkers. In the present study, the rate constants...

  13. Trimetazidine prevents oxidative changes induced in a rat model of sporadic type of Alzheimer's disease.

    Directory of Open Access Journals (Sweden)

    Gholamreza Hassanzadeh

    2015-01-01

    Full Text Available Oxidative stress plays a major role in the pathogenesis of Alzheimer's disease (AD of sporadic origin. The expression of DHCR24 (Seladin-1, marker for neuronal oxidative stress and degeneration, has been reported to be altered in the brains of AD patients. In the present study, we investigated the effect of trimetazidine (TMZ on the hippocampal oxidative parameters and the expression of DHCR24 (Seladin-1 in an animal model of sporadic AD. Male rats were pre-treated with TMZ (25 mg/kg after which injected with intracerebroventricular-streptozotocin (ICV-STZ/Saline. Following 2, 7 and 14 days, animals of different groups were sacrificed with their brain excised to detect the hippocampal lipid peroxidation, superoxide dismutase (SOD, catalase activity, DHCR24 (Seladin-1 expression and possible histopathological changes. ICV-STZ administration induced significant oxidative changes in the hippocampus. Meanwhile, TMZ pre-treatment showed to ameliorate the oxidative stress, which was demonstrated by a significant rise in the hippocampal SOD and catalase activity, as well as a significant decrease in the malondialdehyde (MDA level. TMZ administration also increased the expression of DHCR24 (Seladin-1 gene in the hippocampus. In conclusion, our findings indicated a neuroprotective effect of TMZ possibly related to its antioxidant activity resulting in the up-regulation of DHCR24 (Seladin-1. Such TMZ effects may be beneficial in minimizing oxidative stress in sporadic Alzheimer's disease and possible prevention of disease progression.

  14. Cholesterol photo-oxidation: A chemical reaction network for kinetic modeling.

    Science.gov (United States)

    Barnaba, Carlo; Rodríguez-Estrada, Maria Teresa; Lercker, Giovanni; García, Hugo Sergio; Medina-Meza, Ilce Gabriela

    2016-12-01

    In this work we studied the effect of polyunsaturated fatty acids (PUFAs) methyl esters on cholesterol photo-induced oxidation. The oxidative routes were modeled with a chemical reaction network (CRN), which represents the first application of CRN to the oxidative degradation of a food-related lipid matrix. Docosahexaenoic acid (DHA, T-I), eicosapentaenoic acid (EPA, T-II) and a mixture of both (T-III) were added to cholesterol using hematoporphyrin as sensitizer, and were exposed to a fluorescent lamp for 48h. High amounts of Type I cholesterol oxidation products (COPs) were recovered (epimers 7α- and 7β-OH, 7-keto and 25-OH), as well as 5β,6β-epoxy. Fitting the experimental data with the CRN allowed characterizing the associated kinetics. DHA and EPA exerted different effects on the oxidative process. DHA showed a protective effect to 7-hydroxy derivatives, whereas EPA enhanced side-chain oxidation and 7β-OH kinetic rates. The mixture of PUFAs increased the kinetic rates several fold, particularly for 25-OH. With respect to the control, the formation of β-epoxy was reduced, suggesting potential inhibition in the presence of PUFAs.

  15. Effects of midazolam and phenobarbital on brain oxidative reactions induced by pentylenetetrazole in a convulsion model.

    Science.gov (United States)

    Arai, Yukiko; Maeda, Shigeru; Higuchi, Hitoshi; Tomoyasu, Yumiko; Shimada, Masahiko; Miyawaki, Takuya

    2012-04-01

    Brain oxidative reactions are involved in epilepsy as well as neurodegenerative diseases. In animal convulsion models, some anticonvulsants have been found to suppress oxidative reactions associated with convulsions. However, the effect of anticonvulsants on brain oxidative reactions has not fully been clarified. Midazolam and phenobarbital are often used as an intravenous anesthetic, and are known to have anticonvulsive effect, but antioxidative effect of these drugs has rarely been studied. Thus, the purpose of this study was to evaluate the effects of these drugs on the degree of convulsions and brain oxidative reactions in an animal convulsion model. In order to evaluate brain oxidative reactions, we measured malondialdehyde (MDA) level and heme oxygenase (HO)-1 mRNA expression level in the brain of mice in a convulsion model generated by a single injection of pentylenetetrazole (PTZ). We evaluated the effects of midazolam and phenobarbital on the degree of PTZ-induced convulsions and on the changes in brain MDA level and HO-1 mRNA expression level. After PTZ injection, severe convulsions were observed in all mice. MDA level was increased in the whole brain, while HO-1 mRNA expression level was increased only in the hippocampus. Both midazolam and phenobarbital prevented the convulsions and suppressed the increase in both MDA level and HO-1 mRNA expression level in the brain. In this study, both midazolam and phenobarbital suppressed PTZ-induced MDA and HO-1 reactions in the brain, suggesting that these drugs inhibit brain oxidative reactions in a convulsion model.

  16. Recent Advances in Modeling Transition Metal Oxides for Photo-electrochemistry

    Science.gov (United States)

    Caspary Toroker, Maytal

    Computational research offers a wide range of opportunities for materials science and engineering, especially in the energy arena where there is a need for understanding how material composition and structure control energy conversion, and for designing materials that could improve conversion efficiency. Potential inexpensive materials for energy conversion devices are metal oxides. However, their conversion efficiency is limited by at least one of several factors: a too large band gap for efficiently absorbing solar energy, similar conduction and valence band edge characters that may lead to unfavorably high electron-hole recombination rates, a valence band edge that is not positioned well for oxidizing water, low stability, low electronic conductivity, and low surface reactivity. I will show how we model metal oxides with ab-initio methods, primarily DFT +U. Our previous results show that doping with lithium, sodium, or hydrogen could improve iron (II) oxide's electronic properties, and alloying with zinc or nickel could improve iron (II) oxide's optical properties. Furthermore, doping nickel (II) oxide with lithium could improve several key properties including solar energy absorption. In this talk I will highlight new results on our understanding of the mechanism of iron (III) oxide's surface reactivity. Our theoretical insights bring us a step closer towards understanding how to design better materials for photo-electrochemistry. References: 1. O. Neufeld and M. Caspary Toroker, ``Pt-doped Fe2O3 for enhanced water splitting efficiency: a DFT +U study'', J. Phys. Chem. C 119, 5836 (2015). 2. M. Caspary Toroker, ``Theoretical Insights into the Mechanism of Water Oxidation on Non-stoichiometric and Ti - doped Fe2O3 (0001)'', J. Phys. Chem. C, 118, 23162 (2014). This research was supported by the Morantz Energy Research Fund, the Nancy and Stephen Grand Technion Energy Program, the I-CORE Program of the Planning and Budgeting Committee, and The Israel Science

  17. Therapeutic attenuation of mitochondrial dysfunction and oxidative stress in neurotoxin models of Parkinson's disease

    OpenAIRE

    Stack, Edward C.; Ferro, Joellyn L.; Kim, Jinho; Del Signore, Steven J.; Goodrich, Sarah; Matson, Samantha; Hunt, Bonnie B.; Cormier, Kerry; Smith, Karen; Matson, Wayne R.; Ryu, Hoon; Ferrante, Robert J.

    2008-01-01

    Therapeutic attenuation of mitochondrial dysfunction and oxidative stress in neurotoxin models of Parkinson?s disease correspondence: Corresponding author. GRECC Unit 182B, Bedford VA Medical Center, 200 Springs Road, Bedford, MA 01730, USA. Tel.: +1 781 687 2908; fax: +1 781 687 3515. (Ferrante, Robert J.) (Ferrante, Robert J.) Department of Neurology, Boston University School of Medicine - Boston--> , MA 02118--> ...

  18. A Coarse-Grained Model for Polyethylene Oxide and Polyethylene Glycol : Conformation and Hydrodynamics

    NARCIS (Netherlands)

    Lee, Hwankyu; de Vries, Alex H.; Marrink, Siewert-Jan; Pastor, Richard W.

    2009-01-01

    A coarse-grained (CG) model for polyethylene oxide (PEO) and polyethylene glycol (PEG) developed within the framework of the MARTINI CG force field (FF) using the distributions of bonds, angles, and dihedrals from the CHARMM all-atom FF is presented. Densities of neat low molecular weight PEO agree

  19. Comprehensive atmospheric modeling of reactive cyclic siloxanes and their oxidation products

    Science.gov (United States)

    Janechek, Nathan J.; Hansen, Kaj M.; Stanier, Charles O.

    2017-07-01

    Cyclic volatile methyl siloxanes (cVMSs) are important components in personal care products that transport and react in the atmosphere. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and their gas-phase oxidation products have been incorporated into the Community Multiscale Air Quality (CMAQ) model. Gas-phase oxidation products, as the precursor to secondary organic aerosol from this compound class, were included to quantify the maximum potential for aerosol formation from gas-phase reactions with OH. Four 1-month periods were modeled to quantify typical concentrations, seasonal variability, spatial patterns, and vertical profiles. Typical model concentrations showed parent compounds were highly dependent on population density as cities had monthly averaged peak D5 concentrations up to 432 ng m-3. Peak oxidized D5 concentrations were significantly less, up to 9 ng m-3, and were located downwind of major urban areas. Model results were compared to available measurements and previous simulation results. Seasonal variation was analyzed and differences in seasonal influences were observed between urban and rural locations. Parent compound concentrations in urban and peri-urban locations were sensitive to transport factors, while parent compounds in rural areas and oxidized product concentrations were influenced by large-scale seasonal variability in OH.

  20. Experimental and Kinetic Modeling Study of C2H2Oxidation at High Pressure

    DEFF Research Database (Denmark)

    Lopez, Jorge Gimenez; Rasmussen, Christian Tihic; Hashemi, Hamid

    2016-01-01

    A detailed chemical kinetic model for oxidation of acetylene at intermediate temperatures and high pressure has been developed and evaluated experimentally. The rate coefficients for the reactions of C2H2 with HO2 and O2 were investigated, based on the recent analysis of the potential energy...

  1. Modelling the growth of methane-oxidizing bacteria in a fixed biofilm

    DEFF Research Database (Denmark)

    Bilbo, Carl Morten; Arvin, Erik; Holst, Helle

    1992-01-01

    Methane-oxidizing bacteria were grown in a fixed biofilm reactor in order to study their ability to degrade chlorinated aliphatic hydrocarbons. Focus is on the growth behaviour of the mixed culture. The growth is described by a model that includes methanotrophic bacteria in the active biomass...

  2. A Coarse-Grained Model for Polyethylene Oxide and Polyethylene Glycol : Conformation and Hydrodynamics

    NARCIS (Netherlands)

    Lee, Hwankyu; de Vries, Alex H.; Marrink, Siewert-Jan; Pastor, Richard W.

    2009-01-01

    A coarse-grained (CG) model for polyethylene oxide (PEO) and polyethylene glycol (PEG) developed within the framework of the MARTINI CG force field (FF) using the distributions of bonds, angles, and dihedrals from the CHARMM all-atom FF is presented. Densities of neat low molecular weight PEO agree

  3. Aluminum/Copper Oxide/Copper Memristive Devices: Fabrication, Characterization, and Modeling

    Science.gov (United States)

    McDonald, Nathan R.

    Memristive devices have become very popular in recent years due to their potential to dramatically alter logic processing in CMOS circuitry. Memristive devices function as electrical potentiometers, allowing for such diverse applications as memory storage, multi-state logic, and reconfigurable logic gates. This research covered the fabrication, characterization, and modeling of Al/CuxO/Cu memristive devices created by depositing Al top electrodes atop a CuxO film grown using plasma oxidation to grow the oxide on a Cu wafer. Power settings of the plasma oxidation system were shown to control the grown oxide thickness and oxygen concentration, which subsequently affected memristive device behaviors. These memristive devices demonstrated complete nonpolar behavior and could be switched either in a vertical (Al/Cu xO/Cu) or lateral (Al/CuxO/Cu/CuxO/Al) manner. The switching mechanism of these devices was shown to be filamentary in nature. Physical and empirical models of these devices were created for MATLAB, HSPICE, & Verilog A environments. While the physical model proved of limited practical consequence, the robust empirical model allows for rapid prototyping of CMOS-memristor circuitry.

  4. NITROUS OXIDE EMISSIONS FROM SOUTHERN HIGH PLAINS BEEF CATTLE FEEDYARDS: MEASUREMENT AND MODELING

    Science.gov (United States)

    Predictive models for nitrous oxide emission are crucial for assessing the greenhouse gas footprint of beef cattle production. The Texas Panhandle produces approximately 42% of finished beef in the U.S. and cattle production is estimated to contribute 8 Tg carbon dioxide equivalents from nitrous oxi...

  5. Designing efficient nitrous oxide sampling strategies in agroecosystems using simulation models

    Science.gov (United States)

    Debasish Saha; Armen R. Kemanian; Benjamin M. Rau; Paul R. Adler; Felipe Montes

    2017-01-01

    Annual cumulative soil nitrous oxide (N2O) emissions calculated from discrete chamber-based flux measurements have unknown uncertainty. We used outputs from simulations obtained with an agroecosystem model to design sampling strategies that yield accurate cumulative N2O flux estimates with a known uncertainty level. Daily soil N2O fluxes were simulated for Ames, IA (...

  6. Quantitative analysis of anaerobic oxidation of methane (AOM) in marine sediments: a modeling perspective

    NARCIS (Netherlands)

    Regnier, P.; Dale, A.W.; Arndt, S.; LaRowe, D.E.; Mogollon, J.M.; Van Cappellen, P.

    2011-01-01

    Recent developments in the quantitativemodeling of methane dynamics and anaerobic oxidation of methane (AOM) in marine sediments are critically reviewed. The first part of the review begins with a comparison of alternative kinetic models for AOM. The roles of bioenergetic limitations, intermediate c

  7. Modeling low-dose-rate effects in irradiated bipolar-base oxides

    Energy Technology Data Exchange (ETDEWEB)

    Graves, R.J.; Cirba, C.R.; Schrimpf, R.D.; Milanowski, R.J.; Saigne, F. [Vanderbilt Univ., Nashville, TN (United States); Michez, A. [Univ. Montpellier 2 (France); Fleetwood, D.M. [Sandia National Labs., Albuquerque, NM (United States); Witczak, S.C. [Aerospace Corp., Los Angeles, CA (United States)

    1997-02-01

    A physical model is developed to quantify the contribution of oxide-trapped charge to enhanced low-dose-rate gain degradation in BJTs. Simulations show that space charge limited transport is partially responsible for the low-dose-rate enhancement.

  8. Kinetic modeling of the oxidative degradation of additive free PE in bleach disinfected water

    Science.gov (United States)

    Mikdam, Aïcha; Colin, Xavier; Billon, Noëlle; Minard, Gaëlle

    2016-05-01

    The chemical interactions between PE and bleach were studied at 60°C in immersion in bleach solutions kept at a free chlorine concentration of 100 ppm and a pH of 5 or 7.2. It was found that the polymer undergoes a severe oxidation from the earliest weeks of exposure, in a superficial layer whose thickness (of about 50-70 µm) is almost independent of the pH value, although the superficial oxidation rate is faster in acidic than in neutral medium. Oxidation leads to the formation and accumulation of a large variety of carbonyl products (mostly ketones and carboxylic acids) and, after a few weeks, to a decrease in the average molar mass due to the large predominance of chain scissions over crosslinking. A scenario was elaborated for explaining such unexpected results. According to this scenario, the non-ionic molecules (Cl2 and ClOH) formed from the disinfectant in the water phase, would migrate deeply into PE and dissociate into highly reactive radicals (Cl• and HO•) in order to initiate a radical chain oxidation. A kinetic model was derived from this scenario for predicting the general trends of the oxidation kinetics and its dependence on environmental factors such as temperature, free chlorine concentration and pH. The validity of this model was successfully checked by comparing the numerical simulations with experimental data.

  9. Oxidative stress-driven parvalbumin interneuron impairment as a common mechanism in models of schizophrenia

    Science.gov (United States)

    Steullet, P; Cabungcal, J-H; Coyle, J; Didriksen, M; Gill, K; Grace, A A; Hensch, T K; LaMantia, A-S; Lindemann, L; Maynard, T M; Meyer, U; Morishita, H; O'Donnell, P; Puhl, M; Cuenod, M; Do, K Q

    2017-01-01

    Parvalbumin inhibitory interneurons (PVIs) are crucial for maintaining proper excitatory/inhibitory balance and high-frequency neuronal synchronization. Their activity supports critical developmental trajectories, sensory and cognitive processing, and social behavior. Despite heterogeneity in the etiology across schizophrenia and autism spectrum disorder, PVI circuits are altered in these psychiatric disorders. Identifying mechanism(s) underlying PVI deficits is essential to establish treatments targeting in particular cognition. On the basis of published and new data, we propose oxidative stress as a common pathological mechanism leading to PVI impairment in schizophrenia and some forms of autism. A series of animal models carrying genetic and/or environmental risks relevant to diverse etiological aspects of these disorders show PVI deficits to be all accompanied by oxidative stress in the anterior cingulate cortex. Specifically, oxidative stress is negatively correlated with the integrity of PVIs and the extracellular perineuronal net enwrapping these interneurons. Oxidative stress may result from dysregulation of systems typically affected in schizophrenia, including glutamatergic, dopaminergic, immune and antioxidant signaling. As convergent end point, redox dysregulation has successfully been targeted to protect PVIs with antioxidants/redox regulators across several animal models. This opens up new perspectives for the use of antioxidant treatments to be applied to at-risk individuals, in close temporal proximity to environmental impacts known to induce oxidative stress. PMID:28322275

  10. Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

    Science.gov (United States)

    Abraham, Martin; Fisher, John W.

    1995-01-01

    The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst, prepared at The University of Tulsa, at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

  11. Development of Linear Irreversible Thermodynamic Model for Oxidation Reduction Potential in Environmental Microbial System

    Science.gov (United States)

    Cheng, Hong-Bang; Kumar, Mathava; Lin, Jih-Gaw

    2007-01-01

    Nernst equation has been directly used to formulate the oxidation reduction potential (ORP) of reversible thermodynamic conditions but applied to irreversible conditions after several assumptions and/or modifications. However, the assumptions are sometimes inappropriate in the quantification of ORP in nonequilibrium system. We propose a linear nonequilibrium thermodynamic model, called microbial related reduction and oxidation reaction (MIRROR Model No. 1) for the interpretation of ORP in biological process. The ORP was related to the affinities of catabolism and anabolism. The energy expenditure of catabolism and anabolism was directly proportional to overpotential (η), straight coefficient of electrode (LEE), and degree of coupling between catabolism and ORP electrode, respectively. Finally, the limitations of MIRROR Model No. 1 were discussed for expanding the applicability of the model. PMID:17496027

  12. Modeling nitrous oxide production during biological nitrogen removal via nitrification and denitrification: extensions to the general ASM models.

    Science.gov (United States)

    Ni, Bing-Jie; Ruscalleda, Maël; Pellicer-Nàcher, Carles; Smets, Barth F

    2011-09-15

    Nitrous oxide (N(2)O) can be formed during biological nitrogen (N) removal processes. In this work, a mathematical model is developed that describes N(2)O production and consumption during activated sludge nitrification and denitrification. The well-known ASM process models are extended to capture N(2)O dynamics during both nitrification and denitrification in biological N removal. Six additional processes and three additional reactants, all involved in known biochemical reactions, have been added. The validity and applicability of the model is demonstrated by comparing simulations with experimental data on N(2)O production from four different mixed culture nitrification and denitrification reactor study reports. Modeling results confirm that hydroxylamine oxidation by ammonium oxidizers (AOB) occurs 10 times slower when NO(2)(-) participates as final electron acceptor compared to the oxic pathway. Among the four denitrification steps, the last one (N(2)O reduction to N(2)) seems to be inhibited first when O(2) is present. Overall, N(2)O production can account for 0.1-25% of the consumed N in different nitrification and denitrification systems, which can be well simulated by the proposed model. In conclusion, we provide a modeling structure, which adequately captures N(2)O dynamics in autotrophic nitrification and heterotrophic denitrification driven biological N removal processes and which can form the basis for ongoing refinements.

  13. Modeling and Structural Optimization of Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Panagakos, Grigorios

    The research conducted in the context of this PhD, lies on the cross section between multi-scale modeling of flow in porous media, electrochemical diffusion and reaction, in combination with Shape and Structural Optimization techniques. More specifi-cally, we have followed two lines of action...... requirements. On the one hand, it needs to secure the intake of fuel into the cell, fact that would require an as low hydraulic resistance as possible, i.e. ideally an open channel and on the other hand to exhibit an as high as possible electronic conductance, which in the ideal case would mean an area blocked...... completely by a material with high conductivity such as coated stainless steel. The balance between these two competing, oppositely driving forces, indicate that there should be a design that satisfies in the best way both. Similar problems have been successfully dealt by structural-topology optimization...

  14. Oxidative stress contributes to outcome severity in a Drosophila melanogaster model of classic galactosemia

    Directory of Open Access Journals (Sweden)

    Patricia P. Jumbo-Lucioni

    2013-01-01

    Classic galactosemia is a genetic disorder that results from profound loss of galactose-1P-uridylyltransferase (GALT. Affected infants experience a rapid escalation of potentially lethal acute symptoms following exposure to milk. Dietary restriction of galactose prevents or resolves the acute sequelae; however, many patients experience profound long-term complications. Despite decades of research, the mechanisms that underlie pathophysiology in classic galactosemia remain unclear. Recently, we developed a Drosophila melanogaster model of classic galactosemia and demonstrated that, like patients, GALT-null Drosophila succumb in development if exposed to galactose but live if maintained on a galactose-restricted diet. Prior models of experimental galactosemia have implicated a possible association between galactose exposure and oxidative stress. Here we describe application of our fly genetic model of galactosemia to the question of whether oxidative stress contributes to the acute galactose sensitivity of GALT-null animals. Our first approach tested the impact of pro- and antioxidant food supplements on the survival of GALT-null and control larvae. We observed a clear pattern: the oxidants paraquat and DMSO each had a negative impact on the survival of mutant but not control animals exposed to galactose, and the antioxidants vitamin C and α-mangostin each had the opposite effect. Biochemical markers also confirmed that galactose and paraquat synergistically increased oxidative stress on all cohorts tested but, interestingly, the mutant animals showed a decreased response relative to controls. Finally, we tested the expression levels of two transcripts responsive to oxidative stress, GSTD6 and GSTE7, in mutant and control larvae exposed to galactose and found that both genes were induced, one by more than 40-fold. Combined, these results implicate oxidative stress and response as contributing factors in the acute galactose sensitivity of GALT-null Drosophila and, by

  15. Oxidative stress contributes to outcome severity in a Drosophila melanogaster model of classic galactosemia.

    Science.gov (United States)

    Jumbo-Lucioni, Patricia P; Hopson, Marquise L; Hang, Darwin; Liang, Yongliang; Jones, Dean P; Fridovich-Keil, Judith L

    2013-01-01

    Classic galactosemia is a genetic disorder that results from profound loss of galactose-1P-uridylyltransferase (GALT). Affected infants experience a rapid escalation of potentially lethal acute symptoms following exposure to milk. Dietary restriction of galactose prevents or resolves the acute sequelae; however, many patients experience profound long-term complications. Despite decades of research, the mechanisms that underlie pathophysiology in classic galactosemia remain unclear. Recently, we developed a Drosophila melanogaster model of classic galactosemia and demonstrated that, like patients, GALT-null Drosophila succumb in development if exposed to galactose but live if maintained on a galactose-restricted diet. Prior models of experimental galactosemia have implicated a possible association between galactose exposure and oxidative stress. Here we describe application of our fly genetic model of galactosemia to the question of whether oxidative stress contributes to the acute galactose sensitivity of GALT-null animals. Our first approach tested the impact of pro- and antioxidant food supplements on the survival of GALT-null and control larvae. We observed a clear pattern: the oxidants paraquat and DMSO each had a negative impact on the survival of mutant but not control animals exposed to galactose, and the antioxidants vitamin C and α-mangostin each had the opposite effect. Biochemical markers also confirmed that galactose and paraquat synergistically increased oxidative stress on all cohorts tested but, interestingly, the mutant animals showed a decreased response relative to controls. Finally, we tested the expression levels of two transcripts responsive to oxidative stress, GSTD6 and GSTE7, in mutant and control larvae exposed to galactose and found that both genes were induced, one by more than 40-fold. Combined, these results implicate oxidative stress and response as contributing factors in the acute galactose sensitivity of GALT-null Drosophila and

  16. Single catalytic site model for the oxidation of ferrocytochrome c by mitochondrial cytochrome c oxidase.

    OpenAIRE

    Speck, S.H.; Dye, D.; Margoliash, E

    1984-01-01

    A single catalytic site model is proposed to account for the multiphasic kinetics of oxidation of ferrocytochrome c by cytochrome c oxidase (ferrocytochrome c:oxygen oxidoreductase, EC 1.9.3.1). This model involves nonproductive binding of substrate to sites near the catalytic site on cytochrome c oxidase for cytochrome c, decreasing the binding constant for cytochrome c at the catalytic site. This substrate inhibition results in an increase in the first-order rate constant for the dissociati...

  17. Modeling of Proton-Conducting Solid Oxide Fuel Cells Fueled with Syngas

    OpenAIRE

    2014-01-01

    Solid oxide fuel cells (SOFCs) with proton conducting electrolyte (H-SOFCs) are promising power sources for stationary applications. Compared with other types of fuel cells, one distinct feature of SOFC is their fuel flexibility. In this study, a 2D model is developed to investigate the transport and reaction in an H-SOFC fueled with syngas, which can be produced from conventional natural gas or renewable biomass. The model fully considers the fluid flow, mass transfer, heat transfer and r...

  18. Experimental and Modeling Investigation of the Low-Temperature Oxidation of Dimethyl Ether.

    Science.gov (United States)

    Rodriguez, Anne; Frottier, Ophélie; Herbinet, Olivier; Fournet, René; Bounaceur, Roda; Fittschen, Christa; Battin-Leclerc, Frédérique

    2015-07-16

    The oxidation of dimethyl ether (DME) was studied using a jet-stirred reactor over a wide range of conditions: temperatures from 500 to 1100 K; equivalence ratios of 0.25, 1, and 2; residence time of 2 s; pressure of 106.7 kPa (close to the atmospheric pressure); and an inlet fuel mole fraction of 0.02 (with high dilution in helium). Reaction products were quantified using two analysis methods: gas chromatography and continuous wave cavity ring-down spectroscopy (cw-CRDS). cw-CRDS enabled the quantification of formaldehyde, which is one of the major products from DME oxidation, as well as that of hydrogen peroxide, which is an important branching agent in low-temperature oxidation chemistry. Experimental data were compared with data computed using models from the literature with important deviations being observed for the reactivity at low-temperature. A new detailed kinetic model for the oxidation of DME was developed in this study. Kinetic parameters used in this model were taken from literature or calculated in the present work using quantum calculations. This new model enables a better prediction of the reactivity in the low-temperature region. Under the present JSR conditions, error bars on predictions were given. Simulations were also successfully compared with experimental flow reactor, jet-stirred reactor, shock tube, rapid compression machine, and flame data from literature. The kinetic analysis of the model enabled the highlighting of some specificities of the oxidation chemistry of DME: (1) the early reactivity which is observed at very low-temperature (e.g., compared to propane) is explained by the absence of inhibiting reaction of the radical directly obtained from the fuel (by H atom abstraction) with oxygen yielding an olefin + HO2·; (2) the low-temperature reactivity is driven by the relative importance of the second addition to O2 (promoting the reactivity through branching chain) and the competitive decomposition reactions with an inhibiting

  19. Importance of the Hydrogen Isocyanide Isomer in Modeling Hydrogen Cyanide Oxidation in Combustion

    DEFF Research Database (Denmark)

    Glarborg, Peter; Marshall, Paul

    2017-01-01

    Hydrogen isocyanide (HNC) has been proposed as an important intermediate in oxidation of hydrogen cyanide (HCN) in combustion, but details of its chemistry are still in discussion. At higher temperatures, HCN and HNC equilibrate rapidly, and being more reactive than HCN, HNC offers a fast...... alternative route of oxidation for cyanides. However, in previous modeling, it has been required to omit the HNC subset partly or fully in the reaction mechanisms to obtain satisfactory predictions. In the present work, we re-examine the chemistry of HNC and its role in combustion nitrogen chemistry. The HNC...

  20. Modeling Low-Dose-Rate Effects in Irradiated Bipolar-Base Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Cirba, C.R.; Fleetwood, D.M.; Graves, R.J.; Michez, A.; Milanowski, R.J.; Saigne, F.; Schrimpf, R.D.; Witczak, S.C.

    1998-10-26

    A physical model is developed to quantify the contribution of oxide-trapped charge to enhanced low-dose-rate gain degradation in bipolar junction transistors. Multiple-trapping simulations show that space charge limited transport is partially responsible for low-dose-rate enhancement. At low dose rates, more holes are trapped near the silicon-oxide interface than at high dose rates, resulting in larger midgap voltage shifts at lower dose rates. The additional trapped charge near the interface may cause an exponential increase in excess base current, and a resultant decrease in current gain for some NPN bipolar technologies.

  1. An Abnormal Nitric Oxide Metabolism Contributes to Brain Oxidative Stress in the Mouse Model for the Fragile X Syndrome, a Possible Role in Intellectual Disability

    Science.gov (United States)

    Lima-Cabello, Elena; Garcia-Guirado, Francisco; Calvo-Medina, Rocio; el Bekay, Rajaa; Perez-Costillas, Lucia; Quintero-Navarro, Carolina; Sanchez-Salido, Lourdes

    2016-01-01

    Background. Fragile X syndrome is the most common genetic cause of mental disability. Although many research has been performed, the mechanism underlying the pathogenesis is unclear and needs further investigation. Oxidative stress played major roles in the syndrome. The aim was to investigate the nitric oxide metabolism, protein nitration level, the expression of NOS isoforms, and furthermore the activation of the nuclear factor NF-κB-p65 subunit in different brain areas on the fragile X mouse model. Methods. This study involved adult male Fmr1-knockout and wild-type mice as controls. We detected nitric oxide metabolism and the activation of the nuclear factor NF-κBp65 subunit, comparing the mRNA expression and protein content of the three NOS isoforms in different brain areas. Results. Fmr1-KO mice showed an abnormal nitric oxide metabolism and increased levels of protein tyrosine nitrosylation. Besides that, nuclear factor NF-κB-p65 and inducible nitric oxide synthase appeared significantly increased in the Fmr1-knockout mice. mRNA and protein levels of the neuronal nitric oxide synthase appeared significantly decreased in the knockout mice. However, the epithelial nitric oxide synthase isoform displayed no significant changes. Conclusions. These data suggest the potential involvement of an abnormal nitric oxide metabolism in the pathogenesis of the fragile X syndrome. PMID:26788253

  2. An Abnormal Nitric Oxide Metabolism Contributes to Brain Oxidative Stress in the Mouse Model for the Fragile X Syndrome, a Possible Role in Intellectual Disability

    Directory of Open Access Journals (Sweden)

    Elena Lima-Cabello

    2016-01-01

    Full Text Available Background. Fragile X syndrome is the most common genetic cause of mental disability. Although many research has been performed, the mechanism underlying the pathogenesis is unclear and needs further investigation. Oxidative stress played major roles in the syndrome. The aim was to investigate the nitric oxide metabolism, protein nitration level, the expression of NOS isoforms, and furthermore the activation of the nuclear factor NF-κB-p65 subunit in different brain areas on the fragile X mouse model. Methods. This study involved adult male Fmr1-knockout and wild-type mice as controls. We detected nitric oxide metabolism and the activation of the nuclear factor NF-κBp65 subunit, comparing the mRNA expression and protein content of the three NOS isoforms in different brain areas. Results. Fmr1-KO mice showed an abnormal nitric oxide metabolism and increased levels of protein tyrosine nitrosylation. Besides that, nuclear factor NF-κB-p65 and inducible nitric oxide synthase appeared significantly increased in the Fmr1-knockout mice. mRNA and protein levels of the neuronal nitric oxide synthase appeared significantly decreased in the knockout mice. However, the epithelial nitric oxide synthase isoform displayed no significant changes. Conclusions. These data suggest the potential involvement of an abnormal nitric oxide metabolism in the pathogenesis of the fragile X syndrome.

  3. Thermodynamic Model and Database for Sulfides Dissolved in Molten Oxide Slags

    Science.gov (United States)

    Kang, Youn-Bae; Pelton, Arthur D.

    2009-12-01

    A thermodynamic model has been developed in the framework of the modified quasichemical model in the quadruplet approximation to permit the calculation of solubilities of various gaseous species (sulfide, sulfate, nitride, carbide, water, etc.) in molten slags. The model calculates the solubilities solely from knowledge of the thermodynamic activities of the component oxides and the Gibbs energies of the pure liquid components (oxides, sulfides, sulfates, etc.). In the current article, it is shown that solubilities of sulfur as sulfide in Al2O3-CaO-FeO-Fe2O3-MgO-MnO-SiO2-TiO2-Ti2O3 multicomponent slags, which are predicted from the current model with no adjustable model parameters, are in good agreement with all available experimental data. The article also provides a thorough review of experimental sulfide capacity data for this system. The model applies at all compositions from pure oxides to pure sulfides and from basic to acidic slags. By coupling this database with other evaluated databases, such as those for molten metal and gaseous phases, and with general software for Gibbs energy minimization, practically important slag/metal/gas/solid equilibria can be computed such as S-distribution ratios.

  4. Optimization of a model of red blood cells for the study of anti-oxidant drugs, in terms of concentration of oxidant and phosphate buffer.

    Science.gov (United States)

    Bureau, A; Lahet, J-J; Lenfant, F; Bouyer, F; Petitjean, M; Chaillot, B; Freysz, M

    2005-08-01

    The aggression of erythrocytes by an oxidative stress induces hemolysis. This paper aims to valid a model of erythrocytes in terms of composition of the phosphate buffer solution and of concentration of a well-known oxidant, AAPH. Three compositions of phosphate buffer solution are mixed with three concentrations of oxidant. The influence of these two parameters on hemolysis is independently studied by a variance analysis and a Kruskal-Wallis test when ANOVA is not available. The hemolysis rate increases with time at fixed oxidant concentration, but is not influenced by the composition of the buffer solution. The highest hemolysis rate, 90%, was only measured within 2 h with the highest oxidant concentration. If we retain this concentration of oxidant, the lower concentration of the buffer can by eliminated by a significant less hemolysis and the highest concentration of the buffer can by chosen in regard of the better precision for a similar hemolysis compared to the mean buffer. We hope to study the effect of anti-oxidant agent with such a model of erythrocytes.

  5. Identification of total reversible cysteine oxidation in an atherosclerosis model using a modified biotin switch assay.

    Science.gov (United States)

    Li, Ru; Huang, Jiqing; Kast, Juergen

    2015-05-01

    Oxidative stress due to the imbalance of reactive oxygen species (ROS) and the resulting reversible cysteine oxidation (CysOX) are involved in the early proatherogenic aspect of atherosclerosis. Given that the corresponding redox signaling pathways are still unclear, a modified biotin switch assay was developed to quantify the reversible CysOX in an atherosclerosis model established by using a monocytic cell line treated with platelet releasate. The accumulation of ROS was observed in the model system and validated in human primary monocytes. Through the application of the modified biotin switch assay, we obtained the first reversible CysOX proteome for this model. A total of 75 peptides, corresponding to 53 proteins, were quantified with oxidative modification. The bioinformatics analysis of these CysOX-containing proteins highlighted biological processes including glycolysis, cytoskeleton arrangement, and redox regulation. Moreover, the reversible oxidation of three glycolysis enzymes was observed using this method, and the regulation influence was verified by an enzyme activity assay. NADPH oxidase (NOX) inhibition treatment, in conjunction with the modified biotin switch method, was used to evaluate the global CysOX status. In conclusion, this versatile modified biotin switch assay provides an approach for the quantification of all reversible CysOX and for the study of redox signaling in atherosclerosis as well as in diseases in other biological systems.

  6. Electrocatalysis of hydrogen peroxide reactions on perovskite oxides: experiment versus kinetic modeling.

    Science.gov (United States)

    Poux, T; Bonnefont, A; Ryabova, A; Kéranguéven, G; Tsirlina, G A; Savinova, E R

    2014-07-21

    Hydrogen peroxide has been identified as a stable intermediate of the electrochemical oxygen reduction reaction on various electrodes including metal, metal oxide and carbon materials. In this article we study the hydrogen peroxide oxidation and reduction reactions in alkaline medium using a rotating disc electrode (RDE) method on oxides of the perovskite family (LaCoO3, LaMnO3 and La0.8Sr0.2MnO3) which are considered as promising electrocatalytic materials for the cathode of liquid and solid alkaline fuel cells. The experimental findings, such as the higher activity of Mn-compared to that of Co-perovskites, the shape of RDE curves, and the influence of the H2O2 concentration, are rationalized with the help of a microkinetic model.

  7. Modeling anti-Trypanosoma cruzi activity of N-oxide containing heterocycles.

    Science.gov (United States)

    Boiani, Mariana; Cerecetto, Hugo; Gonzalez, Mercedes; Gasteiger, Johann

    2008-01-01

    In the present study a systematic approach was used to model the anti-T. cruzi activity of a series of N-oxide containing heterocycles belonging to four chemical families with a wide structural diversity. The proposed mode of action implies the reduction of the N-oxide moiety; however, the biochemical mechanism underlying the anti-T. cruzi activity is still unkown. For structural representation two types of descriptors were analyzed: quantum chemical (AM1) global descriptors and properties coded by radial distribution function (RDF). Both types of descriptors point to the relevance of electronic properties. The local-RDF (LRDF) identified an electrophilic center at 4.1-4.9 A from the oxygen atom of the N-oxide moiety, although other properties are required to explain the biological activity. While the mode of action of N-oxide containing heterocycles is still unknown, the results obtained here strengthen the importance of the electrophilic character of the molecule and the possible participation of the heterocycle in a reduction process. The ability of these descriptors to distinguish among activity classes was assessed using Kohonen neural networks, and the best clustering descriptors were later used for model building. Different learning algorithms were used for model development, and stratified 10-fold cross-validation was used to evaluate the performance of each classifier. The best results were obtained using k-nearest neighbors (k-NN) and decision tree (J48) methods combined with global descriptors. Since tree-based methods are easily translated into classification rules, the J48 model is a useful tool in the de novo construction of new N-oxide containing heterocycle lead structures.

  8. Alternative Fabrication Routes toward Oxide-Dispersion-Strengthened Steels and Model Alloys

    Science.gov (United States)

    Bergner, Frank; Hilger, Isabell; Virta, Jouko; Lagerbom, Juha; Gerbeth, Gunter; Connolly, Sarah; Hong, Zuliang; Grant, Patrick S.; Weissgärber, Thomas

    2016-11-01

    The standard powder metallurgy (PM) route for the fabrication of oxide-dispersion-strengthened (ODS) steels involves gas atomization to produce a prealloyed powder, mechanical alloying (MA) with fine oxide powders, consolidation, and finally thermal/thermomechanical treatment (TMT). It is well established that ODS steels with superior property combinations, for example, creep and tensile strength, can be produced by this PM/MA route. However, the fabrication process is complex and expensive, and the fitness for scaling up to the industrial scale is limited. At the laboratory scale, production of small amounts of well-controlled model systems continues to be desirable for specific purposes, such as modeling-oriented experiments. Thus, from the laboratory to industrial application, there is growing interest in complementary or alternative fabrication routes for ODS steels and related model systems, which offer a different balance of cost, convenience, properties, and scalability. This article reviews the state of the art in ODS alloy fabrication and identifies promising new routes toward ODS steels. The PM/AM route for the fabrication of ODS steels is also described, as it is the current default process. Hybrid routes that comprise aspects of both the PM route and more radical liquid metal (LM) routes are suggested to be promising approaches for larger volumes and higher throughput of fabricated material. Although similar uniformity and refinement of the critical nanometer-sized oxide particles has not yet been demonstrated, ongoing innovations in the LM route are described, along with recent encouraging preliminary results for both extrinsic nano-oxide additions and intrinsic nano-oxide formation in variants of the LM route. Finally, physicochemical methods such as ion beam synthesis are shown to offer interesting perspectives for the fabrication of model systems. As well as literature sources, examples of progress in the authors' groups are also highlighted.

  9. Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

    DEFF Research Database (Denmark)

    Aranda, V.; Christensen, J. M.; Alzueta, Maria

    2013-01-01

    A detailed chemical kinetic model for oxidation of CH3OH at high pressure and intermediate temperatures has been developed and validated experimentally. Ab initio calculations and Rice–Ramsperger–Kassel–Marcus/transition state theory (RRKM/TST) analysis were used to obtain rate coefficients for CH...... the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, whereas increasing pressure shifted the ignition temperature toward lower values. Model predictions of the present experimental results, as well as rapid compression machine data from the literature, were...... and lower pressures. At the high pressures, the modeling predictions for onset of reaction were particularly sensitive to the CH 3 OH + HO 2⇌ CH 2 OH +H2O2reaction....

  10. Modeling the oxidative coupling of methane:Heterogeneous chemistry coupled with 3D flow field simulation

    Institute of Scientific and Technical Information of China (English)

    Yaghobi Nakisa; Ghoreishy Mir Hamid Reza

    2009-01-01

    The oxidative coupling of methane (OCM) over titanate perovskite catalyst has been developed by three-dimensional numerical simulations of flow field coupled with heat transfer as well as heterogeneous kinetic model.The reaction was assumed to take place both in the gas phase and on the catalytic surface.Kinetic rate constants were experimentally obtained using a ten step kinetic model.The simulation results agree quite well with the data of OCM experiments,which were used to investigate the effect of temperature on the selectivity and conversion obtained in the methane oxidative coupling process.The conversion of methane linearly increased with temperature and the selectivity of C2 was practically constant in the temperature range of 973-1073 K.The study shows that CFD tools make it possible to implement the heterogeneous kinetic model even for high exothermic reaction such as OCM.

  11. Preliminary Modeling of Corrosion/Oxidation Properties of CrAl Alloy-coated Cladding

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Jong-Dae; Kim, Hyo Chan; Shin, Chang Hwan; Yang, Yong Sik; In, Wang Kee [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2016-10-15

    Accident tolerant fuel (ATF) cladding has been being developed globally after the Fukushima accident with the demands for the nuclear fuel having higher safety at normal operation conditions as well as even in a severe accident conditions. Korea Atomic Energy Research Institute (KAERI) has been developed some of remarkable ATF cladding candidates. They showed a superior oxidation/corrosion resistance in water and steam conditions to the commercial Zr alloys and totally different behaviors from commercial Zr alloys. Prior to evaluate entire fuel performance of newly developed CrAl alloy cladding by KAERI collectively, preliminary model of water-side corrosion and high temperature oxidation model were proposed. They were highly consistent with experimental results. Also this model is useful for the quantitative analysis with given with relative superior characteristics to existing commercial fuel claddings.

  12. Structural phase diagrams of supported oxide nanowires from extended Frenkel-Kontorova models of diatomic chains.

    Science.gov (United States)

    Noguera, C; Goniakowski, J

    2013-08-28

    Relying on Frenkel Kontorova (FK) models of diatomic chains of increasing levels of complexity, this study presents an overall view of the diversity of structural effects that a compound (oxide) chain supported on a metal may display and helps assigning them to precise microscopic mechanisms. At each stage, the models are solved numerically, in order to provide phase diagrams as a function of chain-substrate interaction and misfit. Analytic derivations of transition lines are also provided within the continuum approximation. Their predictions are shown to quantitatively account for the numerical results, thus showing the validity of the continuum approximation in the misfit range under consideration. The present study thus extends our knowledge of the FK model by specifically focusing on diatomic chains and brings new information on a potentially interesting system which experimentalists just start being able to synthesize--oxide chains on metal substrates.

  13. Titanium oxide modeling and design for innovative biomedical surfaces: a concise review.

    Science.gov (United States)

    De Nardo, Luigi; Raffaini, Giuseppina; Ebramzadeh, Edward; Ganazzoli, Fabio

    2012-09-01

    The natural oxide layer on implantable alloys insulates the reactive underlying metal from the physiological environment, preventing substrate corrosion and device failure. This type of oxide film has had a major role in the minimization of functional failure and toxic response after implantation in the first generation biomaterials. Recent advances in theoretical, computational, and experimental surface engineering tools provide the foundation for the design of novel devices with improved performances in this regard based on conventional implantable metal alloys. An increasing number of technologies provide the possibility of tailoring chemico-physical and morphological parameters of the surface oxide layers. For some applications, such as dental implants, surface modifications result in substantial innovation and economic success. However, the selection of novel surfaces is in general based on experimental studies and has a limited theoretical and computational foundation. In this review, we offer a perspective analysis of the correlation between theoretical studies and chemical surface modification technologies, with a special emphasis on titanium oxide on Ti alloys. Theoretical approaches for the surface behavior at an atomistic level of description are presented, together with some adsorption studies on a rutile surface. The role of chemical and electrochemical surface modification technologies in modifying the TiO(2) structure, morphology, and chemistry to tailor in vivo biological response is then briefly reviewed. Finally, we discuss the role of surface modeling as a powerful design tool for a new generation of implantable devices in which metal oxide surface can be tuned to yield specific biological response.

  14. Oxidative damage compromises energy metabolism in the axonal degeneration mouse model of X-adrenoleukodystrophy.

    Science.gov (United States)

    Galino, Jorge; Ruiz, Montserrat; Fourcade, Stéphane; Schlüter, Agatha; López-Erauskin, Jone; Guilera, Cristina; Jove, Mariona; Naudi, Alba; García-Arumí, Elena; Andreu, Antoni L; Starkov, Anatoly A; Pamplona, Reinald; Ferrer, Isidre; Portero-Otin, Manuel; Pujol, Aurora

    2011-10-15

    Chronic metabolic impairment and oxidative stress are associated with the pathogenesis of axonal dysfunction in a growing number of neurodegenerative conditions. To investigate the intertwining of both noxious factors, we have chosen the mouse model of adrenoleukodystrophy (X-ALD), which exhibits axonal degeneration in spinal cords and motor disability. The disease is caused by loss of function of the ABCD1 transporter, involved in the import and degradation of very long-chain fatty acids (VLCFA) in peroxisomes. Oxidative stress due to VLCFA excess appears early in the neurodegenerative cascade. In this study, we demonstrate by redox proteomics that oxidative damage to proteins specifically affects five key enzymes of glycolysis and TCA (Tricarboxylic acid) cycle in spinal cords of Abcd1(-) mice and pyruvate kinase in human X-ALD fibroblasts. We also show that NADH and ATP levels are significantly diminished in these samples, together with decrease of pyruvate kinase activities and GSH levels, and increase of NADPH. Treating Abcd1(-) mice with the antioxidants N-acetylcysteine and α-lipoic acid (LA) prevents protein oxidation; preserves NADH, NADPH, ATP, and GSH levels; and normalizes pyruvate kinase activity, which implies that oxidative stress provoked by VLCFA results in bioenergetic dysfunction, at a presymptomatic stage. Our results provide mechanistic insight into the beneficial effects of antioxidants and enhance the rationale for translation into clinical trials for X-adrenoleukodystrophy.

  15. Modeling of single char combustion, including CO oxidation in its boundary layer

    Energy Technology Data Exchange (ETDEWEB)

    Lee, C.H.; Longwell, J.P.; Sarofim, A.F.

    1994-10-25

    The combustion of a char particle can be divided into a transient phase where its temperature increases as it is heated by oxidation, and heat transfer from the surrounding gas to an approximately constant temperature stage where gas phase reaction is important and which consumes most of the carbon and an extinction stage caused by carbon burnout. In this work, separate models were developed for the transient heating where gas phase reactions were unimportant and for the steady temperature stage where gas phase reactions were treated in detail. The transient char combustion model incorporates intrinsic char surface production of CO and CO{sub 2}, internal pore diffusion and external mass and heat transfer. The model provides useful information for particle ignition, burning temperature profile, combustion time, and carbon consumption rate. A gas phase reaction model incorporating the full set of 28 elementary C/H/O reactions was developed. This model calculated the gas phase CO oxidation reaction in the boundary layer at particle temperatures of 1250 K and 2500 K by using the carbon consumption rate and the burning temperature at the pseudo-steady state calculated from the temperature profile model but the transient heating was not included. This gas phase model can predict the gas species, and the temperature distributions in the boundary layer, the CO{sub 2}/CO ratio, and the location of CO oxidation. A mechanistic heat and mass transfer model was added to the temperature profile model to predict combustion behavior in a fluidized bed. These models were applied to data from the fluidized combustion of Newlands coal char particles. 52 refs., 60 figs.

  16. Determination of oxidative stress and effect of erdosteine on rhinitis medicamentosa in a rat model.

    Science.gov (United States)

    Dokuyucu, Recep; Cevik, Cengiz; Ozler, Gul Soylu; Ozgur, Tumay; Arli, Cengiz; Sefil, Fatih; Yonden, Zafer

    2014-11-05

    We aimed to determine the presence of oxidative stress in rhinitis medicamentosa (RM) and to evaluate the effect of erdosteine (ED) on mucosal changes in a rat model. Twenty-four male rats were used in this experimental study. Three groups were created. Group 1 (n=8) was the control group. Two puffs of 0.05% oxymetazolin were sprayed into the nasal cavities of the remaining rats (n=16) three times daily for eight weeks. One of these 16 rats was scarified at the end of the eight weeks and examined to confirm the presence of RM. Seven of the remaining 16 rats were killed, and venous blood samples were taken (Group 2). Group 3 (n=8) received 10mg/kg of an ED suspension orally for seven days. All rats were put on formalin for light microscopy. The total antioxidant status (TAS) was similar in all groups (p=0.073). The total oxidative status (TOS) of the RM group was significantly higher than that of the control group and RM+ED group (Group 3) (p=0.003 and p=0.011, respectively). The pathological recovery of the nasal mucosa of the rats was similar in the RM+ED and control groups. The TOS was high in this RM rat model, and oxidative stress was associated with RM. ED significantly ameliorated nasal mucosal changes induced by RM, suggesting that oxidative stress may play an important role in the pathophysiology of this condition.

  17. A global model of tropospheric chlorine chemistry: Organic versus inorganic sources and impact on methane oxidation

    Science.gov (United States)

    Hossaini, Ryan; Chipperfield, Martyn P.; Saiz-Lopez, Alfonso; Fernandez, Rafael; Monks, Sarah; Feng, Wuhu; Brauer, Peter; Glasow, Roland

    2016-12-01

    Chlorine atoms (Cl) are highly reactive toward hydrocarbons in the Earth's troposphere, including the greenhouse gas methane (CH4). However, the regional and global CH4 sink from Cl is poorly quantified as tropospheric Cl concentrations ([Cl]) are uncertain by 2 orders of magnitude. Here we describe the addition of a detailed tropospheric chlorine scheme to the TOMCAT chemical transport model. The model includes several sources of tropospheric inorganic chlorine (Cly), including (i) the oxidation of chlorocarbons of natural (CH3Cl, CHBr2Cl, CH2BrCl, and CHBrCl2) and anthropogenic (CH2Cl2, CHCl3, C2Cl4, C2HCl3, and CH2ClCH2Cl) origin and (ii) sea-salt aerosol dechlorination. Simulations were performed to quantify tropospheric [Cl], with a focus on the marine boundary layer, and quantify the global significance of Cl atom CH4 oxidation. In agreement with observations, simulated surface levels of hydrogen chloride (HCl), the most abundant Cly reservoir, reach several parts per billion (ppb) over polluted coastal/continental regions, with sub-ppb levels typical in more remote regions. Modeled annual mean surface [Cl] exhibits large spatial variability with the largest levels, typically in the range of 1-5 × 104 atoms cm-3, in the polluted northern hemisphere. Chlorocarbon oxidation provides a tropospheric Cly source of up to 4320 Gg Cl/yr, sustaining a background surface [Cl] of methane sink of 12-13 Tg CH4/yr due the CH4 + Cl reaction ( 2.5% of total CH4 oxidation). Larger regional effects are predicted, with Cl accounting for 10 to >20% of total boundary layer CH4 oxidation in some locations.

  18. Oxidation of elemental mercury in the atmosphere; Constraints imposed by global scale modelling

    Energy Technology Data Exchange (ETDEWEB)

    Bergan, Torbjoern; Rodhe, Henning [Stockholm Univ. (Sweden). Dept. of Meteorology

    2000-05-01

    Based on the global mercury model published by Bergan et al. (1999), we present here further results from simulations where the central theme has been to evaluate the role of ozone and the hydroxyl radical as possible gas phase oxidants for the oxidation of elemental mercury in the atmosphere. The magnitude of natural and man-made mercury emissions are taken from recent literature estimates and the flux from land areas is assumed to vary by season. We consider only two mercury reservoirs, elemental mercury, Hg{sup 0}, and the more soluble divalent form, Hgll. Wet and dry deposition of Hgll is explicitly treated. Applying monthly mean fields of ozone for the oxidation of gas phase Hg{sup 0} and using the reaction rate by Hall (1995) yields a global transformation of Hg{sup 0} to Hgll which is too slow to keep the simulated concentration of Hg{sup 0} near observed values. This shows that there are additional important removal processes for Hg{sup 0} or that the reaction rate proposed by Hall (1995) is too slow. A simulation in which the oxidation rate was artificially increased, so that the global turn-over time of Hg{sup 0} was one year and the simulated average concentration of Hg{sup 0} was realistic, produced latitudinal and seasonal variations in Hg{sup 0} that did not support the hypothesis that gas phase reaction with O{sub 3} is the major oxidation process for Hg{sup 0}. Recent studies indicate that OH may be an important gas phase oxidant for Hg{sup 0}. Using OH as the oxidant and applying the preliminary oxidation rate by Sommar et al. (1999) gave an unrealistically large removal of Hg{sup 0} from the atmosphere. From calculations using a slower reaction rate, corresponding to a turn-over time of Hg{sup 0} of one year, we calculated concentrations of both Hg{sup 0} in surface air and Hgll in precipitation which correspond, both in magnitude and temporal variation, to seasonal observations in Europe and North America. This result supports the suggestion that

  19. Dynamic modelling of nitrous oxide emissions from three Swedish sludge liquor treatment systems

    DEFF Research Database (Denmark)

    Lindblom, E.; Arnell, M.; Flores-Alsina, X.

    2014-01-01

    The objective of this paper is to model the dynamics and validate the results of nitrous oxide (N2O)emissions from three Swedish nitrifying/denitrifying, nitritation and anammox systems treating real anaerobic digester sludge liquor. The Activated Sludge Model No. 1 is extended to describe N2O......) a moving-bed biofilm reactor. Results show that the calibrated model is partly capable of reproducing the behaviour of N2O as well as the nitritation/nitrification/denitrification dynamics. However, the results emphasize that additional work is required before N2O emissions from sludge liquor treatment...

  20. Dynamic modelling of nitrous oxide emissions from three Swedish sludge liquor treatment systems

    DEFF Research Database (Denmark)

    Lindblom, E.; Arnell, M.; Flores-Alsina, X.

    2016-01-01

    The objective of this paper is to model the dynamics and validate the results of nitrous oxide (N2O)emissions from three Swedish nitrifying/denitrifying, nitritation and anammox systems treating real anaerobic digester sludge liquor. The Activated Sludge Model No. 1 is extended to describe N2O......) a moving-bed biofilm reactor. Results show that the calibrated model is partly capable of reproducing the behaviour of N2O as well as the nitritation/nitrification/denitrification dynamics. However, the results emphasize that additional work is required before N2O emissions from sludge liquor treatment...

  1. Estimating global nitrous oxide emissions by lichens and bryophytes with a process-based productivity model

    Science.gov (United States)

    Porada, Philipp; Pöschl, Ulrich; Kleidon, Axel; Beer, Christian; Weber, Bettina

    2017-04-01

    Lichens and bryophytes have been shown to release significant amounts of nitrous oxide (N2O), which is a strong greenhouse gas and atmospheric ozone - depleting agent. Relative contributions of lichens and bryophytes to nitrous oxide emissions are largest in dryland and tundra regions, with potential implications for the nitrogen balance of these ecosystems. So far, this estimate is based on large-scale values of net primary productivity of lichens and bryophytes, which are derived from empirical upscaling of field measurements. Productivity is then converted to nitrous oxide emissions by empirical relationships between productivity and respiration, as well as respiration and nitrous oxide release. Alternatively, we quantify nitrous oxide emissions using a global process-based non-vascular vegetation model of lichens and bryophytes. The model simulates photosynthesis and respiration of lichens and bryophytes directly as a function of climatic conditions, such as light and temperature. Nitrous oxide emissions are then derived from simulated respiration, assuming a fixed relationship between the two fluxes, which is based on laboratory experiments under varying environmental conditions. Our approach yields a global estimate of 0.27 (0.19 - 0.35) Tg N2O yr-1 released by lichens and bryophytes. This is at the lower end of the range of a previous, empirical estimate, but corresponds to about 50 % of the atmospheric deposition of nitrous oxide into the oceans or 25 % of the atmospheric deposition on land. We conclude that, while productivity of lichens and bryophytes at large scale is relatively well constrained, improved estimates of their respiration may help to reduce uncertainty of predicted N2O emissions. This is particularly important for quantifying the spatial distribution of N2O emissions by lichens and bryophytes, since simulated respiration shows a different global pattern than productivity. We find that both physiological variation among species as well as

  2. Ionic conductivity studies of solid oxide fuel cell electrolytes and theoretical modeling of an entire solid oxide fuel cell

    Science.gov (United States)

    Pornprasertsuk, Rojana

    Because of the steep increase in oil prices, the global warming effect and the drive for energy independence, alternative energy research has been encouraged worldwide. The sustainable fuels such as hydrogen, biofuel, natural gas, and solar energy have attracted the attention of researchers. To convert these fuels into a useful energy source, an energy conversion device is required. Fuel cells are one of the energy conversion devices which convert chemical potentials into electricity. Due to their high efficiency, the ease to scale from 1 W range to megawatts range, no recharging requirement and the lack of CO2 and NOx emission (if H2 and air/O 2 are used), fuel cells have become a potential candidate for both stationary power generators and portable applications. This thesis has been focused primarily on solid oxide fuel cell (SOFC) studies due to its high efficiency, varieties of fuel choices, and no water management problem. At the present, however, practical applications of SOFCs are limited by high operating temperatures that are needed to create the necessary oxide-ion vacancy mobility in the electrolyte and to create sufficient electrode reactivities. This thesis introduces several experimental and theoretical approaches to lower losses both in the electrolyte and the electrodes. Yttria stabilized zirconia (YSZ) is commonly used as a solid electrolyte for SOFCs due to its high oxygen-ion conductivity. To improve the ionic conductivity for low temperature applications, an approach that involves dilating the structure by irradiation and introducing edge dislocations into the electrolyte was studied. Secondly, to understand the activation loss in SOFC, the kinetic Monte Carlo (KMC) technique was implemented to model the SOFC operation to determining the rate-limiting step due to the electrodes on different sizes of Pt catalysts. The isotope exchange depth profiling technique was employed to investigate the irradiation effect on the ionic transport in different

  3. Soot formation and oxidation during bio-oil gasification:experiments and modeling

    Institute of Scientific and Technical Information of China (English)

    Younes; Chhiti; Marine; Peyrot; Sylvain; Salvador

    2013-01-01

    A model is proposed to describe soot formation and oxidation during bio-oil gasification.It is based on the description of bio-oil heating,devolatilization,reforming of gases and conversion of both char and soot solids.Detailed chemistry (159 species and 773 reactions) is used in the gas phase.Soot production is described by a single reaction based on C2H2species concentration and three heterogeneous soot oxidation reactions.To support the validation of the model,three sets of experiments were carried out in a lab-scale Entrained Flow Reactor (EFR) equipped with soot quantification device.The temperature was varied from 1000 to 1400 C and three gaseous atmospheres were considered:default of steam,large excess of steam(H2O/C=8),and the presence of oxygen in the O/C range of 0.075–0.5.The model is shown to accurately describe the evolution of the concentration of the main gas species and to satisfactorily describe the soot concentration under the three atmospheres using a single set of identified kinetic parameters.Thanks to this model the contribution of different mechanisms involved in soot formation and oxidation in various situations can be assessed.

  4. Oxidation of Carbon Fibers in a Cracked Ceramic Matrix Composite Modeled as a Function of Temperature

    Science.gov (United States)

    Halbig, Michael C.; Cawley, James D.; Eckel, Andrew J.

    2003-01-01

    The oxidation model simulates the oxidation of the reinforcing carbon fibers within a ceramic matrix composite material containing as-fabricated microcracks. The physics-based oxidation model uses theoretically and experimentally determined variables as input for the model. The model simulates the ingress of oxygen through microcracks into a two-dimensional plane within the composite material. Model input includes temperature, oxygen concentration, the reaction rate constant, the diffusion coefficient, and the crack opening width as a function of the mechanical and thermal loads. The model is run in an iterative process for a two-dimensional grid system in which oxygen diffuses through the porous and cracked regions of the material and reacts with carbon in short time steps. The model allows the local oxygen concentrations and carbon volumes from the edge to the interior of the composite to be determined over time. Oxidation damage predicted by the model was compared with that observed from microstructural analysis of experimentally tested composite material to validate the model for two temperatures of interest. When the model is run for low-temperature conditions, the kinetics are reaction controlled. Carbon and oxygen reactions occur relatively slowly. Therefore, oxygen can bypass the carbon near the outer edge and diffuse into the interior so that it saturates the entire composite at relatively high concentrations. The kinetics are limited by the reaction rate between carbon and oxygen. This results in an interior that has high local concentrations of oxygen and a similar amount of consumed carbon throughout the cross section. When the model is run for high-temperature conditions, the kinetics are diffusion controlled. Carbon and oxygen reactions occur very quickly. The carbon consumes oxygen as soon as it is supplied. The kinetics are limited by the relatively slow rate at which oxygen is supplied in comparison to the relatively fast rate at which carbon and

  5. Oxidative stress is increased in C. elegans models of Huntington's disease but does not contribute to polyglutamine toxicity phenotypes.

    Science.gov (United States)

    Machiela, Emily; Dues, Dylan J; Senchuk, Megan M; Van Raamsdonk, Jeremy M

    2016-12-01

    Huntington's disease (HD) is an adult onset neurodegenerative disorder for which there is currently no cure. While HD patients and animal models of the disease exhibit increased oxidative damage, it is currently uncertain to what extent oxidative stress contributes to disease pathogenesis. In this work, we use a genetic approach to define the role of oxidative stress in HD. We find that a C. elegans model of HD expressing a disease-length polyglutamine tract in the body wall muscle is hypersensitive to oxidative stress and shows an upregulation of antioxidant defense genes, indicating that the HD worm model has increased levels of oxidative stress. To determine whether this increase in oxidative stress contributes to the development of polyglutamine-toxicity phenotypes in this HD model, we examined the effect of deleting individual superoxide dismutase (sod) genes in the HD worm model. As predicted, we found that deletion of sod genes in the HD worm model resulted in a clear increase in sensitivity to oxidative stress. However, we found that increasing oxidative stress in the HD worm model did not exacerbate deficits caused by polyglutamine toxicity. We confirmed these observations in two worm models expressing disease-length polyglutamine tracts in neurons. Furthermore, we found that treatment with antioxidants failed to rescue movement deficits or decrease aggregation in HD worm models. Combined, this suggests that the increase in oxidative stress in worm models of HD does not contribute to the phenotypic deficits observed in these worms, and provides a possible explanation for the failure of antioxidants in HD clinical trials.

  6. A Two-Dimensional, Finite-Difference Model of the Oxidation of a Uranium Carbide Fuel Pellet

    OpenAIRE

    Shepherd, J; Fairweather, M; Hanson, BC; Heggs, PJ

    2015-01-01

    The oxidation of spent uranium carbide fuel, a candidate fuel for Generation IV nuclear reactors, is an important process in its potential reprocessing cycle. However, the oxidation of uranium carbide in air is highly exothermic. A model has therefore been developed to predict the temperature rise, as well as other useful information such as reaction completion times, under different reaction conditions in order to help in deriving safe oxidation conditions. Finite difference-methods are used...

  7. A comprehensive model for the supported vanadium oxide catalyst: The umbrella model

    NARCIS (Netherlands)

    Lingen, J.N.J. van

    2006-01-01

    Supported vanadium oxide catalysts are widely used in industry. However, the molecular structure of the active species, responsible for the actual catalysis, is for a large part still unknown. This thesis describes four years study on the elucidation of this molecular structure. It mainly focuses on

  8. Modeling selenite adsorption envelopes on oxides, clay minerals, and soils using the triple layer model

    Science.gov (United States)

    Selenite adsorption behavior was investigated on amorphous aluminum and iron oxides, clay minerals: kaolinite, montmorillonite, and illite, and 45 surface and subsurface soil samples from the Southwestern and Midwestern regions of the USA as a function of solution pH. Selenite adsorption decreased ...

  9. Shock tube and chemical kinetic modeling study of the oxidation of 2,5-dimethylfuran.

    Science.gov (United States)

    Sirjean, Baptiste; Fournet, René; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique; Wang, Weijing; Oehlschlaeger, Matthew A

    2013-02-21

    A detailed kinetic model describing the oxidation of 2,5-dimethylfuran (DMF), a potential second-generation biofuel, is proposed. The kinetic model is based upon quantum chemical calculations for the initial DMF consumption reactions and important reactions of intermediates. The model is validated by comparison to new DMF shock tube ignition delay time measurements (over the temperature range 1300-1831 K and at nominal pressures of 1 and 4 bar) and the DMF pyrolysis speciation measurements of Lifshitz et al. [ J. Phys. Chem. A 1998 , 102 ( 52 ), 10655 - 10670 ]. Globally, modeling predictions are in good agreement with the considered experimental targets. In particular, ignition delay times are predicted well by the new model, with model-experiment deviations of at most a factor of 2, and DMF pyrolysis conversion is predicted well, to within experimental scatter of the Lifshitz et al. data. Additionally, comparisons of measured and model predicted pyrolysis speciation provides validation of theoretically calculated channels for the oxidation of DMF. Sensitivity and reaction flux analyses highlight important reactions as well as the primary reaction pathways responsible for the decomposition of DMF and formation and destruction of key intermediate and product species.

  10. Mesoscale modeling of combined aerosol and photo-oxidant processes in the Eastern Mediterranean

    Directory of Open Access Journals (Sweden)

    M. Lazaridis

    2005-01-01

    Full Text Available Particulate matter and photo-oxidant processes in the Eastern Mediterranean have been studied using the UAM-AERO mesoscale air quality model in conjunction with the NILU-CTM regional model. Meteorological data were obtained from the RAMS prognostic meteorological model. The modeling domain includes the eastern Mediterranean area between the Greek mainland and the island of Crete. The modeling system is applied to study the atmospheric processes in three periods, i.e. 13–16 July 2000, 26–30 July 2000 and 7–14 January 2001. The spatial and temporal distributions of both gaseous and particulate matter pollutants have been extensively studied together with the identification of major emission sources in the area. The modeling results were compared with field data obtained in the same period. The objective of the current modeling work was mainly to apply the UAM-AERO mesoscale model in the eastern Mediterranean in order to assess the performed field campaigns and determine that the applied mesoscale model is fit for this purpose. Comparison of the modeling results with measured data was performed for a number of gaseous and aerosol species. The UAM-AERO model underestimates the PM10 measured concentrations during summer and winter campaigns. Discrepancies between modeled and measured data are attributed to unresolved particulate matter emissions. Particulate matter in the area is mainly composed by sulphate, sea salt and crustal materials, and with significant amounts of nitrate, ammonium and organics. During winter the particulate matter and oxidant concentrations were lower than the summer values.

  11. Metallothionein-1 and nitric oxide expression are inversely correlated in a murine model of Chagas disease

    OpenAIRE

    2014-01-01

    Chagas disease, caused by Trypanosoma cruzi, represents an endemic among Latin America countries. The participation of free radicals, especially nitric oxide (NO), has been demonstrated in the pathophysiology of seropositive individuals with T. cruzi. In Chagas disease, increased NO contributes to the development of cardiomyopathy and megacolon. Metallothioneins (MTs) are efficient free radicals scavengers of NO in vitro and in vivo. Here, we developed a murine model of the chronic phase of C...

  12. Simulation of polyethylene oxide : improved structure using better models for hydrogen and flexible walls.

    Energy Technology Data Exchange (ETDEWEB)

    Halley, J. W.; Duan, Y.; Nielsen, B.; Redfern, P. C.; Curtiss, L. A.; Univ. of Minnesota

    2001-08-22

    We describe calculations of the structure of amorphous polyethylene oxide using a previously reported model, but with better treatment of hydrogen positions and in a code which allows relaxation of stresses in the polymerized sample by Rahman-Parrinello techniques. We also report the effects of two different intermolecular force field potentials and find that our earlier, empirical force field produces better agreement with experimental neutron scattering results than a force field derived from ab initio electronic structure calculations.

  13. Hypoxia and oxidation levels of DNA and lipids in humans and animal experimental models

    DEFF Research Database (Denmark)

    Møller, Peter; Risom, Lotte; Lundby, Carsten

    2008-01-01

    The objective of this review was to evaluate the association between hypoxia and oxidative damage to DNA and lipids. Evaluation criteria encompassed specificity and validation status of the biomarkers, study design, strength of the association, dose-response relationship, biological plausibility,...... in subjects at high altitude. Most of the animal experimental models should be interpreted with caution because the assays for assessment of lipid peroxidation products have suboptimal validity....

  14. Dielectric Relaxation of Lanthanide-Based Ternary Oxides: Physical and Mathematical Models

    Directory of Open Access Journals (Sweden)

    Chun Zhao

    2012-01-01

    Full Text Available Cerium-doped hafnium oxides (CexHf1−xO2 and lanthanum-doped zirconium oxides (LaxZr1−xO2 were investigated. The highest dielectric constants, k, were obtained from lightly doped oxides with an La content of x=0.09 and a Ce content of x=0.1, for which k-values of 33~40 were obtained. The dielectric relaxation appears to be related to the size of crystal grains formed during annealing, which was dependent on the doping level. The physical and mathematical models were used to analyze the relationship between k-values and frequencies. The variations in the k-values up to megahertz frequencies for both CexHf1−xO2 and LaxZr1−xO2 are simulated based on the Curie-von Schweidler (CS or Havriliak-Negami (HN relationships. Concerning the lightly doped CexHf1−xO2 and LaxZr1−xO2, the data extracted are best modeled by the HN law, while LaxZr1−xO2 with doping level from x=0.22 to 0.63 are best modelled based on the CS law.

  15. Pyrite oxidation in saturated and Unsaturated Porous Media Flow: AComparison of alternative mathematical modeling approaches

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Tianfu; White, Stephen P.; Pruess, Karsten

    1998-02-15

    Pyrite (FeS{sub 2}) is one of the most common naturally occurring minerals that is present in many subsurface environments. It plays an important role in the genesis of enriched ore deposits through weathering reactions, is the most abundant sulfide mineral in many mine tailings, and is the primary source of acid drainage from mines and waste rock piles. The pyrite oxidation reaction serves as a prototype for oxidative weathering processes with broad significance for geoscientific, engineering, and environmental applications. Mathematical modeling of these processes is extremely challenging because aqueous concentrations of key species vary over an enormous range, oxygen inventory and supply are typically small in comparison to pyrite inventory, and chemical reactions are complex, involving kinetic control and microbial catalysis. We present the mathematical formulation of a general multi-phase advective-diffusive reactive transport model for redox processes. Two alternative implementations were made in the TOUGHREACT and TOUGH2-CHEM simulation codes which use sequential iteration and simultaneous solution, respectively. The simulators are applied to reactive consumption of pyrite in (1) saturated flow of oxidizing water, and (2) saturated-unsaturated flow in which oxygen transport occurs in both aqueous and gas phases. Geochemical evolutions predicted from different process models are compared, and issues of numerical accuracy and efficiency are discussed.

  16. Mesospheric nitric oxide transport: Model-data comparisons and ionospheric implications

    Science.gov (United States)

    Siskind, D. E.; Sassi, F.; Friedrich, M.; Hervig, M. E.

    2016-12-01

    The Whole Atmosphere Community Climate Model (WACCM) with specified dynamics has been used to simulate the vertical and horizontal transport of wintertime nitric oxide. Three simulations have been performed for year 2009. Two are constrained with the NOGAPS-ALPHA (Navy Operational Global Atmospheric Prediction System-Advanced Level Physics High Altitude) analysis which extends up to 92 km, using two different values of the Prandtl number. The third simulation is constrained by the Modern Era Retrospective Analysis for Research and Applications (MERRA) which only extends up to 50 km. Validation of the resultant nitric oxide and methane fields are performed with data from the Solar Occultation for Ice Experiment (SOFIE) instrument on the NASA/AIM satellite. The calculated atomic oxygen is compared with a recently published climatology of lower mesospheric atomic oxygen. These fields are then used to as input to a model of the ionospheric D region and compared with a database of sounding rocket measurements dating back to the 1960s. The results suggest that with an improved model of mesospheric nitric oxide, good agreement can be obtained between calculated and observed D region electron densities. The implication of these results for our understanding of such classic aeronomical problems as the D region winter anomaly is discussed.

  17. Evaluation of Toxicity Ranking for Metal Oxide Nanoparticles via an in Vitro Dosimetry Model.

    Science.gov (United States)

    Liu, Rong; Liu, Haoyang Haven; Ji, Zhaoxia; Chang, Chong Hyun; Xia, Tian; Nel, Andre E; Cohen, Yoram

    2015-09-22

    It has been argued that in vitro toxicity testing of engineered nanoparticles (NPs) should consider delivered dose (i.e., NP mass settled per suspension volume) rather than relying exclusively on administered dose (initial NP mass concentration). Delivered dose calculations require quantification of NP sedimentation in tissue cell culture media, taking into consideration fundamental suspension properties. In this article, we calculate delivered dose using a first-principles "particles in a box" sedimentation model, which accounts for the particle size distribution, fractal dimension, and permeability of agglomerated NPs. The sedimentation model was evaluated against external and our own experimental sedimentation data for metal oxide NPs. We then utilized the model to construct delivered dose-response analysis for a library of metal oxide NPs (previously used for hazard ranking and prediction making) in different cell culture media. Hierarchical hazard ranking of the seven (out of 24) toxic metal oxide NPs in our library, using EC50 calculated on the basis of delivered dose, did not measurably differ from our ranking based on administered dose. In contrast, simplified sedimentation calculations based on the assumption of impermeable NP agglomerates of a single average size significantly underestimated the settled NPs' mass, resulting in misinterpretation of toxicity ranking. It is acknowledged that in vitro dose-response outcomes are likely to be shaped by complex toxicodynamics, which include NP/cellular association, triggering of dynamic cell response pathways involved in NP uptake, and multiple physicochemical parameters that influence NP sedimentation and internalization.

  18. The modeling of a standalone solid-oxide fuel cell auxiliary power unit

    Science.gov (United States)

    Lu, N.; Li, Q.; Sun, X.; Khaleel, M. A.

    In this research, a Simulink model of a standalone vehicular solid-oxide fuel cell (SOFC) auxiliary power unit (APU) is developed. The SOFC APU model consists of three major components: a controller model; a power electronics system model; and an SOFC plant model, including an SOFC stack module, two heat exchanger modules, and a combustor module. This paper discusses the development of the nonlinear dynamic models for the SOFC stacks, the heat exchangers and the combustors. When coupling with a controller model and a power electronic circuit model, the developed SOFC plant model is able to model the thermal dynamics and the electrochemical dynamics inside the SOFC APU components, as well as the transient responses to the electric loading changes. It has been shown that having such a model for the SOFC APU will help design engineers to adjust design parameters to optimize the performance. The modeling results of the SOFC APU heat-up stage and the output voltage response to a sudden load change are presented in this paper. The fuel flow regulation based on fuel utilization is also briefly discussed.

  19. Verification of mathematical models for calculation of viscosity of molten oxide systems

    Directory of Open Access Journals (Sweden)

    S. Rosypalová

    2014-06-01

    Full Text Available The subject of this work is the comparison of numerically obtained values of dynamic viscosity using different types of mathematical models and experimentally measured data of viscosity of oxide systems. The ternary system of SiO2-CaO-Al2O3, which presents simplified base of the casting powders used in technological process, was submitted to the experiment. Experimental research of dynamic viscosity is highly limited by its complexity. That’s why model studies play such an important role in this field. For mathematic calculation of viscosity the NPL model, Iida model and Urbain model were chosen. The results of simulation were compared with the experimentally obtained values of viscosity.

  20. Fuzzy Neural Network Model of 4-CBA Concentration for Industrial Purified Terephthalic Acid Oxidation Process

    Institute of Scientific and Technical Information of China (English)

    刘瑞兰; 苏宏业; 牟盛静; 贾涛; 陈渭泉; 褚健

    2004-01-01

    A fuzzy neural network (FNN) model is developed to predict the 4-CBA concentration of the oxidation unit in purified terephthalic acid process. Several technologies are used to deal with the process data before modeling.First,a set of preliminary input variables is selected according to prior knowledge and experience. Secondly,a method based on the maximum correlation coefficient is proposed to detect the dead time between the process variables and response variables. Finally, the fuzzy curve method is used to reduce the unimportant input variables.The simulation results based on industrial data show that the relative error range of the FNN model is narrower than that of the American Oil Company (AMOCO) model. Furthermore, the FNN model can predict the trend of the 4-CBA concentration more accurately.

  1. Modeling a full scale oxidation ditch system, coupling hydrodynamics and biological kinetics using ASM1 model

    Energy Technology Data Exchange (ETDEWEB)

    Haouech, L.; Sperandio, M.; Cock, A.; Shayeb, H.

    2009-07-01

    Optimising the aeration in oxidation ditch aims on one hand, a better wastewater quality and on the other hand, a reduction of the energy expenses of the treatment. given that the energy expenses relative to the aeration represents 60 to 80% of the operating costs of a wastewater treatment plant and given that the biological activity is strictly dependent on dissolved oxygen, the transfer of oxygen is considered as one of the key parameters of the process. (Author) 8 refs.

  2. Numerical simulation of a combined oxidation ditch flow using 3D k-εturbulence model

    Institute of Scientific and Technical Information of China (English)

    LUO Lin; LI Wei-min; DENG Yong-sen; WANG Tao

    2005-01-01

    The standard three dimensional(3D) k-ε turbulence model was applied to simulate the flow field of a small scale combined oxidation ditch. The moving mesh approach was used to model the rotor of the ditch. Comparison of the computed and the measured data is acceptable. A vertical reverse flow zone in the ditch was found, and it played a very important role in the ditch flow behavior. The flow pattern in the ditch is discussed in detail, and approaches are suggested to improve the hydrodynamic performance in the ditch.

  3. Modelling the growth process of porous aluminum oxide film during anodization

    Science.gov (United States)

    Aryslanova, E. M.; Alfimov, A. V.; Chivilikhin, S. A.

    2015-11-01

    Currently it has become important for the development of metamaterials and nanotechnology to obtain regular self-assembled structures. One such structure is porous anodic alumina film that consists of hexagonally packed cylindrical pores. In this work we consider the anodization process, our model takes into account the influence of layers of aluminum and electrolyte on the rate of growth of aluminum oxide, as well as the effect of surface diffusion. In present work we consider those effects. And as a result of our model we obtain the minimum distance between centers of alumina pores in the beginning of anodizing process.

  4. Establishment and calibration of consensus process model for nitrous oxide dynamics in water quality engineering

    DEFF Research Database (Denmark)

    Domingo-Felez, Carlos

    production pathways have been identified from pure culture studies, while mechanisms are still being unravelled. Heterotrophic bacteria (HB) and ammonium oxidizing bacteria (AOB) are well known to produce N2O. However, the effect of environmental factors on N2O production is not yet well understood. Current...... in heterotrophic processes is explored via an analogy to current intensity through resistors in electric circuits. While further model validation is required, this approach captured the electron competition during denitrification for four different carbon sources. Overall, a combination of modelling...

  5. Therapeutic effects of hydrogen saturated saline on rat diabetic model and insulin resistant model via reduction of oxidative stress

    Institute of Scientific and Technical Information of China (English)

    WANG Qi-jin; ZHA Xiao-juan; KANG Zhi-min; XU Mao-jin; HUANG Qin; ZOU Da-jin

    2012-01-01

    Background Molecular hydrogen,as a novel antioxidant,has been proven effective in treating many diseases.This study aimed to evaluate the therapeutic effects of hydrogen saturated saline in treatment of a rat model of diabetes mellitus and a rat model of insulin resistant.Methods A rat diabetes mellitus model was established by feeding a high fat/high carbohydrate diet followed by injection of a small dose of streptozotocin,and an insulin resistant model was induced with a high glucose and high fat diet.Hydrogen saturated saline was administered to rats with both models conditions on a daily basis for eight weeks.A pioglitazone-treated group and normal saline-treated group served as positive and negative controls.The general condition,body weight,blood glucose,blood lipids,and serum insulin levels of rats were examined at the 8th week after treatment.The oxidative stress indices,including serum superoxide dismutase (SOD),glutathione (GSH) and malondialdehyde (MDA) were also evaluated after eight weeks of treatment using the commercial kits.Results Hydrogen saturated saline showed great efficiency in improving the insulin sensitivity and lowering blood glucose and lipids.Meanwhile,the therapeutic effects of hydrogen saturated saline were superior to those of pioglitazone.Hydrogen saturated saline markedly attenuated the MDA level and elevated the levels of antioxidants SOD and GSH.Conclusion Hydrogen saturated saline may improve the insulin resistance and alleviate the symptoms of diabetes mellitus by reducing the oxidative stress and enhancing the anti-oxidant system.

  6. Modeling Species Inhibition of NO Oxidation in Urea-SCR Catalysts for Diesel Engine NOx Control

    Energy Technology Data Exchange (ETDEWEB)

    Devarakonda, Maruthi N.; Tonkyn, Russell G.; Tran, Diana N.; Lee, Jong H.; Herling, Darrell R.

    2011-04-20

    Urea-selective catalytic reduction (SCR) catalysts are regarded as the leading NOx aftertreatment technology to meet the 2010 NOx emission standards for on-highway vehicles running on heavy-duty diesel engines. However, issues such as low NOx conversion at low temperature conditions still exist due to various factors, including incomplete urea thermolysis, inhibition of SCR reactions by hydrocarbons and H2O. We have observed a noticeable reduction in the standard SCR reaction efficiency at low temperature with increasing water content. We observed a similar effect when hydrocarbons are present in the stream. This effect is absent under fast SCR conditions where NO ~ NO2 in the feed gas. As a first step in understanding the effects of such inhibition on SCR reaction steps, kinetic models that predict the inhibition behavior of H2O and hydrocarbons on NO oxidation are presented in the paper. A one-dimensional SCR model was developed based on conservation of species equations and was coded as a C-language S-function and implemented in Matlab/Simulink environment. NO oxidation and NO2 dissociation kinetics were defined as a function of the respective adsorbate’s storage in the Fe-zeolite SCR catalyst. The corresponding kinetic models were then validated on temperature ramp tests that showed good match with the test data. Such inhibition models will improve the accuracy of model based control design for integrated DPF-SCR aftertreatment systems.

  7. [18F]FDG microPET在评价二次打击所致大鼠急性肺损伤中的应用%Evaluation of the inflammatory response in two -hit acute lung injury model of rats using [18SF]FDG microPET

    Institute of Scientific and Technical Information of China (English)

    周光居; 张茂; 干建新; 徐少文; 江观玉

    2009-01-01

    目的:对一次打击和二次打击进行深入的对比研究,应用[18F]-氟脱氧葡萄糖(FDG)小动物正电子断层扫描仪(microPET)对肺内的炎症反应进行评价.方法:将33只SD雄性大鼠随机分为4组,分别为生理盐水(Ns)组(n=3):生理盐水1 mL/kg腹腔注射(ip)及16 h后生理盐水0.5 mL/kg气道内滴入(it);脂多糖(LPS)组(n=10):LPS 5 mg/ks ip及16 h后生理盐水0.5 mL/kg it;HCl组(n=10):生理盐水1 mL/ks ip及16 h后HCl(pH=1,2,0,5 mL/kg,it);二次打击LPS-HCl组(n=10):LPS 5 mg/ks ip及16 h后HCl(pH=1.2,0.5mL/kg,it).在盐酸或生理盐水气道滴入前,所有大鼠戊巴比妥钠腹腔注射麻醉,行股动脉插管,连续监测平均动脉压(MAP),并于it后0.5 h、1.5 h及4 h后抽血,查动脉血气分析,it后4 h行[18F]FDG micro PET胸部扫描,然后处死动物,取肺组织进行组织病理学观察.结果:血气分析显示LPS-HCl大鼠低氧血症和二氧化碳潴留显著;MAP在气道内滴入盐酸或生理盐水前无差异,但在滴人后,LPs-HCl组中MAP较其它3组显著降低;microPET示感兴趣区(ROI)在右肺与右上肢肌肉之间的比值进行比较,LPS-HCl组中此比值为9,00±1.41,显著高于LPS组4.01±0.60(P<0.01)和HCl组3.33±0.55(P<0.01);肺损伤病理评分在LPS-HCl组中为12.70±0.95,显著高于HCl组8.40±1.26(P<0.01)和LPS组7.00±0.82(P<0.01).结论:二次打击可使机体肺内产生剧烈而且持久的炎症反应,比一次打击更容易诱发急性肺损伤;microPET作为一种无创的检测手段,能很好地评价急性肺损伤时肺内的炎症反应.

  8. Shock-tube and modeling study of ethane pyrolysis and oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Hidaka, Yoshiaki; Sato, Kazutaka; Hoshikawa, Hiroki; Nishimori, Toshihide; Takahashi, Rie; Tanaka, Hiroya; Inami, Koji; Ito, Nobuhiro

    2000-02-01

    Pyrolysis and oxidation of ethane were studied behind reflected shock waves in the temperature range 950--1,900 K at pressures of 1.2--4.0 atm. Ethane decay rates in both pyrolysis and oxidation were measured using time-resolved infrared (IR) laser absorption at 3.39 {micro}m, and CO{sub 2} production rates in oxidation were measured by time-resolved thermal IR emission at 4.24 {micro}m. The product yields were also determined using a single-pulse method. The pyrolysis and oxidation of ethane were modeled using a reaction mechanism with 157 reaction steps and 48 species including the most recent submechanisms for formaldehyde, ketene, methane, acetylene, and ethylene oxidation. The present and previously reported shock tube data were reproduced using this mechanism. The rate constants of the reactions C{sub 2}H{sub 6} {yields} CH{sub 3} + CH{sub 3}, C{sub 2}H{sub 5} + H {yields} H{sub 2} and C{sub 2}H{sub 5} + O{sub 2} {yields} C{sub 2}H{sub 4} + HO{sub 2} were evaluated. These reactions were important in predicting the previously reported and the present data, which were for mixture compositions ranging from ethane-rich (including ethane pyrolysis) to ethane-lean. The evaluated rate constants of the reactions C{sub 2}H{sub 5} + H {yields} C{sub 2}H{sub 4} + H{sub 2} and C{sub 2}H{sub 5} + O{sub 2} {yields} C{sub 2}H{sub 4} + HO{sub 2} were found to be significantly different from currently accepted values.

  9. Kinetics of ethylcyclohexane pyrolysis and oxidation: An experimental and detailed kinetic modeling study

    KAUST Repository

    Wang, Zhandong

    2015-07-01

    Ethylcyclohexane (ECH) is a model compound for cycloalkanes with long alkyl side-chains. A preliminary investigation on ECH (Wang et al., Proc. Combust. Inst., 35, 2015, 367-375) revealed that an accurate ECH kinetic model with detailed fuel consumption mechanism and aromatic growth pathways, as well as additional ECH pyrolysis and oxidation data with detailed species concentration covering a wide pressure and temperature range are required to understand the ECH combustion kinetics. In this work, the flow reactor pyrolysis of ECH at various pressures (30, 150 and 760Torr) was studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS) and gas chromatography (GC). The mole fraction profiles of numerous major and minor species were evaluated, and good agreement was observed between the PIMS and GC data sets. Furthermore, a fuel-rich burner-stabilized laminar premixed ECH/O2/Ar flame at 30Torr was studied using synchrotron VUV PIMS. A detailed kinetic model for ECH high temperature pyrolysis and oxidation was developed and validated against the pyrolysis and flame data performed in this work. Further validation of the kinetic model is presented against literature data including species concentrations in jet-stirred reactor oxidation, ignition delay times in a shock tube, and laminar flame speeds at various pressures and equivalence ratios. The model well predicts the consumption of ECH, the growth of aromatics, and the global combustion properties. Reaction flux and sensitivity analysis were utilized to elucidate chemical kinetic features of ECH combustion under various reaction conditions. © 2015 The Combustion Institute.

  10. Proteomics-Based Metabolic Modeling Reveals That Fatty Acid Oxidation (FAO) Controls Endothelial Cell (EC) Permeability*

    Science.gov (United States)

    Patella, Francesca; Schug, Zachary T.; Persi, Erez; Neilson, Lisa J.; Erami, Zahra; Avanzato, Daniele; Maione, Federica; Hernandez-Fernaud, Juan R.; Mackay, Gillian; Zheng, Liang; Reid, Steven; Frezza, Christian; Giraudo, Enrico; Fiorio Pla, Alessandra; Anderson, Kurt; Ruppin, Eytan; Gottlieb, Eyal; Zanivan, Sara

    2015-01-01

    Endothelial cells (ECs) play a key role to maintain the functionality of blood vessels. Altered EC permeability causes severe impairment in vessel stability and is a hallmark of pathologies such as cancer and thrombosis. Integrating label-free quantitative proteomics data into genome-wide metabolic modeling, we built up a model that predicts the metabolic fluxes in ECs when cultured on a tridimensional matrix and organize into a vascular-like network. We discovered how fatty acid oxidation increases when ECs are assembled into a fully formed network that can be disrupted by inhibiting CPT1A, the fatty acid oxidation rate-limiting enzyme. Acute CPT1A inhibition reduces cellular ATP levels and oxygen consumption, which are restored by replenishing the tricarboxylic acid cycle. Remarkably, global phosphoproteomic changes measured upon acute CPT1A inhibition pinpointed altered calcium signaling. Indeed, CPT1A inhibition increases intracellular calcium oscillations. Finally, inhibiting CPT1A induces hyperpermeability in vitro and leakage of blood vessel in vivo, which were restored blocking calcium influx or replenishing the tricarboxylic acid cycle. Fatty acid oxidation emerges as central regulator of endothelial functions and blood vessel stability and druggable pathway to control pathological vascular permeability. PMID:25573745

  11. Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization

    Directory of Open Access Journals (Sweden)

    Sonali Sengupta

    2013-12-01

    Full Text Available The oxidation of catechol was studied in an eco-friendly process with commercial titanium silicate-1 (TS-1 catalyst and hydrogen peroxide as oxidant in absence of all mass transfer effects. The process was opti-mized by Box-Behnken design in terms of three independent process variables such as reaction tempera-ture, moles of hydrogen peroxide per mole of catechol and catalyst amount whose optimum values of the process variables were found to be 60 °C, 13.2 and 1.24 g respectively for maximum conversion of 75.8 %. The effects of different process parameters such as mole ratio of hydrogen peroxide to catechol, catalyst par-ticle size, catalyst amount, temperature and reaction time were studied. A pseudo first order kinetic model was fitted with the experimental rate data. The apparent activation energy for the reaction was found to be 11.37 kJ/mole.  © 2013 BCREC UNDIP. All rights reservedReceived: 22nd April 2013; Revised: 25th October 2013; Accepted: 1st November 2013[How to Cite: Sengupta, S., Ghosal, D., Basu, J.K. (2013. Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (2: 167-177. (doi:10.9767/bcrec.8.2.4759.167-177][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.2.4759.167-177

  12. Proteomics-based metabolic modeling reveals that fatty acid oxidation (FAO) controls endothelial cell (EC) permeability.

    Science.gov (United States)

    Patella, Francesca; Schug, Zachary T; Persi, Erez; Neilson, Lisa J; Erami, Zahra; Avanzato, Daniele; Maione, Federica; Hernandez-Fernaud, Juan R; Mackay, Gillian; Zheng, Liang; Reid, Steven; Frezza, Christian; Giraudo, Enrico; Fiorio Pla, Alessandra; Anderson, Kurt; Ruppin, Eytan; Gottlieb, Eyal; Zanivan, Sara

    2015-03-01

    Endothelial cells (ECs) play a key role to maintain the functionality of blood vessels. Altered EC permeability causes severe impairment in vessel stability and is a hallmark of pathologies such as cancer and thrombosis. Integrating label-free quantitative proteomics data into genome-wide metabolic modeling, we built up a model that predicts the metabolic fluxes in ECs when cultured on a tridimensional matrix and organize into a vascular-like network. We discovered how fatty acid oxidation increases when ECs are assembled into a fully formed network that can be disrupted by inhibiting CPT1A, the fatty acid oxidation rate-limiting enzyme. Acute CPT1A inhibition reduces cellular ATP levels and oxygen consumption, which are restored by replenishing the tricarboxylic acid cycle. Remarkably, global phosphoproteomic changes measured upon acute CPT1A inhibition pinpointed altered calcium signaling. Indeed, CPT1A inhibition increases intracellular calcium oscillations. Finally, inhibiting CPT1A induces hyperpermeability in vitro and leakage of blood vessel in vivo, which were restored blocking calcium influx or replenishing the tricarboxylic acid cycle. Fatty acid oxidation emerges as central regulator of endothelial functions and blood vessel stability and druggable pathway to control pathological vascular permeability.

  13. Kinetic model of the inhibition of respiration by endogenous nitric oxide in intact cells.

    Science.gov (United States)

    Aguirre, Enara; Rodríguez-Juárez, Félix; Bellelli, Andrea; Gnaiger, Erich; Cadenas, Susana

    2010-05-01

    Nitric oxide (NO) inhibits mitochondrial respiration by decreasing the apparent affinity of cytochrome c oxidase (CcO) for oxygen. Using iNOS-transfected HEK 293 cells to achieve regulated intracellular NO production, we determined NO and O(2) concentrations and mitochondrial O(2) consumption by high-resolution respirometry over a range of O(2) concentrations down to nanomolar. Inhibition of respiration by NO was reversible, and complete NO removal recovered cell respiration above its routine reference values. Respiration was observed even at high NO concentrations, and the dependence of IC(50) on [O(2)] exhibits a characteristic but puzzling parabolic shape; both these features imply that CcO is protected from complete inactivation by NO and are likely to be physiologically relevant. We present a kinetic model of CcO inhibition by NO that efficiently predicts experimentally determined respiration at physiological O(2) and NO concentrations and under hypoxia, and accurately predicts the respiratory responses under hyperoxia. The model invokes competitive and uncompetitive inhibition by binding of NO to the reduced and oxidized forms of CcO, respectively, and suggests that dissociation of NO from reduced CcO may involve its O(2)-dependent oxidation. It also explains the non-linear dependence of IC(50) on O(2) concentration, and the hyperbolic increase of c(50) as a function of NO concentration.

  14. Real-world exposure of airborne particulate matter triggers oxidative stress in an animal model

    Science.gov (United States)

    Wan, Guohui; Rajagopalan, Sanjay; Sun, Qinghua; Zhang, Kezhong

    2010-01-01

    Epidemiological studies have shown a strong link between air pollution and the increase of cardio-pulmonary mortality and morbidity. In particular, inhaled airborne particulate matter (PM) exposure is closely associated with the pathogenesis of air pollution-induced systemic diseases. In this study, we exposed C57BIV6 mice to environmentally relevant PM in fine and ultra fine ranges (diameter < 2.5 μm, PM2.5) using a “real-world” airborne PM exposure system. We investigated the pathophysiologic impact of PM2.5 exposure in the animal model and in cultured primary pulmonary macrophages. We demonstrated that PM2.5 exposure increased the production of reactive oxygen species (ROS) in blood vessels in vivo. Furthermore, in vitro PM2.5 exposure experiment suggested that PM2.5 could trigger oxidative stress response, reflected by an increased expression of the anti-oxidative stress enzymes superoxide dismutase-1 (SOD-1) and heme oxygenase-1(HO-1), in mouse primary macrophages. Together, the results obtained through our “real-world” PM exposure approach demonstrated the pathophysiologic effect of ambient PM2.5 exposure on triggering oxidative stress in the specialized organ and cell type of an animal model. Our results and approach will be informative for the research in air pollution-associated physiology and pathology. PMID:21383899

  15. Mathematical model of a plate fin heat exchanger operating under solid oxide fuel cell working conditions

    Science.gov (United States)

    Kaniowski, Robert; Poniewski, Mieczysław

    2013-12-01

    Heat exchangers of different types find application in power systems based on solid oxide fuel cells (SOFC). Compact plate fin heat exchangers are typically found to perfectly fit systems with power output under 5 kWel. Micro-combined heat and power (micro-CHP) units with solid oxide fuel cells can exhibit high electrical and overall efficiencies, exceeding 85%, respectively. These values can be achieved only when high thermal integration of a system is assured. Selection and sizing of heat exchangers play a crucial role and should be done with caution. Moreover, performance of heat exchangers under variable operating conditions can strongly influence efficiency of the complete system. For that reason, it becomes important to develop high fidelity mathematical models allowing evaluation of heat exchangers under modified operating conditions, in high temperature regimes. Prediction of pressure and temperatures drops at the exit of cold and hot sides are important for system-level studies. Paper presents dedicated mathematical model used for evaluation of a plate fin heat exchanger, operating as a part of micro-CHP unit with solid oxide fuel cells.

  16. Assessment of nitric oxide (NO) redox reactions contribution to nitrous oxide (N2 O) formation during nitrification using a multispecies metabolic network model.

    Science.gov (United States)

    Perez-Garcia, Octavio; Chandran, Kartik; Villas-Boas, Silas G; Singhal, Naresh

    2016-05-01

    Over the coming decades nitrous oxide (N2O) is expected to become a dominant greenhouse gas and atmospheric ozone depleting substance. In wastewater treatment systems, N2O is majorly produced by nitrifying microbes through biochemical reduction of nitrite (NO2(-)) and nitric oxide (NO). However it is unknown if the amount of N2O formed is affected by alternative NO redox reactions catalyzed by oxidative nitrite oxidoreductase (NirK), cytochromes (i.e., P460 [CytP460] and 554 [Cyt554 ]) and flavohemoglobins (Hmp) in ammonia- and nitrite-oxidizing bacteria (AOB and NOB, respectively). In this study, a mathematical model is developed to assess how N2O formation is affected by such alternative nitrogen redox transformations. The developed multispecies metabolic network model captures the nitrogen respiratory pathways inferred from genomes of eight AOB and NOB species. The performance of model variants, obtained as different combinations of active NO redox reactions, was assessed against nine experimental datasets for nitrifying cultures producing N2O at different concentration of electron donor and acceptor. Model predicted metabolic fluxes show that only variants that included NO oxidation to NO2(-) by CytP460 and Hmp in AOB gave statistically similar estimates to observed production rates of N2O, NO, NO2(-) and nitrate (NO3(-)), together with fractions of AOB and NOB species in biomass. Simulations showed that NO oxidation to NO2(-) decreased N2O formation by 60% without changing culture's NO2(-) production rate. Model variants including NO reduction to N2O by Cyt554 and cNor in NOB did not improve the accuracy of experimental datasets estimates, suggesting null N2O production by NOB during nitrification. Finally, the analysis shows that in nitrifying cultures transitioning from dissolved oxygen levels above 3.8 ± 0.38 to <1.5 ± 0.8 mg/L, NOB cells can oxidize the NO produced by AOB through reactions catalyzed by oxidative NirK.

  17. Model study of multiphase DMS oxidation with a focus on halogens

    Directory of Open Access Journals (Sweden)

    R. von Glasow

    2004-01-01

    Full Text Available We studied the oxidation of dimethylsulfide (DMS in the marine boundary layer (MBL with a one-dimensional numerical model and focused on the influence of halogens. Our model runs show that there is still significant uncertainty about the end products of the DMS addition pathway, which is especially caused by uncertainty in the product yield of the reaction of the intermediate product methyl sulfinic acid (MSIA with OH. BrO strongly increases the importance of the addition branch in the oxidation of DMS even when present at mixing ratios smaller than 0.5pmol mol-1. The inclusion of halogen chemistry leads to higher DMS oxidation rates and smaller DMS to SO2 conversion efficiencies. The DMS to SO2 conversion efficiency is also drastically reduced under cloudy conditions. In cloud-free model runs between 5 and 15% of the oxidized DMS reacts further to particulate sulfur, in cloudy runs this fraction is almost 100%. Sulfate production by HOClaq and HOBraq is important in cloud droplets even for small Br- deficits and related small gas phase halogen concentrations. In general, more particulate sulfur is formed when halogen chemistry is included. A possible enrichment of HCO3- in fresh sea salt aerosol would increase pH values enough to make the reaction of S(IV* (=SO2,aq+HSO3-+SO32- with O3 dominant for sulfate production. It leads to a shift from methyl sulfonic acid (MSA to non-sea salt sulfate (nss-SO42- production but increases the total nss-SO42- only somewhat because almost all available sulfur is already oxidized to particulate sulfur in the base scenario. We discuss how realistic this is for the MBL. We found the reaction MSAaq+OH to contribute about 10% to the production of nss-SO42- in clouds. It is unimportant for cloud-free model runs. Overall we find that the presence of halogens leads to processes that decrease the albedo of stratiform clouds in the MBL.

  18. Multi-scale Model of Residual Strength of 2D Plain Weave C/SiC Composites in Oxidation Atmosphere

    Science.gov (United States)

    Chen, Xihui; Sun, Zhigang; Sun, Jianfen; Song, Yingdong

    2016-06-01

    Multi-scale models play an important role in capturing the nonlinear response of woven carbon fiber reinforced ceramic matrix composites. In plain weave carbon fiber/silicon carbon (C/SiC) composites, the carbon fibers and interphases will be oxidized at elevated temperature and the strength of the composite will be degraded when oxygen enters micro-cracks formed in the as-produced parts due to the mismatch in thermal properties between constituents. As a result of the oxidation on fiber surface, fiber shows a notch-like morphology. In this paper, the change rule of fiber notch depth is fitted by circular function. And a multi-scale model based upon the change rule of fiber notch depth is developed to simulate the residual strength and post-oxidation stress-strain curves of the composite. The multi-scale model is able to accurately predict the residual strength and post-oxidation stress-strain curves of the composite. Besides, the simulated residual strength and post-oxidation stress-strain curves of 2D plain weave C/SiC composites in oxidation atmosphere show good agreements with experimental results. Furthermore, the oxidation time and temperature of the composite are investigated to show their influences upon the residual strength and post-oxidation stress-strain curves of plain weave C/SiC composites.

  19. Paeoniflorin Attenuated Oxidative Stress in Rat COPD Model Induced by Cigarette Smoke

    Directory of Open Access Journals (Sweden)

    Jinpei Lin

    2016-01-01

    Full Text Available Paeoniflorin (PF, a monoterpene glucoside, might have an effect on the oxidative stress. However, the mechanism is still unknown. In this study, we made the COPD model in Sprague-Dawley (SD rats by exposing them to the smoke of 20 cigarettes for 1 hour/day and 6 days/week, for 12 weeks, 24 weeks, or 36 weeks. Our findings suggested that smoke inhalation can trigger the oxidative stress from the very beginning. A 24-week treatment of PF especially in the dosage of 40 mg/kg·d can attenuate oxygen stress by partially quenching reactive oxygen species (ROS and upregulating antioxidant enzymes via an Nrf2-dependent mechanism.

  20. Hydroxycitric acid ameliorates inlfammation and oxidative stress in mouse models of multiple sclerosis

    Institute of Scientific and Technical Information of China (English)

    Mahdi Goudarzvand; Shahin Khadem Azarian; Abbas Mirshaifey; Gholamreza Azizi; Sanaz Afraei; Somaye Yaslianifard; Saleh Ghiasy; Ghazal Sadri; Mustafa Kalvandi; Tina Alinia; Ali Mohebbi; Reza Yazdani

    2016-01-01

    Hydroxycitric acid (HCA) is derived primarily from the Garcinia plant and is widely used for its anti-in-lfammatory effects. Multiple sclerosis can cause an inlfammatory demyelination and axonal damage. In this study, to validate the hypothesis that HCA exhibits therapeutic effects on multiple sclerosis, we established female C57BL/6 mouse models of multiple sclerosis,i.e., experimental autoimmune encephalomyelitis, using Complete Freund’s Adjuvant (CFA) emulsion containing myelin oligodendrocyte glycoprotein (35–55). Treatment with HCA at 2 g/kg/d for 3 weeks obviously improved the symptoms of nerve injury of experimental autoimmune encephalomyelitis mice, decreased serum interleulin-6, tumor necrosis factor alpha, nitric oxide, and malondialdehyde levels, and increased superoxide dismutase and glutathione reduc-tase activities. hTese ifndings suggest that HCA exhibits neuroprotective effects on multiple sclerosis-caused nerve injury through ameliorating inlfammation and oxidative stress.

  1. 1,4-Dihydropyridine Derivatives: Dihydronicotinamide Analogues-Model Compounds Targeting Oxidative Stress.

    Science.gov (United States)

    Velena, Astrida; Zarkovic, Neven; Gall Troselj, Koraljka; Bisenieks, Egils; Krauze, Aivars; Poikans, Janis; Duburs, Gunars

    2016-01-01

    Many 1,4-dihydropyridines (DHPs) possess redox properties. In this review DHPs are surveyed as protectors against oxidative stress (OS) and related disorders, considering the DHPs as specific group of potential antioxidants with bioprotective capacities. They have several peculiarities related to antioxidant activity (AOA). Several commercially available calcium antagonist, 1,4-DHP drugs, their metabolites, and calcium agonists were shown to express AOA. Synthesis, hydrogen donor properties, AOA, and methods and approaches used to reveal biological activities of various groups of 1,4-DHPs are presented. Examples of DHPs antioxidant activities and protective effects of DHPs against OS induced damage in low density lipoproteins (LDL), mitochondria, microsomes, isolated cells, and cell cultures are highlighted. Comparison of the AOA of different DHPs and other antioxidants is also given. According to the data presented, the DHPs might be considered as bellwether among synthetic compounds targeting OS and potential pharmacological model compounds targeting oxidative stress important for medicinal chemistry.

  2. 1,4-Dihydropyridine Derivatives: Dihydronicotinamide Analogues—Model Compounds Targeting Oxidative Stress

    Directory of Open Access Journals (Sweden)

    Astrida Velena

    2016-01-01

    Full Text Available Many 1,4-dihydropyridines (DHPs possess redox properties. In this review DHPs are surveyed as protectors against oxidative stress (OS and related disorders, considering the DHPs as specific group of potential antioxidants with bioprotective capacities. They have several peculiarities related to antioxidant activity (AOA. Several commercially available calcium antagonist, 1,4-DHP drugs, their metabolites, and calcium agonists were shown to express AOA. Synthesis, hydrogen donor properties, AOA, and methods and approaches used to reveal biological activities of various groups of 1,4-DHPs are presented. Examples of DHPs antioxidant activities and protective effects of DHPs against OS induced damage in low density lipoproteins (LDL, mitochondria, microsomes, isolated cells, and cell cultures are highlighted. Comparison of the AOA of different DHPs and other antioxidants is also given. According to the data presented, the DHPs might be considered as bellwether among synthetic compounds targeting OS and potential pharmacological model compounds targeting oxidative stress important for medicinal chemistry.

  3. 1,4-Dihydropyridine Derivatives: Dihydronicotinamide Analogues—Model Compounds Targeting Oxidative Stress

    Science.gov (United States)

    Velena, Astrida; Zarkovic, Neven; Gall Troselj, Koraljka; Bisenieks, Egils; Krauze, Aivars; Poikans, Janis; Duburs, Gunars

    2016-01-01

    Many 1,4-dihydropyridines (DHPs) possess redox properties. In this review DHPs are surveyed as protectors against oxidative stress (OS) and related disorders, considering the DHPs as specific group of potential antioxidants with bioprotective capacities. They have several peculiarities related to antioxidant activity (AOA). Several commercially available calcium antagonist, 1,4-DHP drugs, their metabolites, and calcium agonists were shown to express AOA. Synthesis, hydrogen donor properties, AOA, and methods and approaches used to reveal biological activities of various groups of 1,4-DHPs are presented. Examples of DHPs antioxidant activities and protective effects of DHPs against OS induced damage in low density lipoproteins (LDL), mitochondria, microsomes, isolated cells, and cell cultures are highlighted. Comparison of the AOA of different DHPs and other antioxidants is also given. According to the data presented, the DHPs might be considered as bellwether among synthetic compounds targeting OS and potential pharmacological model compounds targeting oxidative stress important for medicinal chemistry. PMID:26881016

  4. Modeling and experimental validation of CO heterogeneous chemistry and electrochemistry in solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Yurkiv, Vitaly

    2010-12-17

    In the present work experimental and numerical modeling studies of the heterogeneously catalyzed and electrochemical oxidation of CO at Nickel/yttria-stabilized zirconia (YSZ) solid oxide fuel cell (SOFC) anode systems were performed to evaluate elementary charge-transfer reaction mechanisms taking place at the three-phase boundary of CO/CO{sub 2} gas-phase, Ni electrode, and YSZ electrolyte. Temperature-programmed desorption and reaction experiments along with density functional theory calculations were performed to determine adsorption/desorption and surface diffusion kinetics as well as thermodynamic data for the CO/CO{sub 2}/Ni and CO/CO{sub 2}/YSZ systems. Based on these data elementary reaction based models with four different charge transfer mechanisms for the electrochemical CO oxidation were developed and applied in numerical simulations of literature experimental electrochemical data such as polarization curves and impedance spectra. Comparison between simulation and experiment demonstrated that only one of the four charge transfer mechanisms can consistently reproduce the electrochemical data over a wide range of operating temperatures and CO/CO{sub 2} gas compositions. (orig.) [German] In der vorliegenden Arbeit wurden experimentelle und numerische Untersuchungen zur heterogen katalysierten und elektrochemischen Oxidation von CO an Anodensystemen (bestehend aus Nickel und yttriumdotiertem Zirkoniumdioxid, YSZ) von Festoxidbrennstoffzellen (engl. Solid Oxide Fuel Cells, SOFCs) ausgefuehrt, um den mikroskopischen Mechanismus der an der CO/CO{sub 2}-Gasphase/Ni-Elektrode/YSZ-Elektrolyt- Dreiphasen-Grenzflaeche ablaufenden Ladungsuebertragungsreaktion aufzuklaeren. Temperaturprogrammierte Desorptionsmessungen (TPD) und Temperaturprogrammierte Reaktionsmessungen (TPR) sowie Dichtefunktionaltheorierechnungen wurden ausgefuehrt, um adsorptions-, desorptions- und reaktionskinetische sowie thermodynamische Daten fuer die CO/CO{sub 2}/Ni- und CO/CO{sub 2}/YSZ

  5. Thermo-oxidative degradation of graphite/epoxy composite laminates: Modeling and long-term predictions

    Directory of Open Access Journals (Sweden)

    2009-12-01

    Full Text Available Thermo-oxidative degradation of graphite/epoxy composite laminates due to exposure to elevated temperatures was characterized using weight loss and short beam strength (SBS reduction data. Test specimens obtained from 24-ply, unidirectional AS4/3501-6 graphite/epoxy laminates were subjected to 100, 150, 175, and 200°C for 5000 hours (208 days in air. Predictive differential models for the weight loss and short beam strength reduction were developed using the isothermal degradation data only up to 2000 hours. Then, the predictive capabilities of both models were demonstrated using the longer term, 5000 hours degradation data. The proposed models were first order differential expressions that can be used to predict degradation in an arbitrary, time-dependent temperature environment. Both models were able to estimate the actual degradation levels accurately. In particular, excellent agreement was obtained when the degradation temperature was lower than 200°C.

  6. Effect of wall growth on the kinetic modeling of nitrite oxidation in a CSTR.

    Science.gov (United States)

    Dokianakis, Spiros N; Kornaros, Michael; Lyberatos, Gerasimos

    2006-03-05

    A simple kinetic model was developed for describing nitrite oxidation by autotrophic aerobic nitrifiers in a continuous stirred tank reactor (CSTR), in which mixed (suspended and attached) growth conditions prevail. The CSTR system was operated under conditions of constant nitrite feed concentration and varying volumetric flow rates. Experimental data from steady-state conditions in the CSTR system and from batch experiments were used for the determination of the model's kinetic parameters. Model predictions were verified against experimental data obtained under transient operating conditions, when volumetric flow rate and nitrite feed concentration disturbances were imposed on the CSTR. The presented kinetic modeling procedure is quite simple and general and therefore can also be applied to other mixed growth biological systems.

  7. Sensitivity analysis in oxidation ditch modelling: the effect of variations in stoichiometric, kinetic and operating parameters on the performance indices

    NARCIS (Netherlands)

    Abusam, A.A.A.; Keesman, K.J.; Straten, van G.; Spanjers, H.; Meinema, K.

    2001-01-01

    This paper demonstrates the application of the factorial sensitivity analysis methodology in studying the influence of variations in stoichiometric, kinetic and operating parameters on the performance indices of an oxidation ditch simulation model (benchmark). Factorial sensitivity analysis investig

  8. Fuel/Oxidizer Injector Modeling in Sub- and Super-Critical Regimes for Deep Throttling Cryogenic Engines Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Accurate CFD modeling of fuel/oxidizer injection and combustion is needed to design and analyze liquid rocket engines. Currently, however, there is no mature...

  9. The Interaction Between Lipoxygenase-Catalyzed Oxidation and Autoxidation in Dry-Cured Bacon and a Model System.

    Science.gov (United States)

    Zhang, Yingyang; Tang, Jing; Zhao, Jianying; Wu, Haizhou; Ditta, Yasir Allah; Zhang, Jianhao

    2015-12-01

    A model system was conducted to characterize the interaction between lipid autoxidation and enzyme-catalyzed oxidation in dry-cured bacon. This involved the use of a hydroxyl radical (HO•) generating system and the extraction and purification of lipoxygenases (LOX) from pork belly. The results showed that LOX activity rapidly (P bacon. This may be because of the hydroxyl-radical-mediated oxidation from LOX-Fe(2+) to LOX-Fe(3+), which activates LOX. In addition, experiments of the model system also showed that LOX activity could be inhibited by increasing the substrate concentration, although substrate type and concentration had no effect on autoxidation. Moreover, LOX enzyme-catalyzed oxidation and autoxidation could act synergistically to promote lipid oxidation irrespective of the substrate (linoleic or arachidonic acid). These results provide useful information for regulating lipid oxidation during the production of dry-cured pork products.

  10. Oxidative DNA damage background estimated by a system model of base excision repair.

    Science.gov (United States)

    Sokhansanj, Bahrad A; Wilson, David M

    2004-08-01

    Human DNA can be damaged by natural metabolism through free radical production. It has been suggested that the equilibrium between innate damage and cellular DNA repair results in an oxidative DNA damage background that potentially contributes to disease and aging. Efforts to quantitatively characterize the human oxidative DNA damage background level, based on measuring 8-oxoguanine lesions as a biomarker, have led to estimates that vary over three to four orders of magnitude, depending on the method of measurement. We applied a previously developed and validated quantitative pathway model of human DNA base excision repair, integrating experimentally determined endogenous damage rates and model parameters from multiple sources. Our estimates of at most 100 8-oxoguanine lesions per cell are consistent with the low end of data from biochemical and cell biology experiments, a result robust to model limitations and parameter variation. Our findings show the power of quantitative system modeling to interpret composite experimental data and make biologically and physiologically relevant predictions for complex human DNA repair pathway mechanisms and capacity.

  11. Mathematical modeling of an exothermic leaching reaction system: pressure oxidation of wide size arsenopyrite participates

    Science.gov (United States)

    Papangelakis, V. G.; Berk, D.; Demopoulos, G. P.

    1990-10-01

    In the design of processes involving exothermic reactions, as is the case of several sulfide leaching systems, it is desirable to utilize the energy liberated by the reaction to drive the reactor toward autogenous operation. For optimal reactor design, models which couple leaching kinetics and heat effects are needed. In this paper, the principles of modeling exothermic leaching reactions are outlined. The system investigated is the high-temperature (160 °C to 200 °C) pressure (O2) oxidation of arsenopyrite (FeAsS). The reaction system is characterized by three consecutive reactions: (1) heterogeneous dissolution of arsenopyrite particles, (2) homogeneous oxidation of iron(II) to iron(III), and (3) precipitation of scorodite (FeAsO4-2H2O). The overall kinetics is controlled by the arsenopyrite surface reaction. There was good agreement between laboratory-scale batch tests and model predictions. The model was expanded to simulate the performance of large-scale batch and single-stage continuous stirred tank reactor (CSTR) for the same rate-limiting regime. Emphasis is given to the identification of steady-state temperatures for autogenous processing. The effects of operating variables, such as feed temperature, slurry density, and retention time, on reactor operation and yield of leaching products are discussed.

  12. Oxidative DNA damage background estimated by a system model of base excision repair

    Energy Technology Data Exchange (ETDEWEB)

    Sokhansanj, B A; Wilson, III, D M

    2004-05-13

    Human DNA can be damaged by natural metabolism through free radical production. It has been suggested that the equilibrium between innate damage and cellular DNA repair results in an oxidative DNA damage background that potentially contributes to disease and aging. Efforts to quantitatively characterize the human oxidative DNA damage background level based on measuring 8-oxoguanine lesions as a biomarker have led to estimates varying over 3-4 orders of magnitude, depending on the method of measurement. We applied a previously developed and validated quantitative pathway model of human DNA base excision repair, integrating experimentally determined endogenous damage rates and model parameters from multiple sources. Our estimates of at most 100 8-oxoguanine lesions per cell are consistent with the low end of data from biochemical and cell biology experiments, a result robust to model limitations and parameter variation. Our results show the power of quantitative system modeling to interpret composite experimental data and make biologically and physiologically relevant predictions for complex human DNA repair pathway mechanisms and capacity.

  13. The need for nano-scale modeling in solid oxide fuel cells.

    Science.gov (United States)

    Ryan, E M; Recknagle, K P; Liu, W; Khaleel, M A

    2012-08-01

    Solid oxide fuel cells (SOFCs) are high temperature fuel cells, which are being developed for large scale and distributed power systems. SOFCs promise to provide cleaner, more efficient electricity than traditional fossil fuel burning power plants. Research over the last decade has improved the design and materials used in SOFCs to increase their performance and stability for long-term operation; however, there are still challenges for SOFC researchers to overcome before SOFCs can be considered competitive with traditional fossil fuel burning and renewable power systems. In particular degradation due to contaminants in the fuel and oxidant stream is a major challenge facing SOFCs. In this paper we discuss ongoing computational and experimental research into different degradation and design issues in SOFC electrodes. We focus on contaminants in gasified coal which cause electrochemical and structural degradation in the anode, and chromium poisoning which affects the electrochemistry of the cathode. Due to the complex microstructures and multi-physics of SOFCs, multi-scale computational modeling and experimental research is needed to understand the detailed physics behind different degradation mechanisms, the local conditions within the cell which facilitate degradation, and its effects on the overall SOFC performance. We will discuss computational modeling research of SOFCs at the macro-, meso- and nano-scales which is being used to investigate the performance and degradation of SOFCs. We will also discuss the need for a multi-scale modeling framework of SOFCs, and the application of computational and multi-scale modeling to several degradation issues in SOFCs.

  14. Metal oxide-graphene field-effect transistor: interface trap density extraction model

    Directory of Open Access Journals (Sweden)

    Faraz Najam

    2016-09-01

    Full Text Available A simple to implement model is presented to extract interface trap density of graphene field effect transistors. The presence of interface trap states detrimentally affects the device drain current–gate voltage relationship Ids–Vgs. At the moment, there is no analytical method available to extract the interface trap distribution of metal-oxide-graphene field effect transistor (MOGFET devices. The model presented here extracts the interface trap distribution of MOGFET devices making use of available experimental capacitance–gate voltage Ctot–Vgs data and a basic set of equations used to define the device physics of MOGFET devices. The model was used to extract the interface trap distribution of 2 experimental devices. Device parameters calculated using the extracted interface trap distribution from the model, including surface potential, interface trap charge and interface trap capacitance compared very well with their respective experimental counterparts. The model enables accurate calculation of the surface potential affected by trap charge. Other models ignore the effect of trap charge and only calculate the ideal surface potential. Such ideal surface potential when used in a surface potential based drain current model will result in an inaccurate prediction of the drain current. Accurate calculation of surface potential that can later be used in drain current model is highlighted as a major advantage of the model.

  15. A two-dimensional, finite-difference model of the oxidation of a uranium carbide fuel pellet

    Science.gov (United States)

    Shepherd, James; Fairweather, Michael; Hanson, Bruce C.; Heggs, Peter J.

    2015-12-01

    The oxidation of spent uranium carbide fuel, a candidate fuel for Generation IV nuclear reactors, is an important process in its potential reprocessing cycle. However, the oxidation of uranium carbide in air is highly exothermic. A model has therefore been developed to predict the temperature rise, as well as other useful information such as reaction completion times, under different reaction conditions in order to help in deriving safe oxidation conditions. Finite difference-methods are used to model the heat and mass transfer processes occurring during the reaction in two dimensions and are coupled to kinetics found in the literature.

  16. Time-Dependent and Light-Induced Fading in Victoreen Model 2600-80 Aluminum Oxide Thermoluminescence Dosemeters

    Science.gov (United States)

    1993-01-01

    2600-80 Aluminium Oxide Thermoluminescence Dosemeters ":"TIC,7 • :+ " 7-t-•CTE S , E 1P 1993 F’ t LEA l E J. H. Musk AFRRI TR93-6 Cleared for Public...SUBTITLE 5. FUNDING NUMBERS Time-Dependent and Light-Induced Fading in Victoreen0 Model 2600-80 Aluminium Oxide Thermoluminescence PE: QAXM...MODEL 2600-80 ALUMINIUM OXIDE THERMOLUMINESCENCE DOSEMETERS J. H. Musk Accesion For NTIS CRA&I DTIC TAB U.,announced D Justification ........ -.. By

  17. Three dimensional CFD modeling and experimental validation of a single chamber solid oxide fuel cell fed by methane

    Science.gov (United States)

    Nguyen, H. T.; Le, M. V.; Nguyen, T. A.; Nguyen, T. A. N.

    2017-06-01

    The solid oxide fuel cell is one of the promising technologies for future energy demand. Solid oxide fuel cell operated in the single-chamber mode exhibits several advantages over conventional single oxide fuel cell due to the simplified, compact, sealing-free cell structure. There are some studies on simulating the behavior of this type of fuel cell but they mainly focus on the 2D model. In the present study, a three-dimensional numerical model of a single chamber solid oxide fuel cell (SOFC) is reported and solved using COMSOL Multiphysics software. Experiments of a planar button solid oxide fuel cell were used to verify the simulation results. The system is fed by methane and oxygen and operated at 700°C. The cathode is LSCF6482, the anode is GDC-Ni, the electrolyte is LDM and the operating pressure is 1 atm. There was a good agreement between the cell temperature and current voltage estimated from the model and measured from the experiment. The results indicate that the model is applicable for the single chamber solid oxide fuel cell and it can provide a basic for the design, scale up of single chamber solid oxide fuel cell system.

  18. The selective oxidation of ammonia over alumina supported catalysts. Experiments and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Jones, J.M.; Pourkashanian, M.; Williams, A.; Backreedy, R.I.; Darvell, L.I. [Energy and Resources Research Institute, School of Process Environmental and Materials Engineering, University of Leeds, Leeds LS29JT (United Kingdom); Simell, P.; Heiskanen, K. [VTT Processes, P.O. Box 1601, FIN-02044 VTT (Finland); Kilpinen, P. [AAbo Akademi Process Chemistry Centre, Laboratory for Industrial Chemistry, Turku (Finland)

    2005-09-01

    Hot gas-clean up will improve the efficiency of emerging gasification technologies. Selective catalytic oxidation (SCO) of ammonia is a promising approach for dealing with the main fixed nitrogen species. The work presented here comprises both laboratory scale experimental measurements of potential SCO catalysts, as well as the development of a simple four-step reaction model to describe the behaviour of one of the more promising catalysts. A range of transition metal oxides supported on {gamma}-alumina were studied for their activity in the SCO of ammonia in a simulated gasification gas mixture containing CO, H{sub 2}O, H{sub 2}, CO{sub 2}, CH{sub 4}, H{sub 2}S and toluene as model tar species. Both copper and chromium based catalysts demonstrated a window of operating temperature over which they were resistant to poisoning by H{sub 2}S; Cu/Al{sub 2}O{sub 3} was in fact promoted by this gas for the SCO reaction. The ammonia conversion over 7% Cu/Al{sub 2}O{sub 3} was studied in more detail, and this data was further used to develop a kinetic model for the reactions taking place over the temperature range 723-906K. Excellent conversion and selectivity to N{sub 2} was found in the temperature window 973-1173K and 2.6vol% O{sub 2}. However, it also catalyses a rapid H{sub 2}-O{sub 2} reaction. This reaction consumes all remaining available oxygen so that no other oxidation reactions take place (e.g. of methane or 'tar'). The four-step reaction model was developed using the PLUG application of Chemkin and Surface Chemkin software coupled with the gas-phase mechanism. Rates for the heterogeneous oxidation of ammonia and hydrogen are included as well as forward and reverse reactions of the water gas shift. Over the temperature range in question, the surface reaction rates are much faster than the gas-phase reactions. The model is applicable for the 723-906K temperature range using a gas mixture containing 0.4vol% ammonia and 0.01vol% H{sub 2}S in the presence

  19. Modeling and Experimental Studies of Mercury Oxidation and Adsorption in a Fixed-Bed Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Buitrago, Paula A.; Morrill, Mike; Lighty, JoAnn S.; Silcox, Geoffrey D.

    2009-06-15

    This report presents experimental and modeling mercury oxidation and adsorption data. Fixed-bed and single-particle models of mercury adsorption were developed. The experimental data were obtained with two reactors: a 300-W, methane-fired, tubular, quartz-lined reactor for studying homogeneous oxidation reactions and a fixed-bed reactor, also of quartz, for studying heterogeneous reactions. The latter was attached to the exit of the former to provide realistic combustion gases. The fixed-bed reactor contained one gram of coconut-shell carbon and remained at a temperature of 150°C. All methane, air, SO2, and halogen species were introduced through the burner to produce a radical pool representative of real combustion systems. A Tekran 2537A Analyzer coupled with a wet conditioning system provided speciated mercury concentrations. At 150°C and in the absence of HCl or HBr, the mercury uptake was about 20%. The addition of 50 ppm HCl caused complete capture of all elemental and oxidized mercury species. In the absence of halogens, SO2 increased the mercury adsorption efficiency to up to 30 percent. The extent of adsorption decreased with increasing SO2 concentration when halogens were present. Increasing the HCl concentration to 100 ppm lessened the effect of SO2. The fixed-bed model incorporates Langmuir adsorption kinetics and was developed to predict adsorption of elemental mercury and the effect of multiple flue gas components. This model neglects intraparticle diffusional resistances and is only applicable to pulverized carbon sorbents. It roughly describes experimental data from the literature. The current version includes the ability to account for competitive adsorption between mercury, SO2, and NO2. The single particle model simulates in-flight sorbent capture of elemental mercury. This model was developed to include Langmuir and Freundlich isotherms, rate equations, sorbent feed rate, and

  20. Mesoscale modeling of combined aerosol and photo-oxidant processes in the eastern Mediterranean

    Directory of Open Access Journals (Sweden)

    M. Lazaridis

    2004-09-01

    Full Text Available Particulate matter and photo-oxidant processes in the Eastern Mediterranean have been studied using the UAM-AERO mesoscale air quality model in conjunction with the NILU-CTM regional model. Meteorological data were obtained from the RAMS prognostic meteorological model. The modeling domain includes the eastern Mediterranean area between the Greek mainland and the island of Crete. The modeling system is applied to study the atmospheric processes in three periods, i.e. 13–16 July 2000, 26–30 July 2000 and 7–14 January 2001. The spatial and temporal distributions of both gaseous and particulate matter pollutants have been extensively studied together with the identification of major emission sources in the area. The modeling results were compared with field data obtained in the same period. Comparison of the modeling results with measured data was performed for a number of gaseous and aerosol species. The UAM-AERO model underestimates the PM10 measured concentrations during summer but better comparison has been obtained for the winter data.

  1. Experimental and model analysis of the co-oxidative behavior of syngas feed in an Intermediate Temperature Solid Oxide Fuel Cell

    Science.gov (United States)

    Donazzi, A.; Rahmanipour, M.; Maestri, M.; Groppi, G.; Bardini, L.; Pappacena, A.; Boaro, M.

    2016-02-01

    By means of model analysis, we show that, in the presence of syngas, the electro-oxidation of H2 and that of CO occur in parallel and contemporarily on Samaria-doped Ceria (Sm0.2Ce0.8O1.9, SDC) Intermediate Temperature Solid Oxide Fuel Cells (IT-SOFCs). The activation of a co-oxidative route is a most distinguishing feature of Ce-based cells, compared to traditional SOFCs. SDC electrolyte supported IT-SOFCs with Cu-Pd-CZ80 composite anodes and LSCF cathodes were tested under a wide range of operating conditions. Polarization and EIS measurements were collected at 600 °C and 650 °C with syngas mixtures (2.3-0.4H2/CO ratio), H2/N2 mixtures (from 97 to 30% H2 v/v) and CO/CO2 mixtures (from 97 to 50% CO v/v). A 1D, dynamic and heterogeneous model of the cell was applied to analyze the polarization and the EIS curves. The kinetics of the reactions of H2 electro-oxidation, CO electro-oxidation and O2 reduction were individually investigated and global power law rates were derived. The syngas experiments were simulated on a fully predictive basis and no parameter adjustment, confirming that the polarization behavior could be best reproduced exclusively by assuming the presence of the co-oxidative route. The IT-SOFCs were also exposed to biogas mixtures, revealing that the dry-reforming reaction was active.

  2. Estimating reaction constants by ab initio molecular modeling: a study on the oxidation of phenol to catechol and hydroquinone in advanced oxidation processes

    Directory of Open Access Journals (Sweden)

    B. Ramos

    2012-03-01

    Full Text Available Molecular modeling is growing as a research tool in Chemical Engineering studies, as can be seen by a simple research on the latest publications in the field. Molecular investigations retrieve information on properties often accessible only by expensive and time-consuming experimental techniques, such as those involved in the study of radical-based chain reactions. In this work, different quantum chemical techniques were used to study phenol oxidation by hydroxyl radicals in Advanced Oxidation Processes used for wastewater treatment. The results obtained by applying a DFT-based model showed good agreement with experimental values available, as well as qualitative insights into the mechanism of the overall reaction chain. Solvation models were also tried, but were found to be limited for this reaction system within the considered theoretical level without further parameterization.

  3. Levels of oxidative stress parameters and the protective effects of melatonin in psychosis model rat testis

    Institute of Scientific and Technical Information of China (English)

    Bekir S.Parlaktas; Birsen Ozyurt; Huseyin Ozyurt; Ayten T.Tunc; Ali Akbas

    2008-01-01

    Aim: To evaluate the effects of melatonin on antioxidant enzyme levels and histopathologic changes in dizocilpine (MK-801)-induced psychosis model rat testis. Methods: A total of 24 adult male Wistar-Albino rats were divided into three groups with 8 in each. Group Ⅰ was used as control. Rats in Group Ⅱ were injected with MK-801 (0.5 mg/kg body weight i.p. for 5 days). In addition to MK-801, melatonin (50 mg/kg body weight i.p. once a day for 5 days) was injected into the rats in Group Ⅲ. The testes were harvested bilaterally for biochemical and histopathological examinations. Antioxidant enzyme activities, malondialdehyde, protein carbonyl and nitric oxide (NO) levels in tes-ticular tissues were analyzed using spectrophotometric analysis methods. Histopathological examinations of the testes were also performed. Results: MK-801 induced testicular damage, which resulted in significant oxidative stress (OS) by increasing the levels of antioxidant enzymes. The malondialdehyde, protein carbonyl and NO levels were increased in testicular tissues of rats. Treatment with melatonin led to significant decrease in oxidative injury.Administration of melatonin also reduced the detrimental histopathologic effects caused by MK-801. Conclusion:The results of the present study showed that MK-801 cause OS in testicular tissues of rats and treatment with melatonin can reduce the harmful effects of MK-801.

  4. Paraoxonase and Arylesterase Activities, Lipid Profile, and Oxidative Damage in Experimental Ischemic Colitis Model

    Directory of Open Access Journals (Sweden)

    Ethem Unal

    2012-01-01

    Full Text Available Objective. In the present study, since PON1 is known as an HDL-associated antioxidant enzyme that inhibits the oxidative modification of LDL and oxidative stress plays a role in the pathogenesis of mesenteric ischemia, we investigated the changes in PON1 activity and lipid profile in an experimental ischemic colitis model. Methods. Forty male Wistar albino rats were divided into two groups: the control group (N=15 and the experimental group (N=25. All animals were anesthetized with ether and ketamine anesthesia to undergo a midline laparotomy. Ischemic colitis was induced by marginal vessel ligation in the splenic flexura (devascularization process. A sham laparotomy was performed in the control group. All animals were sacrificed on the seventh postoperative day. Oxidative stress marker (malonyldialdehyde, MDA, lipid profile, and paraoxonase (PON-1 and arylesterase activities were determined. Histopathological evaluation was done under light microscopy, after sectioning and staining with hematoxyline and eosin. Statistical analysis was conducted using Student’s t-test and Mann-Whitney U test, and P0.05. Conclusions. PON1 and arylesterase play an important role in the pathophysiology of ischemic colitis.

  5. The oxide phase formation modelling at the deoxidization process in yttrium steels

    Directory of Open Access Journals (Sweden)

    Петро Степанович Харлашин

    2016-11-01

    Full Text Available In recent years approaches to high-quality steel production have significantly changed. The influence of the oxide and sulfide non-metallic inclusions should be noted in particular. Modifying is followed with the change in the inclusions chemical composition, they are generally being MnS inclusions and fragile oxidic inclusions. Modification results in the formation of spherical oxides and yttrium sulfides that don’t deform at rolling. Nowadays modifying with rare-earth elements has no broad application because of the use of cheaper lime which possesses similar efficiency. That is why REM are applied generally as microparticles, and their deoxidating and desulphurizing abilities are limited because of their high cost in comparison with the expenditures on modern extra oven processing of steel. Nonmetallic inclusions hardly influence on «volume» processes of plastic deformation and hardening. The use of rare-earth metals and their combinations as nonmetallic inclusions modifiers appear to have considerable promise. Therefore the modelling and further calculation of oxygen and sulfur interaction with yttrium in metal were carried out

  6. Thermodynamic database development-modeling and phase diagram calculations in oxide systems

    Institute of Scientific and Technical Information of China (English)

    Arthur D. Pelton

    2006-01-01

    The databases of the FactSage thermodynamic computer system have been under development for 30 years. These databases contain critically evaluated and optimized data for thousands of compounds and hundreds of multicomponent solutions of solid and liquid metals, oxides, salts, sulfides, etc. The databases are automatically accessed by user-friendly software that calculates complex multiphase equilibria in large multicomponent systems for a wide variety of possible input/output constraints. The databases for solutions have been developed by critical evaluation/optimization of all available phase equilibrium and thermodynamic data. The databases contain parameters of models specifically developed for different types of solutions involving sublattices, ordering, etc. Through the optimization process, model parameters are found which reproduce all thermodynamic and phase equilibrium data within experimental error limits and permit extrapolation into regions of temperature and composition where data are unavailable. The present article focuses on the databases for solid and liquid oxide phases involving 25 elements. A short review of the available databases is presented along with the models used for the molten slag and the solid solutions such as spinel, pyroxene, olivine, monoxide, corundum, etc. The critical evaluation/optimization procedure is outlined using examples from the A12O3-SiO2-CaO-FeO-Fe2O3 system. Sample calculations are presented in which the oxide databases are used in conjunction with the FactSage databases for metallic and other phases. In particular, the use of the FactSage module for the calculation of multicomponent phase diagrams is illustrated.

  7. Experimental and Kinetic Modeling Study of Ethyl Levulinate Oxidation in a Jet-Stirred Reactor

    KAUST Repository

    Wang, Jui-Yang

    2017-06-01

    A jet-stirred reactor was designed and constructed in the Clean Combustion Research Center (CCRC) at King Abdullah University of Science and Technology (KAUST); was validated with n-heptane, iso-octane oxidation and cyclohexene pyrolysis. Different configurations of the setup have been tested to achieve good agreement with results from the literature. Test results of the reactor indicated that installation of a pumping system at the downstream side in the experimental apparatus was necessary to avoid the reoccurrence of reactions in the sampling probe. Experiments in ethyl levulinate oxidation were conducted in the reactor under several equivalence ratios, from 600 to 1000 K, 1 bar and 2 s residence time. Oxygenated species detected included methyl vinyl ketone, levulinic acid and ethyl acrylate. Ethylene, methane, carbon monoxide, hydrogen, oxygen and carbon dioxide were further quantified with a gas chromatography, coupled with a flame ionization detector and a thermal conductivity detector. The ethyl levulinate chemical kinetic model was first developed by Dr. Stephen Dooley, Trinity College Dublin, and simulated under the same conditions, using the Perfect-Stirred Reactor code in Chemkin software. In comparing the simulation results with experimental data, some discrepancies were noted; predictions of ethylene production were not well matched. The kinetic model was improved by updating several classes of reactions: unimolecular decomposition, H-abstraction, C-C and C-O beta-scissions of fuel radicals. The updated model was then compared again with experimental results and good agreement was achieved, proving that the concerted eliminated reaction is crucial for the kinetic mechanism formulation of ethyl levulinate. In addition, primary reaction pathways and sensitivity analysis were performed to describe the role of molecular structure in combustion (800 and 1000 K for ethyl levulinate oxidation in the jet-stirred reactor).

  8. The OH-initiated oxidation of atmospheric peroxyacetic acid: Experimental and model studies

    Science.gov (United States)

    Wu, Huihui; Wang, Yin; Li, Huan; Huang, Liubin; Huang, Dao; Shen, Hengqing; Xing, Yanan; Chen, Zhongming

    2017-09-01

    Peroxyacetic acid (PAA, CH3C(O)OOH) plays an important role in atmospheric chemistry, serving as reactive oxidant and affecting radical recycling. However, previous studies revealed an obvious gap between modelled and observed concentrations of atmospheric PAA, which may be partly ascribed to the uncertainty in the kinetics and mechanism of OH-oxidation. In this study, we measured the rate constant of OH radical reaction with PAA (kPAA+OH) and investigated the products in order to develop a more robust atmospheric PAA chemistry. Using the relative rates technique and employing toluene and meta-xylene as reference compounds, the kPAA+OH was determined to be (9.4-11.9) × 10-12 cm3 molecule-1 s-1 at 298 K and 1 atm, which is about (2.5-3.2) times larger than that parameter used in Master Chemical Mechanism v3.3.1 (MCM v3.3.1) (3.70 × 10-12 cm3 molecule-1 s-1). Incorporation of a box model and MCM v3.3.1 with revised PAA chemistry represented a better simulation of atmospheric PAA observed during Wangdu Campaign 2014, a rural site in North China Plain. It is found that OH-oxidation is an important sink of atmospheric PAA in this rural area, accounting for ∼30% of the total loss. Moreover, the major terminal products of PAA-OH reaction were identified as formaldehyde (HCHO) and formic acid (HC(O)OH). The modelled results show that both primary and secondary chemistry play an important role in the large HCHO and HC(O)OH formation under experimental conditions. There should exist the channel of methyl H-abstraction for PAA-OH reaction, which may also provide routes to HCHO and HC(O)OH formation.

  9. Pyrite oxidation in the presence of hematite and alumina: I. Batch leaching experiments and kinetic modeling calculations.

    Science.gov (United States)

    Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi

    2017-02-15

    Pyrite is one of the most common and geochemically important sulfide minerals in nature because of its role in the redox recycling of iron (Fe). It is also the primary cause of acid mine drainage (AMD) that is considered as a serious and widespread problem facing the mining and mineral processing industries. In the environment, pyrite oxidation occurs in the presence of ubiquitous metal oxides, but the roles that they play in this process remain largely unknown. This study evaluates the effects of hematite (α-Fe2O3) and alumina (α-Al2O3) on pyrite oxidation by batch-reactor type experiments, surface-sensitive characterization of the oxidation layer and thermodynamic/kinetic modeling calculations. In the presence of hematite, dissolved sulfur (S) concentration dramatically decreased independent of the pH, and the formation of intermediate sulfoxy anionic species on the surface of pyrite was retarded. These results indicate that hematite minimized the overall extent of pyrite oxidation, but the kinetic model could not explain how this suppression occurred. In contrast, pyrite oxidation was enhanced in the alumina suspension as suggested by the higher dissolved S concentration and stronger infrared (IR) absorption bands of surface-bound oxidation products. Based on the kinetic model, alumina enhanced the oxidative dissolution of pyrite because of its strong acid buffering capacity, which increased the suspension pH. The higher pH values increased the oxidation of Fe(2+) to Fe(3+) by dissolved O2 (DO) that enhanced the overall oxidative dissolution kinetics of pyrite. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Modelling the growth of methane-oxidizing bacteria in a fixed biofilm

    DEFF Research Database (Denmark)

    Bilbo, Carl Morten; Arvin, Erik; Holst, Helle

    1992-01-01

    Methane-oxidizing bacteria were grown in a fixed biofilm reactor in order to study their ability to degrade chlorinated aliphatic hydrocarbons. Focus is on the growth behaviour of the mixed culture. The growth is described by a model that includes methanotrophic bacteria in the active biomass...... fraction. The inactive biomass fraction consists of exocellular polymers and biodegradable and inert particulate biomass. The model describes the oxygen respiration in detail. Yield coefficients, decay constants and hydrolysis constants are estimated based on the oxygen respiration. An analysis...... of the observability of the system reveals that several of the coefficients cannot be determined explicitly due to the complexity of the model and the limited amount of variables measured. Estimation procedures based on least squares methods are employed and parameter estimates and confidence intervals are computed...

  11. Ionic Model of Some Aspects of Cu NQR Spectra in Superconducting Oxides

    Science.gov (United States)

    Shimizu, Tadashi

    1993-02-01

    We apply an ionic model to explain the pressure and the temperature dependences of copper nuclear quadrupole frequency νQ in superconducting oxides. The pressure and the temperature dependences of νQ can, for the most part, be explained only by the change in the lattice spacing. It has also been shown that the origin of large difference in the 63Cu NQR line width between crystallographically different copper sites in YBa2Cu3O6.5 can be explained in the same model. The result of the present study suggests that the Sternheimer antishielding factor γ∞ is certainly effective in the case of ionic model, although a negligibly small value has been argued from viewpoint of the band calculation.

  12. The effect of consuming oxidized oil supplemented with fiber on lipid profiles in rat model

    Directory of Open Access Journals (Sweden)

    Shila Shafaeizadeh

    2011-01-01

    Conclusions: Pectin consumption could decrease serum malondialdehyde and cholesterol in the diet that contains oxidized oil. Pectin supplementation could decrease the detrimental effects of thermally oxidized oil.

  13. Early life and oxidative stress in psychiatric disorders: what can we learn from animal models?

    Science.gov (United States)

    Mhillaj, Emanuela; Morgese, Maria Grazia; Trabace, Luigia

    2015-01-01

    Schizophrenia is a complex pathology characterized by the occurrence of a variety of symptoms classified as positive, negative and cognitive. Although the exact etiopathogenesis of this disorder has not been unraveled yet, many theories have been endorsed during the last years. Among these, the neurochemical theories have been the most suited, considering the dopaminergic and glutamatergic dysfunctions to be mainly responsible for psychotic symptoms. However, the lack of efficacy of the available drugs, namely antipsychotics, toward negative and cognitive symptoms led to hypothesize alternative approaches. In this regard, the neurodevelopmental theory of schizophrenia has emerged, proposing the association between the occurrence of environmental risk factors in early-life and the development of psychosis in late-life. In particular, exposure to early life stressing situations, such as pre- and peri-natal stress, has been suggested as a risk factor to d evelop psychopathologies in adulthood in people genetically predisposed. A crucial support in favor of this hypothesis came from neurodevelopmental animal models of schizophrenia, such as maternal malnutrition, maternal deprivation, maternal infections as well as post-weaning social isolation rearing. Moreover, data from these models, corroborated by clinical findings, indicate that oxidative and nitrosative stress play a crucial role in the etiopathogenesis of psychiatric disorders. In the present work, we reviewed the recent progress in literature regarding data available from animal models linking oxidative and nitrosative stress to psychiatric disorders in order to evaluate novel biomarkers of pathology as well as novel therapeutical targets.

  14. Compositional Fragmentation Model for the Oxidation of Sulfide Particles in a Flash Reactor

    Science.gov (United States)

    Parra-Sánchez, Víctor Roberto; Pérez-Tello, Manuel; Duarte-Ruiz, Cirilo Andrés; Sohn, Hong Yong

    2014-04-01

    A mathematical model to predict the size distribution and chemical composition of a cloud of sulfide particles during high-temperature oxidation in a flash reactor is presented. The model incorporates the expansion and further fragmentation of the reacting particles along their trajectories throughout the reaction chamber. A relevant feature of the present formulation is its flexibility to treat a variety of flash reacting systems, such as the flash smelting and flash converting processes. This is accomplished by computing the chemical composition of individual particles and the size distribution and overall composition of the particle cloud in separate modules, which are coupled through a database of particle properties previously stored on disk. The flash converting of solid copper mattes is considered as an example. The model predictions showed good agreement with the experimental data collected in a large laboratory reactor in terms of particle size distribution and sulfur remaining in the population of particles. The cumulative contribution and distribution coefficients are introduced to quantify the relationship between specific particle sizes in the feed and those in the reacted products upon oxidation, the latter of which has practical implications on the amount and chemical composition of dust particles produced during the industrial operation.

  15. Experimental and kinetic modeling study of C2H4 oxidation at high pressure

    DEFF Research Database (Denmark)

    Lopez, Jorge Gimenez; Rasmussen, Christian Lund; Alzueta, Maria;

    2009-01-01

    A detailed chemical kinetic model for oxidation of C2H4 in the intermediate temperature range and high pressure has been developed and validated experimentally. New ab initio calculations and RRKM analysis of the important C2H3 + O-2 reaction was used to obtain rate coefficients over a wide range...... of conditions (0.003-100 bar, 200-3000 K). The results indicate that at 60 bar and medium temperatures vinyl peroxide, rather than CH2O and HCO, is the dominant product. The experiments, involving C2H4/O-2 mixtures diluted in N-2, were carried out in a high pressure flow reactor at 600-900 K and 60 bar, varying...... the reaction stoichiometry from very lean to fuel-rich conditions. Model predictions are generally satisfactory. The governing reaction mechanisms are outlined based on calculations with the kinetic model. Under the investigated conditions the oxidation pathways for C2H4 are more complex than those prevailing...

  16. Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations

    DEFF Research Database (Denmark)

    Skulason, Egill; Tripkovic, Vladimir; Björketun, Mårten

    2010-01-01

    Density functional theory calculations have been performed for the three elementary steps―Tafel, Heyrovsky, and Volmer―involved in the hydrogen oxidation reaction (HOR) and its reverse, the hydrogen evolution reaction (HER). For the Pt(111) surface a detailed model consisting of a negatively...... charged Pt(111) slab and solvated protons in up to three water bilayers is considered and reaction energies and activation barriers are determined by using a newly developed computational scheme where the potential can be kept constant during a charge transfer reaction. We determine the rate limiting...

  17. Evaluation of the mitochondrial respiratory chain and oxidative phosphorylation system using yeast models of OXPHOS deficiencies.

    Science.gov (United States)

    Fontanesi, Flavia; Diaz, Francisca; Barrientos, Antoni

    2009-10-01

    The oxidative phosphorylation (OXPHOS) system consists of five multimeric complexes embedded in the mitochondrial inner membrane. They work in concert to drive the aerobic synthesis of ATP. Mitochondrial and nuclear DNA mutations affecting the accumulation and function of these enzymes are the most common cause of mitochondrial diseases and have also been associated with neurodegeneration and aging. Several approaches for the assessment of the OXPHOS system enzymes have been developed. Based on the methods described elsewhere, this unit describes the creation and study of yeast models of mitochondrial OXPHOS deficiencies.

  18. Ability of silybin and its derivatives to prevent protein oxidation in different model systems

    DEFF Research Database (Denmark)

    Purchartová, K.; Baron, C.P.; Křen, V.

    2013-01-01

    to prevent activation of hemoglobin (Hb) to highly reactive hypervalent heme protein species (ferrylHb and perferrylHb) was examined. Indeed, Hb cytotoxicity has been associated with the generation of protein radicals, which are formed when the ferric iron of Hb (Fe3+) is oxidised by H2O2 to (Fe4+) to form...... perferrylHb and ferrylHb, with the later also bearing a radical on its protein. The relationship between the structural properties of silybin and its derivatives and their ability to prevent oxidation of Hb was investigated in model system in the presence or the absence of lipids. The antioxidant activities...

  19. Measurement-based modelling of bromine-induced oxidation of mercury above the Dead Sea

    Science.gov (United States)

    Tas, E.; Obrist, D.; Peleg, M.; Matveev, V.; Faïn, X.; Asaf, D.; Luria, M.

    2012-03-01

    Atmospheric mercury depletion events (AMDEs) outside the polar region - driven by high levels of gaseous Br and BrO (i.e., BrOx) - were observed recently in the warm Dead Sea boundary layer. The efficient oxidation of gaseous elemental mercury (GEM) under temperate conditions by BrOx was unexpected considering that the thermal back dissociation reaction of HgBr is about 2.5 orders of magnitude higher under Dead Sea temperatures compared to polar temperatures, and hence was expected to significantly slow down GEM oxidation under warm temperatures. The goal of this modelling study was to improve understanding of the interaction of reactive bromine and mercury during Dead Sea AMDEs using numerical simulations based on a comprehensive measurement campaign in summer 2009. Our analysis is focused on daytime AMDE when chemical processes dominate concentration changes. Best agreements between simulations and observations were achieved using rate constants for kHg+Br and kHg+BrO of 2.7 × 10-13 cm3 molecule-1 s-1 and 1.5 × 10-13 cm3 molecule-1 s-1, respectively. Our model also predicted that a rate constant kHg+BrO of 5.0 × 10-14 cm3 molecule-1 s-1 may be considered as a minimum, which is higher than most reported values. These rate constants suggest that BrO could be a more efficient oxidant than Br in the troposphere as long as [Br]/[BrO] ratios are smaller than ~0.2 to 0.5. Under Dead Sea conditions, these kinetics demonstrate a high efficiency and central role of BrOx for AMDEs, with relative contributions to GEM depletion of more than ~90%. Unexpectedly, BrO was found to be the dominant oxidant with relative contributions above 80%. The strong contribution of BrO could explain why the efficiency of GEM oxidation at the Dead Sea does not critically depend on Br and, therefore, is comparable to that in cold polar regions. In order to confirm the suggested kinetics, additional studies, particularly for temperature-dependence of rate constants, are required.

  20. Measurement-based modelling of bromine-induced oxidation of mercury above the Dead Sea

    Directory of Open Access Journals (Sweden)

    E. Tas

    2012-03-01

    Full Text Available Atmospheric mercury depletion events (AMDEs outside the polar region – driven by high levels of gaseous Br and BrO (i.e., BrOx – were observed recently in the warm Dead Sea boundary layer. The efficient oxidation of gaseous elemental mercury (GEM under temperate conditions by BrOx was unexpected considering that the thermal back dissociation reaction of HgBr is about 2.5 orders of magnitude higher under Dead Sea temperatures compared to polar temperatures, and hence was expected to significantly slow down GEM oxidation under warm temperatures. The goal of this modelling study was to improve understanding of the interaction of reactive bromine and mercury during Dead Sea AMDEs using numerical simulations based on a comprehensive measurement campaign in summer 2009.

    Our analysis is focused on daytime AMDE when chemical processes dominate concentration changes. Best agreements between simulations and observations were achieved using rate constants for kHg+Br and kHg+BrO of 2.7 × 10−13 cm3 molecule−1 s−1 and 1.5 × 10−13 cm3 molecule−1 s−1, respectively. Our model also predicted that a rate constant kHg+BrO of 5.0 × 10−14 cm3 molecule−1 s−1 may be considered as a minimum, which is higher than most reported values. These rate constants suggest that BrO could be a more efficient oxidant than Br in the troposphere as long as [Br]/[BrO] ratios are smaller than ~0.2 to 0.5. Under Dead Sea conditions, these kinetics demonstrate a high efficiency and central role of BrOx for AMDEs, with relative contributions to GEM depletion of more than ~90%. Unexpectedly, BrO was found to be the dominant oxidant with relative contributions above 80%. The strong contribution of BrO could explain why the efficiency of GEM

  1. Modeling, control and integration of a portable solid oxide fuel cell system

    Science.gov (United States)

    Adhikari, Puran

    This thesis presents an innovative method for the modeling, control and integration of a portable hybrid solid oxide fuel cell system. The control and integration of the fuel cell system is important not only for its efficient operation, but also for issues related to safety and reliability. System modeling is needed in order to facilitate the controller design. Mathematical models of the various components of the system are built in the matlab/simulink environment. Dynamic modeling of the fuel cell stack, catalytic partial oxidation (CPOX) reformer, heat exchanger, tail gas combustor and tail gas splitter of the balance of plant system is performed first. Followed by, modeling of the three input DC/DC converter and energy storage devices (battery and supercapacitor). A two-level control approach, higher level and lower level, is adopted in this research. Each of the two major subsystems, balance of plant subsystem and power electronics subsystem, has its own local level controller (called lower level controller) that are designed such that they follow exactly the command reference from a higher level controller. The higher level controller is an intelligent controller that makes decisions about how the lower level or local controllers should perform based on the status of fuel cell, energy storage device and external load demand. Linear analysis has been done for the design and development of the local controllers as appropriate. For the higher level controller, a finite state machine model is developed and implemented using stateflow and fuzzy logic toolboxes of matlab. Simulations are carried out for the integrated system. The simulation results verify that the controllers are robust in performance during the transient condition when the energy storage devices supplement fuel cells. The temperature and flow rates of the fuel and air are controlled as desired. The output from the designed fuel cell system is a regulated DC voltage, which verifies the overall

  2. Fuzzy-logic modeling of Fenton's oxidation of anaerobically pretreated poultry manure wastewater.

    Science.gov (United States)

    Yetilmezsoy, Kaan

    2012-07-01

    A multiple inputs and multiple outputs (MIMO) fuzzy-logic-based model was proposed to estimate color and chemical oxygen demand (COD) removal efficiencies in the post-treatment of anaerobically pretreated poultry manure wastewater effluent using Fenton's oxidation process. Three main input variables including initial pH, Fe+2, and H2O2 dosages were fuzzified in a new numerical modeling scheme by the use of an artificial intelligence-based approach. Trapezoidal membership functions with eight levels were conducted for the fuzzy subsets, and a Mamdani-type fuzzy inference system was used to implement a total of 70 rules in the IF-THEN format. The product (prod) and the center of gravity (centroid) methods were applied as the inference operator and defuzzification methods, respectively. Fuzzy-logic predicted results were compared with the outputs of two first-order polynomial regression models derived in the scope of this study. Estimated results were also compared to the multiple regression approach by means of various descriptive statistical indicators, such as root mean-squared error, index of agreement, fractional variance, proportion of systematic error, etc. Results of the statistical analysis clearly revealed that, compared to conventional regression models, the proposed MIMO fuzzy-logic model produced very smaller deviations and demonstrated a superior predictive performance on forecasting of color and COD removal efficiencies with satisfactory determination coefficients over 0.98. Due to high capability of the fuzzy-logic methodology in capturing the non-linear interactions, it was demonstrated that a complex dynamic system, such as Fenton's oxidation, could be easily modeled.

  3. Comprehensive Assessment of Oxidatively Induced Modifications of DNA in a Rat Model of Human Wilson's Disease.

    Science.gov (United States)

    Yu, Yang; Guerrero, Candace R; Liu, Shuo; Amato, Nicholas J; Sharma, Yogeshwar; Gupta, Sanjeev; Wang, Yinsheng

    2016-03-01

    Defective copper excretion from hepatocytes in Wilson's disease causes accumulation of copper ions with increased generation of reactive oxygen species via the Fenton-type reaction. Here we developed a nanoflow liquid chromatography-nanoelectrospray ionization-tandem mass spectrometry coupled with the isotope-dilution method for the simultaneous quantification of oxidatively induced DNA modifications. This method enabled measurement, in microgram quantities of DNA, of four oxidative stress-induced lesions, including direct ROS-induced purine cyclonucleosides (cPus) and two exocyclic adducts induced by byproducts of lipid peroxidation, i.e. 1,N(6)-etheno-2'-deoxyadenosine (εdA) and 1,N(2)-etheno-2'-deoxyguanosine (εdG). Analysis of liver tissues of Long-Evans Cinnamon rats, which constitute an animal model of human Wilson's disease, and their healthy counterparts [i.e. Long-Evans Agouti rats] showed significantly higher levels of all four DNA lesions in Long-Evans Cinnamon than Long-Evans Agouti rats. Moreover, cPus were present at much higher levels than εdA and εdG lesions. In contrast, the level of 5-hydroxymethyl-2'-deoxycytidine (5-HmdC), an oxidation product of 5-methyl-2'-deoxycytidine (5-mdC), was markedly lower in the liver tissues of Long-Evans Cinnamon than Long-Evans Agouti rats, though no differences were observed for the levels of 5-mdC. In vitro biochemical assay showed that Cu(2+) ions could directly inhibit the activity of Tet enzymes. Together, these results suggest that aberrant copper accumulation may perturb genomic stability by elevating oxidatively induced DNA lesions, and by altering epigenetic pathways of gene regulation.

  4. An experimental and kinetic modeling study of the oxidation of the four isomers of butanol.

    Science.gov (United States)

    Moss, Jeffrey T; Berkowitz, Andrew M; Oehlschlaeger, Matthew A; Biet, Joffrey; Warth, Valérie; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique

    2008-10-30

    Butanol, an alcohol which can be produced from biomass sources, has received recent interest as an alternative to gasoline for use in spark ignition engines and as a possible blending compound with fossil diesel or biodiesel. Therefore, the autoignition of the four isomers of butanol (1-butanol, 2-butanol, iso-butanol, and tert-butanol) has been experimentally studied at high temperatures in a shock tube, and a kinetic mechanism for description of their high-temperature oxidation has been developed. Ignition delay times for butanol/oxygen/argon mixtures have been measured behind reflected shock waves at temperatures and pressures ranging from approximately 1200 to 1800 K and 1 to 4 bar. Electronically excited OH emission and pressure measurements were used to determine ignition-delay times. The influence of temperature, pressure, and mixture composition on ignition delay has been characterized. A detailed kinetic mechanism has been developed to describe the oxidation of the butanol isomers and validated by comparison to the shock-tube measurements. Reaction flux and sensitivity analysis illustrates the relative importance of the three competing classes of consumption reactions during the oxidation of the four butanol isomers: dehydration, unimolecular decomposition, and H-atom abstraction. Kinetic modeling indicates that the consumption of 1-butanol and iso-butanol, the most reactive isomers, takes place primarily by H-atom abstraction resulting in the formation of radicals, the decomposition of which yields highly reactive branching agents, H atoms and OH radicals. Conversely, the consumption of tert-butanol and 2-butanol, the least reactive isomers, takes place primarily via dehydration, resulting in the formation of alkenes, which lead to resonance stabilized radicals with very low reactivity. To our knowledge, the ignition-delay measurements and oxidation mechanism presented here for 2-butanol, iso-butanol, and tert-butanol are the first of their kind.

  5. Process-Scale Modeling of Atmosphere-Snowpack Exchange of Nitrogen Oxides

    Science.gov (United States)

    Murray, K. A.; Doskey, P. V.; Ganzeveld, L.

    2013-12-01

    Snowpack over glacial ice is a reservoir for reactive nitrogen gases. Previous studies indicate nitrogen oxides (NOx) are generated in snowpack interstitial air through photolysis of nitrate (NO3-). Gradients in NOx mixing ratios between snowpack interstitial air and the overlying atmosphere regulate exchange of NOx with snowpack, which affects the Arctic ozone budget and climate. To better understand the dynamics of cryosphere-atmosphere exchange of NOx in the Arctic, we collected 2 years of meteorological and chemical data in and above the snowpack at Summit, Greenland. The comprehensive dataset indicates NOx emissions are episodic, with NOx enhancements in snowpack in early spring during high wind speed events (10-20 mph), which elevate NOx levels to ~500 pptv at depths of 2.5 m. Analysis of the observations will be based upon application of a 1-D process-scale model of atmosphere-snowpack exchange of NOx. The model will include representations of the snowpack chemistry in gas and aqueous phases, mass transfer of chemical species between phases, and physical transport by diffusion and wind pumping. The model will calculate the chemical and physical tendencies in three dimensions: depth, time, and intensity. Analysis of the tendencies will allow us to perform model sensitivity tests of pertinent snowpack physical and chemical processes. The end-goal of the project is to simplify the major tendencies into a parameterized model add-on for use in global models to determine the importance of properly representing snowpack in global model simulations.

  6. Investigations on boron carbide oxidation for nuclear reactors safety-General modelling for ICARE/CATHARE code applications

    Energy Technology Data Exchange (ETDEWEB)

    Seiler, N. [Institut de Radioprotection et de Surete Nucleaire (IRSN), Cadarache, BP 3, 13 115 Saint Paul lez Durance Cedex (France)], E-mail: nathalie.seiler@irsn.fr; Bertrand, F.; Marchand, O.; Repetto, G. [Institut de Radioprotection et de Surete Nucleaire (IRSN), Cadarache, BP 3, 13 115 Saint Paul lez Durance Cedex (France); Ederli, S. [ENEA, Ente per le Nuove Tecnologie l' Energia et l' Ambiente (Italy)

    2008-04-15

    The present paper deals with the problem of boron carbide pellet oxidation which might occur during a severe accident. A basic correlation, involving global variables, has been developed for the simulation of boron carbide oxidation with the ICARE/CATHARE code. This modelling has been based on available experimental data, including the VERDI separate effects experiments performed by IRSN at low pressures and high temperatures. According to the agreement between the measured and the calculated bundle temperatures as well as hydrogen release and oxidized B{sub 4}C, the ICARE/CATHARE code simulates rather well QUENCH experiments involving B{sub 4}C control rod degradation, Zircaloy oxidation under starvation and cooling with steam. Based on simulations results, it has been noticed that the B{sub 4}C degradation has a slight direct effect on global bundle degradation but a non-negligible influence on Zircaloy oxidation through power release, material melting and flowing down.

  7. Extending the benchmark simulation model no2 with processes for nitrous oxide production and side-stream nitrogen removal

    DEFF Research Database (Denmark)

    2015-01-01

    In this work the Benchmark Simulation Model No.2 is extended with processes for nitrous oxide production and for side-stream partial nitritation/Anammox (PN/A) treatment. For these extensions the Activated Sludge Model for Greenhouse gases No.1 was used to describe the main waterline, whereas...... the Complete Autotrophic Nitrogen Removal (CANR) model was used to describe the side-stream (PN/A) treatment. Comprehensive simulations were performed to assess the extended model. Steady-state simulation results revealed the following: (i) the implementation of a continuous CANR side-stream reactor has...... increased the total nitrogen removal by 10%; (ii) reduced the aeration demand by 16% compared to the base case, and (iii) the activity of ammonia-oxidizing bacteria is most influencing nitrous oxide emissions. The extended model provides a simulation platform to generate, test and compare novel control...

  8. Three-dimensional three-phase model for simulation of hydrodynamics, oxygen mass transfer, carbon oxidation, nitrification and denitrification in an oxidation ditch.

    Science.gov (United States)

    Lei, Li; Ni, Jinren

    2014-04-15

    A three-dimensional three-phase fluid model, supplemented by laboratory data, was developed to simulate the hydrodynamics, oxygen mass transfer, carbon oxidation, nitrification and denitrification processes in an oxidation ditch. The model provided detailed phase information on the liquid flow field, gas hold-up distribution and sludge sedimentation. The three-phase model described water-gas, water-sludge and gas-sludge interactions. Activated sludge was taken to be in a pseudo-solid phase, comprising an initially separated solid phase that was transported and later underwent biological reactions with the surrounding liquidmedia. Floc parameters were modified to improve the sludge viscosity, sludge density, oxygen mass transfer rate, and carbon substrate uptake due to adsorption onto the activated sludge. The validation test results were in very satisfactory agreement with laboratory data on the behavior of activated sludge in an oxidation ditch. By coupling species transport and biological process models, reasonable predictions are made of: (1) the biochemical kinetics of dissolved oxygen, chemical oxygen demand (COD) and nitrogen variation, and (2) the physical kinematics of sludge sedimentation.

  9. Annual and seasonal spatial models for nitrogen oxides in Tehran, Iran

    Science.gov (United States)

    Amini, Heresh; Taghavi-Shahri, Seyed-Mahmood; Henderson, Sarah B.; Hosseini, Vahid; Hassankhany, Hossein; Naderi, Maryam; Ahadi, Solmaz; Schindler, Christian; Künzli, Nino; Yunesian, Masud

    2016-09-01

    Very few land use regression (LUR) models have been developed for megacities in low- and middle-income countries, but such models are needed to facilitate epidemiologic research on air pollution. We developed annual and seasonal LUR models for ambient oxides of nitrogen (NO, NO2, and NOX) in the Middle Eastern city of Tehran, Iran, using 2010 data from 23 fixed monitoring stations. A novel systematic algorithm was developed for spatial modeling. The R2 values for the LUR models ranged from 0.69 to 0.78 for NO, 0.64 to 0.75 for NO2, and 0.61 to 0.79 for NOx. The most predictive variables were: distance to the traffic access control zone; distance to primary schools; green space; official areas; bridges; and slope. The annual average concentrations of all pollutants were high, approaching those reported for megacities in Asia. At 1000 randomly-selected locations the correlations between cooler and warmer season estimates were 0.64 for NO, 0.58 for NOX, and 0.30 for NO2. Seasonal differences in spatial patterns of pollution are likely driven by differences in source contributions and meteorology. These models provide a basis for understanding long-term exposures and chronic health effects of air pollution in Tehran, where such research has been limited.

  10. Accurate geometry scalable complementary metal oxide semiconductor modelling of low-power 90 nm amplifier circuits

    Directory of Open Access Journals (Sweden)

    Apratim Roy

    2014-05-01

    Full Text Available This paper proposes a technique to accurately estimate radio frequency behaviour of low-power 90 nm amplifier circuits with geometry scalable discrete complementary metal oxide semiconductor (CMOS modelling. Rather than characterising individual elements, the scheme is able to predict gain, noise and reflection loss of low-noise amplifier (LNA architectures made with bias, active and passive components. It reduces number of model parameters by formulating dependent functions in symmetric distributed modelling and shows that simple fitting factors can account for extraneous (interconnect effects in LNA structure. Equivalent-circuit model equations based on physical structure and describing layout parasites are developed for major amplifier elements like metal–insulator–metal (MIM capacitor, spiral symmetric inductor, polysilicon (PS resistor and bulk RF transistor. The models are geometry scalable with respect to feature dimensions, i.e. MIM/PS width and length, outer-dimension/turns of planar inductor and channel-width/fingers of active device. Results obtained with the CMOS models are compared against measured literature data for two 1.2 V amplifier circuits where prediction accuracy for RF parameters (S(21, noise figure, S(11, S(22 lies within the range of 92–99%.

  11. Modeling and optimization of the combined carbon dioxide reforming and partial oxidation of natural gas

    Energy Technology Data Exchange (ETDEWEB)

    Larentis, A.L.; De Resende, N.S.; Salim, V.M.M.; Pinto, J.C. [Programa de Engenharia Quimica/COPPE/Universidade Federal do Rio de Janeiro, Cidade Universitaria, CP 68502, RJ, 21945-970 Rio de Janeiro (Brazil)

    2001-07-13

    The optimization of the combined carbon dioxide reforming and partial methane oxidation over a 1% Pt/{gamma}-Al{sub 2}O{sub 3} catalyst was studied in order to produce synthesis gas with hydrogen/carbon monoxide ratio close to 1, for applications in metallurgical and polycarbonates processes and for production of oxygenated compounds and hydrocarbons. The study was performed with the help of experimental design and two mathematical modeling approaches: empirical and phenomenological. Empirical polynomial models were employed to analyze the effects of the process variables on the response factors and the final correlation coefficients obtained were above 95%. The phenomenological model was obtained from individual mass balances and the obtained correlation coefficients were above 95% for CH{sub 4} and N{sub 2}, 90% for CO{sub 2} and H{sub 2}O and near 70% for H{sub 2} and CO. The empirical modeling approach was found to be more efficient, simpler and led to better results than those obtained with the phenomenological model approach. Therefore, the empirical modeling was used for optimization of the process operation conditions. At an oxygen/methane ratio of 0.55gmol/gmol and temperature of 950C, optimized process conditions were obtained with complete methane conversion, maximum carbon monoxide selectivity of 43% and minimum hydrogen/carbon monoxide ratio of 1.3, in absence of water.

  12. A comprehensive adsorption study and modeling of antibiotics as a pharmaceutical waste by graphene oxide nanosheets.

    Science.gov (United States)

    Rostamian, Rahele; Behnejad, Hassan

    2017-08-22

    The adsorption behavior of tetracycline (TCN), doxycycline (DCN) as the most common antibiotics in veterinary and ciprofloxacin (CPN) onto graphene oxide nanosheets (GOS) in aqueous solution was evaluated. The four factors influencing the adsorption of antibiotics (initial concentration, pH, temperature and contact time) were studied. The results showed that initial pH ∼ 6 to 7 and contact time ∼ 100 - 200min are optimum for each drug. The monolayer adsorption capacity was reduced with the increasing temperature from 25°C to 45°C. Non-linear regressions were carried out in order to define the best fit model for every system. To do this, eight error functions were applied to predict the optimum model. Among various models, Hill and Toth isotherm models represented the equilibrium adsorption data of antibiotics while the kinetic data were well fitted by pseudo second-order (PSO) kinetic model (DCN and TCN) and Elovich (CPN) models. The maximum adsorption capacity (qmax) is found to be in the following order: CPN > DCN > TCN, obtained from sips equation at the same temperature. The GOS shows highest adsorption capacity towards CPN up to 173.4mgg(-1). The study showed that GOS can be removed more efficiently from water solution. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. A Microscale Modeling Tool for the Design and Optimization of Solid Oxide Fuel Cells

    Directory of Open Access Journals (Sweden)

    Shixue Liu

    2009-06-01

    Full Text Available A two dimensional numerical model of a solid oxide fuel cell (SOFC with electrode functional layers is presented. The model incorporates the partial differential equations for mass transport, electric conduction and electrochemical reactions in the electrode functional layers, the anode support layer, the cathode current collection layer and at the electrode/electrolyte interfaces. A dusty gas model is used in modeling the gas transport in porous electrodes. The model is capable of providing results in good agreement with the experimental I-V relationship. Numerical examples are presented to illustrate the applications of this numerical model as a tool for the design and optimization of SOFCs. For a stack assembly of a pitch width of 2 mm and an interconnect-electrode contact resistance of 0.025 Ωcm2, a typical SOFC stack cell should consist of a rib width of 0.9 mm, a cathode current collection layer thickness of 200–300 μm, a cathode functional layer thickness of 20–40 μm, and an anode functional layer thickness of 10–20 μm in order to achieve optimal performance.

  14. Atmospheric Oxidation in a Southeastern US Forest: Sensitivity of Differences Between Modeled and Measured Hydroxyl (OH) to Model Mechanism and Inputs

    Science.gov (United States)

    Brune, W. H.; Feiner, P. A.; Zhang, L.; Miller, D. O.

    2014-12-01

    Forests play a critical role in the atmosphere's oxidation chemistry because of their broad global extent and their prodigious emissions of biogenic volatile organic compounds (BVOCs). The high hydroxyl (OH) reactivity of these BVOCs causes much of the initial chemistry to occur near the forest. Some OH measurements in forests are much greater than calculated with models, leading to close examination of the BVOC oxidation mechanisms and the possibility of significant OH recycling. The 2013 Southern Oxidant and Aerosol Study (SOAS) provides a rigorous test of the BVOC oxidation mechanisms and OH recycling with its extensive measurement suite that was positioned in an Alabama forest for six weeks. OH measurements made with the Ground-based Tropospheric Hydrogen Oxides Sensor (GTHOS) are compared to photochemical box models constrained with other simultaneous measurements in order to test the understanding of this forest photochemistry. In this work, we use a global sensitivity analysis (Random Sampling - High Dimensional Model Representation) to examine the sensitivity of the differences between the modeled and measured OH to the model mechanism and inputs. In this presentation, we will discuss the model reactions and inputs that have the most influence on the modeled OH and its difference with measured OH and will provide recommendations for reducing model and measurement uncertainty.

  15. A DFT study of phenol adsorption on a low doping Mn-Ce composite oxide model

    Science.gov (United States)

    D´Alessandro, Oriana; Pintos, Delfina García; Juan, Alfredo; Irigoyen, Beatriz; Sambeth, Jorge

    2015-12-01

    Density functional theory calculations (DFT + U) were performed on a low doping Mn-Ce composite oxide prepared from experimental data, including X-ray diffraction (XRD) and temperature-programmed reduction (TPR). We considered a 12.5% Mn-doped CeO2 solid solution with fluorite-type structure, where Mn replaces Ce4+ leading to an oxygen-deficient bulk structure. Then, we modeled the adsorption of phenol on the bare Ce0.875Mn0.125O1.9375(1 1 1) surface. We also studied the effect of water adsorption and dissociation on phenol adsorption on this surface, and compared the predictions of DFT + U calculations with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements. The experimental results allowed us to both build a realistic model of the low doping Mn-Ce composite oxide and support the prediction that phenol is adsorbed as a phenoxy group with a tilt angle of about 70° with respect to the surface.

  16. Animal models for the study of liver regeneration: role of nitric oxide and prostaglandins.

    Science.gov (United States)

    Hortelano, Sonsoles; Zeini, Miriam; Casado, Marta; Martín-Sanz, Paloma; Boscá, Lisardo

    2007-01-01

    The mechanisms that permit adult tissues to regenerate are the object of intense study. Liver regeneration is a research area of considerable interest both from pathological and from physiological perspectives. One of the best models of the regenerative process is the two-thirds partial hepatectomy (PH). After PH, the remnant liver starts a series of timed responses that first favor cell growth and then halts hepatocyte proliferation once liver function is fully restored. The mechanisms regulating this process are complex and involve many cellular events. Initiation of liver regeneration requires the injury-related cytokines tumor necrosis factor-alpha (TNF-alpha) and interleukin 6 (IL-6), and involves the activation of cytokine-regulated transcription factors such as NF-kappaB and STAT3. An important event that takes place in the hours immediately after PH is the induction of nitric oxide synthase 2 (NOS-2) and cyclooxygenase 2 (COX-2), and the consequent release of nitric oxide (NO) and prostaglandins (PGs). NO is involved in the vascular readaptation after PH, favoring a general permeability to growth factors throughout the organ. This review examines the mechanisms that regulate NO release during liver regeneration and the animal models used to identify these pathways.

  17. Intrinsic point defects in zinc oxide. Modeling of structural, electronic, thermodynamic and kinetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Erhart, P.

    2006-07-01

    The present dissertation deals with the modeling of zinc oxide on the atomic scale employing both quantum mechanical as well as atomistic methods. The first part describes quantum mechanical calculations based on density functional theory of intrinsic point defects in ZnO. To begin with, the geometric and electronic structure of vacancies and oxygen interstitials is explored. In equilibrium oxygen interstitials are found to adopt dumbbell and split interstitial configurations in positive and negative charge states, respectively. Semi-empirical self-interaction corrections allow to improve the agreement between the experimental and the calculated band structure significantly; errors due to the limited size of the supercells can be corrected by employing finite-size scaling. The effect of both band structure corrections and finite-size scaling on defect formation enthalpies and transition levels is explored. Finally, transition paths and barriers for the migration of zinc as well as oxygen vacancies and interstitials are determined. The results allow to interpret diffusion experiments and provide a consistent basis for developing models for device simulation. In the second part an interatomic potential for zinc oxide is derived. To this end, the Pontifix computer code is developed which allows to fit analytic bond-order potentials. The code is subsequently employed to obtain interatomic potentials for Zn-O, Zn-Zn, and O-O interactions. To demonstrate the applicability of the potentials, simulations on defect production by ion irradiation are carried out. (orig.)

  18. Cardiovascular disease-related parameters and oxidative stress in SHROB rats, a model for metabolic syndrome.

    Directory of Open Access Journals (Sweden)

    Eunice Molinar-Toribio

    Full Text Available SHROB rats have been suggested as a model for metabolic syndrome (MetS as a situation prior to the onset of CVD or type-2 diabetes, but information on descriptive biochemical parameters for this model is limited. Here, we extensively evaluate parameters related to CVD and oxidative stress (OS in SHROB rats. SHROB rats were monitored for 15 weeks and compared to a control group of Wistar rats. Body weight was recorded weekly. At the end of the study, parameters related to CVD and OS were evaluated in plasma, urine and different organs. SHROB rats presented statistically significant differences from Wistar rats in CVD risk factors: total cholesterol, LDL-cholesterol, triglycerides, apoA1, apoB100, abdominal fat, insulin, blood pressure, C-reactive protein, ICAM-1 and PAI-1. In adipose tissue, liver and brain, the endogenous antioxidant systems were activated, yet there was no significant oxidative damage to lipids (MDA or proteins (carbonylation. We conclude that SHROB rats present significant alterations in parameters related to inflammation, endothelial dysfunction, thrombotic activity, insulin resistance and OS measured in plasma as well as enhanced redox defence systems in vital organs that will be useful as markers of MetS and CVD for nutrition interventions.

  19. Remediation of a historically Pb contaminated soil using a model natural Mn oxide waste.

    Science.gov (United States)

    McCann, Clare M; Gray, Neil D; Tourney, Janette; Davenport, Russell J; Wade, Matthew; Finlay, Nina; Hudson-Edwards, Karen A; Johnson, Karen L

    2015-11-01

    A natural Mn oxide (NMO) waste was assessed as an in situ remediation amendment for Pb contaminated sites. The viability of this was investigated using a 10 month lysimeter trial, wherein a historically Pb contaminated soil was amended with a 10% by weight model NMO. The model NMO was found to have a large Pb adsorption capacity (qmax 346±14 mg g(-1)). However, due to the heterogeneous nature of the Pb contamination in the soils (3650.54-9299.79 mg kg(-1)), no treatment related difference in Pb via geochemistry could be detected. To overcome difficulties in traditional geochemical techniques due to pollutant heterogeneity we present a new method for unequivocally proving metal sorption to in situ remediation amendments. The method combines two spectroscopic techniques; namely electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS). Using this we showed Pb immobilisation on NMO, which were Pb free prior to their addition to the soils. Amendment of the soil with exogenous Mn oxide had no effect on microbial functioning, nor did it perturb the composition of the dominant phyla. We conclude that NMOs show excellent potential as remediation amendments. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

  20. Comparison of CORA and MELCOR core degradation simulation and the MELCOR oxidation model

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun [College of Engineering, The University of Wisconsin-Madison, Madison, WI 53706 (United States); State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049 (China); Corradini, Michael L., E-mail: corradini@engr.wisc.edu [College of Engineering, The University of Wisconsin-Madison, Madison, WI 53706 (United States); Fu, Wen [College of Engineering, The University of Wisconsin-Madison, Madison, WI 53706 (United States); Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Haskin, Troy [College of Engineering, The University of Wisconsin-Madison, Madison, WI 53706 (United States); Tian, Wenxi; Zhang, Yapei; Su, Guanghui; Qiu, Suizheng [State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049 (China)

    2014-09-15

    Highlights: • Oxidation model of MELCOR is analyzed and the improving suggestion is provided. • MELCOR core degradation calculating results are compared with CORA experiment. • Flow rate of argon and steam, the generating rate of hydrogen is calculated and compared. • Temperature spatial variation and temperature history is calculated and presented. - Abstract: MELCOR is widely used and sufficiently trusted for severe accident analysis. However, the occurrence of Fukushima has increased the focus on severe accident codes and their use. A MELCOR core degradation calculation was conducted at the University of Wisconsin–Madison under the help of Sandia. The calculation results were checked by comparing with a past CORA experiment. MELCOR calculation results included the flow rate of argon and steam, the generation rate of hydrogen. Through this work, the performance of MELCOR COR package was reviewed in detail. This paper compares the hydrogen generation rates predicted by MELCOR to the CORA test data. While agreement is reasonable it could be improved. Additionally, the MELCOR zirconium oxidation model was analyzed.

  1. Reactive Transport Modeling of Microbe-mediated Fe (II) Oxidation for Enhanced Oil Recovery

    Science.gov (United States)

    Surasani, V.; Li, L.

    2011-12-01

    Microbially Enhanced Oil Recovery (MEOR) aims to improve the recovery of entrapped heavy oil in depleted reservoirs using microbe-based technology. Reservoir ecosystems often contain diverse microbial communities those can interact with subsurface fluids and minerals through a network of nutrients and energy fluxes. Microbe-mediated reactions products include gases, biosurfactants, biopolymers those can alter the properties of oil and interfacial interactions between oil, brine, and rocks. In addition, the produced biomass and mineral precipitates can change the reservoir permeability profile and increase sweeping efficiency. Under subsurface conditions, the injection of nitrate and Fe (II) as the electron acceptor and donor allows bacteria to grow. The reaction products include minerals such as Fe(OH)3 and nitrogen containing gases. These reaction products can have large impact on oil and reservoir properties and can enhance the recovery of trapped oil. This work aims to understand the Fe(II) oxidation by nitrate under conditions relevant to MEOR. Reactive transport modeling is used to simulate the fluid flow, transport, and reactions involved in this process. Here we developed a complex reactive network for microbial mediated nitrate-dependent Fe (II) oxidation that involves both thermodynamic controlled aqueous reactions and kinetic controlled Fe (II) mineral reaction. Reactive transport modeling is used to understand and quantify the coupling between flow, transport, and reaction processes. Our results identify key parameter controls those are important for the alteration of permeability profile under field conditions.

  2. Model aging and oxidation effects on varietal, fermentative, and sulfur compounds in a dry botrytized red wine.

    Science.gov (United States)

    Fedrizzi, Bruno; Zapparoli, Giacomo; Finato, Fabio; Tosi, Emanuele; Turri, Arianna; Azzolini, Michela; Versini, Giuseppe

    2011-03-09

    From harvest until wine arrives to the consumer, oxygen plays a crucial role in the definition of the final aroma. In the present research, the effect of the model oxidative aging on a dry red Botrytis wine, such as Italian Amarone, was considered. Amarone wine was submitted to model oxidative aging and then analyzed with two different approaches (SPE-GC-MS and HS-SPME/GC-MS). The same sampling plan was adopted to study the model aging of the same Amarone wine in anaerobic conditions. The HS-SPME/GC-MS method was applied to investigate for the first time the effect of the oxidative aging on a vast number of fermentative sulfur compounds. This research highlighted peculiar evolutions for several volatile compounds. In particular, benzaldehyde showed a sensitive increment during the oxidative aging, with a rate much higher than that reported for non-Botrytis red wines. On the other hand, several sulfides (dimethyl sulfide, 3-(methylthio)-1-propanol, etc.) disappeared after just 15 days of oxidative aging. A wine oxidation marker such as 3-(methylthio)-propanal was not found in any of the oxidized wines; conversely methionol-S-oxide was tentatively identified. This evidence has not been mentioned in the literature. A possible involvement of grape withering process and Botrytis in these mechanisms was supposed: a dry red wine, produced from the same but without any grape withering process and Botrytis infection (e.g., Bardolino wine), was submitted to oxidative aging and analysis. This red wine showed an evolution similar to those reported in the literature for dry red wines but significantly different from the Amarone wine.

  3. Cyclobutyl methyl ketone as a model compound for pinonic acid to elucidate oxidation mechanisms

    Directory of Open Access Journals (Sweden)

    A. P. Praplan

    2012-04-01

    Full Text Available 3-Methyl-1,2,3-tricarboxylic acid (MBTCA, terpenylic acid and diaterpenylic acid acetate were identified in secondary organic aerosol (SOA from α-pinene photooxidation or ozonolysis. These compounds display interesting structural features: MBTCA has a high oxygen to carbon ratio, terpenylic acid contains a lactone ring in its structure and diaterpenylic acid acetate possesses an ester functional group. The reaction mechanisms leading to these products are still unknown, but it was demonstrated experimentally in earlier studies that MBTCA is formed from pinonic acid, a primary ozonolysis product of α-pinene. Because the direct observation of pinonic acid oxidation in a smog chamber would be difficult due to its relatively low volatility, a model compound possessing the substructure of interest was used instead: cyclobutyl methyl ketone (CMK. From its oxidation, several organic acids could be measured with ion chromatography (IC coupled to a mass spectrometer (MS. Succinic acid, the analogous product of MBTCA is formed at molar yields of 2 to 5%. Butyrolactone is detected as butanoic acid, due to hydrolysis in the sampling device. A monocarboxylic acid with nominal mass 146 was detected in the absence of nitrogen oxides (NOx and could be the analogous product of diaterpenylic acid acetate. However, due to a lack of available standards, the exact structure of this compound remains unelucidated. Finally, 4-oxobutanoic acid could also be measured and two structures of its expected analogous compound from pinonic acid oxidation are proposed. Because these compounds are primary products of the CMK oxidation, reaction mechanisms capable of adding one or two carboxylic functional groups without formation of stable intermediate products needs to be formulated. Such a formation mechanism of MBTCA from pinonic acid was found in the literature; however, it includes a hydrogen atom migration to an acyloxy radical, which is expected to loose

  4. Operando X-ray investigation of solid oxide fuel cell model electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Volkov, Sergey Aleksandrovic

    2017-04-15

    A detailed study of three solid oxide fuel cells (SOFCs) related model systems is presented in this work with the aim of the better understanding of the structural changes in cell components associated with their operation. The first model system is an La{sub 0.6}Sr{sub 0.4}CoO{sub 3-d} (LSC) on yttria-stabilized zirconia (YSZ). Changes in the YSZ(100) single crystal surface structure buried under the squared LSC microelectrode were studied at a synchrotron under operational conditions. High flux photon beam at the synchrotron allowed access to the LSC/YSZ interface. Structural information from the substrate surface at an atomic scale was acquired. Element-specific anomalous XRD data allowed to distinguish between Y and Zr scattering contributions. For the first time, it was shown that the Y cation concentration at the electrode/electrolyte interface strongly depends on the sample environment and the applied potential. The second model system is a Pt/YSZ. Buried YSZ(111) surface and dense Pt film morphology changes under operational conditions were addressed. High-energy X-rays were necessary to collect surface-sensitive information from the interface due to highly absorbing Pt film. The main conclusion is - under conditions applied, the YSZ single crystal surface remains stable at an atomic level. A nagging topic of the Pt ''phase oxide'' formation at the Pt/YSZ interface during anodic polarization was also raised. Although XRD data did not show a clear evidence of PtO{sub x} presence at the interface, energy-dispersive X-ray analysis of the film cross-cut profile after the synchrotron experiment revealed distinct oxygen signal from delaminated parts of the film. Last but not least, the structure of a ZrO{sub 2} ultrathin film grown on a Pt{sub 3}Zr(0001) single crystal was studied in ultra-high vacuum for the first time be means of SXRD. This model system is aiming to improve understanding of the electrolyte materials based on ZrO{sub 2} (e

  5. An SOA model for toluene oxidation in the presence of inorganic aerosols.

    Science.gov (United States)

    Cao, Gang; Jang, Myoseon

    2010-01-15

    A predictive model for secondary organic aerosol (SOA) formation including both partitioning and heterogeneous reactions is explored for the SOA produced from the oxidation of toluene in the presence of inorganic seed aerosols. The predictive SOA model comprises the explicit gas-phase chemistry of toluene, gas-particle partitioning, and heterogeneous chemistry. The resulting products from the explicit gas phase chemistry are lumped into several classes of chemical species based on their vapor pressure and reactivity for heterogeneous reactions. Both the gas-particle partitioning coefficient and the heterogeneous reaction rate constant of each lumped gas-phase product are theoretically determined using group contribution and molecular structure-reactivity. In the SOA model, the predictive SOA mass is decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). OM(P) is estimated from the SOA partitioning model developed by Schell et al. (J. Geophys. Res. 2001, 106, 28275-28293 ) that has been used in a regional air quality model (CMAQ 4.7). OM(H) is predicted from the heterogeneous SOA model developed by Jang et al. (Environ. Sci. Technol. 2006, 40, 3013-3022 ). The SOA model is evaluated using a number of the experimental SOA data that are generated in a 2 m(3) indoor Teflon film chamber under various experimental conditions (e.g., humidity, inorganic seed compositions, NO(x) concentrations). The SOA model reasonably predicts not only the gas-phase chemistry, such as the ozone formation, the conversion of NO to NO(2), and the toluene decay, but also the SOA production. The model predicted that the OM(H) fraction of the total toluene SOA mass increases as NO(x) concentrations decrease: 0.73-0.83 at low NO(x) levels and 0.17-0.47 at middle and high NO(x) levels for SOA experiments with high initial toluene concentrations. Our study also finds a significant increase in the OM(H) mass fraction in the SOA generated with low initial toluene

  6. Development of a charge-transfer distribution model for stack simulation of solid oxide fuel cells

    Science.gov (United States)

    Onaka, H.; Iwai, H.; Kishimoto, M.; Saito, M.; Yoshida, H.; Brus, G.; Szmyd, J. S.

    2016-09-01

    An overpotential model for planar solid oxide fuel cells (SOFCs) is developed and applied to a stack numerical simulation. Charge-transfer distribution within the electrodes are approximated using an exponential function, based on which the Ohmic loss and activation overpotential are evaluated. The predicted current-voltage characteristics agree well with the experimental results, and also the overpotentials within the cell can reproduce the results obtained from a numerical analysis where the distribution of the charge-transfer current within the electrodes is fully solved. The proposed model is expected to be useful to maintain the accuracy of SOFC simulations when the cell components, consisting of anode, electrolyte and cathode, are simplified into one layer element.

  7. Solving the master equation without kinetic Monte Carlo: Tensor train approximations for a CO oxidation model

    Energy Technology Data Exchange (ETDEWEB)

    Gelß, Patrick, E-mail: p.gelss@fu-berlin.de; Matera, Sebastian, E-mail: matera@math.fu-berlin.de; Schütte, Christof, E-mail: schuette@mi.fu-berlin.de

    2016-06-01

    In multiscale modeling of heterogeneous catalytic processes, one crucial point is the solution of a Markovian master equation describing the stochastic reaction kinetics. Usually, this is too high-dimensional to be solved with standard numerical techniques and one has to rely on sampling approaches based on the kinetic Monte Carlo method. In this study we break the curse of dimensionality for the direct solution of the Markovian master equation by exploiting the Tensor Train Format for this purpose. The performance of the approach is demonstrated on a first principles based, reduced model for the CO oxidation on the RuO{sub 2}(110) surface. We investigate the complexity for increasing system size and for various reaction conditions. The advantage over the stochastic simulation approach is illustrated by a problem with increased stiffness.

  8. Estimation of component activities in some oxide solid solutions by the molecular interaction vacancy model

    Institute of Scientific and Technical Information of China (English)

    Dongping TAO

    2011-01-01

    The molecular interaction vacancy model (MIVM) is used to estimate simultaneously activities of all components in a range of entire composition of six binary oxide solid solutions and the MnO-FeO-CaO ternary solid solution by their binary infinite dilute activity coefficients.The average errors are the 0.03%-5.0% for the binaries and the 4.11%-25.2% for the ternary which is less than that (4.84%-41.2%) of the sub-regular solution model (SRSM).This shows that MIVM is more effective and reliable than SRSM for the ternary and does not depend on a polynomial approximation with some ternary adjustable parameters.

  9. Model of porous aluminium oxide growth during initial stage of anodization

    Science.gov (United States)

    Aryslanova, E. M.; Alfimov, A. V.; Chivilikhin, S. A.

    2014-10-01

    Currently, the development of nanotechnology and metamaterials requires the ability to obtain regular self-assembled structures with different parameters. One such structure is porous alumina in which the pores grow perpendicular to the substrate and are hexagonally packed. Pore size and the distance between them can be varied depending on the anodization voltage, the electrolyte and the anodization time (pore diameter - from 2 to 350 nm, the distance between the pores - from 5 to 50 nm). At the moment, there are different models describing the process of anodizing aluminum, in this paper we propose a model that takes into account the effect of layers of aluminum, aluminum oxide, and the electrolyte, as well as the influence of the effect of surface diffusion.

  10. SOLID OXIDE FUEL CELL CATHODES: Polarization Mechanisms and Modeling of the Electrochemical Performance

    Science.gov (United States)

    Fleig, Jurgen

    2003-08-01

    Several recent experimental and numerical investigations have contributed to the improved understanding of the electrochemical mechanisms taking place at solid oxide fuel cell (SOFC) cathodes and yielded valuable information on the relationships between alterable parameters (geometry/material) and the cathodic polarization resistance. Efforts to reduce the polarization resistance in SOFCs can benefit from these results, and some important aspects of the corresponding studies are reviewed. Experimental results, particularly measurements using geometrically well-defined Sr-doped LaMnO3 (LSM) cathodes, are discussed. In regard to simulations, the different levels of sophistication used in SOFC electrode modeling studies are summarized and compared. Exemplary simulations of mixed conducting cathodes that show the capabilities and limits of different modeling levels are described.

  11. Fenton Process Coupled to Ultrasound and UV Light Irradiation for the Oxidation of a Model Pollutant

    Directory of Open Access Journals (Sweden)

    Karen E. Barrera-Salgado

    2016-01-01

    Full Text Available The Fenton process coupled to photosonolysis (UV light and Us, using Fe2O3 catalyst supported on Al2O3, was used to oxidize a model pollutant like acid green 50 textile dye (AG50. Dye degradation was followed by AG50 concentration decay analyses. It was observed that parameters like iron content on a fixed amount of catalyst supporting material, catalyst annealing temperature, initial dye concentration, and the solution pH influence the overall treatment efficiency. High removal efficiencies of the model pollutant are achieved. The stability and reusability tests of the Fe2O3 catalyst show that the catalyst can be used up to three cycles achieving high discoloration. Thus, this catalyst is highly efficient for the degradation of AG50 in the Fenton process.

  12. Analytical, 1-Dimensional Impedance Model of a Composite Solid Oxide Fuel Cell Cathode

    DEFF Research Database (Denmark)

    Mortensen, Jakob Egeberg; Søgaard, Martin; Jacobsen, Torben

    2014-01-01

    An analytical, 1-dimensional impedance model for a composite solid oxide fuel cell cathode is derived. It includes geometrical parameters of the cathode, e.g., the internal surface area and the electrode thickness, and also material parameters, e.g., the surface reaction rate and the vacancy...... diffusion coefficient. The model is successfully applied to a total of 42 impedance spectra, obtained in the temperature range 555°C–852°C and in the oxygen partial pressure range 0.028 atm–1.00 atm for a cathode consisting of a 50/50 wt% mixture of (La0.6Sr0.4)0.99CoO3 − δ and Ce0.9Gd0.1O1.95 − δ...... and providing both qualitative and quantitative information on the evolution of the impedance spectra of cathodes with changing parameters....

  13. Modeling of diffusion mechanism of conductive channel oxidation in a Pt/NiO/Pt memory switching structure

    Science.gov (United States)

    Sysun, V. I.; Bute, I. V.; Boriskov, P. P.

    2016-09-01

    The transition process from the low resistance state into the high resistance state in a Pt/NiO/Pt memory switching structure has been studied by numerical modeling. Detailed analysis shows, that thermally induced diffusion oxidation by nickel vacancies is the key factor for distortion of the channel metallic conductivity. Spatial dynamics of the process of oxidation defines channel narrowing mainly in its central part, and also sets the critical current through the structure sufficient for final rupture of the channel and the transition to high resistance state. The increase in critical current above the limit even by 10% reduces the switching time by an order of magnitude, which is in agreement with experiments. The developed radial diffusion model of conductive channel (or filaments) oxidation may be suitable for the analysis of switching effect a number of other ReRAM oxide structures.

  14. Oxidative stress and age-related changes in T cells: is thalassemia a model of accelerated immune system aging?

    Science.gov (United States)

    Ghatreh-Samani, Mahdi; Esmaeili, Nafiseh; Soleimani, Masoud; Asadi-Samani, Majid; Ghatreh-Samani, Keihan; Shirzad, Hedayatolah

    2016-01-01

    Iron overload in β-thalassemia major occurs mainly due to blood transfusion, an essential treatment for β-thalassemia major patients, which results in oxidative stress. It has been thought that oxidative stress causes elevation of immune system senescent cells. Under this condition, cells normally enhance in aging, which is referred to as premature immunosenescence. Because there is no animal model for immunosenescence, most knowledge on the immunosenescence pattern is based on induction of immunosenescence. In this review, we describe iron overload and oxidative stress in β-thalassemia major patients and how they make these patients a suitable human model for immunosenescence. We also consider oxidative stress in some kinds of chronic virus infections, which induce changes in the immune system similar to β-thalassemia major. In conclusion, a therapeutic approach used to improve the immune system in such chronic virus diseases, may change the immunosenescence state and make life conditions better for β-thalassemia major patients.

  15. Modeling Strength Degradation of Fiber-Reinforced Ceramic-Matrix Composites Subjected to Cyclic Loading at Elevated Temperatures in Oxidative Environments

    Science.gov (United States)

    Longbiao, Li

    2017-04-01

    In this paper, the strength degradation of non-oxide and oxide/oxide fiber-reinforced ceramic-matrix composites (CMCs) subjected to cyclic loading at elevated temperatures in oxidative environments has been investigated. Considering damage mechanisms of matrix cracking, interface debonding, interface wear, interface oxidation and fibers fracture, the composite residual strength model has been established by combining the micro stress field of the damaged composites, the damage models, and the fracture criterion. The relationships between the composite residual strength, fatigue peak stress, interface debonding, fibers failure and cycle number have been established. The effects of peak stress level, initial and steady-state interface shear stress, fiber Weibull modulus and fiber strength, and testing temperature on the degradation of composite strength and fibers failure have been investigated. The evolution of residual strength versus cycle number curves of non-oxide and oxide/oxide CMCs under cyclic loading at elevated temperatures in oxidative environments have been predicted.

  16. Fuzzy-logic modeling of Fenton's strong chemical oxidation process treating three types of landfill leachates.

    Science.gov (United States)

    Sari, Hanife; Yetilmezsoy, Kaan; Ilhan, Fatih; Yazici, Senem; Kurt, Ugur; Apaydin, Omer

    2013-06-01

    Three multiple input and multiple output-type fuzzy-logic-based models were developed as an artificial intelligence-based approach to model a novel integrated process (UF-IER-EDBM-FO) consisted of ultrafiltration (UF), ion exchange resins (IER), electrodialysis with bipolar membrane (EDBM), and Fenton's oxidation (FO) units treating young, middle-aged, and stabilized landfill leachates. The FO unit was considered as the key process for implementation of the proposed modeling scheme. Four input components such as H(2)O(2)/chemical oxygen demand ratio, H(2)O(2)/Fe(2+) ratio, reaction pH, and reaction time were fuzzified in a Mamdani-type fuzzy inference system to predict the removal efficiencies of chemical oxygen demand, total organic carbon, color, and ammonia nitrogen. A total of 200 rules in the IF-THEN format were established within the framework of a graphical user interface for each fuzzy-logic model. The product (prod) and the center of gravity (centroid) methods were performed as the inference operator and defuzzification methods, respectively, for the proposed prognostic models. Fuzzy-logic predicted results were compared to the outputs of multiple regression models by means of various descriptive statistical indicators, and the proposed methodology was tested against the experimental data. The testing results clearly revealed that the proposed prognostic models showed a superior predictive performance with very high determination coefficients (R (2)) between 0.930 and 0.991. This study indicated a simple means of modeling and potential of a knowledge-based approach for capturing complicated inter-relationships in a highly non-linear problem. Clearly, it was shown that the proposed prognostic models provided a well-suited and cost-effective method to predict removal efficiencies of wastewater parameters prior to discharge to receiving streams.

  17. The investigation of gadolinium oxide porous structure and refinement of the pore size distribution based on the NLDFT-models

    Science.gov (United States)

    Mashkovtsev, Maxim A.; Botalov, Maxim S.; Smyshlyaev, Denis V.; Kasimova, Renata E.; Bereskina, Polina A.; Vereshchagin, Artem O.

    2016-09-01

    The study focuses on the characterization of gadolinium oxide surface by the method of low-temperature adsorption/desorption of nitrogen. The specific surface area of gadolinium oxide, the average pore diameter and fractal dimensions were determined. The refinement of the pore distribution was performed on the basis of the NLDFT model. It was shown that there were three kinds of pores with average sizes of 150, 300 and 600 Å.

  18. An extended secondary organic aerosol formation model: effect of oxidation aging and implications

    Directory of Open Access Journals (Sweden)

    F. Yu

    2010-08-01

    Full Text Available The widely used 2-product secondary organic aerosol (SOA formation model has been extended in this study to consider the volatility changes of secondary organic gases (SOGs arising from the aging process. In addition to semi-volatile SOG (SV-SOG and medium-volatile SOG (MV-SOG, we add a third component representing low-volatile SOG (LV-SOG and design a scheme to transfer MV-SOG to SV-SOG and SV-SOG to LV-SOG associated with oxidation aging. This extended SOA formation model has been implemented in a global aerosol model (GEOS-Chem and the co-condensation of H2SO4 and LV-SOG on pre-existing particles is explicitly simulated. We show that, over many parts of the continents, LV-SOG concentrations are generally a factor of ~2–20 higher than those of H2SO4 and LV-SOG condensation significantly enhances particle growth rates. Comparisons of the simulated and observed evolution of particle size distributions in a boreal forest site (Hyytiälä, Finland clearly show that LV-SOG condensation is critical in order to bring the simulations closer to the observations. With the new SOA formation scheme, annual mean SOA mass increases by a fact of 2–10 in many parts of the boundary layer and reaches above 1 μg m−3 in most parts of the main continents. As a result of enhanced surface area and reduced nucleation rates, the new scheme generally decreases the concentration of condensation nuclei larger than 10 nm (CN10 by 3–30% in the lower boundary layer, which slightly improves agreement between simulated annual mean CN10 values and those observed in 21 surface sites around the globe. SOG oxidation aging and LV-SOG condensation substantially increases the concentration of cloud condensation nuclei at a water supersaturation ratio of 0.2%, ranging from ~3–10% over a large fraction of oceans to ~10–100% over major continents. Our study highlights the importance for global aerosol models to

  19. Parameter Identification of the 2-Chlorophenol Oxidation Model Using Improved Differential Search Algorithm

    Directory of Open Access Journals (Sweden)

    Guang-zhou Chen

    2015-01-01

    Full Text Available Parameter identification plays a crucial role for simulating and using model. This paper firstly carried out the sensitivity analysis of the 2-chlorophenol oxidation model in supercritical water using the Monte Carlo method. Then, to address the nonlinearity of the model, two improved differential search (DS algorithms were proposed to carry out the parameter identification of the model. One strategy is to adopt the Latin hypercube sampling method to replace the uniform distribution of initial population; the other is to combine DS with simplex method. The results of sensitivity analysis reveal the sensitivity and the degree of difficulty identified for every model parameter. Furthermore, the posteriori probability distribution of parameters and the collaborative relationship between any two parameters can be obtained. To verify the effectiveness of the improved algorithms, the optimization performance of improved DS in kinetic parameter estimation is studied and compared with that of the basic DS algorithm, differential evolution, artificial bee colony optimization, and quantum-behaved particle swarm optimization. And the experimental results demonstrate that the DS with the Latin hypercube sampling method does not present better performance, while the hybrid methods have the advantages of strong global search ability and local search ability and are more effective than the other algorithms.

  20. An analytical model of hydrogen evolution and oxidation reactions on electrodes partially covered with a catalyst.

    Science.gov (United States)

    Kemppainen, Erno; Halme, Janne; Lund, Peter D

    2016-05-11

    Our previous theoretical study on the performance limits of the platinum (Pt) nanoparticle catalyst for the hydrogen evolution reaction (HER) had shown that the mass transport losses at a partially catalyst-covered planar electrode are independent of the catalyst loading. This suggests that the two-dimensional (2D) numerical model used could be simplified to a one-dimensional (1D) model to provide an easier but equally accurate description of the operation of these HER electrodes. In this article, we derive an analytical 1D model and show that it indeed gives results that are practically identical to the 2D numerical simulations. We discuss the general principles of the model and how it can be used to extend the applicability of existing electrochemical models of planar electrodes to low catalyst loadings suitable for operating photoelectrochemical devices under unconcentrated sunlight. Since the mass transport losses of the HER are often very sensitive to the H2 concentration, we also discuss the limiting current density of the hydrogen oxidation reaction (HOR) and how it is not necessarily independent of the reaction kinetics. The results give insight into the interplay of kinetic and mass-transport limitations at HER/HOR electrodes with implications for the design of kinetic experiments and the optimization of catalyst loadings in the photoelectrochemical cells.

  1. A novel parameter estimation method for metal oxide surge arrester models

    Indian Academy of Sciences (India)

    Mehdi Nafar; Gevork B Gharehpetian; Taher Niknam

    2011-12-01

    Accurate modelling and exact determination of Metal Oxide (MO) surge arrester parameters are very important for arrester allocation, insulation coordination studies and systems reliability calculations. In this paper, a new technique, which is the combination of Adaptive Particle Swarm Optimization (APSO) and Ant Colony Optimization (ACO) algorithms and linking the MATLAB and EMTP, is proposed to estimate the parameters of MO surge arrester models. The proposed algorithm is named Modified Adaptive Particle Swarm Optimization (MAPSO). In the proposed algorithm, to overcome the drawback of the PSO algorithm (convergence to local optima), the inertia weight is tuned by using fuzzy rules and the cognitive and the social parameters are self-adaptively adjusted. Also, to improve the global search capability and prevent the convergence to local minima, ACO algorithm is combined to the proposed APSO algorithm. The transient models of MO surge arrester have been simulated by using ATP-EMTP. The results of simulations have been applied to the program, which is based on MAPSO algorithm and can determine the fitness and parameters of different models. The validity and the accuracy of estimated parameters of surge arrester models are assessed by comparing the predicted residual voltage with experimental results.

  2. Modelling of chalcopyrite oxidation reactions in the Outokumpu flash smelting process

    Energy Technology Data Exchange (ETDEWEB)

    Ahokainen, T.; Jokilaakso, A. [Helsinki Univ. of Technology, Otaniemi (Finland)

    1996-12-31

    A mathematical model for simulating oxidation reactions of chalcopyrite particles together with momentum, heat and mass transfer between particle and gas phase in a flash smelting furnace reaction shaft is presented. In simulation, the equations governing the gas flow are solved numerically with a commercial fluid flow package, Phoenics. The particle phase is introduced into the gas flow by a Particle Source In Cell (PSIC) - technique, where a number of discrete particles is tracked in a gas flow and the relevant source terms for momentum, mass, and heat transfer are added to the gas phase equations. The gas phase equations used are elliptic in nature and the fluid turbulence is described by the (k-{epsilon}) -model. Thermal gas phase radiation is simulated with a six-flux radiation model. The chemical reactions of concentrate particles are assumed to happen at two sharp interfaces, and a shrinking core model is applied to describe the mass transfer of chemical species through the reaction product layer. In a molten state, the oxygen consumption is controlled by a film penetration concept. The reacting concentrate particles are a mixture of chalcopyrite and silica. Also a certain amount of pure inert silica is fed to the process as flux. In the simulations the calculation domain includes the concentrate burner and a cylindrical reaction shaft of an industrial scale flash smelting furnace. Some examples about the simulations carried out by the combustion model are presented. (author)

  3. 3-D GCM modelling of thermospheric nitric oxide during the 2003 Halloween storm

    Energy Technology Data Exchange (ETDEWEB)

    Dobbin, A.L.; Griffin, E.M.; Aylward, A.D.; Millward, G.H. [University College London (United Kingdom). Atmospheric Physics Lab.

    2006-07-01

    Numerical modelling of thermospheric temperature changes associated with periods of high geomagnetic activity are often inaccurate due to unrealistic representation of nitric oxide (NO) densities and associated 5.3-{mu}m radiative cooling. In previous modelling studies, simplistic parameterisations of NO density and variability have often been implemented in order to constrain thermospheric temperature predictions and post storm recovery timescales during and following periods of high auroral activity. In this paper we use the University College London (UCL) 3-D Coupled Thermosphere and Middle Atmosphere (CMAT) General Circulation Model to simulate the 11-day period from 23 October to 3 November 2003, during which the Earth experienced some of the largest geomagnetic activity ever recorded; the so called ''Halloween storm''. This model has recently been updated to include a detailed self consistent calculation of NO production and transport. Temperatures predicted by the model compare well with those observed by the UCL Fabry Perot Interferometer at Kiruna, northern Sweden, when changes in solar and auroral activity are taken into account in the calculation of NO densities. The spatial distribution of predicted temperatures at approximately 250-km altitude is also discussed. Simulated NO densities at approximately 110 km are presented. Large quantities of NO are found to be present at to the equator, one to two days after the most intense period of geomagnetic activity. This is the first 3-D GCM simulation of NO production and transport over the 2003 Halloween storm period. (orig.)

  4. Modelling the descent of nitric oxide during the elevated stratopause event of January 2013

    Science.gov (United States)

    Orsolini, Yvan J.; Limpasuvan, Varavut; Pérot, Kristell; Espy, Patrick; Hibbins, Robert; Lossow, Stefan; Raaholt Larsson, Katarina; Murtagh, Donal

    2017-03-01

    Using simulations with a whole-atmosphere chemistry-climate model nudged by meteorological analyses, global satellite observations of nitrogen oxide (NO) and water vapour by the Sub-Millimetre Radiometer instrument (SMR), of temperature by the Microwave Limb Sounder (MLS), as well as local radar observations, this study examines the recent major stratospheric sudden warming accompanied by an elevated stratopause event (ESE) that occurred in January 2013. We examine dynamical processes during the ESE, including the role of planetary wave, gravity wave and tidal forcing on the initiation of the descent in the mesosphere-lower thermosphere (MLT) and its continuation throughout the mesosphere and stratosphere, as well as the impact of model eddy diffusion. We analyse the transport of NO and find the model underestimates the large descent of NO compared to SMR observations. We demonstrate that the discrepancy arises abruptly in the MLT region at a time when the resolved wave forcing and the planetary wave activity increase, just before the elevated stratopause reforms. The discrepancy persists despite doubling the model eddy diffusion. While the simulations reproduce an enhancement of the semi-diurnal tide following the onset of the 2013 SSW, corroborating new meteor radar observations at high northern latitudes over Trondheim (63.4°N), the modelled tidal contribution to the forcing of the mean meridional circulation and to the descent is a small portion of the resolved wave forcing, and lags it by about ten days.

  5. Modeling a reversible solid oxide fuel cell as a storage device within AC power networks

    Energy Technology Data Exchange (ETDEWEB)

    Ren, J.; Roscoe, A.J.; Burt, G. [Department of Electronic and Electrical Engineering, Royal College, University of Strathclyde, Glasgow (United Kingdom); Gamble, S.R.; Irvine, J.T.S. [School of Chemistry, University of St. Andrews, Purdie Building, St. Andrews (United Kingdom)

    2012-10-15

    A reversible solid oxide fuel cell (RSOFC) system, consisting of a RSOFC stack, heat store, and electrical inverters to convert DC to AC power, is shown by computer modeling to have the potential to efficiently store electrical energy. This paper describes the modeling of a single RSOFC, based on a proposed cell geometry, empirical data on the resistivities of the components, and calculation of activation and diffusion polarization resistances from electrochemical theory. Data from ac impedance spectroscopy measurements on symmetrical cells are used to model RSOFC impedance. A RSOFC stack is modeled by electrically linking the individual cells inside a pressurized vessel. A phase change heat store is added to improve energy storage efficiency. The model is implemented in MATLAB {sup registered} /Simulink {sup registered}. Two competing inverter control schemes are compared, trading off DC bus ripple against AC power quality. It is found that selection of appropriate DC bus capacitance is important in certain scenarios, with potential system cost implications. It is shown that the system can store electrical energy at an efficiency of 64% over a single discharge-charge cycle, i.e., hydrogen to electricity and heat to hydrogen. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Microstrain in nanostructured nickel oxide studied using isotropic and anisotropic models

    Energy Technology Data Exchange (ETDEWEB)

    Madhu, G. [Department of Physics, University of Kerala, Kariavattom Campus, Thiruvananthapuram, Kerala 695581 (India); Department of Physics, University College, Thiruvananthapuram, Kerala 695034 (India); Bose, Vipin C.; Maniammal, K.; Aiswarya Raj, A.S. [Department of Physics, University of Kerala, Kariavattom Campus, Thiruvananthapuram, Kerala 695581 (India); Biju, V., E-mail: bijunano@gmail.com [Department of Physics, University of Kerala, Kariavattom Campus, Thiruvananthapuram, Kerala 695581 (India)

    2013-07-15

    Nanostructured nickel oxide, NiO is synthesized through a novel chemical route using nickel chloride and ethanol amine as starting materials. The prepared samples are annealed at higher temperatures, viz. 350 °C, 400 °C, 500 °C and 600 °C. The samples are characterized using XRD, TEM, antioxidant activity and DC conductivity measurements. The crystallite size and microstrain in the samples are studied using Williamson-Hall (W-H) analysis assuming uniform deformation model, uniform deformation stress model and uniform deformation energy density model. The results obtained using three models yield microstrain values which decreases with increase of crystallite size. The average crystallite size and the microstrain of the samples measured from modified W-H plot using uniform energy density model are found to be most suitable. The study shows that the microstrain in nanostructured NiO originates due to the presence of Ni{sup 2+} and O{sup 2−} vacancies and it is confirmed by the measurement of antioxidant activity and dc conductivity of the samples in vacuum and air ambience.

  7. Modeling mass transfer in solid oxide fuel cell anode: II. H2/CO co-oxidation and surface diffusion in synthesis-gas operation

    Science.gov (United States)

    Bao, Cheng; Jiang, Zeyi; Zhang, Xinxin

    2016-08-01

    Following the previous work on comparing performance of Fickian, Stefan-Maxwell and dusty-gas model for mass transfer in single fuel system, this article is focused on the electrochemistry and transport in the anode of solid oxide fuel cell using H2sbnd H2Osbnd COsbnd CO2sbnd N2 hybrid fuel. Under the standard framework of the dusty-gas model combined with the Butler-Volmer equation, it carries out a macroscopic area-specific modeling work. More specifically, two variables of hydrogen current fraction and enhancement factor are well defined and solved for the electrochemical co-oxidation of H2 and CO, and the diffusion equivalent circuit model is introduced to describe more comprehensively the resistance of mass transfer including molecular/Knudsen diffusion and surface diffusion. The model has been validated well in full region of Vsbnd I performance of an experimental anode-supported button cell. An approximate analytical solution of the hydrogen current fraction is also presented for explicit computation. Comparison between the results by different approaches for the effective diffusivity shows the importance of right mass-transfer modeling.

  8. Kinetic Monte Carlo Simulation of the oscillatory catalytic CO oxidation using a modified Ziff-Gulari-Barshad model

    Science.gov (United States)

    Sinha, Indrajit; Mukherjee, Ashim K.

    2014-03-01

    The oxidation of CO on Pt-group metal surfaces has attracted widespread attention since a long time due to its interesting oscillatory kinetics and spatiotemporal behavior. The use of STM in conjunction with other experimental data has confirmed the validity of the surface reconstruction (SR) model under low pressure and the more recent surface oxide (SO) model which is possible under sub-atmospheric pressure conditions [1]. In the SR model the surface is periodically reconstructed below a certain low critical CO-coverage and this reconstruction is lifted above a second, higher critical CO-coverage. Alternatively the SO model proposes periodic switching between a low-reactivity metallic surface and a high-reactivity oxide surface. Here we present an overview of our recent kinetic Monte Carlo (KMC) simulation studies on the oscillatory kinetics of surface catalyzed CO oxidation. Different modifications of the lattice gas Ziff-Gulari-Barshad (ZGB) model have been utilized or proposed for this purpose. First we present the effect of desorption on the ZGB reactive to poisoned irreversible phase transition in the SR model. Next we discuss our recent research on KMC simulation of the SO model. The ZGB framework is utilized to propose a new model incorporating not only the standard Langmuir-Hinshelwood (LH) mechanism, but also introducing the Mars-van Krevelen (MvK) mechanism for the surface oxide phase [5]. Phase diagrams, which are plots between long time averages of various oscillating quantities against the normalized CO pressure, show two or three transitions depending on the CO coverage critical threshold (CT) value beyond which all adsorbed oxygen atoms are converted to surface oxide.

  9. A lumped model of venting during thermal runaway in a cylindrical lithium cobalt oxide lithium-ion cell

    DEFF Research Database (Denmark)

    Coman, Paul Tiberiu; Rayman, Sean; White, Ralph

    2016-01-01

    This paper presents a mathematical model built for analyzing the intricate thermal behavior of a 18650 LCO (Lithium Cobalt Oxide) battery cell during thermal runaway when venting of the electrolyte and contents of the jelly roll (ejecta) is considered. The model consists of different ODEs (Ordinary...

  10. Studies and analyses of the space shuttle main engine: High-pressure oxidizer turbopump failure information propagation model

    Science.gov (United States)

    Glover, R. C.; Rudy, S. W.; Tischer, A. E.

    1987-01-01

    The high-pressure oxidizer turbopump (HPOTP) failure information propagation model (FIPM) is presented. The text includes a brief discussion of the FIPM methodology and the various elements which comprise a model. Specific details of the HPOTP FIPM are described. Listings of all the HPOTP data records are included as appendices.

  11. Modelling a Combined Heat and Power Plant based on Gasification, Micro Gas Turbine and Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Bang-Møller, Christian; Rokni, Masoud

    2009-01-01

    A system level modelling study on two combined heat and power (CHP) systems both based on biomass gasification. One system converts the product gas in a micro gas turbine (MGT) and the other in a combined solid oxide fuel cell (SOFC) and MGT arrangement. An electrochemical model of the SOFC has...

  12. Modelling a Combined Heat and Power Plant based on Gasification, Micro Gas Turbine and Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Bang-Møller, Christian; Rokni, Masoud

    2009-01-01

    A system level modelling study on two combined heat and power (CHP) systems both based on biomass gasification. One system converts the product gas in a micro gas turbine (MGT) and the other in a combined solid oxide fuel cell (SOFC) and MGT arrangement. An electrochemical model of the SOFC has...

  13. Model testing for nitrous oxide (N2O) fluxes from Amazonian cattle pastures

    Science.gov (United States)

    Meurer, Katharina H. E.; Franko, Uwe; Spott, Oliver; Stange, C. Florian; Jungkunst, Hermann F.

    2016-10-01

    Process-oriented models have become important tools in terms of quantification of environmental changes, for filling measurement gaps, and building of future scenarios. It is especially important to couple model application directly with measurements for remote areas, such as Southern Amazonia, where direct measurements are difficult to perform continuously throughout the year. Processes and resulting matter fluxes may show combinations of steady and sudden reactions to external changes. The potent greenhouse gas nitrous oxide (N2O) is known for its sensitivity to e.g. precipitation events, resulting in intense but short-term peak events (hot moments). These peaks have to be captured for sound balancing. However, prediction of the effect of rainfall events on N2O peaks is not trivial, even for areas under distinct wet and dry seasons. In this study, we used process-oriented models in both a pre-and post-measurement manner in order to (a) determine important periods for N2O-N emissions under Amazonian conditions and (b) calibrate the models to Brazilian pastures based on measured data of environment conditions (soil moisture and Corg) and measured N2O-N fluxes. During the measurement period (early wet season), observed emissions from three cattle pastures did not react to precipitation events, as proposed by the models. Here both process understanding and models have to be improved by long-term data in high resolution in order to prove or disprove a lacking of N2O-N peaks. We strongly recommend the application of models as planning tools for field campaigns, but we still suggest model combinations and simultaneous usage.

  14. Quantitative analysis of anaerobic oxidation of methane (AOM) in marine sediments: A modeling perspective

    Science.gov (United States)

    Regnier, P.; Dale, A. W.; Arndt, S.; LaRowe, D. E.; Mogollón, J.; Van Cappellen, P.

    2011-05-01

    Recent developments in the quantitative modeling of methane dynamics and anaerobic oxidation of methane (AOM) in marine sediments are critically reviewed. The first part of the review begins with a comparison of alternative kinetic models for AOM. The roles of bioenergetic limitations, intermediate compounds and biomass growth are highlighted. Next, the key transport mechanisms in multi-phase sedimentary environments affecting AOM and methane fluxes are briefly treated, while attention is also given to additional controls on methane and sulfate turnover, including organic matter mineralization, sulfur cycling and methane phase transitions. In the second part of the review, the structure, forcing functions and parameterization of published models of AOM in sediments are analyzed. The six-orders-of-magnitude range in rate constants reported for the widely used bimolecular rate law for AOM emphasizes the limited transferability of this simple kinetic model and, hence, the need for more comprehensive descriptions of the AOM reaction system. The derivation and implementation of more complete reaction models, however, are limited by the availability of observational data. In this context, we attempt to rank the relative benefits of potential experimental measurements that should help to better constrain AOM models. The last part of the review presents a compilation of reported depth-integrated AOM rates (ΣAOM). These rates reveal the extreme variability of ΣAOM in marine sediments. The model results are further used to derive quantitative relationships between ΣAOM and the magnitude of externally impressed fluid flow, as well as between ΣAOM and the depth of the sulfate-methane transition zone (SMTZ). This review contributes to an improved understanding of the global significance of the AOM process, and helps identify outstanding questions and future directions in the modeling of methane cycling and AOM in marine sediments.

  15. Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model – Part 1: Assessing the influence of constrained multi-generational ageing

    Directory of Open Access Journals (Sweden)

    S. H. Jathar

    2015-09-01

    Full Text Available Multi-generational oxidation of volatile organic compound (VOC oxidation products can significantly alter the mass, chemical composition and properties of secondary organic aerosol (SOA compared to calculations that consider only the first few generations of oxidation reactions. However, the most commonly used state-of-the-science schemes in 3-D regional or global models that account for multi-generational oxidation (1 consider only functionalization reactions but do not consider fragmentation reactions, (2 have not been constrained to experimental data; and (3 are added on top of existing parameterizations. The incomplete description of multi-generational oxidation in these models has the potential to bias source apportionment and control calculations for SOA. In this work, we used the Statistical Oxidation Model (SOM of Cappa and Wilson (2012, constrained by experimental laboratory chamber data, to evaluate the regional implications of multi-generational oxidation considering both functionalization and fragmentation reactions. SOM was implemented into the regional UCD/CIT air quality model and applied to air quality episodes in California and the eastern US. The mass, composition and properties of SOA predicted using SOM are compared to SOA predictions generated by a traditional "two-product" model to fully investigate the impact of explicit and self-consistent accounting of multi-generational oxidation. Results show that SOA mass concentrations predicted by the UCD/CIT-SOM model are very similar to those predicted by a two-product model when both models use parameters that are derived from the same chamber data. Since the two-product model does not explicitly resolve multi-generational oxidation reactions, this finding suggests that the chamber data used to parameterize the models captures the majority of the SOA mass formation from multi-generational oxidation under the conditions tested. Consequently, the use of low and high NOx yields

  16. The antagonism of cholecystokinin octapeptide-8 to the peroxynitrite oxidation on a diabetic cataractal rat model

    Institute of Scientific and Technical Information of China (English)

    HAO Li-na; LING Yi-qun; MAO Qi-yan; LING Yi-ling; HE Shou-zhi

    2006-01-01

    Background Cataracts is considered be formed because of an abnormal glucose metabolic pathway or oxidative stress. We explored the damaging role of ONOO- and antagonism of cholecystokinin octapeptide-8(CCK-8) in diabetic cataractal rat lenses.Methods A diabetic cataractal animal model was established by peritoneal injection of streptozotocine (STZ).Thirty-six normal SD rats were taken as control group; seventy-two were given STZ (45 mg/kg) and then divided into STZ group and CCK-8 group (peritoneal injection CCK-8). STZ induced diabetic rats were treated with CCK-8 for 60 days. Lenses were examined with slit lamp at 20, 40 and 60 days. Immunofluorescent staining and Western blot analysis were used for determining nitrotyrosine (NT, a marker for ONOO-). RT-PCR and gene array analysis were used for determining the expression of inducible nitric oxide synthetase mRNA (iNOS mRNA) in lens epithelium (LEC).Results STZ group rats developed lens opacity by 20 days that reached a high level by 60 days after STZ injection. CCK-8 group rats delayed the cataract formation. There was no distinct expression of NT and iNOS mRNA in control group. In STZ group, there were distinct expression of NT and upregulation of iNOS mRNA;however, CCK-8 group showed weak expression of NT and downregulation of iNOS mRNA.Conclusions NT, which may be a new form of oxidative stress, was expressed in diabetic rat LEC although CCK-8 could reverse NT damage in LEC. The results suggested that CCK-8 might be a useful therapeutic agent against diabetic cataract. The antagonizing mechanism of CCK-8 may be related to direct antagonism of ONOO-as well as its inhibition of the expression of iNOS mRNA for production of NO and therefore decrease in the formation of ONOO-.

  17. alpha-Synuclein budding yeast model: toxicity enhanced by impaired proteasome and oxidative stress.

    Science.gov (United States)

    Sharma, Nijee; Brandis, Katrina A; Herrera, Sara K; Johnson, Brandon E; Vaidya, Tulaza; Shrestha, Ruja; Debburman, Shubhik K

    2006-01-01

    Parkinson's disease (PD) is a common neurodegenerative disorder that results from the selective loss of midbrain dopaminergic neurons. Misfolding and aggregation of the protein alpha-synuclein, oxidative damage, and proteasomal impairment are all hypotheses for the molecular cause of this selective neurotoxicity. Here, we describe a Saccharomyces cerevisiae model to evaluate the misfolding, aggregation, and toxicity-inducing ability of wild-type alpha-synuclein and three mutants (A30P, A53T, and A30P/A53T), and we compare regulation of these properties by dysfunctional proteasomes and by oxidative stress. We found prominent localization of wild-type and A53T alpha-synuclein near the plasma membrane, supporting known in vitro lipid-binding ability. In contrast, A30P was mostly cytoplasmic, whereas A30P/A53T displayed both types of fluorescence. Surprisingly, alpha-synuclein was not toxic to several yeast strains tested. When yeast mutants for the proteasomal barrel (doa3-1) were evaluated, delayed alpha-synuclein synthesis and membrane association were observed; yeast mutant for the proteasomal cap (sen3-1) exhibited increased accumulation and aggregation of alpha-synuclein. Both sen3-1and doa3-1 mutants exhibited synthetic lethality with alpha-synuclein. When yeasts were challenged with an oxidant (hydrogen peroxide), alpha-synuclein was extremely lethal to cells that lacked manganese superoxide dismutase Mn-SOD (sod2Delta) but not to cells that lacked copper, zinc superoxide dismutase Cu,Zn-SOD (sod1Delta). Despite the toxicity, sod2Delta cells never displayed intracellular aggregates of alpha-synuclein. We suggest that the toxic alpha-synuclein species in yeast are smaller than the visible aggregates, and toxicity might involve alpha-synuclein membrane association. Thus, yeasts have emerged effective organisms for characterizing factors and mechanisms that regulate alpha-synuclein toxicity.

  18. Dual effect of nitric oxide on uterine prostaglandin synthesis in a murine model of preterm labour.

    Science.gov (United States)

    Cella, M; Farina, M G; Dominguez Rubio, A P; Di Girolamo, G; Ribeiro, M L; Franchi, A M

    2010-10-01

    Maternal infections are one of the main causes of adverse developmental outcomes including embryonic resorption and preterm labour. In this study a mouse model of inflammation-associated preterm delivery was developed, and used to study the relationship between nitric oxide (NO) and prostaglandins (PGs). The murine model of preterm labour was achieved by assaying different doses of bacterial lipopolysaccharides (LPS). Once established, it was used to analyse uterine levels of prostaglandins E(2) and F(2α) (by radioimmunoassay), cyclooxygenases (COX) and NOS proteins (by Western blot) and NO synthase (NOS) activity. Effects of inhibitors of COX and NOS on LPS-induced preterm labour were also studied. In vitro assays with a nitric oxide donor (SNAP) were performed to analyse the modulation of prostaglandin production by NO. Lipopolysaccharide increased uterine NO and PG synthesis and induced preterm delivery. Co-administration of meloxicam, a cyclooxygenase-2 inhibitor, or aminoguanidine, an inducible NOS inhibitor, prevented LPS-induced preterm delivery and blocked the increase in PGs and NO. Notably, the levels of NO were found to determine its effect on PG synthesis; low concentrations of NO reduced PG synthesis whereas high concentrations augmented them. An infection-associated model of preterm labour showed that preterm delivery can be prevented by decreasing PG or NO production. NO was found to have a dual effect on PG synthesis depending on its concentration. These data contribute to the understanding of the interaction between NO and PGs in pregnancy and parturition, and could help to improve neonatal outcomes. © 2010 The Authors. British Journal of Pharmacology © 2010 The British Pharmacological Society.

  19. Toluene removal by oxidation reaction in spray wet scrubber: experimental, modeling and optimization

    Directory of Open Access Journals (Sweden)

    Roumporn Nikom

    2006-11-01

    Full Text Available Toluene, an important volatile organic compound (VOC, is used in many kinds of industries, such as painting, printing, coating, and petrochemical industries. The emission of toluene causes serious air pollution, odor problem, flammability problem and affects human health. This paper proposes the removal of toluene from waste air using a spray wet scrubber combining the absorption and oxidation reaction. Aqueous sodium hypochlorite (NaOCl solution was used as the scrubbing liquid in the system. NaOCl, the strongest oxidative agent, presents an effective toluene removal. As the scrubbed toluene is reacted, recirculation of the scrubbing liquid could be operated with a constant removal efficiency throughout the operting time. The investigated variables affecting the removal efficiency were air flow rate, inlet toluene concentration, NaOCl concentration, scrubbing liquid flow rate and size of spray nozzle. Influence of the scrubbing parameters was experimentally studied to develop a mathematical model of the toluene removal efficiency. The removal model reveals that the increase of scrubbing liquid flow rate, toluene concentration, and NaOCl concentration together with the decrease of air flow rate and size of spray nozzle can increase the toluene removal efficiency. Optimization problem with an objective function and constraints was set to provide the maximum toluene removal efficiency and solved by Matlab optimization toolbox. The optimization constraints were formed from the mathematical model and process limitation. The solution of the optimization was an air flow rate of 100 m3/h, toluene concentration of 1500 ppm, NaOCl concentration of 0.02 mol/l, NaOCl solution feed rate of 0.8 m3/h, and spray nozzle size of 0.5 mm. Solution of the optimization gave the highest toluene removal efficiency of 91.7%.

  20. Paricalcitol may improve oxidative DNA damage on experimental amikacin-induced nephrotoxicity model.

    Science.gov (United States)

    Bulut, Gulay; Basbugan, Yildiray; Ari, Elif; Erten, Remzi; Bektas, Havva; Alp, Hamit Hakan; Bayram, Irfan

    2016-06-01

    This study aimed to investigate the possible protective effect of paricalcitol on experimental amikacin-induced nephrotoxicity model in rats. Wistar albino rats (n = 32) were allocated into four equal groups of eight each, the control (Group C), paricalcitol (Group P), amikacin-induced nephrotoxicity (Group A), and paricalcitol-treated amikacin-induced nephrotoxicity (Group A + P) groups. Paricalcitol was given intra-peritoneally at a dose of 0.4 μg/kg/d for 5 consecutive days prior to induction of amikacin-induced nephrotoxicity. Intra-peritoneal amikacin (1.2 g/kg) was used to induce nephrotoxicity at day 4. Renal function parameters, oxidative stress biomarkers, oxidative DNA damage (8-hydroxy-2'-deoxyguanosine/deoxyguanosine ratio), kidney histology, and vascular endothelial growth factor (VEGF) immunoexpression were determined. Group A + P had lower mean fractional sodium excretion (p < 0.001) as well as higher creatinine clearance (p = 0.026) than the amikacin group (Group A). Renal tissue malondialdehyde levels (p = 0.035) and serum 8-hydroxy-2'-deoxyguanosine/deoxyguanosine ratio (8-OHdG/dG ratio) (p < 0.001) were significantly lower; superoxide dismutase (p = 0.024) and glutathione peroxidase (p = 0.007) activities of renal tissue were significantly higher in group A + P than in group A. The mean scores of tubular necrosis (p = 0.024), proteinaceous casts (p = 0.038), medullary congestion (p = 0.035), and VEGF immunoexpression (p = 0.018) were also lower in group A + P when compared with group A. This study demonstrates the protective effect of paricalcitol in the prevention of amikacin-induced nephrotoxicity in an experimental model. Furthermore, it is the first study to demonstrate that paricalcitol improves oxidative DNA damage in an experimental acute kidney injury model.

  1. Theoretical modeling of a self-referenced dual mode SPR sensor utilizing indium tin oxide film

    Science.gov (United States)

    Srivastava, Sachin K.; Verma, Roli; Gupta, Banshi D.

    2016-06-01

    A prism based dual mode SPR sensor was theoretically modeled to work as a self-referenced sensor in spectral interrogation scheme. Self-referenced sensing was achieved by sandwiching an indium tin oxide thin film in between the prism base and the metal layer. The proposed sensor possesses two plasmon modes similar to long and short range SPRs (LR- and SR-SPRs) and we have analogically used LRSPR and SRSPR for them. However, these modes do not possess usual long range character due to the losses introduced by the imaginary part of indium tin oxide (ITO) dielectric function. One of the two plasmon modes responds to change in analyte refractive index while the other remains fixed. The influence of various design parameters on the performance of the sensor was evaluated. The performance of the proposed sensor was compared, via control simulations, with established dual mode geometries utilizing silicon dioxide (SiO2), Teflon AF-1600 and Cytop. The design parameters of the established geometries were optimized to obtain self-referenced sensing operation. Trade-offs between the resonance spectral width, minimum reflectivity, shift in resonance wavelength and angle of incidence were examined for optimal design. The present study will be useful in the fabrication of self-referenced sensors where the ambient conditions are not quite stable.

  2. Infliximab improves endothelial dysfunction in a mouse model of antiphospholipid syndrome: Role of reduced oxidative stress.

    Science.gov (United States)

    Benhamou, Ygal; Miranda, Sébastien; Armengol, Guillaume; Harouki, Najah; Drouot, Laurent; Zahr, Noel; Thuillez, Christian; Boyer, Olivier; Levesque, Hervé; Joannides, Robinson; Richard, Vincent

    2015-08-01

    Antiphospholipid syndrome (APS), induces endothelial dysfunction, oxidative stress and systemic inflammation that may be mediated by TNFα. Thus, we investigated the possible protective effect of the anti-TNFα antibody infliximab (5μg/g) on endothelial function in a mouse APS model (induced by injection of purified human anti-β2GP1-IgG). Seven days after anti-β2GPI-IgG injection, we observed an increase in plasma sVCAM-1 and sE-selectin levels and in aortic mRNA expression of VCAM-1 and E-selectin. This was associated with a decreased endothelium-dependent relaxation of isolated mesenteric arteries to acetylcholine, together with decreased mesenteric eNOS mRNA expression and increased eNOS uncoupling, accompanied by increased iNOS and gp91phox mRNA and increased left ventricular GSH/GSSH ratio. Infliximab significantly improved the NO-mediated relaxing responses to acetylcholine, and induced a decrease in iNOS and gp91phox mRNA expression. The õpro-adhesive and pro-coagulant phenotypes induced by the anti-β2GP1-IgG were also reversed. This study provides the first evidence that TNFα antagonism improves endothelial dysfunction in APS and suggests that endothelial dysfunction is mediated by TNFα and oxidative stress. Therefore, infliximab may be of special relevance in clinical practice.

  3. NMR Metabolomics Show Evidence for Mitochondrial Oxidative Stress in a Mouse Model of Polycystic Ovary Syndrome.

    Science.gov (United States)

    Selen, Ebru Selin; Bolandnazar, Zeinab; Tonelli, Marco; Bütz, Daniel E; Haviland, Julia A; Porter, Warren P; Assadi-Porter, Fariba M

    2015-08-07

    Polycystic ovary syndrome (PCOS) is associated with metabolic and endocrine disorders in women of reproductive age. The etiology of PCOS is still unknown. Mice prenatally treated with glucocorticoids exhibit metabolic disturbances that are similar to those seen in women with PCOS. We used an untargeted nuclear magnetic resonance (NMR)-based metabolomics approach to understand the metabolic changes occurring in the plasma and kidney over time in female glucocorticoid-treated (GC-treated) mice. There are significant changes in plasma amino acid levels (valine, tyrosine, and proline) and their intermediates (2-hydroxybutyrate, 4-aminobutyrate, and taurine), whereas in kidneys, the TCA cycle metabolism (citrate, fumarate, and succinate) and the pentose phosphate (PP) pathway products (inosine and uracil) are significantly altered (p metabolic substrates in the plasma and kidneys of treated mice are associated with altered amino acid metabolism, increased cytoplasmic PP, and increased mitochondrial activity, leading to a more oxidized state. This study identifies biomarkers associated with metabolic dysfunction in kidney mitochondria of a prenatal gluococorticoid-treated mouse model of PCOS that may be used as early predictive biomarkers of oxidative stress in the PCOS metabolic disorder in women.

  4. Direct Observation of Enhanced Nitric Oxide in a Murine Model of Diabetic Nephropathy

    Science.gov (United States)

    Boels, Margien G. S.; van Faassen, Ernst E. H.; Avramut, M. Cristina; van der Vlag, Johan; van den Berg, Bernard M.; Rabelink, Ton J.

    2017-01-01

    Uncoupling of nitric oxide synthase (NOS) secondary to redox signaling is a central mechanism in endothelial and macrophage activation. To date studies on the production of nitric oxide (NO) during the development of diabetic complications show paradoxical results. We previously showed that recoupling eNOS by increasing the eNOS cofactor tetrahydrobiopterin (BH4) could restore endothelial function and prevent kidney injury in experimental kidney transplantation. Here, we employed a diabetic mouse model to investigate the effects of diabetes on renal tissue NO bioavailability. For this, we used in vivo NO trapping, followed by electron paramagnetic resonance spectroscopy. In addition, we investigated whether coupling of NOS by supplying the cofactor BH4 could restore glomerular endothelial barrier function. Our data show that overall NO availability at the tissue level is not reduced sixteen weeks after the induction of diabetes in apoE knockout mice, despite the presence of factors that cause endothelial dysfunction, and the presence of the endogenous NOS inhibitor ADMA. Targeting uncoupled NOS with the BH4 precursor sepiapterin further increases NO availability, but did not modify renal glomerular injury. Notably, glomerular heparanase activity as a driver for loss of glomerular barrier function was not reduced, pointing towards NOS-independent mechanisms. This was confirmed by unaltered increased glomerular presence of cathepsin L, the protease that activates heparanase. PMID:28103268

  5. Daily sesame oil supplement attenuates joint pain by inhibiting muscular oxidative stress in osteoarthritis rat model.

    Science.gov (United States)

    Hsu, Dur-Zong; Chu, Pei-Yi; Jou, I-Ming

    2016-03-01

    Osteoarthritis (OA) is the most common form of arthritis, affecting approximately 15% of the population. The aim of this study was to evaluate the efficacy of sesame oil in controlling OA pain in rats. Rat joint pain was induced by medial meniscal transection in Sprague-Dawley rats and assessed by using hindlimb weight distribution method. Muscular oxidative stress was assessed by determining lipid peroxidation, reactive oxygen species and circulating antioxidants. Sesame oil significantly decreased joint pain compared with positive control group in a dose-dependent manner. Sesame oil decreased lipid peroxidation in muscle but not in serum. Further, sesame oil significantly decreased muscular superoxide anion and peroxynitrite generations but increased muscular glutathione and glutathione peroxidase levels. Further, sesame oil significantly increased nuclear factor erythroid-2-related factor (Nrf2) expression compared with positive control group. We concluded that daily sesame oil supplement may attenuate early joint pain by inhibiting Nrf2-associated muscular oxidative stress in OA rat model. Copyright © 2015 Elsevier Inc. All rights reserved.

  6. Detailed dynamic solid oxide fuel cell modeling for electrochemical impedance spectra simulation

    Energy Technology Data Exchange (ETDEWEB)

    Hofmann, Ph. [Laboratory of Steam Boilers and Thermal Plants, School of Mechanical Engineering, Thermal Engineering Section, National Technical University of Athens, Heroon Polytechniou 9, 15780 Athens (Greece); Panopoulos, K.D. [Institute for Solid Fuels Technology and Applications, Centre for Research and Technology Hellas, 4th km. Ptolemais-Mpodosakeio Hospital, Region of Kouri, P.O. Box 95, GR 502, 50200 Ptolemais (Greece)

    2010-08-15

    This paper presents a detailed flexible mathematical model for planar solid oxide fuel cells (SOFCs), which allows the simulation of steady-state performance characteristics, i.e. voltage-current density (V-j) curves, and dynamic operation behavior, with a special capability of simulating electrochemical impedance spectroscopy (EIS). The model is based on physico-chemical governing equations coupled with a detailed multi-component gas diffusion mechanism (Dusty-Gas Model (DGM)) and a multi-step heterogeneous reaction mechanism implicitly accounting for the water-gas-shift (WGS), methane reforming and Boudouard reactions. Spatial discretization can be applied for 1D (button-cell approximation) up to quasi-3D (full size anode supported cell in cross-flow configuration) geometries and is resolved with the finite difference method (FDM). The model is built and implemented on the commercially available modeling and simulations platform gPROMS trademark. Different fuels based on hydrogen, methane and syngas with inert diluents are run. The model is applied to demonstrate a detailed analysis of the SOFC inherent losses and their attribution to the EIS. This is achieved by means of a step-by-step analysis of the involved transient processes such as gas conversion in the main gas chambers/channels, gas diffusion through the porous electrodes together with the heterogeneous reactions on the nickel catalyst, and the double-layer current within the electrochemical reaction zone. The model is an important tool for analyzing SOFC performance fundamentals as well as for design and optimization of materials' and operational parameters. (author)

  7. Experimental and Chemical Kinetic Modeling Study of Dimethylcyclohexane Oxidation and Pyrolysis

    KAUST Repository

    Eldeeb, Mazen A.

    2016-08-30

    A combined experimental and chemical kinetic modeling study of the high-temperature ignition and pyrolysis of 1,3-dimethylcyclohexane (13DMCH) is presented. Ignition delay times are measured behind reflected shock waves over a temperature range of 1049–1544 K and pressures of 3.0–12 atm. Pyrolysis is investigated at average pressures of 4.0 atm at temperatures of 1238, 1302, and 1406 K. By means of mid-infrared direct laser absorption at 3.39 μm, fuel concentration time histories are measured under ignition and pyrolytic conditions. A detailed chemical kinetic model for 13DMCH combustion is developed. Ignition measurements show that the ignition delay times of 13DMCH are longer than those of its isomer, ethylcyclohexane. The proposed chemical kinetic model predicts reasonably well the effects of equivalence ratio and pressure, with overall good agreement between predicted and measured ignition delay times, except at low dilution levels and high pressures. Simulated fuel concentration profiles agree reasonably well with the measured profiles, and both highlight the influence of pyrolysis on the overall ignition kinetics at high temperatures. Sensitivity and reaction pathway analyses provide further insight into the kinetic processes controlling ignition and pyrolysis. The work contributes toward improved understanding and modeling of the oxidation and pyrolysis kinetics of cycloalkanes.

  8. Application of Mathematical Modeling on Copper Recovery Optimization of Oxide Ores

    Science.gov (United States)

    Hoseinian, Fatemeh Sadat; Bahadori, Moein; Hashemzadeh, Mohsen; Rezai, Bahram; Soltani-Mohammadi, Saeed

    2017-10-01

    In this study, a mathematical modeling method was used to predict the optimum conditions of column leaching of copper oxide ore. Important parameters such as column height (m), particle sizes (m), acid rate (kg/ton) and leaching time (day) were studied and their impacts on copper recovery were investigated. Experiments were performed on samples with particle size distributions of -25.4 mm and -50.8 mm in six columns with the heights of 2 m, 4 m and 6 m. The results showed that the copper recovery has an inverse relation with column height and particle sizes, and direct relation with leaching time and acid rate. According to the results, the mathematical models based on the macro model predict the copper recovery based on operation conditions. The obtained values of determination coefficient (0.97), root mean square error (2.86) and relative error (0.089) testing datasets, showed the capability of the model in predicting the copper recovery.

  9. Model uncertainties affecting satellite-based inverse modeling of nitrogen oxides emissions and implications for surface ozone simulation

    Directory of Open Access Journals (Sweden)

    J.-T. Lin

    2012-06-01

    Full Text Available Errors in chemical transport models (CTMs interpreting the relation between space-retrieved tropospheric column densities of nitrogen dioxide (NO2 and emissions of nitrogen oxides (NOx have important consequences on the inverse modeling. They are however difficult to quantify due to lack of adequate in situ measurements, particularly over China and other developing countries. This study proposes an alternate approach for model evaluation over East China, by analyzing the sensitivity of modeled NO2 columns to errors in meteorological and chemical parameters/processes important to the nitrogen abundance. As a demonstration, it evaluates the nested version of GEOS-Chem driven by the GEOS-5 meteorology and the INTEX-B anthropogenic emissions and used with retrievals from the Ozone Monitoring Instrument (OMI to constrain emissions of NOx. The CTM has been used extensively for such applications. Errors are examined for a comprehensive set of meteorological and chemical parameters using measurements and/or uncertainty analysis based on current knowledge. Results are exploited then for sensitivity simulations perturbing the respective parameters, as the basis of the following post-model linearized and localized first-order modification. It is found that the model meteorology likely contains errors of various magnitudes in cloud optical depth, air temperature, water vapor, boundary layer height and many other parameters. Model errors also exist in gaseous and heterogeneous reactions, aerosol optical properties and emissions of non-nitrogen species affecting the nitrogen chemistry. Modifications accounting for quantified errors in 10 selected parameters increase the NO2 columns in most areas with an average positive impact of 22% in July and 10% in January. This suggests a possible systematic model bias such that the top-down emissions will be overestimated by the same magnitudes if the model is used

  10. Optical modeling and electrical properties of cadmium oxide nanofilms: Developing a meta–heuristic calculation process model

    Energy Technology Data Exchange (ETDEWEB)

    Abdolahzadeh Ziabari, Ali, E-mail: ali.abd.ziabari@gmail.com [Nano Research Lab, Lahijan Branch, Islamic Azad University, P.O. Box 1616, Lahijan (Iran, Islamic Republic of); Refahi Sheikhani, A. H. [Department of Applied Mathematics, Lahijan Branch, Islamic Azad University, Lahijan (Iran, Islamic Republic of); Nezafat, Reza Vatani [Department of Civil Engineering, Faculty of Technology, University of Guilan, Rasht (Iran, Islamic Republic of); Haghighidoust, Kasra Monsef [Department of Mechanical Engineering, Faculty of Technology, University of Guilan, Rasht (Iran, Islamic Republic of)

    2015-04-07

    Cadmium oxide thin films were deposited onto glass substrates by sol–gel dip-coating method and annealed in air. The normal incidence transmittance of the films was measured by a spectrophotometer. D.C electrical parameters such as carrier concentration and mobility were analyzed by Hall Effect measurements. A combination of Forouhi–Bloomer and standard Drude model was used to simulate the optical constants and thicknesses of the films from transmittance data. The transmittance spectra of the films in the visible domain of wavelengths were successfully fitted by using the result of a hybrid particle swarm optimization method and genetic algorithm. The simulated transmittance is in good accordance with the measured spectrum in the whole measurement wavelength range. The electrical parameters obtained from the optical simulation are well consistent with those measured electrically by Hall Effect measurements.

  11. A Model of Reduced Kinetics for Alkane Oxidation Using Constituents and Species for N-Heptane

    Science.gov (United States)

    Harstad, Kenneth G.; Bellan, Josette

    2011-01-01

    The reduction of elementary or skeletal oxidation kinetics to a subgroup of tractable reactions for inclusion in turbulent combustion codes has been the subject of numerous studies. The skeletal mechanism is obtained from the elementary mechanism by removing from it reactions that are considered negligible for the intent of the specific study considered. As of now, there are many chemical reduction methodologies. A methodology for deriving a reduced kinetic mechanism for alkane oxidation is described and applied to n-heptane. The model is based on partitioning the species of the skeletal kinetic mechanism into lights, defined as those having a carbon number smaller than 3, and heavies, which are the complement of the species ensemble. For modeling purposes, the heavy species are mathematically decomposed into constituents, which are similar but not identical to groups in the group additivity theory. From analysis of the LLNL (Lawrence Livermore National Laboratory) skeletal mechanism in conjunction with CHEMKIN II, it is shown that a similarity variable can be formed such that the appropriately non-dimensionalized global constituent molar density exhibits a self-similar behavior over a very wide range of equivalence ratios, initial pressures and initial temperatures that is of interest for predicting n-heptane oxidation. Furthermore, the oxygen and water molar densities are shown to display a quasi-linear behavior with respect to the similarity variable. The light species ensemble is partitioned into quasi-steady and unsteady species. The reduced model is based on concepts consistent with those of Large Eddy Simulation (LES) in which functional forms are used to replace the small scales eliminated through filtering of the governing equations; in LES, these small scales are unimportant as far as the overwhelming part of dynamic energy is concerned. Here, the scales thought unimportant for recovering the thermodynamic energy are removed. The concept is tested by

  12. Impact of oxide thickness on gate capacitance – Modelling and comparative analysis of GaN-based MOSHEMTs

    Indian Academy of Sciences (India)

    Kanjalochan Jena; Raghunandan Swain; T R Lenka

    2015-12-01

    In this paper, we have developed a mathematical model to predict the behaviour of gate capacitance and threshold voltage with nanoscale variation of oxide thickness in AlInN/GaN and AlGaN/GaN metal oxide semiconductor high electron mobility transistor (MOSHEMT). The results obtained from the model are compared with the TCAD simulation results to validate the model. It is observed that AlInN/GaN MOSHEMT has an advantage of significant decrease in gate capacitance up to 0.0079 pF/m2 with increase in oxide thickness up to 5 nm as compared to conventional AlGaN/GaN MOSHEMT. This decrease in gate capacitance in AlInN/GaN MOSHEMT reduces the propagation delay and hence improves the RF performance of the device.

  13. An MCM modeling study of nitryl chloride (ClNO2) impacts on oxidation, ozone production and nitrogen oxide partitioning in polluted continental outflow

    Science.gov (United States)

    Riedel, T. P.; Wolfe, G. M.; Danas, K. T.; Gilman, J. B.; Kuster, W. C.; Bon, D. M.; Vlasenko, A.; Li, S.-M.; Williams, E. J.; Lerner, B. M.; Veres, P. R.; Roberts, J. M.; Holloway, J. S.; Lefer, B.; Brown, S. S.; Thornton, J. A.

    2014-04-01

    Nitryl chloride (ClNO2) is produced at night by reactions of dinitrogen pentoxide (N2O5) on chloride containing surfaces. ClNO2 is photolyzed during the morning hours after sunrise to liberate highly reactive chlorine atoms (Cl·). This chemistry takes place primarily in polluted environments where the concentrations of N2O5 precursors (nitrogen oxide radicals and ozone) are high, though it likely occurs in remote regions at lower intensities. Recent field measurements have illustrated the potential importance of ClNO2 as a daytime Cl· source and a nighttime NOx reservoir. However, the fate of the Cl· and the overall impact of ClNO2 on regional photochemistry remain poorly constrained by measurements and models. To this end, we have incorporated ClNO2 production, photolysis, and subsequent Cl· reactions into an existing master chemical mechanism (MCM version 3.2) box model framework using observational constraints from the CalNex 2010 field study. Cl· reactions with a set of alkenes and alcohols, and the simplified multiphase chemistry of N2O5, ClNO2, HOCl, ClONO2, and Cl2, none of which are currently part of the MCM, have been added to the mechanism. The presence of ClNO2 produces significant changes to oxidants, ozone, and nitrogen oxide partitioning, relative to model runs excluding ClNO2 formation. From a nighttime maximum of 1.5 ppbv ClNO2, the daytime maximum Cl· concentration reaches 1 × 105 atoms cm-3 at 07:00 model time, reacting mostly with a large suite of volatile organic compounds (VOC) to produce 2.2 times more organic peroxy radicals in the morning than in the absence of ClNO2. In the presence of several ppbv of nitrogen oxide radicals (NOx = NO + NO2), these perturbations lead to similar enhancements in hydrogen oxide radicals (HOx = OH + HO2). Neglecting contributions from HONO, the total integrated daytime radical source is 17% larger when including ClNO2, which leads to a similar enhancement in integrated ozone production of 15%. Detectable

  14. Modeling the effects of vegetation on methane oxidation and emissions through soil landfill final covers across different climates.

    Science.gov (United States)

    Abichou, Tarek; Kormi, Tarek; Yuan, Lei; Johnson, Terry; Francisco, Escobar

    2015-02-01

    Plant roots are reported to enhance the aeration of soil by creating secondary macropores which improve the diffusion of oxygen into soil as well as the supply of methane to bacteria. Therefore, methane oxidation can be improved considerably by the soil structuring processes of vegetation, along with the increase of organic biomass in the soil associated with plant roots. This study consisted of using a numerical model that combines flow of water and heat with gas transport and oxidation in soils, to simulate methane emission and oxidation through simulated vegetated and non-vegetated landfill covers under different climatic conditions. Different simulations were performed using different methane loading flux (5-200 g m(-2) d(-1)) as the bottom boundary. The lowest modeled surface emissions were always obtained with vegetated soil covers for all simulated climates. The largest differences in simulated surface emissions between the vegetated and non-vegetated scenarios occur during the growing season. Higher average yearly percent oxidation was obtained in simulations with vegetated soil covers as compared to non-vegetated scenario. The modeled effects of vegetation on methane surface emissions and percent oxidation were attributed to two separate mechanisms: (1) increase in methane oxidation associated with the change of the physical properties of the upper vegetative layer and (2) increase in organic matter associated with vegetated soil layers. Finally, correlations between percent oxidation and methane loading into simulated vegetated and non-vegetated covers were proposed to allow decision makers to compare vegetated versus non-vegetated soil landfill covers. These results were obtained using a modeling study with several simplifying assumptions that do not capture the complexities of vegetated soils under field conditions.

  15. Numerical modelling of methane oxidation efficiency and coupled water-gas-heat reactive transfer in a sloping landfill cover.

    Science.gov (United States)

    Feng, S; Ng, C W W; Leung, A K; Liu, H W

    2017-10-01

    Microbial aerobic methane oxidation in unsaturated landfill cover involves coupled water, gas and heat reactive transfer. The coupled process is complex and its influence on methane oxidation efficiency is not clear, especially in steep covers where spatial variations of water, gas and heat are significant. In this study, two-dimensional finite element numerical simulations were carried out to evaluate the performance of unsaturated sloping cover. The numerical model was calibrated using a set of flume model test data, and was then subsequently used for parametric study. A new method that considers transient changes of methane concentration during the estimation of the methane oxidation efficiency was proposed and compared against existing methods. It was found that a steeper cover had a lower oxidation efficiency due to enhanced downslope water flow, during which desaturation of soil promoted gas transport and hence landfill gas emission. This effect was magnified as the cover angle and landfill gas generation rate at the bottom of the cover increased. Assuming the steady-state methane concentration in a cover would result in a non-conservative overestimation of oxidation efficiency, especially when a steep cover was subjected to rainfall infiltration. By considering the transient methane concentration, the newly-modified method can give a more accurate oxidation efficiency. Copyright © 2017. Published by Elsevier Ltd.

  16. A feasible kinetic model for the hydrogen oxidation on ruthenium electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Rau, M.S.; Gennero de Chialvo, M.R. [Programa de Electroquimica Aplicada e Ingenieria Electroquimica (PRELINE), Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2829, 3000 Santa Fe (Argentina); Chialvo, A.C., E-mail: achialvo@fiq.unl.edu.a [Programa de Electroquimica Aplicada e Ingenieria Electroquimica (PRELINE), Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2829, 3000 Santa Fe (Argentina)

    2010-07-01

    The hydrogen oxidation reaction (hor) was studied on a polycrystalline ruthenium electrode in H{sub 2}SO{sub 4} solution at different rotation rates ({omega}). The experimental polarization curves recorded on steady state show the existence of a maximum current with a non-linear dependence of the current density on {omega}{sup 1/2}. On the basis of the Tafel-Heyrovsky-Volmer kinetic mechanism, coupled with a process of inhibition of active sites by the reversible electroadsorption of hydroxyl species, it was possible to appropriately describe the origin of the maximum current. The corresponding set of kinetic parameters was also calculated from the correlation of the experimental results with the proposed kinetic model.

  17. Micromechanical Modeling of Solid Oxide Fuel Cell Anode Supports based on Three-dimensional Reconstructions

    DEFF Research Database (Denmark)

    Kwok, Kawai; Jørgensen, Peter Stanley; Frandsen, Henrik Lund

    2014-01-01

    The efficiency and lifetime of solid oxide fuel cells (SOFCs) is compromised by mechanical failure of cells in the system. Improving the mechanical reliability is a major step in ensuring feasibility of the technology. To quantify the stress in a cell, mechanical properties of the different layers...... need to be accurately known. Since the mechanical properties are heavily dependent on the microstructures of the materials, it is highly advantageous to understand the impact of microstructures and to be able to determine accurate effective mechanical properties for cell or stack scale analyses...... are computed by the finite element method. The macroscopic creep response of the porous anode support is determined based on homogenization theory. It is shown that micromechanical modeling provides an effective tool to study the effect of microstructures on the macroscopic properties....

  18. Alzheimer's Proteins, Oxidative Stress, and Mitochondrial Dysfunction Interplay in a Neuronal Model of Alzheimer's Disease

    Directory of Open Access Journals (Sweden)

    Antonella Bobba

    2010-01-01

    Full Text Available In this paper, we discuss the interplay between beta-amyloid (A peptide, Tau fragments, oxidative stress, and mitochondria in the neuronal model of cerebellar granule neurons (CGNs in which the molecular events reminiscent of AD are activated. The identification of the death route and the cause/effect relationships between the events leading to death could be helpful to manage the progression of apoptosis in neurodegeneration and to define antiapoptotic treatments acting on precocious steps of the death process. Mitochondrial dysfunction is among the earliest events linked to AD and might play a causative role in disease onset and progression. Recent studies on CGNs have shown that adenine nucleotide translocator (ANT impairment, due to interaction with toxic N-ter Tau fragment, contributes in a significant manner to bioenergetic failure and mitochondrial dysfunction. These findings open a window for new therapeutic strategies aimed at preserving and/or improving mitochondrial function.

  19. Modeling Methodologies for Design and Control of Solid Oxide Fuel Cell APUs

    Science.gov (United States)

    Pianese, C.; Sorrentino, M.

    2009-08-01

    Among the existing fuel cell technologies, Solid Oxide Fuel Cells (SOFC) are particularly suitable for both stationary and mobile applications, due to their high energy conversion efficiencies, modularity, high fuel flexibility, low emissions and noise. Moreover, the high working temperatures enable their use for efficient cogeneration applications. SOFCs are entering in a pre-industrial era and a strong interest for designing tools has growth in the last years. Optimal system configuration, components sizing, control and diagnostic system design require computational tools that meet the conflicting needs of accuracy, affordable computational time, limited experimental efforts and flexibility. The paper gives an overview on control-oriented modeling of SOFC at both single cell and stack level. Such an approach provides useful simulation tools for designing and controlling SOFC-APUs destined to a wide application area, ranging from automotive to marine and airplane APUs.

  20. An atomic charge model for graphene oxide for exploring its bioadhesive properties in explicit water.

    Science.gov (United States)

    Stauffer, D; Dragneva, N; Floriano, W B; Mawhinney, R C; Fanchini, G; French, S; Rubel, O

    2014-07-28

    Graphene Oxide (GO) has been shown to exhibit properties that are useful in applications such as biomedical imaging, biological sensors, and drug delivery. The binding properties of biomolecules at the surface of GO can provide insight into the potential biocompatibility of GO. Here we assess the intrinsic affinity of amino acids to GO by simulating their adsorption onto a GO surface. The simulation is done using Amber03 force-field molecular dynamics in explicit water. The emphasis is placed on developing an atomic charge model for GO. The adsorption energies are computed using atomic charges obtained from an ab initio electrostatic potential based method. The charges reported here are suitable for simulating peptide adsorption to GO.

  1. Impact of Fluorescent Lighting on Oxidation of Model Wine Solutions Containing Organic Acids and Iron.

    Science.gov (United States)

    Grant-Preece, Paris; Barril, Celia; Schmidtke, Leigh M; Clark, Andrew C

    2017-03-22

    Previous studies have provided evidence that light exposure can increase oxygen consumption in wine and that the photodegradation of iron(III) tartrate could contribute to this process. In the present study, model wine solutions containing iron(III) and various organic acids, either alone or combined, were stored in sealed clear glass wine bottles and exposed to light from fluorescent lamps. Dissolved oxygen was monitored, and afterward the organic acid degradation products were determined and the capacity of the solutions to bind sulfur dioxide, the main wine preservative, was assessed. In the dark controls, little or no dissolved oxygen was consumed and the organic acids were stable. In the irradiated solutions, dissolved oxygen was consumed at a rate that was dependent on the specific organic acid present, and the latter were oxidized to various carbonyl compounds. For the solutions containing tartaric acid, malic acid, and/or citric acid, irradiation increased their sulfur dioxide-binding capacity.

  2. Importance of pressure gradient in solid oxide fuel cell electrodes for modeling study

    Science.gov (United States)

    Ni, Meng; Leung, Dennis Y. C.; Leung, Michael K. H.

    The pressure gradients in the electrodes of a solid oxide fuel cell (SOFC) are frequently neglected without any justification in calculating the concentration overpotentials of the SOFC electrodes in modeling studies. In this short communication, a comparative study has been conducted to study the effect of pressure gradients on mass transfer and the resulting concentration overpotentials of an SOFC running on methane (CH 4) fuel. It is found that the pressure gradients in both anode and cathode are significant in the fuel cell electrochemical activities. Neglecting the anode pressure gradient in the calculation can lead to underestimation of the concentration overpotential by about 20% at a typical current density of 5000 A m -2 and at a temperature of 1073 K. The deviation can be even larger at a higher temperature. At the cathode, neglecting the pressure gradient can result in overestimation of the concentration overpotential by about 10% under typical working conditions.

  3. Surface complexation modeling of Cu(II adsorption on mixtures of hydrous ferric oxide and kaolinite

    Directory of Open Access Journals (Sweden)

    Schaller Melinda S

    2008-09-01

    Full Text Available Abstract Background The application of surface complexation models (SCMs to natural sediments and soils is hindered by a lack of consistent models and data for large suites of metals and minerals of interest. Furthermore, the surface complexation approach has mostly been developed and tested for single solid systems. Few studies have extended the SCM approach to systems containing multiple solids. Results Cu adsorption was measured on pure hydrous ferric oxide (HFO, pure kaolinite (from two sources and in systems containing mixtures of HFO and kaolinite over a wide range of pH, ionic strength, sorbate/sorbent ratios and, for the mixed solid systems, using a range of kaolinite/HFO ratios. Cu adsorption data measured for the HFO and kaolinite systems was used to derive diffuse layer surface complexation models (DLMs describing Cu adsorption. Cu adsorption on HFO is reasonably well described using a 1-site or 2-site DLM. Adsorption of Cu on kaolinite could be described using a simple 1-site DLM with formation of a monodentate Cu complex on a variable charge surface site. However, for consistency with models derived for weaker sorbing cations, a 2-site DLM with a variable charge and a permanent charge site was also developed. Conclusion Component additivity predictions of speciation in mixed mineral systems based on DLM parameters derived for the pure mineral systems were in good agreement with measured data. Discrepancies between the model predictions and measured data were similar to those observed for the calibrated pure mineral systems. The results suggest that quantifying specific interactions between HFO and kaolinite in speciation models may not be necessary. However, before the component additivity approach can be applied to natural sediments and soils, the effects of aging must be further studied and methods must be developed to estimate reactive surface areas of solid constituents in natural samples.

  4. Nitric oxide levels in the aqueous humor vary in different ocular hypertension experimental models

    Directory of Open Access Journals (Sweden)

    Da-Wen Lu

    2014-12-01

    Full Text Available This study investigated the relationships among intraocular pressure (IOP, nitric oxide (NO levels, and aqueous flow rates in experimental ocular hypertension models. A total of 75 rabbits were used. One of four different materials [i.e., α-chymotrypsin, latex microspheres (Polybead, red blood cell ghosts, or sodium hyaluronate (Healon GV] was injected into the eyes of the 15 animals in each experimental group; the remaining 15 rabbits were reserved for a control group. The IOP changes in the five groups were recorded on postinduction Days 1–3, Day 7, Day 14, Day 30, Day 60, Day 90, and Day 120. On postinduction Day 7, the dynamics and NO levels in the aqueous humor were recorded. Significant IOP elevations were induced by α-chymotrypsin (p < 0.01 and Polybead (p < 0.01 on each postinduction day. In the red blood cell ghosts model, significant elevations (p < 0.01 were found on postinduction Days 1–3; Healon GV significantly elevated IOP (p < 0.01 on postinduction Day 1 and Day 2. On postinduction Day 7, the aqueous humor NO levels increased significantly in the models of α-chymotrypsin, Polybead, and red blood cell ghosts (all p < 0.01, while the aqueous flow rates were significantly reduced in the models of α-chymotrypsin and Polybead (p < 0.005. Persistent ocular hypertension models were induced with α-chymotrypsin and Polybead in the rabbits. The Polybead model exhibited the characteristic of an increased aqueous humor NO level, similar to human eyes with acute angle-closure glaucoma and neovascular glaucoma.

  5. Mainz Isoprene Mechanism 2 (MIM2: an isoprene oxidation mechanism for regional and global atmospheric modelling

    Directory of Open Access Journals (Sweden)

    D. Taraborrelli

    2009-04-01

    Full Text Available We present an oxidation mechanism of intermediate size for isoprene (2-methyl-1,3-butadiene suitable for simulations in regional and global atmospheric chemistry models, which we call MIM2. It is a reduction of the corresponding detailed mechanism in the Master Chemical Mechanism (MCM v3.1 and intended as the second version of the well-established Mainz Isoprene Mechanism (MIM. Our aim is to improve the representation of tropospheric chemistry in regional and global models under all NOx regimes. We evaluate MIM2 and re-evaluate MIM through comparisons with MCM v3.1. We find that MIM and MIM2 compute similar O3, OH and isoprene mixing ratios. Unlike MIM, MIM2 produces small relative biases for NOx and organic nitrogen-containing species due to a good representation of the alkyl and peroxy acyl nitrates (RONO2 and RC(OOONO2. Moreover, MIM2 computes only small relative biases with respect to hydrogen peroxide (H2O2, methyl peroxide (CH3OOH, methanol (CH3OH, formaldehyde (HCHO, peroxy acetyl nitrate (PAN, and formic and acetic acids (HCOOH and CH3C(OOH, being always below ≈6% in all NOx scenarios studied. Most of the isoprene oxidation products are represented explicitly, including methyl vinyl ketone (MVK, methacrolein (MACR, hydroxyacetone and methyl glyoxal. MIM2 is mass-conserving with respect to carbon, including CO2 as well. Therefore, it is suitable for studies assessing carbon monoxide (CO from biogenic sources, as well as for studies focused on the carbon cycle. Compared to MIM, MIM2 considers new species like acetaldehyde (CH3CHO, propene (CH2=CHCH3 and glyoxal (CHOCHO with global chemical production rates for the year 2005 of 7.3, 9.5 and 33.8 Tg/yr, respectively. Our new mechanism is expected to substantially improve the results of atmospheric chemistry models by

  6. Large scale computational chemistry modeling of the oxidation of highly oriented pyrolytic graphite.

    Science.gov (United States)

    Poovathingal, Savio; Schwartzentruber, Thomas E; Srinivasan, Sriram Goverapet; van Duin, Adri C T

    2013-04-04

    Large scale molecular dynamics (MD) simulations are performed to study the oxidation of highly oriented pyrolytic graphite (HOPG) by hyperthermal atomic oxygen beam (5 eV). Simulations are performed using the ReaxFF classical reactive force field. We present here additional evidence that this method accurately reproduces ab initio derived energies relevant to HOPG oxidation. HOPG is modeled as multilayer graphene and etch-pit formation and evolution is directly simulated through a large number of sequential atomic oxygen collisions. The simulations predict that an oxygen coverage is first established that acts as a precursor to carbon-removal reactions, which ultimately etch wide but shallow pits, as observed in experiments. In quantitative agreement with experiment, the simulations predict the most abundant product species to be O2 (via recombination reactions), followed by CO2, with CO as the least abundant product species. Although recombination occurs all over the graphene sheet, the carbon-removal reactions occur only about the edges of the etch pit. Through isolated defect analysis on small graphene models as well as trajectory analysis performed directly on the predicted etch pit, the activation energies for the dominant reaction mechanisms leading to O2, CO2, and CO product species are determined to be 0.3, 0.52, and 0.67 eV, respectively. Overall, the qualitative and quantitative agreement between MD simulation and experiment is very promising. Thus, the MD simulation approach and C/H/O ReaxFF parametrization may be useful for simulating high-temperature gas interactions with graphitic materials where the microstructure is more complex than HOPG.

  7. Behavioral despair associated with a mouse model of Crohn's disease: Role of nitric oxide pathway.

    Science.gov (United States)

    Heydarpour, Pouria; Rahimian, Reza; Fakhfouri, Gohar; Khoshkish, Shayan; Fakhraei, Nahid; Salehi-Sadaghiani, Mohammad; Wang, Hongxing; Abbasi, Ata; Dehpour, Ahmad Reza; Ghia, Jean-Eric

    2016-01-01

    Crohn's disease (CD) is associated with increased psychiatric co-morbidities. Nitric oxide (NO) is implicated in inflammation and tissue injury in CD, and it may also play a central role in pathogenesis of the accompanying behavioral despair. This study investigated the role of the NO pathway in behavioral despair associated with a mouse model of CD. Colitis was induced by intrarectal (i.r.) injection of 2,4,6-trinitrobenzenesulfonic acid (10mg TNBS in 50% ethanol). Forced swimming test (FST), pharmacological studies and tissues collection were performed 72 h following TNBS administration. To address a possible inflammatory origin for the behavioral despair following colitis induction, tumor necrosis factor-alpha (TNF-α) level was measured in both the hippocampal and colonic tissue samples. In parallel, hippocampal inducible nitric oxide synthase (iNOS) and nitrite level were evaluated. Pharmacological studies targeting the NO pathway were performed 30-60 min before behavioral test. Colitis was confirmed by increased colonic TNF-α level and microscopic score. Colitic mice demonstrated a significantly higher immobility time in the FST associated to a significant increase of hippocampal TNF-α, iNOS expression and nitrite content. Acute NOS inhibition using either Nω-nitro-l-arginine methyl ester (a non-specific NOS inhibitor) or aminoguanidine hydrochloride (a specific iNOS inhibitor) decreased the immobility time in colitic groups. Moreover, acute treatment with both NOS inhibitors decreased the TNF-α level and nitrite content in the hippocampal samples. This study suggests that the NO pathway may be involved in the behavioral effects in the mouse TNBS model of CD. These findings endow new insights into the gut-brain communication during the development of colonic inflammation, which may ultimately lead to improved therapeutic strategies to combat behavior changes associated with gastrointestinal disorders.

  8. Simulation of nitrous oxide effluxes, crop yields and soil physical properties using the LandscapeDNDC model in managed ecosystem

    Science.gov (United States)

    Nyckowiak, Jedrzej; Lesny, Jacek; Haas, Edwin; Juszczak, Radoslaw; Kiese, Ralf; Butterbach-Bahl, Klaus; Olejnik, Janusz

    2014-05-01

    Modeling of nitrous oxide emissions from soil is very complex. Many different biological and chemical processes take place in soils which determine the amount of emitted nitrous oxide. Additionaly, biogeochemical models contain many detailed factors which may determine fluxes and other simulated variables. We used the LandscapeDNDC model in order to simulate N2O emissions, crop yields and soil physical properties from mineral cultivated soils in Poland. Nitrous oxide emissions from soils were modeled for fields with winter wheat, winter rye, spring barley, triticale, potatoes and alfalfa crops. Simulations were carried out for the plots of the Brody arable experimental station of Poznan University of Life Science in western Poland and covered the period 2003 - 2012. The model accuracy and its efficiency was determined by comparing simulations result with measurements of nitrous oxide emissions (measured with static chambers) from about 40 field campaigns. N2O emissions are strongly dependent on temperature and soil water content, hence we compared also simulated soil temperature at 10cm depth and soil water content at the same depth with the daily measured values of these driving variables. We compared also simulated yield quantities for each individual experimental plots with yield quantities which were measured in the period 2003-2012. We conclude that the LandscapeDNDC model is capable to simulate soil N2O emissions, crop yields and physical properties of soil with satisfactorily good accuracy and efficiency.

  9. Determination of Model Kinetics for Forced Unsteady State Operation of Catalytic CH4 Oxidation

    Directory of Open Access Journals (Sweden)

    Effendy Mohammad

    2016-01-01

    Full Text Available The catalytic oxidation of methane for abating the emission vented from coal mine or natural gas transportation has been known as most reliable method. A reverse flow reactor operation has been widely used to oxidize this methane emission due to its capability for autothermal operation and heat production. The design of the reverse flow reactor requires a proper kinetic rate expression, which should be developed based on the operating condition. The kinetic rate obtained in the steady state condition cannot be applied for designing the reactor operated under unsteady state condition. Therefore, new approach to develop the dynamic kinetic rate expression becomes indispensable, particularly for periodic operation such as reverse flow reactor. This paper presents a novel method to develop the kinetic rate expression applied for unsteady state operation. The model reaction of the catalytic methane oxidation over Pt/-Al2O3 catalyst was used with kinetic parameter determined from laboratory experiments. The reactor used was a fixed bed, once-through operation, with a composition modulation in the feed gas. The switching time was set at 3 min by varying the feed concentration, feed flow rate, and reaction temperature. The concentrations of methane in the feed and product were measured and analysed using gas chromatography. The steady state condition for obtaining the kinetic rate expression was taken as a base case and as a way to judge its appropriateness to be applied for dynamic system. A Langmuir-Hinshelwood reaction rate model was developed. The time period during one cycle was divided into some segments, depending on the ratio of CH4/O2. The experimental result shows that there were kinetic regimes occur during one cycle: kinetic regime controlled by intrinsic surface reaction and kinetic regime controlled by external diffusion. The kinetic rate obtained in the steady state operation was not appropriate when applied for unsteady state operation

  10. Glyoxal as a tracer of VOC oxidation chemistry: Comparison of measurements with model results for Blodgett Forest, California

    Science.gov (United States)

    Huisman, Andrew; Carlton, Annmarie; Keutsch, Frank

    2010-05-01

    We present a study investigating Volatile Organic Compound (VOC) oxidation chemistry in the context of regional ozone (O3) production during the BEARPEX 2007 and 2009 campaigns at Blodgett Forest Research Station (BFRS) in the Sierra Nevada mountains, CA. Measurements are compared with results from a regional model (US EPA CMAQ) and a zero dimensional (0-D) box model based on the Master Chemical Mechanism (MCM). We use glyoxal (CHOCHO) and formaldehyde (HCHO) as tracers for generalized oxidation processes and employ ratios of compounds (e.g. CHOCHO / HCHO, CHOCHO / MPAN) to study plume evolution as doing so attenuates the influence of meteorology. One of the goals of this study is to investigate the utility of glyoxal as a tracer of VOC oxidation chemistry for measurement/model comparisons, for which formaldehyde has served in the past. In this context, we investigate the discrepancies between models and measurements, and the degree to which these can be attributed to the representation of glyoxal chemistry (e.g. yields) or whether these discrepancies reflect VOC-HOx-NOx oxidation more generally, which has implications for ozone and secondary organic aerosol formation. Model results from CMAQ and the 0-D box model substantially overestimate the absolute measured concentration of CHOCHO at BFRS, and the CMAQ model also shows poor agreement with the diurnal profile. The 0-D box model also overestimates CHOCHO in data taken at the Caltech Indoor Air Chambers, suggesting that 2nd- and/or higher-generation yields of CHOCHO from isoprene are substantially overestimated in the MCM. 0-D model results that use attenuated 2nd- and higher-generation production of CHOCHO from isoprene show enhanced agreement with chamber results. We will present model results of the 0-D Box Model from BFRS employing these reduced yields that show improved agreement with measurements and also compare these results with the other models. We also present results obtained with two modifications of

  11. Sensorineural hearing loss and ischemic injury: Development of animal models to assess vascular and oxidative effects.

    Science.gov (United States)

    Olivetto, E; Simoni, E; Guaran, V; Astolfi, L; Martini, A

    2015-09-01

    Hearing loss may be genetic, associated with aging or exposure to noise or ototoxic substances. Its aetiology can be attributed to vascular injury, trauma, tumours, infections or autoimmune response. All these factors could be related to alterations in cochlear microcirculation resulting in hypoxia, which in turn may damage cochlear hair cells and neurons, leading to deafness. Hypoxia could underlie the aetiology of deafness, but very few data about it are presently available. The aim of this work is to develop animal models of hypoxia and ischemia suitable for study of cochlear vascular damage, characterizing them by electrophysiology and gene/protein expression analyses. The effects of hypoxia in infarction were mimicked in rat by partial permanent occlusion of the left coronary artery, and those of ischemia in thrombosis by complete temporary carotid occlusion. In our models both hypoxia and ischemia caused a small but significant hearing loss, localized at the cochlear apex. A slight induction of the coagulation cascade and of oxidative stress pathways was detected as cell survival mechanism, and cell damages were found on the cuticular plate of outer hair cells only after carotid ischemia. Based on these data, the two developed models appear suitable for in vivo studies of cochlear vascular damage. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Structural and vibrational study of graphene oxide via coronene based models: theoretical and experimental results

    Science.gov (United States)

    Almeida de Mendonça, João Paulo; Henrique de Lima, Alessandro; Amaral Junqueira, Georgia Maria; Gianini Quirino, Welber; Legnani, Cristiano; Oliveira Maciel, Indhira; Sato, Fernando

    2016-05-01

    We use the Coronene (C24H12), a simple and finite molecule, to make a model to study the spectroscopic and structural alterations generated by oxygenated groups in graphene oxide (GO). Based on the Lerf-Klinowski model, we chose the hydroxyl [OH-], the carboxyl [COOH-] and the epoxy [the ring C2O inside the molecule] as our radicals of interest and study their collective and isolated effects. We perform geometry optimization, vibrational IR (via AM1 and DFT-B3LYP) and Raman spectra (via DFT-B3LYP) of a series of functionalized coronene molecules. As results, we obtain some useful data for the analysis of IR and Raman spectra of GO, which facilitate the understanding and identification of the peaks found in the experiment. Finally, we suggest a new model to study GO, producing an accurate signature when compared to our experimental data. Such molecule shows in more details of the structural effects caused by functionalization when compared to experimental data.

  13. A Theoretical Solid Oxide Fuel Cell Model for Systems Controls and Stability Design

    Science.gov (United States)

    Kopasakis, George; Brinson, Thomas; Credle, Sydni

    2008-01-01

    As the aviation industry moves toward higher efficiency electrical power generation, all electric aircraft, or zero emissions and more quiet aircraft, fuel cells are sought as the technology that can deliver on these high expectations. The hybrid solid oxide fuel cell system combines the fuel cell with a micro-turbine to obtain up to 70% cycle efficiency, and then distributes the electrical power to the loads via a power distribution system. The challenge is to understand the dynamics of this complex multidiscipline system and the design distributed controls that take the system through its operating conditions in a stable and safe manner while maintaining the system performance. This particular system is a power generation and a distribution system, and the fuel cell and micro-turbine model fidelity should be compatible with the dynamics of the power distribution system in order to allow proper stability and distributed controls design. The novelty in this paper is that, first, the case is made why a high fidelity fuel cell mode is needed for systems control and stability designs. Second, a novel modeling approach is proposed for the fuel cell that will allow the fuel cell and the power system to be integrated and designed for stability, distributed controls, and other interface specifications. This investigation shows that for the fuel cell, the voltage characteristic should be modeled but in addition, conservation equation dynamics, ion diffusion, charge transfer kinetics, and the electron flow inherent impedance should also be included.

  14. Quantitative assessment of uncertainties for a model of tropospheric ethene oxidation using the European Photoreactor (EUPHORE)

    Science.gov (United States)

    Zádor, Judit; Wagner, Volker; Wirtz, Klaus; Pilling, Michael J.

    Methods of uncertainty analysis were used for comparison of the Master Chemical Mechanism version 3 (MCMv3) with measurements made in the European Photoreactor (EUPHORE) at Valencia (Spain) to investigate model-measurement discrepancies and to obtain information on the importance of wall effects. Two EUPHORE smog chamber measurements of ethene oxidation, under high and low NO x conditions were analysed by the following methods: (i) local uncertainty analysis, (ii) the global screening method of Morris and (iii) Monte Carlo (MC) analysis with Latin hypercube sampling. For both experiments, ozone (by 25% and 30%, respectively) and formaldehyde (by 34% and 40%, respectively) are significantly over-predicted by the model calculations, while the disagreement for other species is less substantial. According to the local uncertainty analysis and the Morris method, the most important contributor to ozone uncertainty under low NO x conditions is HOCH 2CH 2O 2+NO→HOCH 2CH 2O+NO 2, while under high NO x conditions OH+NO 2→HNO 3 is the main contributor. The MC simulations give an estimate of the 2σ uncertainty for ozone as ˜20% in both scenarios at the end of the experiment. The results suggest systematic disagreement between measurements and model calculations, although the origin of this is not clear. It seems that chamber effects alone are not responsible for the observed discrepancies.

  15. Numerical modeling of oxides of nitrogen based on density of biodiesel fuels

    Directory of Open Access Journals (Sweden)

    A. Gopinath, Sukumar Puhan, G. Nagarajan

    2010-03-01

    Full Text Available Biodiesel is an alternative fuel derived from vegetable oils or animal fats. Research has shown that biodiesel fueled engines produce lesser carbon monoxide, unburned hydrocarbon, and particulate emissions compared to mineral based diesel fuel but emit higher oxides of nitrogen (NOx emissions. NOx could be strongly correlated with density or cetane number of a fuel. The objective of the present work is to predict the NOx concentration of a neat biodiesel fueled compression ignition engine from the density of biodiesel fuels using regression model. Experiments were conducted at different engine loads and the results were given as inputs to develop the regression model. A single cylinder, four stroke, constant speed, air cooled, direct injection diesel engine was used for the experiments. Five different biodiesel fuels were used and NOx were measured at different engine loads. The NOx concentration was taken as response (dependent variable and the density values were taken as explanatory (independent variables. The regression model has yielded R2 values between 0.918 and 0.995. The maximum prediction error was found to be 3.01 %.

  16. Lithium perchlorate ion pairing in a model of amorphous polyethylene oxide

    Energy Technology Data Exchange (ETDEWEB)

    Halley, J.W.; Duan, Y. [School of Physics and Astronomy, University of Minnesota, Minneapolis, Minnesota 55455 (United States); Curtiss, L.A.; Baboul, A.G. [Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    1999-08-01

    We report a molecular dynamics study of pairing and dynamics of lithium cation and perchlorate anion in a previously reported model of amorphous polyethylene oxide. We are particularly interested in the question of whether these ions pair in the model, as previously reported experimentally. We calculate the potential of mean force between a lithium and perchlorate ion in the system for several temperatures when a pair of ions is at various separation distances in our model. We find evidence for two minima in the potential of mean force, one at lithium{endash}chlorine separations of 3.5 {Angstrom} and about 6.5 {Angstrom}. We studied the same system with five ion pairs in the system and again find two minima at the same separation distances but in this case there is evidence of entropic effects in the binding free energy of the pairs at 3.5 {Angstrom}. A study of radial distribution functions permits us to deduce information concerning the structure of the paired states. {copyright} {ital 1999 American Institute of Physics.}

  17. Supercritical water oxidation of quinazoline: Reaction kinetics and modeling.

    Science.gov (United States)

    Gong, Yanmeng; Guo, Yang; Wang, Shuzhong; Song, Wenhan; Xu, Donghai

    2017-03-01

    This paper presents a first quantitative kinetic model for supercritical water oxidation (SCWO) of quinazoline that describes the formation and interconversion of intermediates and final products at 673-873 K. The set of 11 reaction pathways for phenol, pyrimidine, naphthalene, NH3, etc, involved in the simplified reaction network proved sufficient for fitting the experimental results satisfactorily. We validated the model prediction ability on CO2 yields at initial quinazoline loading not used in the parameter estimation. Reaction rate analysis and sensitivity analysis indicate that nearly all reactions reach their thermodynamic equilibrium within 300 s. The pyrimidine yielding from quinazoline is the dominant ring-opening pathway and provides a significant contribution to CO2 formation. Low sensitivity of NH3 decomposition rate to concentration confirms its refractory nature in SCWO. Nitrogen content in liquid products decreases whereas that in gaseous phase increases as reaction time prolonged. The nitrogen predicted by the model in gaseous phase combined with the experimental nitrogen in liquid products gives an accurate nitrogen balance of conversion process.

  18. Three-dimensional random resistor-network model for solid oxide fuel cell composite electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Abbaspour, Ali [Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB T6G 2G6 (Canada); Luo Jingli, E-mail: jingli.luo@ualberta.c [Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB T6G 2G6 (Canada); Nandakumar, K. [Cain Department of Chemical Engineering, Louisiana State University, Baton Rouge, LA (United States)

    2010-04-30

    A three-dimensional reconstruction of solid oxide fuel cell (SOFC) composite electrodes was developed to evaluate the performance and further investigate the effect of microstructure on the performance of SOFC electrodes. Porosity of the electrode is controlled by adding pore former particles (spheres) to the electrode and ignoring them in analysis step. To enhance connectivity between particles and increase the length of triple-phase boundary (TPB), sintering process is mimicked by enlarging particles to certain degree after settling them inside the packing. Geometrical characteristics such as length of TBP and active contact area as well as porosity can easily be calculated using the current model. Electrochemical process is simulated using resistor-network model and complete Butler-Volmer equation is used to deal with charge transfer process on TBP. The model shows that TPBs are not uniformly distributed across the electrode and location of TPBs as well as amount of electrochemical reaction is not uniform. Effects of electrode thickness, particle size ratio, electron and ion conductor conductivities and rate of electrochemical reaction on overall electrochemical performance of electrode are investigated.

  19. Simulation of nitrous oxide emissions at field scale using the SPACSYS model

    Science.gov (United States)

    Wu, L.; Rees, R.M.; Tarsitano, D.; Zhang, Xubo; Jones, S.K.; Whitmore, A.P.

    2015-01-01

    Nitrous oxide emitted to the atmosphere via the soil processes of nitrification and denitrification plays an important role in the greenhouse gas balance of the atmosphere and is involved in the destruction of stratospheric ozone. These processes are controlled by biological, physical and chemical factors such as growth and activity of microbes, nitrogen availability, soil temperature and water availability. A comprehensive understanding of these processes embodied in an appropriate model can help develop agricultural mitigation strategies to reduce greenhouse gas emissions, and help with estimating emissions at landscape and regional scales. A detailed module to describe the denitrification and nitrification processes and nitrogenous gas emissions was incorporated into the SPACSYS model to replace an earlier module that used a simplified first-order equation to estimate denitrification and was unable to distinguish the emissions of individual nitrogenous gases. A dataset derived from a Scottish grassland experiment in silage production was used to validate soil moisture in the top 10 cm soil, cut biomass, nitrogen offtake and N2O emissions. The comparison between the simulated and observed data suggested that the new module can provide a good representation of these processes and improve prediction of N2O emissions. The model provides an opportunity to estimate gaseous N emissions under a wide range of management scenarios in agriculture, and synthesises our understanding of the interaction and regulation of the processes. PMID:26026411

  20. A two-dimensional modeling of solid oxide fuel cell button cells with detailed electrochemistry mechanism

    Science.gov (United States)

    Li, Jingde; Bai, Zhengyu; Croiset, Eric

    2016-11-01

    A two-dimensional model of nickel/yttria-stabilized zirconia (Ni/YSZ) solid oxide fuel cell (SOFC) was developed for a button cell system. The model integrates the detailed catalytic, electrochemical elementary reactions with ionic/electronic conduction and multiple gas transport processes in SOFC. The model is validated using published experimental data for H2-H2O fuel gas under different cell sizes and operating conditions. The distributions of gas/surface phase species concentration and current density were predicted and the effects of operating temperature, fuel gas composition and fuel channel tube design on the cell performance were studied. The results show that the electrochemical reaction processes occurs mainly within a 20 μm distance from the anode/electrolyte interface and that the Ni catalyst surface is covered mainly by H(s). For the chamber channel design, the calculations show that the tube chamber should have a diameter no smaller than the cathode electrode to obtain the best SOFC performance.

  1. Extractive oxidative desulfurization of model oil/crude oil using KSF montmorillonite-supported 12-tungstophosphoric acid

    Directory of Open Access Journals (Sweden)

    Ezzat Rafiee

    2016-10-01

    Full Text Available Abstract 12-Tungstophosphoric acid (PW supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization (ODS of mixed thiophenic compounds in model oil and crude oil under mild conditions using hydrogen peroxide (H2O2 as an oxidizing agent. A one-factor-at-a-time method was applied for optimizing the parameters such as temperature, reaction time, amount of catalyst, type of extractant and oxidant-to-sulfur compounds (S-compounds molar ratio. The corresponding products can be easily removed from the model oil by using ethanol as the best extractant. The results showed high catalytic activity of PW/KSF in the oxidative removal of dibenzothiophene (DBT and mixed thiophenic model oil under atmospheric pressure at 75 °C in a biphasic system. To investigate the oxidation and adsorption effects of crude oil composition on ODS, the effects of cyclohexene, 1,7-octadiene and o-xylene with different concentrations were studied.

  2. Global sensitivity analysis of the GEOS-Chem chemical transport model: ozone and hydrogen oxides during ARCTAS (2008)

    Science.gov (United States)

    Christian, Kenneth E.; Brune, William H.; Mao, Jingqiu

    2017-03-01

    Developing predictive capability for future atmospheric oxidation capacity requires a detailed analysis of model uncertainties and sensitivity of the modeled oxidation capacity to model input variables. Using oxidant mixing ratios modeled by the GEOS-Chem chemical transport model and measured on the NASA DC-8 aircraft, uncertainty and global sensitivity analyses were performed on the GEOS-Chem chemical transport model for the modeled oxidants hydroxyl (OH), hydroperoxyl (HO2), and ozone (O3). The sensitivity of modeled OH, HO2, and ozone to model inputs perturbed simultaneously within their respective uncertainties were found for the flight tracks of NASA's Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) A and B campaigns (2008) in the North American Arctic. For the spring deployment (ARCTAS-A), ozone was most sensitive to the photolysis rate of NO2, the NO2 + OH reaction rate, and various emissions, including methyl bromoform (CHBr3). OH and HO2 were overwhelmingly sensitive to aerosol particle uptake of HO2 with this one factor contributing upwards of 75 % of the uncertainty in HO2. For the summer deployment (ARCTAS-B), ozone was most sensitive to emission factors, such as soil NOx and isoprene. OH and HO2 were most sensitive to biomass emissions and aerosol particle uptake of HO2. With modeled HO2 showing a factor of 2 underestimation compared to measurements in the lowest 2 km of the troposphere, lower uptake rates (γHO2 < 0. 055), regardless of whether or not the product of the uptake is H2O or H2O2, produced better agreement between modeled and measured HO2.

  3. Mainz Isoprene Mechanism 2 (MIM2: an isoprene oxidation mechanism for regional and global atmospheric modelling

    Directory of Open Access Journals (Sweden)

    D. Taraborrelli

    2008-07-01

    Full Text Available We present an oxidation mechanism of intermediate size for isoprene (2-methyl-1,3-butadiene suitable for simulations in regional and global atmospheric chemistry models, which we call MIM2. It is a reduction of the corresponding detailed mechanism in the Master Chemical Mechanism (MCM v3.1 and intended as the second version of the well-established Mainz Isoprene Mechanism (MIM. Our aim is to improve the representation of tropospheric chemistry in regional and global models under all NOx regimes. We evaluate MIM2 and re-evaluate MIM through comparisons with MCM v3.1. We find that MIM and MIM2 compute similar O3, OH and isoprene mixing ratios. Unlike MIM, MIM2 produces small relative biases for NOx and organic nitrogen-containing species due to a good representation of the alkyl and peroxy acyl nitrates (RONO2 and RC(OOONO2. Moreover, MIM2 computes only small relative biases with respect to hydrogen peroxide (H2O2, methyl peroxide (CH3OOH, methanol (CH3OH, formaldehyde (HCHO, peroxy acetyl nitrate (PAN, and formic and acetic acids (HCOOH and CH3C(OOH, being always below ≈6% in all NOx scenarios studied. Most of the isoprene oxidation products are represented explicitly, including methyl vinyl ketone (MVK, methacrolein (MACR, hydroxyacetone and methyl glyoxal. MIM2 is mass-conserving with respect to carbon, including CO2 as well. Therefore, it is suitable for studies assessing carbon monoxide (CO from biogenic sources, as well as for studies focused on the carbon cycle. Compared to MIM, MIM2 considers new species like acetaldehyde (CH3CHO, propene (CH2=CHCH3 and glyoxal (CHOCHO with global chemical production rates for the year 2005 of 7.3, 9.5 and 33.8 Tg/yr, respectively. Our new mechanism is expected to substantially improve the results of atmospheric chemistry models by more

  4. Understanding DNA Under Oxidative Stress and Sensitization: The Role of Molecular Modeling

    Directory of Open Access Journals (Sweden)

    Antonio eMonari

    2015-07-01

    Full Text Available DNA is constantly exposed to damaging threats coming from oxidative stress, i.e. from the presence of free radicals and reactive oxygen species. Sensitization from exogenous and endogenous compounds that strongly enhance the frequency of light-induced lesions also plays an important role. The experimental determination of DNA lesions, though a difficult subject, is somehow well established and allows to elucidate even extremely rare DNA lesions. In parallel, molecular modeling has become fundamental to clearly understand the fine mechanisms related to DNA defects induction. Indeed, it offers an unprecedented possibility to get access to an atomistic or even electronic resolution. Ab initio molecular dynamics may also describe the time-evolution of the molecular system and its reactivity. Yet the modeling of DNA (photo-reactions does necessitate elaborate multi-scale methodologies to tackle a damage induction reactivity that takes place in a complex environment. The double-stranded DNA environment is first characterized by a very high flexibility, that dynamical effects are to be taken into account, but also a strongly inhomogeneous electrostatic embedding. Additionally, one aims at capturing more subtle effects, such as the sequence selectivity which is of critical important for DNA damage. The structure and dynamics of the DNA/sensitizers complexes, as well as the photo-induced electron- and energy-transfer phenomena taking place upon sensitization, should be carefully modeled. Finally the factors inducing different repair ratios for different lesions should also be rationalized.In this review we will critically analyze the different computational strategies used to model DNA lesions. A clear picture of the complex interplay between reactivity and structural factors will be sketched. The use of proper multi-scale modeling leads to the in-depth comprehension of DNA lesions mechanism and also to the rational design of new chemo-therapeutic agents.

  5. Anti-oxidative and anti-inflammatory effects of spirulina on rat model of non-alcoholic steatohepatitis

    Science.gov (United States)

    Pak, Wing; Takayama, Fusako; Mine, Manaka; Nakamoto, Kazuo; Kodo, Yasumasa; Mankura, Mitsumasa; Egashira, Toru; Kawasaki, Hiromu; Mori, Akitane

    2012-01-01

    The pathogenesis of nonalcoholic steatohepatitis (NASH) remains unclear, but accumulating data suggest oxidative stress and the relationship between inflammation and immunity plays a crucial role. The aim of this study is to investigate the spirulina, which is a blue-green algae rich in proteins and other nutritional elements, and its component-phycocyanin effect on a rat model of NASH. NASH model rats were established by feeding male Wistar rats with choline-deficient high-fat diet (CDHF) and intermittent hypoxemia by sodium nitrite challenge after 5 weeks of CDHF. After experimental period of 10 weeks, blood and liver were collected to determine oxidative stress injuries and efficacies of spirulina or phycocyanin on NASH model rats. In the NASH model rats, increase in plasma liver enzymes and liver fibrosis, increases in productions of reactive oxygen species from liver mitochondria and from leukocytes, the activation of nuclear factor-kappa B, and the change in the lymphocyte surface antigen ratio (CD4+/CD8+) were observed. The spirulina and phycocyanin administration significantly abated these changes. The spirulina or phycocyanin administration to model rats of NASH might lessen the inflammatory response through anti-oxidative and anti-inflammatory mechanisms, breaking the crosstalk between oxidative stress and inflammation, and effectively inhibit NASH progression. PMID:23170052

  6. Hepatocyte cytotoxicity induced by hydroperoxide (oxidative stress model) or glyoxal (carbonylation model): prevention by bioactive nut extracts or catechins.

    Science.gov (United States)

    Banach, Monica S; Dong, Qiang; O'Brien, Peter J

    2009-03-16

    Carbonyl and oxidative stress play important roles in the development of diabetic complications and have been shown to be augmented by various natural compounds and pharmacological agents. Nuts are a rich source of bioactive compounds and antioxidants and various beneficial health effects of nuts have been reported. This study was conducted to evaluate the cytoprotectiveness of various nut extracts and bioactive compounds found in nuts for decreasing cytotoxicity, lipid peroxidation and protein carbonylation in cell toxicity models of diabetes-related carbonyl (glyoxal) and oxidative stress (hydroperoxide). Methanol, ethyl acetate or water were used to prepare crude hazelnut and walnut extracts, which were then used to screen for in vitro cytoprotection of freshly isolated rat hepatocytes against these toxins. The order of protection by nut extracts against hydroperoxide induced cell death was: walnut methanolic extract>walnut aqueous extract>lipophilic walnut extract>hazelnut aqueous extract>hazelnut methanolic extract whereas the lipophilic hazelnut extract did not protect against cell death. The order of protection against lipid peroxidation was the same except for the hazelnut methanolic extract, which prevented lipid peroxidation better than the hazelnut aqueous extract. Catechin, epicatechin and epigallocatechin gallate (EGCG) were investigated for possible protective effects against carbonyl stress cell death and protein carbonylation in hepatocytes. Catechin protected against glyoxal induced cell death and protein carbonylation, and even elicited protection when added to hepatocytes 30 min after the addition of glyoxal. When catechin and epicatechin were compared for protectiveness against glyoxal induced carbonyl stress in hepatocytes, epicatechin protected more effectively than catechin against cell death and protein carbonylation at 120 min. Both compounds also elicited better protection when premixed with glyoxal before addition to hepatocytes, compared

  7. Modeling aerosol surface chemistry and gas-particle interaction kinetics with K2-SURF: PAH oxidation

    Science.gov (United States)

    Shiraiwa, M.; Garland, R.; Pöschl, U.

    2009-04-01

    Atmospheric aerosols are ubiquitous in the atmosphere. They have the ability to impact cloud properties, radiative balance and provide surfaces for heterogeneous reactions. The uptake of gaseous species on aerosol surfaces impacts both the aerosol particles and the atmospheric budget of trace gases. These subsequent changes to the aerosol can in turn impact the aerosol chemical and physical properties. However, this uptake, as well as the impact on the aerosol, is not fully understood. This uncertainty is due not only to limited measurement data, but also a dearth of comprehensive and applicable modeling formalizations used for the analysis, interpretation and description of these heterogeneous processes. Without a common model framework, comparing and extrapolating experimental data is difficult. In this study, a novel kinetic surface model (K2-SURF) [Ammann & Pöschl, 2007; Pöschl et al., 2007] was used to describe the oxidation of a variety of polycyclic aromatic hydrocarbons (PAHs). Integrated into this consistent and universally applicable kinetic and thermodynamic process model are the concepts, terminologies and mathematical formalizations essential to the description of atmospherically relevant physicochemical processes involving organic and mixed organic-inorganic aerosols. Within this process model framework, a detailed master mechanism, simplified mechanism and parameterizations of atmospheric aerosol chemistry are being developed and integrated in analogy to existing mechanisms and parameterizations of atmospheric gas-phase chemistry. One of the key aspects to this model is the defining of a clear distinction between various layers of the particle and surrounding gas phase. The processes occurring at each layer can be fully described using known fluxes and kinetic parameters. Using this system there is a clear separation of gas phase, gas-surface and surface bulk transport and reactions. The partitioning of compounds can be calculated using the flux

  8. A predictive model of iron oxide nanoparticles flocculation tuning Z-potential in aqueous environment for biological application

    Energy Technology Data Exchange (ETDEWEB)

    Baldassarre, Francesca, E-mail: francesca.baldassarre@unisalento.it [University of Salento, Department of Cultural Heritage (Italy); Cacciola, Matteo, E-mail: matteo.cacciola@unirc.it [University “Mediterranea” of Reggio Calabria, DICEAM (Italy); Ciccarella, Giuseppe, E-mail: giuseppe.ciccarella@unisalento.it [University of Salento, Department of Innovation Engineering (Italy)

    2015-09-15

    Iron oxide nanoparticles are the most used magnetic nanoparticles in biomedical and biotechnological field because of their nontoxicity respect to the other metals. The investigation of iron oxide nanoparticles behaviour in aqueous environment is important for the biological applications in terms of polydispersity, mobility, cellular uptake and response to the external magnetic field. Iron oxide nanoparticles tend to agglomerate in aqueous solutions; thus, the stabilisation and aggregation could be modified tuning the colloids physical proprieties. Surfactants or polymers are often used to avoid agglomeration and increase nanoparticles stability. We have modelled and synthesised iron oxide nanoparticles through a co-precipitation method, in order to study the influence of surfactants and coatings on the aggregation state. Thus, we compared experimental results to simulation model data. The change of Z-potential and the clusters size were determined by Dynamic Light Scattering. We developed a suitable numerical model to predict the flocculation. The effects of Volume Mean Diameter and fractal dimension were explored in the model. We obtained the trend of these parameters tuning the Z-potential. These curves matched with the experimental results and confirmed the goodness of the model. Subsequently, we exploited the model to study the influence of nanoparticles aggregation and stability by Z-potential and external magnetic field. The highest Z-potential is reached up with a small external magnetic influence, a small aggregation and then a high suspension stability. Thus, we obtained a predictive model of Iron oxide nanoparticles flocculation that will be exploited for the nanoparticles engineering and experimental setup of bioassays.

  9. Sperm Oxidative Stress Is Detrimental to Embryo Development: A Dose-Dependent Study Model and a New and More Sensitive Oxidative Status Evaluation

    Directory of Open Access Journals (Sweden)

    Letícia S. de Castro

    2016-01-01

    Full Text Available Our study aimed to assess the impact of sperm oxidative stress on embryo development by means of a dose-dependent model. In experiment 1, straws from five bulls were subjected to incubation with increasing H2O2 doses (0, 12.5, 25, and 50 μM. Motility parameters were evaluated by Computed Assisted System Analysis (CASA. Experiment 2 was designed to study a high (50 μM and low dose (12.5 μM of H2O2 compared to a control (0 μM. Samples were incubated and further used for in vitro fertilization. Analyses of motility (CASA, oxidative status (CellROX green and 2’-7’ dichlorofluorescein diacetate, mitochondrial potential (JC-1, chromatin integrity (AO, and sperm capacitation status (chlortetracycline were performed. Embryos were evaluated based on fast cleavage (30 h.p.i., cleavage (D=3, development (D=5, and blastocyst rates (D=8. We observed a dose-dependent deleterious effect of H2O2 on motility and increase on the percentages of positive cells for CellROX green, capacitated sperm, and AO. A decrease on cleavage and blastocyst rates was observed as H2O2 increased. Also, we detected a blockage on embryo development. We concluded that sperm when exposed to oxidative environment presents impaired motility traits, prooxidative status, and premature capacitation; such alterations resulting in embryo development fail.

  10. Vanillin Attenuated Behavioural Impairments, Neurochemical Deficts, Oxidative Stress and Apoptosis Against Rotenone Induced Rat Model of Parkinson's Disease.

    Science.gov (United States)

    Dhanalakshmi, Chinnasamy; Janakiraman, Udaiyappan; Manivasagam, Thamilarasan; Justin Thenmozhi, Arokiasamy; Essa, Musthafa Mohamed; Kalandar, Ameer; Khan, Mohammed Abdul Sattar; Guillemin, Gilles J

    2016-08-01

    Vanillin (4-hydroxy-3-methoxybenzaldehyde), a pleasant smelling organic aromatic compound, is widely used as a flavoring additive in food, beverage, cosmetic and drug industries. It is reported to cross the blood brain barrier and also displayed antioxidant and neuroprotective activities. We previously reported the neuroprotective effect of vanillin against rotenone induced in in vitro model of PD. The present experiment was aimed to analyze the neuroprotective effect of vanillin on the motor and non-motor deficits, neurochemical variables, oxidative, anti-oxidative indices and the expression of apoptotic markers against rotenone induced rat model of Parkinson's disease (PD). Rotenone treatment exhibited motor and non-motor impairments, neurochemical deficits, oxidative stress and apoptosis, whereas oral administration of vanillin attenuated the above-said indices. However further studies are needed to explore the mitochondrial protective and anti-inflammatory properties of vanillin, as these processes play a vital role in the cause and progression of PD.

  11. A deposit model for magmatic iron-titanium-oxide deposits related to Proterozoic massif anorthosite plutonic suites: Chapter K in Mineral Deposit Models for Resource Assessment

    Science.gov (United States)

    Woodruff, Laurel G.; Nicholson, Suzanne W.; Fey, David L.

    2013-01-01

    This descriptive model for magmatic iron-titanium-oxide (Fe-Ti-oxide) deposits hosted by Proterozoic age massif-type anorthosite and related rock types presents their geological, mineralogical, geochemical, and geoenvironmental attributes. Although these Proterozoic rocks are found worldwide, the majority of known deposits are found within exposed rocks of the Grenville Province, stretching from southwestern United States through eastern Canada; its extension into Norway is termed the Rogaland Anorthosite Province. This type of Fe-Ti-oxide deposit dominated by ilmenite rarely contains more than 300 million tons of ore, with between 10- to 45-percent titanium dioxide (TiO2), 32- to 45-percent iron oxide (FeO), and less than 0.2-percent vanadium (V).

  12. Adsorption and Wetting in Model Mesoporous Silicas and in Complex Metal Oxide Catalysts

    Science.gov (United States)

    Jayaraman, Karthik

    The surface of most metal oxides is covered by hydroxyl groups which influence many surface phenomena such as adsorption and wetting, catalysis and surface reactions. Surface chemistry of silica is a subject of exhaustive studies owing to a wide variety of practical applications of silica. In Chapter 1, a brief review of classification, synthesis and characterization of silica is provided. The hydroxylation of silica surface i.e the number of hydroxyl (-OH) groups on the surface is of utmost importance for its practical applications. In Chapter 2, a brief introduction to surface hydration of silica is provided followed by the gas adsorption measurements and characterization. Pore wetting is critical to many applications of mesoporous adsorbents, catalysts, and separation materials. In the work presented in Chapter 3, we employed the combined vapor adsorption study using nitrogen (77K) and water (293K) isotherms to evaluate the water contact angles for a series of ordered mesoporous silicas (ex:SBA-15). The proposed method of contact angle relies on the statistical film thickness (t-curve) of the adsorbed water. There were no t-curves for water for dehydroxylated or hydrophobic surfaces in literature and we addressed this issue by measuring t-curves for a series of model surfaces with known and varying silanol coverage. Using the radius of menisci ((H2O)), statistical film thickness t(H2O) from water isotherm, and the true radius of pores (rp(N 2)), from nitrogen isotherms, the water contact angle inside pores were calculated. As it was anticipated, the results obtained showed that the silica pore contact angles were strongly influenced by the number of the surface silanol groups and, therefore, by the thermal and hydration treatments of silicas. Phthalocyanines (Pcs) present an interesting class of catalytically active of molecules with unique spectroscopic, photoelectric, and sometimes magnetic properties. In the work presented in Chapter 4, we have undertaken a

  13. Hyperlipidemia affects neuronal nitric oxide synthase expression in brains of focal cerebral ischemia rat model

    Institute of Scientific and Technical Information of China (English)

    Jianji Pei; Liqiang Liu; Jinping Pang; Xiaohong Tian

    2008-01-01

    BACKGROUND: Hyperlipidemia, a risk factor for ischemic cerebrovascular disease, may mediate production of neuronal nitric oxide synthase (nNOS) to induce increased nitric oxide levels, resulting in brain neuronal injury. OBJECTIVE: To investigate effects of hyperlipidemia on brain nNOS expression, and to verify changes in infarct volume and pathology during reperfusion, as well as neuronal injury following ischemia/reperfusion in a rat model of focal cerebral ischemia. DESIGN, TIME AND SETTING: Complete, randomized grouping experiment was performed at the Laboratory of Physiology, Shanxi Medical University from March 2005 to March 2006. MATERIALS: A total of 144 eight-week-old, male, Wistar rats, weighing 160-180 g, were selected. A rat model of middle cerebral artery occlusion was established by suture method after 4 weeks of formulated diet. Nitric oxide kit and rabbit anti-rat nNOS kit were respectively purchased from Nanjing Jiancheng Bioengineering Institute, China and Wuhan Boster Biological Technology, Ltd., China. METHODS: The rats were equally and randomly divided into high-fat diet and a normal diet groups. Rats in the high-fat diet group were fed a high-fat diet, consisting of 10% egg yolk powder, 5% pork fat, and 0.5% pig bile salt combined with standard chow to create hyperlipidemia. Rats in the normal diet group were fed a standard rat chow. A total of 72 rats in both groups were randomly divided into 6 subgroups: sham-operated, 4-hour ischemia, 4-hour ischemia/2-hour reperfusion, 4-hour ischemia/4-hour reperfusion, 4-hour ischemia/6-hour reperfusion, and 4-hour ischemia/12-hour reperfusion, with 12 rats in each subgroup. MAIN OUTCOME MEASURES: nNOS expression was measured by immunohistochemistry, and pathomorphology changes were detected by hematoxylin-eosin staining. Infarct volume and nitric oxide levels were respectively measured using 2, 3, 5-triphenyltetrazolium chloride (TTC) and immunohistochemistry. RESULTS: In the ischemic region, pathology

  14. Carnitine Deficiency and Oxidative Stress Provoke Cardiotoxicity in an Ifosfamide-Induced Fanconi Syndrome Rat Model

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    Mohamed M. Sayed-Ahmed

    2010-01-01

    Full Text Available In addition to hemorrhagic cystitis, Fanconi Syndrome is a serious clinical side effect during ifosfamide (IFO therapy. Fanconi syndrome is a generalized dysfunction of the proximal tubule which is characterized by excessive urinary excretion of glucose, phosphate, bicarbonate, amino acids and other solutes excreted by this segment of the nephron including L-carnitine. Carnitine is essential cofactor for β-oxidation of long-chain fatty acids in the myocardium. IFO therapy is associated with increased urinary carnitine excretion with subsequent secondary deficiency of the molecule. Cardiac abnormalities in IFO-treated cancer patients were reported as isolated clinical cases. This study examined whether carnitine deficiency and oxidative stress, secondary to Fanconi Syndrome, provoke IFO-induced cardiomyopathy as well as exploring if carnitine supplementation using Propionyl-L-carnitine (PLC could offer protection against this toxicity. In the current study, an animal model of carnitine deficiency was developed in rats by D-carnitine-mildronate treatment Adult male Wistar albino rats were assigned to one of six treatment groups: the first three groups were injected intraperitoneally with normal saline, D-carnitine (DC, 250 mg/kg/day combined with mildronate (MD, 200 mg/kg/day and PLC (250 mg/kg/day, respectively, for 10 successive days. The 4th, 5th and 6th groups were injected with the same doses of normal saline, DC-MD and PLC, respectively for 5 successive days before and 5 days concomitant with IFO (50 mg/kg/day. IFO significantly increased serum creatinine, blood urea nitrogen (BUN, urinary carnitine excretion and clearance, creatine phosphokinase isoenzyme (CK-MB, lactate dehydrogenase (LDH, intramitochondrial acetyl-CoA/CoA-SH and thiobarbituric acid reactive substances (TBARS in cardiac tissues and significantly decreased adenosine triphosphate (ATP and total carnitine and reduced glutathione (GSH content in cardiac tissues. In carnitine

  15. Sir2 is induced by oxidative stress in a yeast model of Huntington disease and its activation reduces protein aggregation.

    Science.gov (United States)

    Sorolla, M Alba; Nierga, Clara; Rodríguez-Colman, M José; Reverter-Branchat, Gemma; Arenas, Alicia; Tamarit, Jordi; Ros, Joaquim; Cabiscol, Elisa

    2011-06-01

    Huntington disease (HD) is a neurodegenerative disorder caused by expansion of CAG trinucleotide repeats, leading to an elongated polyglutamine sequence (polyQ) in the huntingtin protein. Misfolding of mutant polyQ proteins with expanded tracts results in aggregation, causing cytotoxicity. Oxidative stress in HD has been documented in humans as important to disease progression. Using yeast cells as a model of HD, we report that when grown at high glucose concentration, cells expressing mutant polyQ do not show apparent oxidative stress. At higher cell densities, when glucose becomes limiting and cells are metabolically shifting from fermentation to respiration, protein oxidation and catalase activity increases in relation to the length of the polyQ tract. Oxidative stress, either endogenous as a result of mutant polyQ expression or exogenously generated, increases Sir2 levels. Δ sir2 cells expressing expanded polyQ lengths show signs of oxidative stress even at the early exponential phase. In a wild-type background, isonicotinamide, a Sir2 activator, decreases mutant polyQ aggregation and the stress generated by expanded polyQ. Taken together, these results describe mutant polyQ proteins as being more toxic in respiring cells, causing oxidative stress and an increase in Sir2 levels. Activation of Sir2 would play a protective role against this toxicity. Copyright © 2011 Elsevier Inc. All rights reserved.

  16. Endothelial nitric oxide synthase uncoupling and perivascular adipose oxidative stress and inflammation contribute to vascular dysfunction in a rodent model of metabolic syndrome.

    Science.gov (United States)

    Marchesi, Chiara; Ebrahimian, Talin; Angulo, Orlando; Paradis, Pierre; Schiffrin, Ernesto L

    2009-12-01

    The metabolic syndrome represents a constellation of cardiovascular risk factors that promote the development of cardiovascular disease. Oxidative stress is a mediator of endothelial dysfunction and vascular remodeling. We investigated vascular dysfunction in the metabolic syndrome and the oxidant mechanisms involved. New Zealand obese (NZO) mice with metabolic syndrome and New Zealand black control mice were studied. NZO mice showed insulin resistance and increased visceral fat and blood pressure compared with New Zealand black mice. Mesenteric resistance arteries from NZO mice exhibited increased media:lumen ratio and media cross-sectional area, demonstrating hypertrophic vascular remodeling. Endothelium-dependent relaxation to acetylcholine, assessed by pressurized myography, was impaired in NZO mice, not affected by N(G)-nitro-l-arginine methyl ester, inhibitor of endothelial NO synthase, and improved by the antioxidant Tempol, suggesting reduced NO bioavailability and increased oxidative stress. Dimer:monomer ratio of endothelial NO synthase was decreased in NZO mice compared with New Zealand black mice, suggesting endothelial NO synthase uncoupling. Furthermore, vascular superoxide and peroxynitrite production was increased, as well as adhesion molecule expression. Perivascular adipose tissue of NZO mice showed increased superoxide production and NADPH oxidase activity, as well as adipocyte hypertrophy, associated with inflammatory Mac-3-positive cell infiltration. Vasoconstriction to norepinephrine decreased in the presence of perivascular adipose tissue in New Zealand black mice but was unaffected by perivascular adipose tissue in NZO mice, suggesting loss of perivascular adipose tissue anticontractile properties. Our data suggest that this rodent model of metabolic syndrome is associated with perivascular adipose inflammation and oxidative stress, hypertrophic resistance artery remodeling, and endothelial dysfunction, the latter a result of decreased NO

  17. Iodine's impact on tropospheric oxidants: a global model study in GEOS-Chem

    Science.gov (United States)

    Sherwen, T.; Evans, M. J.; Carpenter, L. J.; Andrews, S. J.; Lidster, R. T.; Dix, B.; Koenig, T. K.; Sinreich, R.; Ortega, I.; Volkamer, R.; Saiz-Lopez, A.; Prados-Roman, C.; Mahajan, A. S.; Ordóñez, C.

    2016-02-01

    We present a global simulation of tropospheric iodine chemistry within the GEOS-Chem chemical transport model. This includes organic and inorganic iodine sources, standard gas-phase iodine chemistry, and simplified higher iodine oxide (I2OX, X = 2, 3, 4) chemistry, photolysis, deposition, and parametrized heterogeneous reactions. In comparisons with recent iodine oxide (IO) observations, the simulation shows an average bias of ˜ +90 % with available surface observations in the marine boundary layer (outside of polar regions), and of ˜ +73 % within the free troposphere (350 hPa terms of global tropospheric IY burden (contributing up to 70 %). The iodine chemistry leads to a significant global tropospheric O3 burden decrease (9.0 %) compared to standard GEOS-Chem (v9-2). The iodine-driven OX loss rate1 (748 Tg OX yr-1) is due to photolysis of HOI (78 %), photolysis of OIO (21 %), and reaction between IO and BrO (1 %). Increases in global mean OH concentrations (1.8 %) by increased conversion of hydroperoxy radicals exceeds the decrease in OH primary production from the reduced O3 concentration. We perform sensitivity studies on a range of parameters and conclude that the simulation is sensitive to choices in parametrization of heterogeneous uptake, ocean surface iodide, and I2OX (X = 2, 3, 4) photolysis. The new iodine chemistry combines with previously implemented bromine chemistry to yield a total bromine- and iodine-driven tropospheric O3 burden decrease of 14.4 % compared to a simulation without iodine and bromine chemistry in the model, and a small increase in OH (1.8 %). This is a significant impact and so halogen chemistry needs to be considered in both climate and air quality models. 1 Here OX is defined as O3 + NO2 + 2NO3 + PAN + PMN+PPN + HNO4 + 3N2O5 + HNO3 + BrO + HOBr + BrNO2+2BrNO3 + MPN + IO + HOI + INO2 + 2INO3 + 2OIO+2I2O2 + 3I2O3 + 4I2O4, where PAN = peroxyacetyl nitrate, PPN = peroxypropionyl nitrate, MPN = methyl peroxy nitrate, and MPN

  18. Modeling-based optimization of a fixed-bed industrial reactor for oxidative dehydrogenation of propane

    Institute of Scientific and Technical Information of China (English)

    Ali Darvishi; Razieh Davand; Farhad Khorasheh; Moslem Fattahi

    2016-01-01

    An industrial scale propylene production via oxidative dehydrogenation of propane (ODHP) in multi-tubular re-actors was modeled. Multi-tubular fixed-bed reactor used for ODHP process, employing 10000 of smal diameter tubes immersed in a shel through a proper coolant flows. Herein, a theory-based pseudo-homogeneous model to describe the operation of a fixed bed reactor for the ODHP to correspondence olefin over V2O5/γ-Al2O3 catalyst was presented. Steady state one dimensional model has been developed to identify the operation parameters and to describe the propane and oxygen conversions, gas process and coolant temperatures, as well as other pa-rameters affecting the reactor performance such as pressure. Furthermore, the applied model showed that a double-bed multitubular reactor with intermediate air injection scheme was superior to a single-bed design due to the increasing of propylene selectivity while operating under lower oxygen partial pressures resulting in propane conversion of about 37.3%. The optimized length of the reactor needed to reach 100%conversion of the oxygen was theoretically determined. For the single-bed reactor the optimized length of 11.96 m including 0.5 m of inert section at the entrance region and for the double-bed reactor design the optimized lengths of 5.72 m for the first and 7.32 m for the second reactor were calculated. Ultimately, the use of a distributed oxygen feed with limited number of injection points indicated a significant improvement on the reactor performance in terms of propane conversion and propylene selectivity. Besides, this concept could overcome the reactor run-away temperature problem and enabled operations at the wider range of conditions to obtain enhanced propyl-ene production in an industrial scale reactor.

  19. Controlled Hydrogen Peroxide Decomposition for a Solid Oxide Fuel Cell (SOFC) Oxidant Source with a Microreactor Model

    Science.gov (United States)

    2007-10-01

    microchannel reactor for hydrogen peroxide decomposition is being developed for integration with fuel cell systems that can power undersea vehicles...the subunits of a microchemical reactor system. The basis of the present model is a microchannel reactor . The model description, governing equations...the 2007 COMSOL Users Conference Boston, 4-6 Oct, Newton. MA 14. ABSTRACT A microchannel reactor for hydrogen peroxide decomposition is being

  20. Assessment of the toxic potential of engineered metal oxide nanomaterials using an acellular model: citrated rat blood plasma.

    Science.gov (United States)

    Gormley, Patrick Thomas; Callaghan, Neal Ingraham; MacCormack, Tyson James; Dieni, Christopher Anthony

    2016-10-01

    Citrated Sprague-Dawley rat blood plasma was used as a biologically relevant exposure medium to assess the acellular toxic potential of two metal oxide engineered nanomaterials (ENMs), zinc oxide (nZnO), and cerium oxide (nCeO2). Plasma was incubated at 37 °C for up to 48 h with ENM concentrations ranging between 0 and 200 mg/L. The degree of ENM-induced oxidation was assessed by assaying for reactive oxygen species (ROS) levels using dichlorofluorescein (DCF), pH, ferric reducing ability of plasma (FRAP), lipase activity, malondialdehyde (MDA), and protein carbonyls (PC). Whereas previous in vitro studies showed linear-positive correlations between ENM concentration and oxidative damage, our results suggested that low concentrations were generally pro-oxidant and higher concentrations appeared antioxidant or protective, as indicated by DCF fluorescence trends. nZnO and nCeO2 also affected pH in a manner dependent on concentration and elemental composition; higher nZnO concentrations maintained a more alkaline pH, while nCeO2 tended to decrease pH. No other biomarkers of oxidative damage (FRAP, MDA, PC, lipase activity) showed changes at any ENM concentration or time-point tested. Differential dissolution of the two ENMs was also observed, where as much as ∼31.3% of nZnO was instantaneously dissolved to Zn(2+ )and only negligible nCeO2 was degraded. The results suggest that the direct oxidative potential of nZnO and nCeO2 in citrated rat blood plasma is low, and that a physiological or immune response is needed to generate appreciable damage biomarkers. The data also highlight the need for careful consideration when selecting a model for assessing ENM toxicity.

  1. Anticonvulsant and proconvulsant roles of nitric oxide in experimental epilepsy models

    Directory of Open Access Journals (Sweden)

    Del-Bel E.A.

    1997-01-01

    Full Text Available The effect of acute (120 mg/kg and chronic (25 mg/kg, twice a day, for 4 days intraperitonial injection of the nitric oxide (NO synthase (NOS inhibitor NG-nitro-L-arginine (L-NOARG was evaluated on seizure induction by drugs such as pilocarpine and pentylenetetrazole (PTZ and by sound stimulation of audiogenic seizure-resistant (R and audiogenic seizure-susceptible (S rats. Seizures were elicited by a subconvulsant dose of pilocarpine (100 mg/kg only after NOS inhibition. NOS inhibition also simultaneously potentiated the severity of PTZ-induced limbic seizures (60 mg/kg and protected against PTZ-induced tonic seizures (80 mg/kg. The audiogenic seizure susceptibility of S or R rats did not change after similar treatments. In conclusion, proconvulsant effects of NOS inhibition are suggested to occur in the pilocarpine model and in the limbic components of PTZ-induced seizures, while an anticonvulsant role is suggested for the tonic seizures induced by higher doses of PTZ, revealing inhibitor-specific interactions with convulsant dose and also confirming the hypothesis that the effects of NOS inhibitors vary with the model of seizure

  2. Oxidation of a model alkane aerosol by OH radical: the emergent nature of reactive uptake.

    Science.gov (United States)

    Houle, F A; Hinsberg, W D; Wilson, K R

    2015-02-14

    An accurate description of the evolution of organic aerosol in the Earth's atmosphere is essential for climate models. However, the complexity of multiphase chemical and physical transformations has been challenging to describe at the level required to predict aerosol lifetimes and changes in chemical composition. In this work a model is presented that reproduces experimental data for the early stages of oxidative aging of squalane aerosol by hydroxyl radical (OH), a process governed by reactive uptake of gas phase species onto the particle surface. Simulations coupling free radical reactions and Fickian diffusion are used to elucidate how the measured uptake coefficient reflects the elementary steps of sticking of OH to the aerosol as a result of a gas-surface collision, followed by very rapid abstraction of hydrogen and subsequent free radical reactions. It is found that the uptake coefficient is not equivalent to a sticking coefficient or an accommodation coefficient: it is an intrinsically emergent process that depends upon particle size, viscosity, and OH concentration. An expression is derived to examine how these factors control reactive uptake over a broad range of atmospheric and laboratory conditions, and is shown to be consistent with simulation results. Well-mixed, liquid behavior is found to depend on the reaction conditions in addition to the nature of the organic species in the aerosol particle.

  3. Special quasirandom structure modeling of fluorite-structured oxide solid solutions with aliovalent cation substitutions

    Science.gov (United States)

    Wolff-Goodrich, Silas; Hanken, Benjamin E.; Solomon, Jonathan M.; Asta, Mark

    2015-07-01

    The accuracy of the special quasirandom structure (SQS) approach for modeling the structure and energetics of fluorite-structured oxide solid solutions with aliovalent cation substitutions is assessed in an ionic-pair potential study of urania and ceria based systems mixed with trivalent rare-earth ions. Mixing enthalpies for SQS supercells containing 96 and 324 lattice sites were calculated using ionic pair potentials for U0.5La0.5O1.75, U0.5Y0.5O1.75, Ce0.5La0.5O1.75, Ce0.5Y0.5O1.75, and Ce0.5Gd0.5O1.75, which all have stoichiometries of pyrochlores. The SQS results were compared to benchmark values for random substitutional disorder obtained using large supercell models. The calculations show significant improvement of the mixing enthalpy for the larger 324 site SQS, which is attributed to a better description of the structural distortions, as characterized by the radial distribution functions in relaxed systems.

  4. Role of Renin-Angiotensin System and Oxidative Stress on Vascular Inflammation in Insulin Resistence Model

    Directory of Open Access Journals (Sweden)

    N. F. Renna

    2013-01-01

    Full Text Available (1 This study aims to demonstrate the causal involvement of renin angiotensin system (RAS and oxidative stress (OS on vascular inflammation in an experimental model of metabolic syndrome (MS achieved by fructose administration to spontaneously hypertensive rats (FFHR during 12 weeks. (2 Chronic treatment with candesartan (C (10 mg/kg per day for the last 6 weeks or 4OH-Tempol (T (10−3 mmol/L in drinking water for the last 6 weeks reversed the increment in metabolic variables and systolic blood pressure. In addition, chronic C treatment reverted cardiovascular remodeling but not T. (3 Furthermore, chronic treatment with C was able to completely reverse the expression of NF-κB and VCAM-1, but T only reduced the expression. C reduced the expression of proatherogenic cytokines as CINC2, CINC3, VEGF, Leptin, TNF-alpha, and MCP-1 and also significantly reduced MIP-3, beta-NGF, and INF-gamma in vascular tissue in this experimental model. T was not able to substantially modify the expression of these cytokines. (4 The data suggest the involvement of RAS in the expression of inflammatory proteins at different vascular levels, allowing the creation of a microenvironment suitable for the creation, perpetuation, growth, and destabilization of vascular injury.

  5. Multi-scale modeling of oxidation of CFRP induced by CW laser

    Science.gov (United States)

    Nan, Pengyu; Shen, Zhonghua; Ni, Xiaowu

    2017-05-01

    A multiscale approach is used to analyze the oxidation ablation of parallel carbon fiber (the fibers are parallel to the material surface) reinforced polymer composites(CFRP). The matrix and fiber will be eroded at extreme temperatures. Because the ablation rate of matrix is bigger than fiber, the fiber will be exposed in a certain depth from surface. In the microscale, a model is developed for analyzing the number of exposed fibers and the fiber geometry at low air flow and different temperatures. The model shows that the exposed number increases with the growth of ratio of ablation rate of matrix and fiber, and the ratio doesn't monotonously increase with the rise of temperature. Surface ablation gradually turns to volume ablation with the increase of the number of exposed fibers. In the macroscale, the effective reactivity of the material is equal to the integral over the ablation zone. Compared with perpendicular carbon fiber reinforced polymer composites, both of them reach maximum number or length of exposed fibers during the transition temperature region where "reactivity limit" turns to "diffusion limit". When the fibers are perpendicular to the surface, the macro ablation behavior agrees with "weakest link law", in other words the matrix recession rate is the most determining parameter for the effective behavior, but it may be not reasonable for parallel fibers.

  6. Exploring the chemical kinetics of partially oxidized intermediates by combining experiments, theory, and kinetic modeling.

    Science.gov (United States)

    Hoyermann, Karlheinz; Mauß, Fabian; Olzmann, Matthias; Welz, Oliver; Zeuch, Thomas

    2017-07-19

    Partially oxidized intermediates play a central role in combustion and atmospheric chemistry. In this perspective, we focus on the chemical kinetics of alkoxy radicals, peroxy radicals, and Criegee intermediates, which are key species in both combustion and atmospheric environments. These reactive intermediates feature a broad spectrum of chemical diversity. Their reactivity is central to our understanding of how volatile organic compounds are degraded in the atmosphere and converted into secondary organic aerosol. Moreover, they sensitively determine ignition timing in internal combustion engines. The intention of this perspective article is to provide the reader with information about the general mechanisms of reactions initiated by addition of atomic and molecular oxygen to alkyl radicals and ozone to alkenes. We will focus on critical branching points in the subsequent reaction mechanisms and discuss them from a consistent point of view. As a first example of our integrated approach, we will show how experiment, theory, and kinetic modeling have been successfully combined in the first infrared detection of Criegee intermediates during the gas phase ozonolysis. As a second example, we will examine the ignition timing of n-heptane/air mixtures at low and intermediate temperatures. Here, we present a reduced, fuel size independent kinetic model of the complex chemistry initiated by peroxy radicals that has been successfully applied to simulate standard n-heptane combustion experiments.

  7. Modelling of gaseous dimethylamine in the global atmosphere: impacts of oxidation and aerosol uptake

    Directory of Open Access Journals (Sweden)

    F. Yu

    2014-07-01

    Full Text Available Recent laboratory studies indicate that while a dimethylamine concentration ([DMA] of several pptv can substantially enhance nucleation rates, such an enhancement drops significantly as [DMA] decreases below a few pptv. Here we study global distributions of amines with a chemistry transport model. DMA's lifetime is quite short (1–2 h in some regions due to aerosol uptake and oxidation. Aerosol uptake is important over regions of high anthropogenic emissions, while the decrease of the uptake coefficient (γ from 0.03 to 0.001 in these regions increases the modeled amine concentrations by a factor of ~5. Further decrease of γ from 0.001 to 0 has a small (<10% effect on the predicted amine concentrations. With the estimated global emission flux, from the reference, our simulations indicate that [DMA] in the surface layer is generally less than 1 pptv over major continents and below 0.1 pptv over oceans, decreasing quickly with altitude. Total concentrations of methylamines are about one order of magnitude higher than that of DMA. A comparison of simulated and observed [DMA] shows that the values of the simulated [DMA] are close to the measured values for the various urban sites but are substantially lower (by 1–2 orders of magnitude than those measured at the rural, coastal, and marine sites.

  8. Modelling of gaseous dimethylamine in the global atmosphere: impacts of oxidation and aerosol uptake

    Science.gov (United States)

    Yu, F.; Luo, G.

    2014-07-01

    Recent laboratory studies indicate that while a dimethylamine concentration ([DMA]) of several pptv can substantially enhance nucleation rates, such an enhancement drops significantly as [DMA] decreases below a few pptv. Here we study global distributions of amines with a chemistry transport model. DMA's lifetime is quite short (1-2 h in some regions) due to aerosol uptake and oxidation. Aerosol uptake is important over regions of high anthropogenic emissions, while the decrease of the uptake coefficient (γ) from 0.03 to 0.001 in these regions increases the modeled amine concentrations by a factor of ~5. Further decrease of γ from 0.001 to 0 has a small (<10%) effect on the predicted amine concentrations. With the estimated global emission flux, from the reference, our simulations indicate that [DMA] in the surface layer is generally less than 1 pptv over major continents and below 0.1 pptv over oceans, decreasing quickly with altitude. Total concentrations of methylamines are about one order of magnitude higher than that of DMA. A comparison of simulated and observed [DMA] shows that the values of the simulated [DMA] are close to the measured values for the various urban sites but are substantially lower (by 1-2 orders of magnitude) than those measured at the rural, coastal, and marine sites.

  9. Aggregation kinetics of graphene oxides in aqueous solutions: experiments, mechanisms, and modeling.

    Science.gov (United States)

    Wu, Lei; Liu, Lin; Gao, Bin; Muñoz-Carpena, Rafael; Zhang, Ming; Chen, Hao; Zhou, Zuhao; Wang, Hao

    2013-12-10

    Although graphene oxide (GO) has been used in many applications to improve human life quality, its environmental fate and behavior are still largely unknown. In this work, a novel approach that combines experimental measurements and theoretical calculations was used to determine the aggregation kinetics of GO sheets in aqueous solutions under different chemistry conditions (e.g., cation valence and pH). Experimental data showed that both cation valence and pH showed significant effect on the aggregation of GO sheets. The measured critical coagulation concentrations were in good agreement with the predictions of the extended Schulze-Hardy rule. Ca(2+) and Mg(2+) were more effective than Na(+) in aggregating the GO sheets, which could be attributed to the cross-linking between GO sheets by the divalent cations through "bridging" the functional groups at the edges of the GO sheets. When solution pH increases, deprotonation of carboxylic groups was found to play a key role in increasing GO sheet stability and surface charge development. These results suggested that edge-to-edge and face-to-face interactions were the dominant modes of GO aggregation in the presence of divalent metal ions and H(+), respectively. A modified attachment efficiency (α) model was developed on the basis of the Maxwell approach with considerations of both primary and secondary minima. The model predictions matched the experimental measurements of the aggregation kinetics of GO sheets in aqueous solutions under all of the tested experimental conditions well.

  10. Modeling and optimization of catalytic partial oxidation methane reforming for fuel cells

    Science.gov (United States)

    Chaniotis, A. K.; Poulikakos, D.

    The objective of this paper is the investigation and optimization of a micro-reformer for a fuel cell unit based on catalytic partial oxidation using a systematic numerical study of chemical composition and inflow conditions. The optimization targets hydrogen production from methane. Additionally, the operating temperature, the amount of carbon formation and the methane conversion efficiency are taking into account. The fundamental investigation is first based on simplified reactor models (surface perfectly stirred reactor (SPRS)). A detailed surface chemistry mechanism is adopted in order to capture all the important features of the reforming process. As a consequence, the residence time of the process is taken into account, which means that the products are not necessary in equilibrium. Subsequently, in order to test the validity of the findings from the simplified reactor model, more detailed simulations (involving the Navier-Stokes equations) were performed for the regions of interest. A region where all the targeted operating conditions are satisfied and the yield of hydrogen is around 80% is identified.